MXPA02003450A - Elastic article. - Google Patents

Abstract

An elastic article is provided which comprises a foam matrix formed from a polymeric material and a plasticiser, a stabilising agent and an active ingredient, such as a detergent active ingredient, typically to be delivered to an aqueous environment. Said elastic article provides a means to deliver an active ingredient to an aqueous environment, preferably the active ingredients being a detergent active ingredient, preferably enzymes, and the aqueous environment being the wash water.

Description

ELASTIC ARTICLE TECHNICAL FIELD OF THE INVENTION The present invention discloses elastic articles, usually particles, comprising a matrix formed of a polymeric material and a plasticizer, a stabilizing agent and an active ingredient, as a detergent active ingredient, which are generally to be administered in a medium aqueous.

BACKGROUND OF THE INVENTION Compositions such as cleaning products, personal care products, cosmetics and pharmaceuticals often comprise active ingredients that are administered in water or that require to be active in an aqueous environment. Many of these active ingredients are sensitive to moisture, changes in temperature, light and / or air during storage. Another problem with many of these active ingredients, in particular enzymes, is that they tend to form dust due to the physical forces directed to them during handling. This not only creates a waste product but also dust can cause problems of hygiene and health.

Attempts to overcome these problems have led to the development of a protection for these active ingredients by coating agents or encapsulating agents. The problem with many of these coated particles is that they do not always show sufficient impact resistance during their handling, and when they are affected by physical forces during their handling, dust is formed which causes health and hygiene problems. The inventors have found an improved method for protecting the active ingredients and administering these active ingredients to aqueous environments. They have found that the specific elastic articles comprising a foam matrix formed of polymeric material and a plasticizer, are very resistant to impacts and the active ingredient that is incorporated therein is protected against the physical forces acting on said elastic article. . In addition, the inventors have found that when a stabilizing agent is also incorporated into the elastic article, the active ingredient is more protected against air, moisture and chemical reactions that can cause the active ingredient to deteriorate. Therefore, the elastic article of the present invention is very resistant to impacts, resulting in reduced abrasion or breakage during handling and reduced powder formation, and the active ingredient that is incorporated therein is protected against air, humidity or chemical reactions and remains stable in said article during storage. For example, elastic articles can be obtained, such as particles or beads, which comprise enzymes, which are safer and more efficient to handle and use. In addition, these articles can be made in such a way that they administer the active ingredients incorporated therein, such as enzymes, very efficiently into an aqueous environment. Typically, the article of the invention is present in the form of a foam article that is stable to air under normal storage moisture conditions, but unstable upon contact with water, so as to administer the active ingredient. The active ingredient is useful in any product, especially useful in cleaning products, pharmaceuticals, personal care products, cosmetics products and fabric care products.

BRIEF DESCRIPTION OF THE INVENTION The present invention provides an elastic article comprising; a) an active ingredient; and b) a foam matrix formed of a polymeric material and a plasticizer; and c) a stabilizing agent; wherein said article is capable of administering said active ingredient to a liquid environment.

The elastic article of the present invention preferably comprises a foam matrix having a glass transition temperature (Tg) below 50 ° C, preferably below 40 ° C. Preferably, the elastic article in the form of a foam and is stable on contact with air and unstable on contact with water, said article preferably having an elastic modulus of less than 0.1 GN.m "2, preferably less than 0.01 GN.m "2. The stabilizing agent is capable of stabilizing the active ingredient of the article of the present invention. The stability of the active ingredient depends on the stability of the foam matrix and / or the stability of the active ingredient itself. Therefore, the stabilizing agent may be, or may comprise, an agglomerate stabilizing agent, which is capable of stabilizing the foam matrix in the elastic article and during storage or the preparation process of the elastic article. The active ingredient can also be stabilized through the stabilizing agent directly. For example, by increasing the structural stability of the active ingredient. Therefore, it may also be preferred that the stabilizing agent be, or comprise, an active ingredient stabilizing agent. It may also be preferred that the active ingredient of said elastic article comprises at least one enzyme. If the elastic article comprises an enzyme, then the enzyme may be sensitive to, and denatured or begin to denature in the presence of moisture, air or bleach (if present). Therefore, it may be preferred that the stabilizing agent be an enzyme stabilizing agent, which is capable of stabilizing the enzyme in the elastic particle and during the process of preparing the elastic particle. The present invention also describes methods for making the elastic article. Preferably, the elastic article is obtained by a process comprising the steps of; a) obtaining a mixture of a polymeric material and a plasticizer, preferably water and another plasticizer; and b) chemically or physically introducing a gas into said mixture; and c) before step b) and / or simultaneously with step b) and / or after step b), contacting an active ingredient with said mixture; and d) before step c) and / or simultaneously with step c) and / or after step c), contacting a stabilizing agent with said mixture; and e) shaping the article of the resulting mixture; wherein, preferably one or more steps a) to e) are followed or accompanied by the removal of part of the water, if present. In another embodiment of the present invention, there is provided the use of an elastic article for administering active ingredients to an aqueous environment, preferably that the active ingredients are detergent active ingredients, preferably enzymes, and that the aqueous environment is rinse water.

DETAILED DESCRIPTION OF THE INVENTION Elastic article The elastic article of the present invention, hereinafter the "article", comprises an active ingredient, a matrix and a stabilizing agent. Said active ingredient, matrix and stabilizing agent are described in more detail below. Said article of the present invention is preferably hydrodispersible, water soluble and hydrodisintegration. Preferably the hydrodispersible articles of the present invention have a dispersibility of at least 50%, preferably at least 75% or even at least 95%, as measured by the method stipulated hereafter employing a glass filter with a size maximum pore 50 microns; more preferably the article of the present invention is water-soluble or hydrodisintegrable and has a solubility or disintegration of at least 50%, preferably at least 75% or even at least 95%, as measured by the method stipulated hereafter employing a glass filter with a maximum pore size of 20 microns, mainly: The gravimetric method for determining the water solubility, hydrodisintegrability or hydrodispersibility of the article of the present invention: 50 grams ± 0.1 grams of the article of the present invention are added in a 400 ml beaker, where the weight has been determined, and Add 245 ml ± 1 ml of distilled water. This is vigorously agitated on a magnetic stirrer set at 600 rpm for 30 minutes. Subsequently, the water-polymer mixture is filtered through a qualitative sintered glass filter folded with the pore sizes as defined above (maximum 20 or 50 microns). The water is removed from the collected filtrate by any conventional method, and the weight of the remaining article (which is the dissolved, disintegrated or dispersed fraction) is determined. Subsequently, the% solubility, disintegration or dispersibility can be calculated. The article of the present invention is usually used to administer active to aqueous environments. Therefore, the article of the present invention, and preferably the matrix thereof, is preferably unstable when placed in contact with water. This occurs in such a way that the active ingredients or part thereof, present in the article are administered to a liquid, preferably an aqueous environment such as water. Preferably the article or part thereof is denatured, disintegrated, preferably dispersed or dissolved in liquid, preferably in an aqueous environment, more preferably in water. It may be preferred that the active ingredient be rapidly administered to the water and that the elastic be such that it disperses or dissolves rapidly; preferably at least 10% of the article, by weight, is dissolved or dispersed in 30 minutes after said article comes in contact with water, or more preferably at least 30% or even at least 50% or even at least 70% % or even at least 90% (introduced in water at 1% by weight concentration). You can even prefer this to happen within the first 20 minutes or even 10 minutes or even 5 minutes after the item came into contact with water. The solution or dispersion can be measured by the method described above to measure the dissolution, disintegration and dispersion of the article of the present invention. Preferably the elastic article is such that the total volume of the article changes, preferably it is reduced, at least 10%, compared to the initial total volume, for example, it can be determined when 1cm3 of the article is added to 100ml of water demineralized and stirred for 5 minutes at a speed of 200 rpm, at a temperature of 25 ° C. Preferably, the change, or preferably the reduction, in the total volume is at least 20% or even at least 40% or even at least 60% or even at least 90% or even around 100%, for example, because It may be preferred that almost the entire article disintegrate, disperse or dissolve in the water quickly.

This can be measured by the use of any method known in the art, in particular in the present invention with a method as presented below (double immersion technique): 1cm3 of elastic article is obtained and inserted into a micro measuring cylinder volumetric 100 ml that is filled with 50 ml ± 0.1 ml of an inert organic solvent. For example, acetone is used when it results that it is not denatured and / or does not interact with the polymeric material in the elastic article matrix of the present invention, for example when it is PVA. Another neutral organic medium can be used according to the nature of the article under investigation; the inert solvent is such that the article does not dissolve, disperse, disintegrate or substantially denature the article. The cylinder is sealed so that no air enters and is allowed to stand for 1 minute for the solvent to penetrate the entire elastic article. The change in volume is measured and taken as the original volume V, of the foam specimen. The article is removed from the solvent and allowed to air dry in such a way that the solvent evaporates. The article is placed in a 250 ml beaker containing 100 ml of demineralised water, kept at 25 ° C, under agitation at 200 rpm with the aid of a magnetic stirrer, for 5 minutes. The rest of the article specimen, if present, is filtered with a 60mm copper mesh filter and placed in an oven at a temperature and for a period so that the wastewater is completely removed. The remaining dry article is reintroduced into the measuring cylinder whose volume of acetone has been readjusted to 50 ml.

The increase in the total volume is monitored and taken as the final volume of the elastic article Vf. The decrease in the total volume? V of Specimen of the elastic article is: %? F = ^ * 100 Vi The elastic article preferably has a relative density p * from 0.01 to 0.95, more preferably from 0.05 to 0.9 or even from 0.1 to 0.8 or even from 0.3 to 0.7. The relative density is the ratio of the density of the article (p *), to the sum of the partial densities of the entire volume of materials used to form the article (ps) The preferred foam forming article as used in the present invention is usually stable to air or stable to contact with air, which in the present invention means that the volume of the article or matrix thereof remains substantially the same when the exposes air. This means in particular that the article retains preferably 75% to 125% or even 90% to 110% or even 95% to 100% of its volume when stored in an open beaker (9 cm in diameter; without any protective barrier) in an incubator under conditions of controlled environment (humidity = RH 60%, temperature = 25 ° C) for 24 hours. Preferably the elastic article retains 75% to 125% or even 90% to 110% or even 95% to 100% of its volume under the aforementioned storage conditions where the humidity is 80%. The volume change can be measured by any conventional method. In particular, a digital image registration system containing a digital camera coupled to a personal computer equipped with a calibrated image analyzer software is useful. A specimen of 1 cm3 of article is obtained and placed in an open beaker with a diameter of 9 cm and stored for 24 hours under the aforementioned conditions. After 24 hours, the size in the three dimensions is measured with the image analysis registration system. Each specimen measurement is repeated three times, and the average volume change is calculated in%. Preferably, the elastic article is such that, when in the form of particles of a particle size of medium of 2000 microns or less, these particles also retain 75% to 125% or even 90% to 110% or even from 95% to 100% of its volume. This, for example, can be measured by placing 20 grams of said particles, or a weight comprising more than 500 particles, in a beaker of volumetric precipitation having a diameter of 9 cm. The beaker is bled slightly at its base until the elastic particles rearrange themselves in a stable position with a horizontal top surface. The volume is measured. The open beaker with the particles of the foam component is carefully placed in the incubator for 24 hours, set at the desired% RH and temperature. The volume after 24 hours is measured and the change in volume is calculated in%. The elastic article comprises (by weight) preferably at least 1% active ingredients, more preferably from 5% to 70%, more preferably at least 10% by weight of the article, more preferably 15% or even 20% or even 25% to 50%. The elastic article comprises (by weight) preferably 10% to 90% agglomerate, more preferably at least 20% or even 30% to 99%, more preferably 20% or 30% to 90% to 80%. The elastic article comprises (by weight) at least 1% stabilizing agent, more preferably 5%, or 10%, or 15%, or 20% and 50%, or 40%, or 30%, or 25% Agglomerated Material The matrix of the elastic article of the present invention, hereinafter the "matrix", is formed of a polymeric material and a plasticizer. Said polymeric material and said plasticizer are described in more detail below. The ratio of the plasticizer to the polymeric material in the matrix is preferably 1 to 100, more preferably 1 to 70 or 1 to 50, more preferably 1 to 30 or even 1 to 20, depending on the type of plasticizer and polymeric material used. For example, when the polymeric material ftátfa. mr comprises PVA and the plasticizer comprises glycerin or glycerol derivatives and optionally water, the ratio is preferably about 1: 15 to 1: 8, a preferred ratio is about 10: 1. The matrix of the present invention further comprises the active ingredient of the article of the present invention and / or the stabilizing agent of the article. Said active ingredient and said stabilizing agent are described in more detail hereinafter. Interlacing agents can also be added to modify the properties of the matrix or the resulting article as appropriate. Borate may be useful in the matrix of the present invention. The matrix of the present invention has a glass transition temperature (Tg) of less than 50 ° C, preferably less than 40 ° C, preferably less than 20 ° C or even less than 10 ° C or even less than 0 ° C. Preferably the matrix of the present invention has a Tg above -20 ° C or above -10 ° C. The Tg of the matrix when used in the present invention is the Tg of the matrix as presented in the article, which should therefore be a mixture of polymeric material and a plasticizer only, or a mixture of polymeric material, plasticizer , active ingredient and / or stabilizing agent, and in any case, optional additional ingredients (such as, densification aids, fillers, lubricants, etc., as described hereinafter) may be present.

The Tg as used in the present invention is as defined in the textbook "Dynamic Mechanical Analysis" (page 53, Figure 3.11c on page 57), the temperature of a material (matrix) where the material (matrix) changes from a glassy state to a rubbery state, mainly where the chains gain enough mobility to slip between them. The Tg of the matrix of the article of the invention can be measured in Perkin-Elmer DMA 7e equipment, following the instructions in the operations manual for this equipment, generating a curve as illustrated in the book Dynamic Mechanical Analysis - page 57, figure 3-11c. The Tg is the temperature or frequency of recording as measured with this equipment, between the glass and the "leathery region", as defined in that text. The matrix, and preferably the elastic article as a whole, has a specific elasticity and flexibility due to its transition temperature of the specific vitreous state. In particular, this means that the matrix and the article are deformed in a reversible manner, absorbing the energy of the impacts or forces in such a way that the article or matrix substantially maintains its original volume after the physical forces cease to apply. the component. The elasticity can be defined by the elastic modulus of the matrix, or even the article, which once again can be defined by the Young modulus. This can be calculated from mechanical strain or deformation tests as are known in the art, for example when using the Perkin-Elmer DMA 7e equipment following the manufacturer's experimental procedure on a static strain scale of%, mainly in the static deformation scale of 10-40%. This represents a maximum deformation that could be applied during normal manufacturing or handling. Therefore, the elastic modulus as defined in the present invention is the maximum modulus as measured with this equipment in the 10% to 40% scale of static deformation. For example you can use a piece of matrix (or article) of 1cm3 in the test with this equipment. The matrix of the present invention usually has an elastic modulus or Young modulus of less than 4GN.m "2, or usually less than 2GN.m "2, even more preferably less than 1GN.m" 2, but usually even less than 0.5GN.m "2, or even less than 0.1 GN.m" 2, or even less than 0.01 GN.m "2, as measured by the Perkin-Elmer DMA 7e kit.In particular, a matrix containing gas bubbles, for example, formed by processes involving the introduction of air into the matrix, has an elastic modulus below 0.1 GN.m "2, or even 0.01 GN.m" 2 or even below O.OOdGN.m "2 or even below 0.0001 GN.m" 2. Preferably, the matrix It is flexible, so that it has a relative deformation greater than 2%, and preferably greater than 15% or even greater than 50%, as measured with the Perkin-Elmer DMA 7e equipment. (The deformation is, in this measurement , the limit of deformation at which a piece of matrix is irreversibly deformed.) In particular, this means that when a sample of matrix having a cross section of a length e specifica, for example 1 cm, is compressed with a static force applied along the axis of that cross section, the static force variable but at least equivalent to twice the atmospheric pressure, the change of this length after removing the force is of at least 90% to 110% of the original length. This, for example, can be measured by using Perkin-Elmer DMA 7e equipment. Similarly, the matrix is preferably flexible to such an extent that when a matrix sample having a cross section of a specific length, for example 1 cm, is compressed with a static force applied along the axis of that cross section , the static force variable but at least equivalent to twice the atmospheric pressure, the change of this length after removing the force is at least 90% to 110% of the original length. For example, this can be measured by using Perkin-Elmer DMA 7e equipment. In particular, when this equipment is used, these static forces applied along the axis of a cross section of a 1 cm 3 matrix sample increase gradually until the deformation of the component, in the direction of the cross section, is 70%. %. Then, the force is removed and the final deformation of the matrix sample in the direction in which the cross section is measured is measured. Preferably, this length of the cross section after this experiment is preferably 90% to 110% of the original length of the cross section, preferably 95% to 105% or even 98% to 100%. 7 The elastic modulus or Young module is related to the relative density, mainly E * P * E. where p * is the relative density of the matrix or even the article, and ps is the relative densities of the components of the matrix or article, as described in the present invention, and E * is the Young's modulus of the matrix or even of the elastic article itself, and It is that of the components of the matrix or even of the article. This means that even a rigid polymeric material, with an elevated Es, can become an elastic flexible matrix by adjusting the levels and / or type of plasticizer and optionally by modifying the density (or for example when introducing gas during the process of making elastic foam articles as described below). The matrix, or even the article as a whole, is present, of Preference, in the form of a foam and preferably in such a way that form an interconnected network of open and / or closed cells, in particular a network of solid struts or plates that form the edges and faces of the open and / or closed cells. The space inside the cells can contain part of the active ingredient and / or a gas, such as air. Preferably, the ratio of closed cells to cells open in the article matrix, or the article as a whole is more than 1: 1, of preference more than 3: 2 or even more than 2: 1 or even more than 3: 1. This relationship can be determined by calculating the Total Volume of a specimen of the matrix or article, VT, (assuming a spherical shape), and later measuring with a Mercury Porosimetry Test Method the Open Cell Volume (Vo) and subtracting the Volume of Open Cell to Total Volume should result in the Volume of Closed Cell (See: VT = Vo + Vc).

Polymeric Material Any polymeric material can be used to form the matrix of the present invention, as long as it has a Tg as defined above or more typically, a matrix can be formed with the Tg as defined above by the use of an amount appropriate plasticizer. Preferably, the polymeric material comprises or consists of amorphous polymers. The polymeric material may consist of a single type of homologous polymer or may be a mixture of polymers. The polymer blends can, in particular, be beneficial for controlling the mechanical properties and / or dissolution of the elastic article, depending on the application thereof and the requirements thereof. Preferably that the polymeric material comprises a hydrodispersible polymer or more preferably a water-soluble polymer.

Hydrodispersible and water-soluble are normally defined as described above with respect to the method for determining the water solubility and hydrodispersibility of the article of the present invention. The hydrodispersible polymers of the present invention have a dispersion capacity of at least 50%, preferably at least 75% or even at least 95%, as measured by the method set forth above using a glass filter with a maximum pore size of 50 microns; more preferably the polymer of the present invention is a water-soluble polymer having a solubility of at least 50%, preferably at least 75% or even at least 95%, as measured by the method set forth above using a glass filter with a maximum pore size of 20 microns. The polymer can have any average molecular weight, preferably from about 1000 to 1,000,000 or even from 4000 to 250,000 or even from 10,000 to 200,000 or even from 20,000 to 75,000. The highly preferred polymeric material can be that with an average molecular weight of 30,000 to 70,000. Depending on the properties required of the article of the present invention, the polymeric material can be adjusted. For example, to reduce solubility, polymers can be included in the material, which has high molecular weights usually above 50,000 or even above 100,000 and vice versa. For example, to change the solubility, polymers of varying level of hydrolysis can be used. For example, to improve (reduce) the elastic modulus, the entanglement of the polymers can be increased and / or the molecular weight can be increased.

It may be preferable that the polymer used in the elastic article of the present invention have a secondary function, for example a function in the composition in which the article is to be incorporated. Therefore, for example for cleaning products, it is useful when the polymer in the polymeric material is a polymer for inhibiting transfer of dye, dispersant, etc. Preferred are polymers selected from polyvinyl alcohols and derivatives thereof, polyethylene glycols and derivatives thereof, polyvinyl pyrrolidone and derivatives thereof, cellulose ethers and derivatives thereof, and copolymers of these polymers with themselves or with other monomers or oligomers. Most preferred are PVP's (and derivatives thereof) and / or PEG's (and derivatives thereof) and most preferably PVA's (and derivatives thereof) or mixtures of PVA's with PEG and / or PVP (or derivatives thereof). the same). The most preferred may also be a polymeric material comprising only PVA. Preferably, said polymers have a hydrolysis level of at least 50%, more preferably at least 70% or even from 85% to 95%.

Plasticizer Any plasticizer that is suitable to assist in the formation of a matrix as defined in the present invention can be used. It is also possible to use mixtures of plasticizers. Preferably, when water is used, an additional plasticizer is present. Preferably, the plasticizer or at least one of the plasticizers has a boiling point above 40 ° C, preferably above 60 ° C, or even above 95 ° C, or even above of 120 ° C, or even above 150 ° C. Preferred plasticizers include glycerol or glycerin, glycol derivatives including ethylene glycol, digomeric polyethylene glycols such as diethylene glycol, triethylene glycol and tetraethylene glycol, polyethylene glycol with an average weight M.W. less than 1000, wax and carbocera, ethanolacetamide, ethanolformamide, triethanolamine or acetate thereof, and salts of ethanolamine, sodium thiocyanates, ammonium thiocyanates, polyols such as 1,3-butanediol, sugars, sugar alcohols, ureas, dibutyl or dimethyl phthalate, oxamonoacids, oxadiazines, diglycolic acids and other linear carboxylic acids with at least one ether group distributed along the chain thereof, water or mixtures thereof. The plasticizer is preferably present at a level of at least 0.5% by weight of the article, preferably by weight of the matrix, provided that in the case that water is the only plasticizer, it is present at a level of at least 3%, by weight of the article, or preferably by weight of the matrix. Preferably, the plasticizer is present at a level of 1% to 35% by weight of the article or matrix, more preferably 2% to 25% or even 2 to 15% or even 10% or even 8% by weight of the article or by weight of the matrix. The exact level will depend on the poiimeric material and the plasticizer used, but it must be such that the matrix of the article has the desired Tg. For example, when urea is used, the level is preferably 1% to 10% by weight of the matrix, whereas when glycerin or ethylene glycol or other glycol derivatives are used, higher levels, for example 2% to 15%, may be preferred. % by weight of the article or matrix.

Active ingredient The active ingredient can be any material to be administered in a liquid environment, or preferably an aqueous environment and preferably an ingredient that is active in an aqueous environment. For example, when employed in cleaning compositions the article may contain any active cleaning ingredients. The articles may also comprise compositions, such as cleaning compositions or personal care compositions. In particular, this is beneficial for incorporating into the article elastic active ingredients that are sensitive to moisture or that react to contact with moisture, or solid ingredients that have a limited impact robustness and tend to form dust during handling. The active ingredient is usually a moisture sensitive ingredient, a temperature sensitive ingredient, an oxidizable ingredient, a volatile ingredient, or a combination thereof. The active ingredient and, ^ ^ ^ ^ ^ EtSt may be viable biological material, hazardous or toxic material, an agricultural ingredient such as an agrochemical or pharmaceutical ingredient as a medicine or drug, or a cleaning ingredient. In particular, active ingredients such as enzymes, perfumes, bleaches, bleach activators, silicone and / or cationic fabric softeners and / or conditioners, antibacterial agents, effervescence systems, brighteners, photo bleaches and mixtures are preferred in elastic articles. thereof. A preferred active ingredient is a perhydrate bleach, such as metal perborates, metal percarbonates, in particular sodium salts. Also the preferred active ingredients are the organic peroxyacid bleach precursor or activator compound, the preferred are the alkylpercarboxylic precursor compounds, of the imide type, include the N-, N, N1N1-tetraacetylated alkylenediamines wherein the alkylene group contains from 1 to 6 atoms carbon, particularly those compounds wherein the alkylene group contains 1, 2 and 6 carbon atoms such as tetracetylethylenediamine (TAED), sodium 3,5,5-tri-methyl hexanoyloxybenzenesulfonate (iso-NOBS), sodium nonanoyloxybenzenesulfonate (NOBS) sodium acetoxybenzenesulfonate (ABS) and pentaacetyl glucose, but also substituted amide peroxy acid precursor compounds. The highly preferred active ingredients for use in the elastic article of the present invention are one or more enzymes. Preferred enzymes include lipases, cutinases, amylases, neutral and alkaline proteases, cellulases, endolases, esterases, pectinases, lactases and peroxidases incorporated in a conventional manner in detergent compositions and which are commercially available. Suitable enzymes are those mentioned in US patents 3,519,570 and 3,533,139. Commercially available protease enzymes include those sold under the tradename Alcalase, Satinase, Primase, Durazym, and Esperase by Novo Industries A / S (Denmark), those sold under the trade name Maxatase, Maxacal and Maxapen by Gist-Brocades, those sold by Genencor Internacional, and those sold under the trade name Opticlean and Optimase by Solvay Enzymes. Preferred amylases include, for example, α-amylases obtained from a special strain of B-licheniform, described in more detail in GB-1, 269,839 (Novo). Preferred commercially available amylases include, for example, those sold under the tradename Rapidase by Gist-Brocades, and those sold under the trade name Termamyl, Duramyl and BAN by Novo Industries A / S. Highly preferred amylase enzymes can be those described in PCT / EUA 9703635, and in WO95 / 26397 and WO96 / 23873. The lipase can be fungal or bacterial in origin obtained, for example, from a lipase that produces the strain of Humicola, thermomyces or Pseudomonas species including Pseudomonas pseudoalcaligenes or Pseudomas fluorescens. The lipase of chemically or genetically modified mutants of these strains is also useful in the present invention. A preferred lipase is derived from Pseudomonas pseudoalcaligenes, which is described in the European patent granted, EP-B-0218272. Another preferred lipase in the present invention is obtained by cloning the Humicola lanuginosa gene and expressing the gene in Aspergillus oryza as a host, as described in the European patent application, EP-A-0258 068, which is commercially available from Novo Industri A / S, Bagsvaerd, Denmark, under the trade name Lipolase. This lipase is also described in U.S. Patent 4,810,414, Huge-Jensen et al, issued March 7, 1989.

Stabilizing Agent The article of the present invention comprises a stabilizing agent, which is usually capable of stabilizing the active ingredient of the article of the present invention, this is especially preferred when the active ingredient (s) comprises an active ingredient sensitive to moisture u oxidative, such as one or more enzymes. The stabilizing agent can also stabilize the matrix of the article of the present invention, and therefore indirectly stabilize the active ingredient. The stabilizing agent is preferably a compound that stabilizes the active ingredient, or matrix of oxidative degradation and / or moisture during storage. The stabilizing agent is also for the active ingredient of the article of the present invention. If the article comprises more than one active ingredient, it is preferable that one of the active ingredients be selected in such a way that it is, or acts as, a stabilizing agent. For the purposes of the present invention, the stabilizing agent is always an additional component of the article for the active ingredient of the article of the present invention. Therefore, for the purposes of the present invention, for an article that will be defined as comprising a stabilizing agent and an active ingredient, wherein said article comprises a component that has a dual function and can function as an active ingredient or an active ingredient. stabilizing agent as defined in the present invention, a stabilizing agent or additional active ingredient, which is also for the compound having a double function, must be present in the article to obtain an article comprising an active ingredient and a stabilizing auxiliary which is in accordance with the present invention. The above statements with respect to the ingredients that have a dual function are also true when considering other embodiments of the present invention. It is essential for the article of the present invention to comprise an active ingredient, a polymeric material and a plasticizer (which forms the matrix), and a stabilizing aid. Therefore, in order to obtain an article in accordance with the present invention, at least four different ingredients must be present in said article. It is preferable to select essential ingredients that have a double function.

The above statements with respect to the dual-function ingredients are also true when considering highly preferred embodiments of the present invention, for example preferred articles comprising additional ingredients as a dissolution aid. The stabilizing agent can be, or comprise, a foam matrix stabilizer. The stabilizing agent can be, or comprise, an active ingredient stabilizer; especially an enzyme stabilizer. Stabilizing agents that are able to stabilize the active ingredient indirectly by keeping the foam matrix of the article stable, hereinafter the "foam stabilizer" preferably comprises a surfactant such as a fatty alcohol, fatty acid, alkanolamide, amine oxide or derivatives thereof, or combinations thereof. The foam stabilizer may comprise betaine, sulfobetaine, phosphine oxide, alkylsulfoxide, derivatives thereof, or combinations thereof. Other preferred foam stabilizers comprise one or more anions or cations such as mono-, di-, tri-valent, or other multivalent metal ions, the preferred salts being sodium, calcium, magnesium, potassium, aluminum, zinc, copper, nickel , cobalt, iron, manganese and silver, preferably having an anionic counter-ion which is a sulfate, carbonate, oxide, chloride, bromide, podide, phosphate, borate, acetate, citrate and nitrate and combinations thereof. The foam stabilizer may comprise finely divided particles, preferably finely divided particles with an average particle size of less than 10 micrometers, more preferably less than 1 micrometer, even more preferably less than 0. 5 micrometers, or less than 0.1 micrometers. The preferred finely divided particles are the aluminosilicates such as zeolite, silica or electrolytes described above in the form of finely divided particles. The foam stabilizer may comprise agar-agar, sodium alginate, sodium dodecyl sulfate, polyethylene oxide, guar gum, polyacrylate, or derivatives thereof, or combinations thereof. The foam stabilizer may be coated which is independent of the matrix of the article of the present invention. The foam stabilizer is usually partially covered, preferably completely covering the article in the present invention or the active ingredient thereof. The cover is usually in contact with, preferably in such a manner to form a layer, the active ingredient before said active ingredient comes into contact with the polymeric material or the plasticizer of the matrix, and is preferably incorporated in the article of the present invention.

The cover can usually be in contact with, preferably in such a manner to form a layer, the article of the present invention subsequent to the polymeric material and the plasticizer forming the matrix, and preferably subsequent to the active ingredient which comes into contact with said matrix or incorporating it into the article of the present invention. The preferred shell comprises polymers, polyvinyl alcohols and derivatives thereof, polyethylene glycols and derivatives thereof, polyvinylpyrrolidone and derivatives thereof, cellulose ethers and derivatives thereof, and copolymers of these polymers with them are usually selected from polyvinyl alcohols and derivatives thereof same or with other monomers or oligomers. Most preferred are PVP's (and derivatives thereof) and / or PEG's (and derivatives thereof) and most preferably PVA's (and derivatives thereof) or mixtures of PVA's with PEG and / or PVP (or derivatives thereof). the same). These polymers do not form the matrix of the article of the present invention. Therefore, these polymers are different from the polymeric materials of the foam matrix. A preferred coating comprises compounds such as glycerol or glycerin, glycol derivatives including ethylene glycol, digomeric polyethylene glycols such as diethylene glycol, triethylene glycol and tetraethylene glycol, polyethylene glycol with an average weight M.W. less than 1000, wax and carbocera, ethanolacetamide, ethanolformamide, triethanolamine or acetate thereof, and salts of ethanolamine, sodium thiocyanates, ammonium thiocyanates, polyols such as 1,3-butanediol, sugars, sugar alcohols, ureas, dibutyl or dimethyl phthalate, oxamonoacids, oxadiazines, diglycolic acids and other linear carboxylic acids with at least one ether group distributed along the chain thereof, water or mixtures thereof. These compounds do not form the foam matrix of the article of the present invention. Therefore, these compounds are different from the plasticizer of the foam matrix. Preferred stabilizing agents that are capable of directly stabilizing the active ingredient, especially if said active ingredient comprises one or more enzymes, are defined in the present invention as "active stabilizers" or "enzyme stabilizers". Usually, the active stabilizers interact directly with, and stabilize, the active ingredient. In general, active stabilizers for use in the present invention preferably comprise a surfactant. Suitable surfactants for use in the present invention are those described hereinafter as suitable surfactants for use as matrix stabilizers. In addition to these surfactants, other surfactants suitable for use in the present invention may comprise surfactants such as sodium alkylene sulfonates, sodium alkoxysulfonates, preferred alkoxysulfonates are those comprising from 10 to 18 carbon atoms in any conformation, preferably linear , and having an average degree of ethoxylation of 1 to 7, preferably 2 to 5.

Other preferred active stabilizers include boric acid, formic acid, acetic acid, and salts thereof. These acid salts preferably comprise counter-ions such as calcium and / or sodium. Preferred active stabilizers include cations such as calcium and / or sodium. Preferably calcium chloride and / or sodium chloride. Other preferred active stabilizers comprise small peptide chains with an average of 3 to 20, preferably 3 to 10 amino acids, which interact with and stabilize the active ingredient, especially enzyme (s). Other active stabilizers comprise small nucleic acid molecules, typically comprising from 3 to 300, preferably from 10 to 100 nucleotides. In general, the nucleic acid molecules are deoxyribonucleic acid and ribonucleic acid. The nucleic acid molecules can be present in the form of a complex with other molecules as proteins, or can complex with the active ingredient of the article of the present invention, especially enzyme (s). Active stabilizers suitable for use in the present invention, especially when the article of the present invention comprises a bleach, comprise antioxidants and / or reducing agents such as thiosulfate, methionine, urea, thiourea dioxide, guanidine hydrochloride, guanidine carbonate , guanidine sulfamate, monoethanolamine, diethanolamine, triethanolamine, amino acids such as glycine, sodium glutamate, proteins such as casein and bovine serum albumin, tert-butylhydroxytoluene, 4-4, butylidenebis (6-tert-butyl-3-methyl-phenol ), 2,2'-butylidenebis (6-tert-butyl-4-methylphenol), (monosterelated cresol, cresol distylene, monostearylated phenol, phenol-disatinate, 1,1-bis (4-hydroxy-phenyl) -cyclohexane, or the same or a combination thereof Other active stabilizers may comprise a reversible inhibitor of the active ingredient Without wishing to be limited by theory, it is believed that a reversible inhibitor of the active ingredient may be present. Vo, especially if the active ingredient comprises one or more enzymes, can complex with, and improve the stability of, said active ingredient, and in this way, stabilizes the active ingredient during storage. When the active ingredient is released, usually in a liquid environment, the reversible inhibitor is separated from the active ingredient and the active ingredient is then able to perform the desired action for which it was designed or the action that it was determined to perform. The active stabilizers suitable for use in the present invention may comprise sugars. Typical sugars for use in the present invention include those which are selected from the group consisting of sucrose, glucose, fructose, raffinose, trehalose, lactose, maltose, derivatives thereof and combinations thereof. The active stabilizer may also comprise sugar alcohol such as sorbitol, mannitol, inositol, derivatives thereof and combinations thereof.

It may be preferred that the active stabilizer be in the form of a cover or barrier that at least partially covers the article of the present invention or the active ingredient thereof, preferably covering in its entirety the article of the present invention or the ingredient active thereof, especially an enzyme. The article in the present invention may comprise (by weight) 0.01%, or 0.1%, or 1%, or 2%, or 5%, or 7%, or 10%, or 15% , or 20% stabilizing agent, and may comprise (by weight) at 70%, or at 60%, or at 50%, or at 40%, or at 30%, or at 25% stabilizing agent. The amount of stabilizing agent present in the article depends on the amount and type of active ingredient and the amount and type of the matrix of the present invention.

Additional ingredients The component of the invention preferably comprises additional ingredients that can improve the dissolution properties of the article of the present invention. The preferred additional ingredient that improves dissolution of the article of the present invention preferably comprises; a sulfonated compound such as C 1 -C 4 alkenyl sulfonates, C 1 CA alisulfonates, di iso-butylbenzenesulfonate, toluenesulfonate, cumenesulfonate, xylene sulfonate, salts thereof as sodium salts thereof, derivatives thereof, or combinations thereof, preference of iso-butylbenzenesulfonate, sodium toluenesulfonate, sodium cumensulfonate, sodium xylene sulfonate, and combinations thereof; and / or a C1-C4 alcohol such as methanol, ethanol, propanol such as isopropanol and derivatives thereof, and combinations thereof, preferably ethanol and / or iso-propanol; and / or a C4-C10 diol such as hexanediol and / or cyclohexanediol, preferably 1,6-hexanediol and / or 1,4-cyclohexanedimethanol; and / or ingredients that are capable of acting as absorption agents, such as cellulose-based ingredients, especially modified cellulose; and / or numbing agents such as clays, the preferred clays are the smectite clays, especially the diocthedral or trioctraedral smectite clays, the most preferred clays are montmorilonitic clay and hectoritic clay, or other types of clay found in bentonite clay formations; and / or an effervescence system, a preferred effervescence system comprises an acid source capable of reacting with an alkaline source in the presence of water to produce a gas.

PROCEDURE FOR THE PROMOTION OF AN ELASTIC ARTICLE The elastic article of the invention can be made by any process of manufacturing a polymer matrix of the defined Tg of a polymeric material and a plasticizer, and combining an active ingredient and a stabilizing agent with said matrix . Preferred methods involve the chemical or physical introduction of a gas into a mixture of the polymeric material and plasticizer and optionally the active ingredient. A preferred process for the preparation of the article of the present invention comprises the step of a) obtaining a mixture of a polymeric material and a plasticizer, preferably water and an additional plasticizer; b) chemically or physically introducing gas into said mixture of polymeric material and water; c) before step b) and / or simultaneously with step b) and / or after step b), add the active ingredient to said mixture; d) before step c) and / or simultaneously with step c) and / or after step c), contact said stabilizing agent with said mixture; e) shape the articles of the resulting mixture; wherein one or more of steps a) to e) are followed or accompanied by the elimination of part of the water, if any. In step a) the mixture is preferably an aqueous mixture or a thick aqueous suspension and then or in step b), c) and / or d), part of the water is removed in such a way that the resulting article comprises 3% by weight. Free moisture weight, or more. Step c) preferably comprises the step of obtaining a body comprising the active ingredient or part thereof and covering said body with the mixture of step b).

Step d) preferably comprises the step of mixing, more preferably mixing perfectly well or covering, the active ingredient with the stabilizing agent. Preferably, the article comprises open and / or closed cells and the method comprises the steps of a) forming a mixture of the polymeric material, the active material, a stabilizing agent, a plasticizer and a liquid, wherein the liquid and the plasticizer can be the same compound; b) shaping the bodies of the mixture of point b) and c) evaporating the liquid or part thereof to form spaces in the mixture that constitute the internal area of the cells of the article, wherein step c) is carried out preferably by lyophilization or by heating bodies, resulting in the liquid or part thereof evaporating. Step b) can also be carried out by subjecting the mixture of a) under pressure, preferably under mixing and / or increasing the temperature, and subsequently removing the pressure or part thereof, resulting in the liquid evaporating . For example, an extrusion process can be used. Therefore, it is preferable that the mixture of the polymeric material, plasticizer, preferably including water, and optionally the active ingredient, is introduced into an extruder, where the mixture is mixed and heated, due to mixing or due to the application of heat, preferably in such a way that the mixture forms a melt, and subsequently decreasing the pressure to the exit point where the extruded mixture (to which the desired shape, for example granules, can be given) is taken out of the extruder, where the liquid or part thereof evaporates, or preferably the water is evaporated. evaporates as steam from the extruded mixture. This results in the formation of cells with spaces, as described above, which may contain a gas, preferably air, and optionally the active ingredient. These spaces constitute the internal area of the cells of the elastic article matrix of the invention. Step b) in the process can also be performed by heating the mixture so that the liquid or part thereof evaporates, resulting in the formation of spaces, as mentioned above. This can be achieved, preferably, feeding the mixture in a spray dehydration tower, preferably in such a way that the mixture is fed through a spray nozzle that forms droplets of the mixture, and spray-drying the droplets in a conventional manner, giving as Result granulos of the elastic article. Foaming or physical introduction and / or gas chemistry, as mentioned above can be carried out by any known method, the preferred ones being - physical foam formation by gas injection (dry or aqueous route), under high shear agitation (dry or aqueous route), gas dissolution and relaxation including critical gas diffusion (dry or aqueous route); - chemical foam formation by in-situ gas formation (by chemical reaction of one or more ingredients, including the formation of CO2 by means of an effervescence system), - vapor blowing, curing of UV radiation. These foaming steps are followed by a drying step or additional drying step to remove excess liquid or part thereof, such as water. In particular, the drying step sd is carried out after the polymer matrix is formed and optionally after the active ingredient is added, preferably as a final step in the process. The drying step is preferably carried out in such a way that the final elastic article is about the same volume after the drying step as before the drying step. Therefore, the drying step is preferably carried out by lyophilization, wherein the solvent, for example water, is removed under vacuum and reduced temperatures. Slow drying in the oven at slightly increased temperatures, such as 40-80 ° C or even 40-60 ° C, may also be helpful. Preferred methods involve at least the step of forming a mixture of polymeric material and a liquid, preferably a solution of polymeric material and a solvent, preferably comprising water, and adding a plasticizer (or as the case may be, additional plasticizer) to this. If the presence of the active ingredient and / or the stabilizing agent in the matrix is required, these are also added to the solvent mixture of polymeric material and plasticizer. Alternatively, or in addition, it may be preferred that the matrix be formed around the active material, preferably a core of the active material and the carrier material. This is then processed, for example, to form bodies of the shape of the final article, for example particles or beads, and they are usually dried to obtain the articles. Preferably, a gas is added before the step that consists of shaping. Shaping steps include granulation steps such as atomization, spray dehydration, extrusion, micro-tablet formation. Freeze-drying is the preferred method for drying the bodies in order to form the articles. The following are preferred procedures that result in low dust generation or even null dust particles, as measured by the stress Heubach test described below, having a matrix with a Tg below 10 ° C and a modulus elastic below O.dGN.m "2, as indicated in more detail in the following specific examples.

A first preferred process is as follows: The required amount of a solution of the polymer material (or a mixture of polymer and a liquid) is obtained, and for example (it is introduced) in a resonant mixing circuit. Subsequently, the required amount of (a solution of) active material, for example an enzyme solution, and stabilizing agent is added and the required amount of plasticizer and optionally other additional ingredients, such as fillers, agents are also added. of densification, etc. This is stirred to make it a homogeneous mixture. Preferably, a gas, such as air, can be introduced into the solution by any of the above methods, preferably physically through high shear mixing. Subsequently, the particles are formed from this mixture by atomization, preferably using a pump Positive Displacement to transfer the solution of the mixture to a spray nozzle, preferably using single or multiple fluid nozzles to create liquid droplets. Next, the droplets of liquid are frozen, preferably by passing them through a cooling medium (may include liquid nitrogen, freon, cooling oils). Later, the frozen particles are transferred to a vacuum chamber, preferably having a temperature (as measured on the surface of the particles) below 0 ° C. The frozen particles are preferably collected from the drying column and transferred without increasing the temperature. The temperature of the walls and contact trays of the lyophilizer is preferably kept below 0 ° C to keep the particles frozen. A vacuum is applied, and the frozen ice crystals will sublimate said gas to a gaseous form resulting in cells in the particle. *. & amp; *.

The total drying degree can be controlled with the level of vacuum and contact temperature of the walls and trays of the chamber. After the particles have dried to the desired moisture content, they will be floating freely. Subsequently, preferably, the particles can be classified by a variety of screens and / or process equipment. The previous optional step that consists in introducing gas (bubbles) in the polymer solution mixture has been much better in terms of the impact resistance of the particle, this is reflected through its electrical modules. The introduction of gas bubbles can be carried out in a variety of ways. In the atomization step, the atomization nozzle should preferably be located in a drying column with sufficient height to achieve freezing of the droplets at the same time as the severity decreases. The type of nozzle can have different shapes - single fluid pressure nozzle, spiral insert, sonic, or multiple fluid nozzle. The important aspect is to interrupt the liquid stream to form discrete liquid droplets. As these droplets fall with gravity, they need to be cooled to freeze. The freezing medium is preferably non-aqueous or liquid gas that can provide rapid freezing of the liquid droplets. The actual temperatures for cooling these droplets and forming particles are preferably below 0 ° C and preferably below -20 ° C.

It may also be preferred that the above process be modified in the following manner: a gas, preferably CO2 gas, is introduced into the mixture and the mixture is introduced into a spray dehydration tower, as mentioned above, thus forming particles of foam dehydrated by sprinkling, which can be classified if necessary. Preferably, the inlet temperature in the tower is around 130 ° C and the outlet temperature is around 75 ° C and the spray rate is 12.5g / min. For example, a Niro Mobil Minor can be used with two fluid nozzles. The resulting particle may already have the desired shape, or it may be subjected to lyophilization under vacuum.

Another preferred method is as follows: The required amount of a solution of the polymer material is obtained (or alternatively, a polymer powder can be used as long as a liquid is added) and for example is introduced into a resonant circuit of mixture. Subsequently, the required amount of plasticizer is added, and optionally additional ingredients, such as fillers, densification agents, etc. are added. This is stirred to make it a homogeneous mixture. Preferably, a gas, such as air, can be introduced into the solution by any of the above methods, preferably physically, through high shear mixing.

Also, particles comprising the active ingredient, such as an enzyme, and the stabilizing agent, and optionally other ingredients, such as fillers or carriers are prepared, for example by fluidized bed covering, by first charging the "cores" (usually when the assets are enzymes, these core particles are particles of sugar or starch), to a bed of fluid and spraying the active material or a solution of the active material on these cores and then drying any solvent such as water the active solution with warm fluidizing air. Subsequently, the above polymer mixture is introduced into these actives / cores, for example by means of a positive displacement pump leading to an atomization nozzle inside the fluidized bed as described above. More than one nozzle can be used and it is preferred that different ingredients are added to the core by different nozzles. The fluidizing air requirements are preferably below 0 ° C, preferably around -20 ° C. Subsequently, the fluidizing air freezes the polymer mixture / solution on the outside of the core-active. This is a critical parameter to control and usually the air temperature should be below 0 ° C to quickly freeze the polymer mixture / solution in the core particles. 4 Subsequently, the frozen particles obtained are preferably transferred to a vacuum chamber as mentioned above and classification is carried out. This technology results in the particles of the invention comprising a matrix around the active ingredient. It has been discovered that the above optional step of introducing gas (bubbles) into the polymer solution mixture provides a better impact resistance of the particles, this is reflected through its Young module.

Another preferred method is as follows: The required amount of a solution of the polymer material (or solid polymer and a suitable amount of liquid) is obtained, and for example is introduced into a resonant mixing circuit. Subsequently, (in a resonant mixing circuit) the required amount of (a solution of) active material, for example an enzyme solution, and stabilizing agent (a solution of) is added and the required amount of plasticizer and optionally other additional ingredients, such as fillers, densification agents, etc. This is stirred to make it a homogeneous mixture. Preferably, a gas, such as air, can be introduced into the solution by any of the above methods, preferably physically through high shear mixing.

Subsequently, the polymer solution is pumped out of the mixing resonant circuit into an extruder or into a cavity with a stretching drill plate at the end. Before entering the extruder or the cavity, the gas can be injected into the mixture and dispersed by a mechanical shear mixer or a static mixer. As the extruded material leaves the beading die, the change in pressure causes puffing or swelling in the extruded material. Subsequently, the extruded material is cut to the correct length with a die facing cutter or with some other device (eg hot wire, rotary cutter, etc.). The extruded material can pass through additional rounding steps to become more spherical. The procedure equipment that can perform this function includes (rotating trays, agglomeration trays, granulators, agitation drums, mixing drums, etc.). For example, a paste is prepared by mixing 75g of PVOH, 15g of citric acid, 2g of PEO and 22.5g of glycerol in a Braun mixer with high shear, mainly fixed at maximum speed for 40 seconds: subsequently 80g of H2O and 80g of enzyme were added and mixed at high shear, mainly fixed at maximum speed to form a soft foam, approximately in the lapse of 2 minutes. The foam was expelled through a 10ml syringe onto a plastic sheet. This was allowed to dry for 24 hours. Once dry, the foam strips were cut into sections of approximately 1-2mm to form particles of the formula (dry) 63.2% polyvinyl alcohol, 19% glycerol, 12.7% citric acid, 1.6% PEO, 4% of water, 3.2% enzyme. The resulting particles had an elastic modulus of 0.00016 GN.m "2. The resulting particles yielded 0% dust when tested in a Heubach stress test, which indicated a very good impact robustness. carried out in the manner known in the art, using equipment as provided by Heubach Engineering GMbH, Germany, with the modification of tension of the rotation speed of the propeller at 75 ± 1 rpm and the Tungsten carbide balls and each of 82 grams).

Preferred molding / pellet making process: A highly preferred process involves shaping the mixture particles as described above by using a mold; wherein the mixtures, as described in the present invention, they are introduced in a mold and subsequently dried (lyophilized). Also preferred is the process employing equipment for the manufacture of pellets, wherein the mixtures as described above, preferably also comprise introduced gas, are passed through a rotary perforated drum to a moving conveyor belt, shaping the pills (droplets or particles). When they dry or harden, the particles or beads formed are removed from the conveyor belt by means of a scraper. Preferably, the first step is to make the mixture of polymeric material and plasticizer, a liquid component and, optionally, the active ingredient. Preferably, gas is introduced into this mixture as described above. Preferably this should be free of large undissolved particles that could block the perforations in the drum. Preferably, the mixture is on the 0-50 ° C temperature scale. The mixture is pumped into a pipe which is inserted into the rotating drilled drum and which is parallel to the longitudinal axis of the drum. The mixture is pumped into the drum and, as the drum rotates, it is brought into contact with an internal laminated scraper which is in contact and along the length of the inner surface of the perforated drum, parallel to the feed pipe. The distance of the outer surface of the perforated drum lies within the height of the desired particle height (which is less than the diameter of the perforations) but does not touch a moving conveyor belt or a flat-surface rotating drum at the point where the The internal scraper is in contact with the inner surface of the perforated drum, the tangential speed of the perforated drum combines with the speed of the conveyor belt or the tangential speed of the flat surface drum. As the mixture is passed through the perforations, which are usually on the 300-2000 m scale (but may be smaller or larger), it is deposited on the lower surface. The rotation of the perforated drum cuts the feed material away from the material on the flat surface leaving a drop or pellet that will form the required particle. These pills can be adjusted either by cooling or evaporating parturition or all solvent fluid. If cooling is required, the temperature of the conveyor belt or flatbed drum can be in the ambient temperature range to -20 ° C. If the evaporation of a solvent is required, then this can be achieved by the heat conduction of the conveyor belt which can be in the range of ambient temperature to 70 ° C or by drying air (which can be heated up to 200 ° C to reduce the drying time) by passing over the surface of the tablets or both. Subsequently, the resulting particles are removed from the drum or the conveyor belt by means of a scraper. This removal procedure can be improved by the use of a suitable lubricant (releasing agent) in the drum, such as a silicone oil. This lubricant or releasing agent can show an additional benefit to the particle by reducing the adhesive properties between the polymer mixture and the belt / drum and thus increasing the height of the pellet, if desired.

EXAMPLE 1 A process for preparing an elastic article according to the present invention 4700g of 33% w / w of polyvinyl alcohol solution (MW average weight of 30,000 to 70,000) is mixed with 3360g of enzyme solution (5% by weight of active enzyme and 85% by weight of water), 159.3g of glycerol and 168g of ammonium sulfate in a high shear mixer to form a soft foam. This mixture is tranred to a feed tank, and using a gear pump, it is pumped into a micro-tablet processing equipment, for example that provided by Sandvik Process Systems, Totowa New York, using a drilled drum with perforations of 1 mm in diameter, separated 2.5mm. The apparatus deposits the pellets on a flat surface drum covered with a film of silicone oil and heated to ~ 30 ° C. When a quarter of the drum is covered with pellets, the drum stops rotating. The pads are dried using a hot air heater until the surfaces of the pads are dry to the touch. Subsequently, the resulting particles are scraped and collected.

EXAMPLE 2 A process for making foam articles of the present invention, in the form of tablets, beads or particles Apparatus: 100 ml graduated microbalance flask, food processor "Chef" from Kenwood that provides a container of whisker and mixed, glass or plastic molds, spatula. Guimic compounds: Poly (vinyl) alcohols (Aldrich chemicals, molecular weight Mw = 30-70k) Glycerol (99% Aldrich chemicals), Citric acid (Aldrich, Citrus acid, Anhydrous USP), distilled water, dry ice (or CO2 in phase) solid), thermally insulated box. Procedure: 1.- Weigh 50 ± 0.2 grams of PVA, 30 ± 0.2 grams of glycerol. 2.- Mix the PVA and glycerol using the mixer fixed at low speed (mark 2). 3.- Add 50 ± 1 ml of water gradually to the mixture containing little water, maintaining the mechanical mixture for 2 minutes. A soft gel should be obtained. 4.- Increase the mixing speed to the maximum (mark 8). Add 10-20 ml of water until a PVA foam is forming. Keep the mixture at high shear for 3 minutes. 5. The active ingredients, for example 2-10 grams of enzyme, are progressively added to the foam under mechanical mixing maintained in such a way that a uniform active foam is obtained. 6.- Stop mixing. Spread the PVA foam in molds avoiding any collapse of the structure. 7.- Place the filled molds in a thermally insulated box 1/3 filled with dry ice. Leave to freeze for 5 hours. 8.- Quickly place the frozen samples in a vacuum freeze dryer (Edwards XX) for 24 hours. 9.- Remove the dry sample from the molds. Any active ingredient can be added in step 5, at any level, usually up to about 50 grams, for example fabric softeners, bleaching species, nonionic surfactants. Any stabilizing agent can be added in step 5, at any level, usually up to about 50 grams, for example bovine serum albumin, ammonium sulfate, sucrose and monostearated phenol.

EXAMPLE 3 A process for making elastic articles of the present invention, in the form of tablets, beads or particles Apparatus: as described in example 1. Guimic compounds: Polyvinyl alcohols (chemical Aldrich, molecular weight Mw = 30-70k) Glycerol (99% chemical Aldrich), citric acid (Aldrich, Citrus acid, USP Anhydrous), sodium carbonate (Aldrich, Anhydrous), dodecyl sulfate surfactant (Aldrich) distilled water, Petri dish (diameter 90 mm), oven (set at 45 ° C ± 2 ° C).

Procedure: 1.- Weigh 50 ± 0.2 grams of PVA, 30 ± 0.2 grams of glycerol, 20 ± 0.2 grams of sodium carbonate and 20 ± 0.2 grams of sodium dodecyl sulfate. 2.- Mix the PVA, glycerol and sodium dodecylisphate using the mixer fixed at low speed (mark 2). 3.- Add 50 ± 1 ml of water gradually to the mixture containing little water, maintaining the mechanical mixture for 2 minutes. A soft gel should be obtained. 4.- Add the active ingredient, for example 5 grams of enzyme and sodium carbonate and mix vigorously for 30 seconds until a completely expanded foam is obtained. 5.- Spread the foam in the Petri dish in a uniform thin layer of 1cm thickness. 6.- Place the petri dish in an oven at 40 ° C for 24 hours. 7.- Remove the dry foam film from the mold. Any active ingredient can be added in step 4, at any level, usually up to about 50 grams, for example fabric softeners, bleaching species, nonionic surfactants.

This was repeated using for example 55% by weight of polcarboxylic acid polymer, 20% by weight of sodium carbonate anhydride and 25% by weight of enzyme, softening clay etc .; and it was repeated using 44% by weight of polyocarboxylic acid polymer, 15% by weight of polyethylene glycol, 20% by weight of sodium carbonate anhydride and 20% by weight of enzyme, softening clay, etc. & s &c * f & Jt? ? iitk *? i ifctr

Claims (15)

NOVELTY OF THE INVENTION CLAIMS

1. - An elastic article comprising; a) an active ingredient; and b) a foam matrix formed of at least one polymeric material and a plasticizer; and c) a stabilizing agent; wherein said article is capable of administering said active ingredient to a liquid environment.

2. The elastic article according to claim 1, further characterized in that said active ingredient is in an aqueous environment, and further characterized in that said article is hydrodispersible, hydrodisintegrable or water-soluble, preferably water-soluble.

3. The elastic article according to any of the preceding claims, further characterized in that said matrix has a glass transition temperature (Tg) below 50 ° C, preferably below 40 ° C and optionally between -20 ° C and 20 ° C, preferably between -10 ° C and 10 ° C.

4. The elastic article according to any of the preceding claims, further characterized in that said matrix has an elastic modulus of less than IGN.nrf2, preferably less than 0.1 GN.m "2, or even less than 0.01 GN. m "2.

5. - The elastic article according to any of the preceding claims, further characterized in that said stabilizing agent comprises a foam stabilizing agent.

6. The elastic article according to any of the preceding claims, further characterized in that said active ingredient is an ingredient of cleaning product, fabric care ingredient, pharmaceutical ingredient or cosmetic ingredient, which is preferably selected from enzymes, agents surfactants, brighteners, colorants, foam suppressants, bleaches, bleach activators, fabric softeners, cloth conditioners, antibacterial agents, effervescence systems and mixtures thereof.

7. The elastic article according to any of the preceding claims, further characterized in that said active ingredient comprises at least one enzyme, and further characterized in that said stabilizing agent comprises a stabilizing agent above, preferably said stabilizing agent is a stabilizing agent from above.

8. The elastic article according to any of the preceding claims, further characterized in that said polymeric material comprises a water-soluble polymer, preferably a water-soluble polyvinyl alcohol.

9. The elastic article according to any of the preceding claims, further characterized in that it is present in the form of a particle having an average particle size of 50 to 4000 microns, preferably 100 to 1500 microns.

10. The elastic article according to any of the preceding claims, further characterized by having a relative density of 0.05 to 0.9, preferably 0.3 to 0.7.

11. The elastic article according to any of the preceding claims, further characterized in that said matrix forms a series of open and closed cells, further characterized in that the ratio in number of cells closed to open cells is preferably at least 1: 1.

12. The elastic article according to claim 7, further characterized in that it can be obtained by a process comprising the steps of; a) obtaining a mixture of a polymeric material and a plasticizer, preferably water and another plasticizer; and b) chemically or physically introducing a gas into said mixture; and c) before step b) and / or simultaneously with step b) and / or after step b), contacting an active ingredient with said mixture; and d) before step c) and / or simultaneously with step c) and / or after step c), contacting a stabilizing agent with said mixture; and e) shaping the article of the resulting mixture 20; wherein, preferably one or more steps a) to e) are followed or accompanied by the removal of part of the water, if present.

13. The elastic article according to claim 12, further characterized in that said active ingredient comes in contact with - * - * * - --- .l.j í-t < . ' -. _. ^ fc ^,. This stabilizing agent is then added before said active ingredient comes into contact with said mixture of polymeric material and plasticizer.

14. The use of an elastic article as claimed in any of claims 1 to 14, wherein active ingredients are administered to an aqueous environment, preferably the active ingredients are detergent active ingredients, preferably enzymes and the environment watery is the rinse water.

15. The use of an elastic article as claimed in any of claims 1 to 14, in cleaning compositions, fabric care compositions, personal care compositions, cosmetic compositions or pharmaceutical compositions, preferably for incorporating ingredients active ingredients that are selected from enzymes, perfumes, surfactants, brighteners, dyes, suds suppressors, bleaches, bleach activators, fabric softeners, antibacterial agents, effervescence systems, and mixtures thereof.