CN1402778A - 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 products

technical field

The present invention relates to elastomeric articles, generally granules, which comprise a matrix formed of polymeric material and plasticizers, stabilizers and active ingredients, such as detergent active ingredients, which are typically released into an aqueous environment.

Background of the invention

Compositions, such as cleaning and personal care products, cosmetics and pharmaceuticals, often contain active ingredients that are released into water or are required to be active in an aqueous environment. Many of these active ingredients are sensitive to humidity, temperature changes, light and/or air during storage.

Another problem with many of these active ingredients, especially enzymes, is their tendency to form dust due to the physical forces exerted on them during handling. Not only does this generate waste products, but the dust can also cause hygiene and health problems.

Attempts to overcome these problems have led to the development of coatings or encapsulating agents to protect these active ingredients. The problem with many of these coated granules is that they often do not exhibit sufficient impact resistance during handling, and when subjected to the physical forces normally encountered during handling, form dust which can lead to hygienic and health problems.

The present inventors have discovered improved methods of protecting active ingredients and releasing these active ingredients into aqueous media. They have found that certain elastomeric articles comprising a foam matrix formed from polymeric materials and plasticizers are very impact resistant and protect active ingredients incorporated therein from physical forces acting on the elastomeric article. Furthermore, the present inventors have discovered that when stabilizers are simultaneously added to the elastic article, the active ingredient can be further protected from air, humidity and chemical reactions which can lead to degradation of the active ingredient.

Thus, the elastic article of the present invention is high impact resistant, thus resulting in reduced breakage or abrasion during handling, and reduced dust formation, and protects active ingredients incorporated therein from air, humidity or chemical reactions, and in Remains stable in this preparation during storage. For example, enzyme-containing elastomeric articles, such as granules or beads, are available which are safer and more effective in handling and use. In addition, these preparations can be made to have the effect that they release the active ingredients incorporated therein, such as enzymes, very efficiently into the aqueous environment. Generally, the preparations of the present invention are in the form of foams which are air-stable when stored at ordinary humidity but which are unstable when in contact with water and thus tend to release the active ingredient. Elastic articles are useful in any product, but are especially useful in cleaning products, pharmaceuticals, personal care products, cosmetics and fabric care products.

Brief description of the invention

Elastic articles provided by the invention comprise:

a) the active ingredient; and

b) a foam matrix formed from a polymeric material and a plasticizer; and

c) stabilizers;

Wherein, said article is capable of releasing said active ingredient into a liquid medium.

The elastic articles herein preferably comprise a foam matrix having a glass transition temperature (Tg) below 50°C, preferably below 40°C.

The elastic article is preferably in the form of foam and is stable when in contact with air but unstable when in contact with water, preferably the elastic modulus of the article is less than 0.1GN.m ^-2 , preferably less than 0.01GN.m ^-2 .

Stabilizers stabilize the active ingredients in this product. The stability of the active ingredient is dependent on the stability of the foam matrix and/or on the stability of the active ingredient itself.

Thus, the stabilizer can be, or can comprise, a matrix stabilizer capable of stabilizing the foam matrix in the elastic article during storage or processing of the elastic article.

Stabilizers can also be used to directly stabilize the active ingredient. For example, by increasing the structural stability of the active ingredient. Accordingly, it may also be preferred that the stabilizer is or comprises an active ingredient stabilizer.

It is also preferred that the active ingredient of the elastic article comprises at least one enzyme. If enzymes are included in the elastic article, the enzymes are sensitive to moisture, air or bleach (if present) and denature or begin to denature in the presence of air, moisture or bleach. Therefore, it is preferred that the stabilizer is an enzyme stabilizer which stabilizes the enzyme in the elastic granule and also stabilizes the enzyme during the preparation of the elastic granule.

The invention also relates to processes for making elastic articles. The elastic article is preferably obtained by a process comprising the following steps:

a) obtaining a mixture of polymer material and plasticizer, preferably water and other plasticizers; and

b) introducing a gas into the mixture by chemical or physical means; and

c) contacting the mixture with an active ingredient before, and/or simultaneously, and/or after step b); and

d) contacting the mixture with a stabilizing agent before, and/or simultaneously, and/or after step c); and

e) shaping the resulting mixture into an article;

Herein, it is preferred to remove part of the water, if present, after or simultaneously with one or more of the steps a) to e).

In another embodiment of the invention there is provided the use of an elastic article to release an active ingredient, preferably a cleaning active ingredient, preferably an enzyme, into an aqueous environment, and preferably the aqueous environment is wash water. DETAILED DESCRIPTION OF THE INVENTION Elastic article

The elastic articles of the present invention, referred to herein as "articles", comprise an active ingredient, a matrix and a stabilizer. The active ingredient, matrix and stabilizer are described in more detail later.

Preferably the present article is water dispersible, water disintegratable or water soluble. Preferred herein are water-dispersible articles having a degree of dispersibility of at least 50%, preferably at least 75% or even at least 95%, as measured with a glass filter having a maximum pore size of 50 microns as described hereinafter; more preferably the articles herein are water-soluble Sexual or water decomposable, and solubility or disintegration is at least 50%, preferably at least 75% or even at least 95%, with the maximum pore size of 20 micron glass filter, measured with the method described below, namely:

Measure the water solubility, water disintegration or water dispersibility of this product by specific gravity method:

Add 50g±0.1g of this product into a weighed 400ml beaker, and add 245ml±1ml of distilled water. Stir the material vigorously with a magnetic stirrer at a speed of 600 rpm for 30 minutes. The preparation-mixture is then filtered through an origami quantitative sintered glass filter with a pore size as defined above (up to 20 or 50 microns). Water is evaporated to dryness from the collected filtrate by any usual method, and the weight of the remaining product portion (dissolved, decomposed or dispersed portion) is determined. Then, the percentage of solubility, disintegration or dispersibility can be calculated.

This article is generally used to deliver active substances into aqueous media. Preferably the article, preferably its matrix, is unstable when in contact with water. It occurs by releasing the active ingredient in the preparation, or a part thereof, into a liquid, preferably an aqueous medium such as water. Preferably the preparation or a part thereof denatures, decomposes, preferably disperses or dissolves in a liquid, preferably in an aqueous medium, more preferably in water. Rapid release of the active ingredient into water may be preferred, and rapid dispersion or dissolution of the elastic article is preferred; preferably at least 10% by weight of the article dissolves or disperses within 30 minutes after contact of the article with water, or more preferably at least 30% or even At least 50% or even at least 70% or even at least 90% [into water at a concentration of 1% by weight]. It may even be preferred that dissolution or dispersion occurs within 20 minutes or even 10 minutes or even 5 minutes after contact of the preparation with water. Dissolution or dispersion may be measured by the methods described below for measuring dissolution, disintegration and dispersion of the present article.

Preferably the elastic article is such that the total volume of the article will change, preferably by at least 10% compared to the initial total volume, this value can be determined as follows: 1 ^cm3 of the article is placed in 100 ml of deionized water, and the Stir at 200 rpm for 5 minutes at a temperature of 25°C. Preferably the change in overall volume, or preferably the reduction in overall volume, is at least e.g. 20% or even at least 40% or even at least 60% or even at least 90% or even about 100% since it may be preferred that substantially the entire article rapidly disintegrates, disperses or It is preferably dissolved in water.

This can be determined by any method known in the art, here in particular the following method (double immersion method): take a 1 cm ³ elastic article and add it to a 100 ml microvolume graduated cylinder filled with 50 ml ± 0.1 ml Organic inert solvent. For example, acetone is used when it is found that acetone does not change and/or interact with the polymeric material in the matrix of the present elastomeric article, for example when the polymeric material is PVA. Other neutral organic media may be used depending on the nature of the article under study; an inert solvent is one in which the article is not substantially dissolved, dispersed, decomposed or denatured by the solvent.

The graduated cylinder is air-tight and left for 1 minute to allow the solvent to penetrate the entire elastomeric article. The change in volume is measured and taken as the initial volume V _i of the foam sample. The article is then removed from the solvent and air dried to evaporate the solvent.

The product was then placed in a 250ml beaker containing 100ml deionized water, kept at 25°C, and stirred with a magnetic stirrer at a speed of 200 rpm for 5 minutes. The remaining product samples, if any, are filtered with a 60mm copper mesh filter, and placed in an oven at a certain temperature for a period of time to remove residual water. The dried remaining preparation was placed again in the graduated cylinder in which the volume of acetone had been readjusted to 50 ml.

The overall volume increase is monitored and taken as the final volume _Vf of the elastic article. Then the reduction ΔV of the total volume of the elastic product sample is: $\%\mathrm{\ΔV}=\frac{V_f}{V_i}*100$

Preferably the relative density p ^* of the elastic article is 0.01-0.95, more preferably 0.05-0.9 or even 0.1-0.8 or even 0.3-0.7. Relative density refers to the ratio of the density of the article (ρ ^* ) to the sum of the individual densities of all materials used to form the article ( _ρs ).

Preferred foam articles for use herein are generally air stable or stable in contact with air, meaning that the article or its substrate remains substantially unchanged in overall volume when exposed to air. This shows especially that, when stored in an open beaker (9 cm in diameter, without any protective layer) in an incubator for 24 hours, preferably the preparation retains 75%-125% or even 90%-110% or even 95% of the total volume. %-100%, the incubator is controlled at ambient conditions (humidity = RH60%, temperature = 25°C). Preferably the elastic article retains 75% to 125% or even 90% to 110% or even 95% to 100% of its total volume under the storage conditions described above with a humidity of 80%.

The change in total volume can be determined by any conventional method. Particularly useful are digital image recording systems comprising a digital video camera connected to a personal computer equipped with standard image analysis software. Take a 1 cm ³ sample of the product and add it to an open beaker with a diameter of 9 cm and store it under the above conditions for 24 hours. After 24 hours, all three-dimensional dimensions were measured using an image analysis recording system. Each sample was measured in triplicate and the change in average total volume was calculated as a percentage.

Preferred elastic articles are such that when present in the form of particles having an average particle size of 2000 microns or less, these particles also retain 75% to 125% or even 90% to 110% or even 95% to 100% of the total volume . This can be measured, for example, by adding 20 g of such particles or a weight containing more than 500 particles to a volumetric analytical beaker with a diameter of 9 cm. Gently tap the bottom of the beaker until the elastic particles rearrange into a stable position with a level surface. Measure the volume. The open beaker containing the elastomeric particles was then carefully placed into an incubator for 24 hours and set at the desired %RH and temperature. The total volume was measured after 24 hours and the change in total volume was calculated as a percentage.

The elastic article preferably comprises (by weight) at least 1% active ingredient, more preferably 5%-70%, more preferably at least 10% by weight of the article, more preferably 15% or even 20% or even 25%-50%.

The elastic article preferably comprises (by weight) 10%-99% matrix, more preferably at least 20% or even 30%-99%, more preferably 20% or 30%-90%-80%.

The elastic article comprises (weight percent) at least 1% stabilizer, more preferably from 5% or 10% or 15% or 20% to 50% or 40% or 30% or 25%. matrix.

The matrix of the elastic articles of the present invention, referred to herein as the "matrix", is formed from a polymeric material and a plasticizer. The polymer material and the plasticizer will be described in further detail below.

The ratio of plasticizer to polymer material in the matrix is preferably 1:100, more preferably 1:70 or 1:50, more preferably 1:30 or even 1:20, depending on the plasticizer and polymer material used type. For example, when the polymeric material comprises PVA and the plasticizer comprises glycerol or a derivative of glycerol and optionally water, the ratio is preferably about 1:15 to 1:8, with a preferred ratio of about 10:1.

The matrix here can further contain the active ingredient of the product and/or the stabilizer of the product. The active ingredient and the stabilizer will be described in further detail below. Crosslinking agents can also be added to suitably adjust the properties of the matrix or final article. Borates may be useful in the matrix herein.

The glass transition temperature (Tg) of the substrate herein is below 50°C, preferably below 40°C, preferably below 20°C or even below 10°C or even below 0°C. Preferably the substrate herein has a Tg above -20°C or even above -10°C.

The Tg of the matrix used here is the Tg of the matrix present in the article, so it can be just a mixture of polymer material and plasticizer, or it can be polymer material, plasticizer, active ingredient and/or stabilizer Agents, and in any event, optional additional ingredients (thickeners, fillers, lubricants, etc. as described below) may be present.

The Tg used here is the same as defined in the textbook "Dynamic Mechanical Analysis" (page 53, Figure 3.11c in page 57), that is, when the material (matrix) changes from a glassy state to a rubbery state, that is, when the chain obtains enough The temperature of the material (substrate) at which the mobility comes to slide against each other.

The Tg of the matrix in the article of the invention can be measured on a Perkin-Elmer DMA 7e apparatus, referring to the instructions in the operating manual of the apparatus, to produce a curve as shown in Figure 3-11c on page 57 of the textbook "Dynamic Mechanical Analysis". Tg is the temperature, or logarithm of frequency, between the glassy state, as defined herein, and the "leathery region", as measured with the device.

The substrate, and preferably the entire elastic article, has a specific elasticity and flexibility due to its specific glass transition temperature. In particular, this means that the substrate and article are capable of reversibly deforming, absorbing the energy of an impact or force such that the article or substrate is able to return substantially to its original total volume after the application of physical pressure on the part ceases.

Elasticity can be defined in terms of the modulus of elasticity of the matrix or even the article, but also in terms of Young's modulus. This can be calculated from strain or stress mechanical tests known in the art, e.g., using Perkin-Elmer DMA 7e equipment per manufacturer's protocol, over a specified range of static strain percentages, i.e., 10-40% static strain test within the range. This represents the maximum strain that may be applied during ordinary production and handling. Therefore, the modulus of elasticity defined here is the maximum modulus measured with this equipment in the static strain range of 10%-40%. For example, a 1 cm ³ substrate (or article) can be used in tests with this device.

The modulus of elasticity or Young's modulus of this matrix is generally less than 4GN.m ^-2 , or generally less than 2GN.m ^-2 , even more preferably less than 1GN.m ^-2 , but generally 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 , measured with a Perkin-Elmer DMA 7e device. In particular, such a matrix containing gas bubbles, such as formed by a process involving the introduction of air in the matrix, has a modulus of elasticity of less than 0.1GN.m ^-2 , or even less than 0.01GN.m ^-2 , or even less than 0.005 GN.m ^-2 or even less than 0.0001 GN.m ^-2 .

Preferably the present substrate is flexible such that its relative yield strain is greater than 2%, preferably greater than 15% or even greater than 50%, as measured with a Perkin-Elmer DMA 7e apparatus. (In this test, yield strain is the limit of strain at which a substrate is irreversibly deformed.)

In particular, this means that when a matrix sample having a cross-section of a certain length, say 1 cm, is compressed by a static load axially along the section, the static force being variable but at least equal to 2 times the atmospheric pressure, the length changes after unloading to the original At least 90%-110% of the length. This can be determined with, for example, a Perkin-Elmer DMA 7e device.

Equally, preferably matrix has certain flexibility, thereby when the matrix sample with the cross-section of specific length such as 1cm is subjected to axial static force stretching along this cross-section, this static force is variable but at least 2 times of atmospheric pressure, unloading The back length changes to at least 90%-110% of the original length. This can be determined using, for example, a Perkin-Elmer DMA 7e device.

In particular, when using this device, the static force acting on the axial direction of the cross-section of the 1 cm ³ matrix sample is gradually increased until the deformation of the specimen in the cross-sectional direction is 70%. It is then unloaded and the final deformation of the base sample in the direction of the cross-section is determined. Preferably, the length of the section after this experiment is preferably 90%-110%, preferably 95%-105% or even 98%-100% of the original length of the section.

The modulus of elasticity or Young's modulus is related to the relative density, that is $\frac{{\mathrm{E.}}^{*}}{{\mathrm{E.}}_S}\≈{\left(\frac{{\mathrm{\ρ}}^{*}}{{\mathrm{\ρ}}_S}\right)}^2,$

Among them, ρ ^* is the relative density of the matrix or even the product, ρ _s is the relative density of each component in the matrix or the product described here, E ^* is the Young's modulus of the matrix or even the elastic product itself, and E _s is The Young's modulus of the components in the matrix or even in the article. This means that by adjusting the amount and/or type of plasticizer and optionally by adjusting the density (or, for example, by introducing a gas during the manufacturing process to form a resilient foam article, as described below), it is possible to convert even high The rigid polymer material of E _s is made into a flexible, soft matrix.

Preferably the matrix, or even the entire article, is in the form of a foam, and preferably it forms an interconnected network of open and/or closed cells, especially a network consisting of a solid skeleton or plates forming open and/or closed cell edges and surfaces . The space within the pores may contain part of the active ingredient and/or a gas, such as air.

Preferably the ratio of closed cells to open cells is greater than 1:1, preferably greater than 3:2 or even greater than 2:1 or even greater than 3:1 in the matrix of the article or in the entire article. This ratio can be determined by calculating the total volume V _T of the matrix or article sample, (assuming a spherical shape), then determining the open pore volume (V ₀ ) by the mercury porosimetry method, and subtracting the open pore volume from the total volume, then The closed cell volume (V _C : V _T =V ₀ +V _C ) is obtained. polymer material

Any polymeric material may be used to form the matrix herein, provided that it has a Tg as defined above, or more typically, it will form a matrix with a Tg as defined above using an appropriate amount of plasticizer.

Preferably the polymeric material comprises or consists of one (or more) amorphous polymer(s).

The polymeric material may consist of a single type of homopolymer or of a mixture of polymers. Polymer mixtures are especially advantageous for controlling the mechanical and/or dissolution properties of elastic articles, depending on their application and requirements.

Preferably the polymeric material comprises a water dispersible or more preferably water soluble polymer. Water dispersibility and water solubility are generally defined as hereinbefore, and are determined according to the method used to determine the water solubility and water dispersibility of the present product. Preferably the water dispersible polymer herein has a degree of dispersibility of at least 50%, preferably at least 75% or even at least 95%, as measured by the method described above with a glass filter having a maximum pore size of 50 microns; more preferably the polymer herein is a water-soluble polymer having a solubility of at least 50%, preferably at least 75% or even at least 95%, as determined by a glass filter having a maximum pore size of 20 microns as previously described.

The polymer may have any average molecular weight, preferably about 1000-1,000,000, or even 4000-250,000 or even 10,000-200,000 or even 20,000-75,000. Very preferably the polymeric material has a weight average molecular weight of 30,000-70,000.

Depending on the desired properties of the article, the polymeric material can be adjusted. For example, to reduce solubility, the material may contain polymers in high fractions, typically above 50,000 or even above 100,000, and vice versa. For example, to vary solubility, polymers with different degrees of hydrolysis can be used. For example, to increase (decrease) the modulus of elasticity, the degree of crosslinking and/or the molecular weight of the polymer can be increased.

It may be preferred that the polymer used in the present elastic article has an auxiliary function, such as a function to be incorporated into the composition of the article. Thus, eg for cleaning products, it is useful when the polymer in the polymeric material is a dye transfer inhibiting polymer, dispersant or the like.

Preferred polymers are selected from the group consisting of polyvinyl alcohol and its derivatives, polyethylene glycol and its derivatives, polyvinylpyrrolidone and its derivatives, cellulose ethers and its derivatives, and these polymers with each other or with other single Copolymers or oligomers. Very preferably PVP (and derivatives thereof) and/or PEG (and derivatives thereof), very preferably PVA (and derivatives thereof) or a mixture of PVA and PEG and/or PVP (or derivatives thereof). Polymer materials comprising only PVA may also be very preferred.

Preferably these polymers have a degree of hydrolysis of at least 50%, more preferably at least 70% or even from 85% to 95%. plasticizer

Any plasticizer suitable to facilitate matrix formation as defined herein may be used. Mixtures of plasticizers may also be used. 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 120°C, or even above 150°C.

Preferred plasticizers include glycerol, glycol derivatives including ethylene glycol, oligomeric polyethylene glycols such as diethylene glycol, triethylene glycol and tetraethylene glycol, polyethylene glycols with a weight average molecular weight M.W. below 1000, Waxes and hydrocarbon waxes, ethanol acetamide, ethanol formamide, triethanolamine or its acetate, and ethanolamine salts, sodium thiocyanate, ammonium thiocyanate, polyols such as 1,3-butanediol, sugars, sugar alcohols , urea, dibutyl or dimethyl phthalate, oxymonoacids, oxydiacids, diglycolic acid, and other linear carboxylic acids with at least one ether group distributed along the molecular chain, water or mixture.

Preferably the plasticizer is used in an amount of at least 0.5% by weight of the article, preferably by weight of the matrix, provided that when water is the only plasticizer it is present in an amount by weight of the article, or preferably at least 3% by weight of the matrix.

Preferably the plasticizer is used in an amount of 1%-35% by weight of the article or matrix, more preferably 2%-25% or even up to 15% or even up to 10% or even up to 8% by weight of the article or matrix. The exact amount depends on the polymeric material and plasticizer used, but should be such that the matrix of the article has the desired Tg. For example, when urea is used, it is preferably used in an amount of 1% to 10% by weight of the matrix, while when glycerol or ethylene glycol or other glycol derivatives are used, higher amounts are preferred, such as 1% by weight of the product or matrix. 2%-15%. active ingredient

The active ingredient may be any substance to be released into a liquid environment, or preferably an aqueous environment, and is preferably an ingredient active in an aqueous environment. For example, when used in a cleaning composition, the article can contain any active cleaning ingredient. The articles may also comprise compositions, such as cleaning compositions or personal care compositions.

In particular, it is beneficial to incorporate in elastic articles active ingredients which are sensitive to or react on contact with moisture, or solid ingredients which have limited impact strength and tend to Dust formed.

Active ingredients are generally moisture sensitive ingredients, temperature sensitive ingredients, oxidizable ingredients, volatile ingredients or combinations thereof. The active ingredient may be a biologically active material, a hazardous or toxic material, an agricultural ingredient such as an agrochemical, a pharmaceutical ingredient such as an internal medicine or an anesthetic, or a cleaning ingredient.

Particularly preferred active ingredients in elastic articles are, for example, enzymes, fragrances, bleaches, bleach activators, fabric cationic and/or silicone softeners and/or conditioners, antibacterial agents, effervescent agents, brighteners, light Bleach and their mixtures.

A preferred active ingredient is a perhydrate bleach, such as metal perborate, metal percarbonate, especially sodium salt. Also preferred active ingredients are organic peroxyacid bleach precursors or activator compounds, preferably imide-type alkyl percarboxylic acid precursor compounds, including N,N,N ¹ N ¹ -tetraacetylated alkylene di Amines in which the alkylene group contains 1 to 6 carbon atoms, especially those compounds in which the alkylene group contains 1, 2 and 6 carbon atoms, such as tetraacetylethylenediamine (TAED), 3,5,5,-tri Sodium methylhexanoyloxybenzenesulfonate (iso-NOBS), sodium nonanoyloxybenzenesulfonate (NOBS), sodium acetoxybenzenesulfonate (ABS) and pentaacetylglucose, but can also be amide substituted alkyl peroxyacid precursor compounds.

Highly preferred active ingredients for use in such elastic articles are one or more enzymes. Preferred enzymes include the commercially available lipases, cutinases, amylases, neutral and alkaline proteases, cellulases, enolases, esterases, pectinases, lactases and peroxidases, which are typically Add to cleaning compositions.

Suitable enzymes are discussed in US Patent Nos. 3,519,570 and 3,533,139. Preferred commercially available proteases include: those with the trade names Alcalase, Savinase, Primase, Durazym and Esperase, produced by Novo Industries (Denmark); those with the trade names Maxatase, Maxacal and Maxapem, produced by Gist-Brocades; by Genencor International and those sold under the tradenames Opticlean and Optimase by Solvay Enzymes. Preferred amylases include, for example, the alpha-amylase produced by the special strain Blicheniformis described in more detail in GB-1,269,839 (Novo). Preferred commercially available amylases include, for example, those supplied under the tradename Rapidase by Gist-Brocades, and those sold under the tradename Termamyl, Duramyl and BAN by Novo Industries. Highly preferred amylases may be those described in PCT/US9703635 and WO95/26397 and WO96/23873. Lipases can be obtained in the form of fungal or bacterial origin, e.g. from lipase-producing strains: Humicola species, Thermomyces species or Pseudomonas species, including Pseudomonas pseudoalcaligenes or Pseudomonas fluorescens Pick. Lipases produced by chemically or genetically modified mutants of such strains can also be used here. A preferred lipase derived from Pseudomonas pseudoalcaligenes is described in granted European patent EP-B-0218272. Another lipase preferred herein is obtained by cloning the Humicola lanuginosa gene and expressing the gene in an Aspergillus oryzae host, described in European Patent Application EP-A-0258 068 by Novo Industries (Bagsvaerd, Denmark) is commercially available under the tradename Lipolase. This lipase is also described in US Patent 4,810,414, Huge-Jensen et al., issued March 7, 1989. stabilizer

The preparation includes a stabilizer which generally stabilizes the active ingredient in the preparation, such stabilizers being especially preferred when the active ingredient comprises an oxidative or moisture sensitive active ingredient, such as one or more enzymes. Stabilizers also stabilize the matrix in the preparation and thus indirectly the active ingredient.

The stabilizer is preferably a compound which stabilizes the active ingredient or the matrix against oxidation and/or moisture degradation during storage.

Stabilizers are added to the active ingredients of the preparation. If more than one active ingredient is included in the preparation, one of the active ingredients may preferably be selected to be or act as a stabilizer. For the purposes of the present invention, stabilizers are always added to the active ingredient of the preparation as an additional ingredient of the preparation.

Thus, for the purposes of the present invention, for a preparation to be defined as comprising a stabilizer and an active ingredient, wherein the preparation comprises a dual function component capable of functioning as an active ingredient or a stabilizer as defined herein, for In order to obtain a preparation according to the invention comprising an active ingredient and a co-stabilizer, the preparation must contain an additional stabilizer or active ingredient in addition to the compound having a dual function.

The above statements regarding ingredients with dual functionality are equally true when considering other embodiments of the invention. For the present article, the inclusion of an active ingredient, polymeric material and plasticizer (which form the matrix) and co-stabilizers are essential requirements. Therefore, in order to obtain an article according to the invention, at least four different components are included in the article. Essential ingredients may preferably be selected to have a dual function.

The above remarks regarding ingredients having a dual function are also true when considering highly preferred embodiments of the invention, eg preferred preparations comprising additional ingredients such as co-solvents.

The stabilizer can be, or comprise, a foam matrix stabilizer. The stabilizer can be, or comprise, an active ingredient stabilizer, especially an enzyme stabilizer.

Those stabilizers that indirectly stabilize the active ingredient by maintaining a stable foam matrix in the product, referred to herein as "foam stabilizers", preferably comprise surfactants such as fatty alcohols, fatty acids, alkanolamides, amine oxides or derivatives thereof. objects, or a combination of them. Foam stabilizers may comprise betaines, sultaines, phosphine oxides, alkyl sulfoxides, derivatives thereof, or combinations thereof.

Other preferred foam stabilizers comprise one or more anions or cations such as monovalent, divalent, trivalent or other polyvalent metal ions, preferably sodium, calcium, magnesium, potassium, aluminum, zinc, copper Salts, nickel salts, cobalt salts, iron salts, manganese salts, and silver salts, preferably with anionic counterions sulfate, carbonate, oxide, chloride, bromide, iodide, phosphate, borate, acetate , citrate, and nitrate and combinations thereof.

The foam stabilizer may comprise finely divided particles, preferably having an average particle size of less than 10 μm, more preferably less than 1 μm, even more preferably less than 0.5 μm, or less than 0.1 μm. Preferred finely divided particles are aluminosilicates such as zeolites, silica or the electrolytes described above in the form of finely divided particles.

The foam stabilizer may comprise agar-agar, sodium alginate, sodium lauryl sulfate, polyethylene oxide, guar gum, polyacrylate, or derivatives thereof, or combinations thereof.

The foam stabilizer may be a separate coating from the substrate of the article herein. Foam stabilizers generally partially, preferably completely, envelop the article herein or its active ingredients.

The coating typically contacts the active ingredient prior to said active ingredient contacting the polymeric material or plasticizer of the substrate, preferably in such a way as to form a coating on the surface of the active ingredient, preferably incorporated into the article herein.

The coating may contact the article herein in such a manner as to form a coating on the article after the polymeric material and plasticizer form the matrix, preferably after the active ingredient contacts said matrix or is incorporated into the article herein.

Preferred coatings comprise polymers, typically selected from polyvinyl alcohol and its derivatives, polyethylene glycol and its derivatives, polyvinylpyrrolidone and its derivatives, cellulose ethers and their derivatives, and these polymers Copolymers with each other or with other monomers or oligomers. Most preferred are PVP (and derivatives thereof) and/or PEG (and derivatives thereof), very preferably PVA (and derivatives thereof) or mixtures of PVA with PEG and/or PVP (or derivatives thereof). These polymers do not form the matrix of the articles herein. Therefore, these polymers are different from the polymeric material of the foam matrix.

Preferred coatings comprise compounds such as: glycerol, glycol derivatives including ethylene glycol, oligoethylene glycols such as diethylene glycol, triethylene glycol and tetraethylene glycol, polyethylene glycols with a weight average molecular weight M.W. below 1000 Glycols, waxes and hydrocarbon waxes, ethanolacetamide, ethanolformamide, triethanolamine or its acetate, and ethanolamine salts, sodium thiocyanate, ammonium thiocyanate, polyols such as 1,3-butanediol, sugars , sugar alcohols, urea, dibutyl or dimethyl phthalate, oxymonoacids, oxydiacids, diglycolic acid, and other linear carboxylic acids with at least one ether group distributed along the molecular chain, water and its mixtures. These compounds do not form the foam matrix of the articles herein. Therefore, these compounds are different from the plasticizers of the foam matrix.

Preferred stabilizers which directly stabilize the active ingredient, especially when said active ingredient comprises one or more enzymes, are defined herein as "active stabilizers" or "enzyme stabilizers". Typical active stabilizers interact directly with and stabilize the active ingredient.

Typical active stabilizers used herein preferably comprise a surfactant. Surfactants suitable for use herein are those previously described suitable as matrix stabilizers. In addition to these surfactants, other suitable surfactants for use herein may include surfactants such as: sodium alk(ene)sulfonate, sodium alkoxysulfonate, preferably alkoxysulfonate containing 10 to 18 carbon atoms, whatever the configuration, preferably those that are linear and have 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 their salts. The salts of these acids preferably contain counterions such as calcium and/or sodium.

Preferred active stabilizers contain cations such as calcium and/or sodium. Calcium chloride and/or sodium chloride are preferred.

Other preferred active stabilizers comprise small peptide chains of an average of 3 to 20, preferably 3 to 10 amino acids, which interact with and stabilize active ingredients, especially enzymes.

Other active stabilizers comprise small nucleic acid molecules, generally comprising 3-300, preferably 10-100 nucleotides. Typical nucleic acid molecules are deoxyribonucleic acid and ribonucleic acid. The nucleic acid molecule may be in the form of a complex with other molecules, such as proteins, or may form a complex with active ingredients of the preparation, especially enzymes.

Active stabilizers suitable for use herein, especially when the article herein contains bleaching agents, include antioxidants and/or reducing agents such as thiosulfates, methionine, urea, thiourea dioxide, guanidine hydrochloride, guanidine carbonate, sulfamic acid Guanidine, monoethanolamine, diethanolamine, triethanolamine, amino acids such as glycine, sodium glutamate, proteins such as bovine serum albumin and casein, tert-butylhydroxytoluene, 4-4'-butylene bis(6-tert-butyl -3-methyl-phenol), 2,2'-butylene bis(6-tert-butyl-4-methylphenol), monostyrenated cresol, distyrenated cresol, monostyrenated phenol , distyrenated phenol, 1,1-bis(4-hydroxyphenyl)cyclohexane, or derivatives thereof, or combinations thereof.

Other active stabilizers may comprise reversible inhibitors of the active ingredient. Without intending to be bound by theory, it is believed that a reversible inhibitor of an active ingredient, especially when the active ingredient comprises one or more enzymes, forms a complex with the active ingredient and improves its stability, thereby rendering the active ingredient Remains stable during storage. When the active ingredient is released, typically into a liquid environment, the reversible inhibitor dissociates from the active ingredient so that the active ingredient can achieve the desired effect it was designed or intended to achieve.

Active stabilizers suitable herein include sugars. Sugars used herein generally include those selected from the group consisting of sucrose, glucose, fructose, raffinose, trehalose, lactose, maltose, derivatives thereof, and combinations thereof.

Active stabilizers may also include sugar alcohols such as sorbitol, mannitol, inositol (inositol), derivatives thereof, and combinations thereof.

It may be preferred that the active stabilizer takes the form of a coating or barrier layer at least partially enclosing the article or active ingredient thereof, preferably completely enclosing the article or active ingredient thereof, especially the enzyme.

The preparation may contain (by weight) from 0.01%, or from 0.1%, or from 1%, or from 2%, or from 5%, or from 7%, or from 10%, or from 15%, or from 20% % stabilizer, and may contain (by weight) to 70%, or to 60%, or to 50%, or to 40%, or to 30%, or to 25% stabilizer. The amount of stabilizer used in the preparation depends on the amount and type of active ingredient, and also depends on the amount and type of the matrix. additional ingredients

The components of the present invention preferably contain additional ingredients which improve the dissolution properties of the articles herein.

Preferred additional ingredients to improve the dissolution of the articles herein preferably include: sulfonated compounds such as C ₁ -C ₄ alk(en)yl sulfonate, C ₁ -C ₄ aryl sulfonate, diisobutylbenzene sulfonic acid Esters, tosylate, cumene sulfonate, xylene sulfonate, their salts such as sodium salt, their derivatives or their combinations, preferably diisobutylbenzene sulfonate, sodium toluene sulfonate, Sodium cumene sulfonate, sodium xylene sulfonate and their combinations; and/or C ₁ -C ₄ alcohols such as methanol, ethanol, propanol such as isopropanol, and their derivatives, and their combinations, preferably ethanol and/or isopropanol; and/or C ₄ -C ₁₀ diols such as hexanediol and/or cyclohexanediol, preferably 1,6-hexanediol and/or 1,4-cyclohexanedimethanol; and and/or components capable of acting as wicking agents, such as cellulose-based components, especially modified cellulose; and/or swelling agents such as clays, preferably clays being smectites, especially of the dioctahedral or trioctahedral type Smectite clays, highly preferred clays are montmorillonite clays and hectorite clays or other clays in the form of bentonite clays; and/or effervescent systems, preferably effervescent systems comprising A source of acid that reacts to form gas. Process for making elastic articles

The elastic articles of the present invention can be prepared using any process that prepares a polymeric matrix having a specified Tg from a polymeric material and a plasticizer and incorporates active ingredients and stabilizers in this matrix. The preferred process involves chemically or physically introducing a gas into the mixture of polymeric material and plasticizer optionally with active ingredients.

A preferred process for preparing the product comprises the steps of:

a) obtaining a mixture of polymer material and plasticizer, preferably water and an additional plasticizer;

b) chemically or physically introducing a gas into the mixture of the polymeric material and water;

c) adding the active ingredient to the mixture before or simultaneously with or after step b);

d) bringing a stabilizer into contact with the mixture before or simultaneously with or after step c);

e) shaping the resulting mixture into an article;

wherein part of the water, if any, is removed after or simultaneously with one or more of steps a)-e).

In step a), the mixture is preferably an aqueous mixture or slurry, and part of the water is removed after or during steps b), c) and/or d), so that the final product contains 3% by weight or more free water.

Step c) preferably comprises the step of obtaining a core comprising the active ingredient or part of the active ingredient and coating the core with the mixture in step b).

Step d) preferably comprises a mixing step, more preferably intimately mixing the active ingredient with a stabilizer or coating the active ingredient with a stabilizer.

Preferably the article comprises open cells and/or closed cells and the process comprises the steps of:

a) forming a mixture of polymeric material, active material, a stabilizer, a plasticizer and a liquid, wherein the liquid and the plasticizer may be the same compound;

b) forming a core from the mixture of claim b), and

c) evaporating off the liquid or part of the liquid to form cavities within the mixture, which cavities form the inner regions of the pores in the article,

Wherein step c) is preferably carried out by freeze-drying or heating the core so that the liquid or part of the liquid evaporates.

Step b) can also be carried out by applying pressure to the mixture of step a), preferably with mixing and/or increasing temperature, and then removing the pressure or part of the pressure so that the liquid evaporates. For example, an extrusion process can be used. In this case the mixture of polymer material, plasticizer, preferably water, and optionally active ingredients is introduced into the extruder, in which the mixture is further mixed and heated, wherein the mixture is preferably formed as a result of mixing or as a result of heating melt and then reduce the pressure at the exit of the extruder where the extruded mixture (which can be formed into the desired shape, e.g. pellets) exits the extruder so that the liquid or part of the liquid evaporates, or preferably water emerges from the extruded mixture as vapor evaporated. This leads to the formation of pores, with cavities as described above, which may then contain a gas, preferably air, and optionally active ingredients. These cavities form the interior regions of the pores in the matrix of the elastic articles of the present invention.

Step b) in the process may also be performed by heating the mixture to evaporate the liquid or part of the liquid, as above leading to the formation of cavities. This is preferably accomplished by feeding the mixture to a spray drying tower, preferably through nozzles, to form droplets of the mixture, and conventionally spray drying these droplets to form particles of the elastomeric article.

As mentioned above, the physical and/or chemical introduction of gas or blowing agent can use any known method, preferably

- Physical foaming by: gas (dry or aqueous route) injection, optionally with mixing, high shear agitation (dry or aqueous route), gas dissolution and relaxation, including critical gas diffusion (dry or aqueous route ) in;

- chemical foaming, by in situ gas formation (by chemical reaction of one or more components, including _CO2 formation from effervescent systems);

-Steam foaming, cured by UV radiation.

These foaming steps are preferably followed by a drying step or an additional drying step to remove excess liquid or part of liquid, such as water. In particular, this drying step is carried out at least after the formation of the polymer matrix and optionally after the addition of the active ingredients, preferably as the last step of the process. Preferably the drying step is such that the volume of the final elastic article after the drying step is about the same as before the drying step. In addition, the drying step is preferably carried out by freeze-drying, during which the solvent, such as water, is removed under vacuum and at reduced temperature. Slow fluid bed or oven drying at elevated temperatures, such as 40-80°C, or even 40-60°C, is also useful.

A preferred process involves at least one step of forming a mixture of a polymeric material and a liquid, preferably a solution of a polymeric material and a solvent, preferably comprising water, to which a plasticizer (or when the circumstances permit, additional plasticizing agent). If active ingredients and/or stabilizers are required to be present in the matrix, these are also added to the mixture of polymer material, solvent and plasticizer. Alternatively, or in addition, it may be preferred to form a matrix around the active material, preferably around a core of active material and carrier material.

This is then further processed eg into cores in the shape of the final product, such as granules or pellets, and typically dried to give the product. Preferably, a gas is added prior to the shaping step. The molding step includes a granulation step, such as atomization or spray drying, extrusion, and micro-ingot formation. Freeze drying is the preferred process for drying the cores to form the article.

The following is a preferred process which forms low-dust or even zero-dust particles, as determined by the prestressed Heubach test described below, with a matrix having a Tg below 10°C and a modulus of elasticity below 0.5GNm ^-2 , in the following specific examples will be described in more detail. The first preferred process is as follows:

A solution of polymer material (or a mixture of polymer and a liquid) is obtained in the desired amount, for example (into) a mixing tank. The required amount of active substance (in solution), such as an enzyme solution, and stabilizer is then added, and the required amount of plasticizer, and optionally other additional ingredients, such as fillers, thickeners, etc. are added. Stir these materials to form a homogeneous mixture. Preferably, a gas such as air can be introduced into the solution by any of the above methods, preferably physically, by high shear mixing.

Particles are then formed from the mixture by atomization, preferably using a positive displacement pump to transfer the mixture solution to a nozzle, preferably using one or more fluid nozzles to form droplets.

The droplets are then frozen, preferably by a freezing medium (which may include liquid nitrogen, freon, freezing oil). Then, the frozen particles are moved to a vacuum chamber, preferably at a temperature below 0°C (measured at the surface of the particles).

Preferably the frozen particles are collected from the spray column and transferred without increasing the temperature. The temperature of the walls and trays of the freeze-drying tower is preferably maintained below 0°C to keep the particles frozen. Applying a vacuum, the frozen ice crystals will sublimate the gas to gaseous form, creating pores in the particles. The total dryness can be controlled by the vacuum level and the contact temperature of the vacuum chamber wall with the tray.

After the granules have dried to the desired moisture content, they are free flowing. The particles can then preferably be sorted by passing through different screens and/or other process equipment.

The above optional step of introducing gas (bubbles) into the polymer solution mixture was found to improve the impact resistance of the particles very well, which was reflected in the electronic modules. Bubbles can be introduced in different ways.

During the atomization step, it is preferred that the spray nozzles be located at a sufficient height within the spray column that freezing of the droplets is accomplished as they descend under the force of gravity. Nozzle types can come in different designs - single fluid pressure nozzles, rotary insert, sonic or multi-fluid nozzles. An important inventive point is breaking up the liquid flow to form separate droplets. As these droplets fall due to gravity, they need to be cooled to freezing. The freezing medium is preferably a non-aqueous gas or liquid capable of rapidly freezing liquid droplets. The actual temperature at which these droplets are cooled to form particles is preferably below 0°C, and preferably below -20°C.

It is also preferred that the above-mentioned process is modified as follows:

A gas, preferably _CO2 gas, is introduced into the mixture and the mixture is introduced into a spray drying tower as described above, thereby forming spray dried expanded particles, which may be classified if necessary. Preferably, the inlet temperature is about 130°C, the outlet temperature is about 75°C, and the injection rate is 12.5g/min. For example a Niro Mobil Minor with two fluid nozzles can be used here. The resulting particles may already be in the desired shape or may be further freeze-dried under vacuum.

Another preferred process is as follows:

A solution of the desired amount of polymer material is obtained (or powdered polymer can be used and liquid added), for example introduced into a mixing tank. The desired amount of plasticizer is then added, and optionally other additional ingredients such as fillers, thickeners, etc. are added. Stir the material to form a homogeneous mixture. Preferably, a gas such as air is introduced into the solution by any of the above methods, preferably physically, by high shear mixing.

In addition, granules comprising active ingredients such as enzymes, stabilizers and optionally other ingredients such as fillers or carriers are prepared, for example by fluidized bed coating, by applying a first "core" (generally when the active ingredient is an enzyme, these Cores (which are sugar or starch granules) are fed into the fluidized bed and the active or active solution is sprayed onto these cores and any solvents such as water are dried from the active solution with warm flowing air.

The polymer mixture described above is then applied to these active substances/cores, eg by means of positive displacement pumps directed to atomizing nozzles in the fluidized bed as described above. More than one nozzle may be used and it may be preferred that different components are applied to the core through different nozzles.

The required fluidizing air is preferably below 0°C, preferably about -20°C. The fluidizing air then freezes the polymer mixture/solution on the outside of the active core. This is a critical parameter of control and generally the air temperature must be below 0°C in order to allow the polymer mixture/solution to freeze rapidly on the core particles.

The frozen particles thus obtained are then preferably transferred to a vacuum chamber, where, as mentioned above, they can also be sorted.

The particles of the invention formed by this technique comprise a matrix surrounding the active ingredient.

The above optional step of introducing gas (bubbles) into the polymer solution mixture has been found to significantly increase the impact resistance of the particles, as reflected by the Young's modulus.

Another preferred process is as follows:

A solution of the desired amount of polymer material (or solid polymer and appropriate amount of liquid) is obtained, for example introduced into a mixing tank. The required amount of active substance (solution) such as enzyme solution, and stabilizer (solution) are then added (in the mixing tank) and the required amount of plasticizer and optionally other additional ingredients such as fillers, thickener. Stir the material to make a homogeneous mixture. Preferably, a gas such as air can be added to the solution by any of the methods described above, preferably physically, by high shear mixing.

The polymer solution is then pumped from the mixing tank into an extruder or a die cavity with a platen at the end. Gases may be injected into the mixture before entering the extruder or die cavity, for example by mechanical shear mixers or static mixers for dispersion.

As the extrudate exits the die, the change in pressure creates mild bubbling or swelling in the extrudate. The extrudate is then cut to suitable lengths with a die face cutter or other equipment (eg, hot wire, rotary plunger cutter, etc.). The extrudate can optionally be passed through an additional milling step to make it more rounded. Process equipment that can accomplish this function includes (rotating grinding disc, coalescing disc, pelletizing machine, tumbling drum, mixing drum, etc.).

For example, a paste is made by mixing 75 g PVOH, 15 g citric acid, 2 g PEO, and 22.5 g glycerin in a Braun mixer with high shear agitation set at full speed for 40 seconds; then add 80 g water and 80 g enzyme and high speed shear Cut to mix, ie set on full speed, until a homogeneous foam forms in about 2 minutes. Use a 10 mL syringe to squeeze the foam onto a plastic plate. Let it dry for 24 hours. Once dry, the foam strips are cut into small pieces of approximately 1-2 mm to form granules, the formula (dry state): 63.2% polyvinyl alcohol, 19% glycerin, 12.7% citric acid, 1.6% PEO, 4% of water, 3.2% of enzymes.

The elastic modulus of the obtained particles was 0.00016GM.m ^-2 .

The resulting granules had 0% dust when tested in the prestressed Heubach test, which means very good impact resistance. (The prestressed Heubach test is carried out by methods known in the art, adopting the equipment provided by Herbach Engineering GmbH in Germany, changing the rotational speed of the propeller by stress to be 75 ± 1 revolution/minute, the ball is tungsten carbide, and each grain is 82g).

Preferred Molding/Ingot Process:

A highly preferred process involves forming pellets of the mixture described above with a mold into which the mixture described herein is added and subsequently dried (freeze-dried). Also preferred is a process utilizing a tablet-making apparatus in which the above-mentioned mixture, preferably containing added gas, is pressed through a rotating perforated drum onto a moving conveyor belt to form tablets (droplets or granules). When dry or hardened, the formed particles or beads are scraped off the conveyor belt with a scraper.

A preferred first step is the preparation of a mixture of polymeric material and plasticizer, liquid components and optionally active ingredients. Gas is preferably added to the mixture as described herein. This must preferably be free of undissolved large particles, which would clog the holes in the drum. Preferably the temperature range of the mixture is 0-50°C. The mixture is pumped into a branch pipe connected to the rotating perforated drum parallel to the drum's longitudinal axis. The mixture is drawn into the drum and, as the drum rotates, the mixture is brought into contact with an internal scraper with blades which contact the perforated drum and run along the length of the inner surface, parallel to the feed branch.

The distance of the outer surface of the porous drum is within the height range of the desired particle height (less than the diameter of the hole), but not in contact with the moving conveyor belt or the smooth surface of the drum at the point where the inner scraper contacts the inner surface of the porous drum, the porous drum The tangential speed of the belt matches the speed of the conveyor belt or the tangential speed of the smooth surface drum. The mixture is deposited onto the lower surface as it is forced through pores that typically range in size from 300-2000 μm (but can be smaller or larger). The rotation of the perforated drum cuts the fed material away from the material on the smooth surface, thus leaving droplets or pastilles which will form the desired granules. These lozenges can be solidified by freezing or evaporating some or all of the solvent liquid. If freezing is required, the temperature of the conveyor belt or smooth surface drum can range from ambient to -20°C. If solvent evaporation is required, this can be achieved by heat conduction from a conveyor belt, which can range in temperature from ambient to 70°C, or by passing dry air (which can be heated to 200°C to shorten drying time) through the pastilles. surfaces, or both.

The resulting granules are then removed from the drum or conveyor belt with a scraper. This process can be improved by using a suitable lubricant (release agent) such as silicone oil on the drum. Lubricants or release agents can present an additional benefit to the pellets by reducing the adhesion between the polymer material and the belt/drum, and thus increase the tablet height, if this is also desired.

Example

Embodiment 1 according to the preparation method of elastic article of the present invention

4700g of 33% by weight polyvinyl alcohol (weight average molecular weight 30,000-70,000) solution and 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 were mixed under high shear Blend in the machine until a homogeneous foam forms. This mixture was transferred to a feed tank and pumped using a gear pump into a micro-tabletting apparatus, such as that supplied by Sandvik Process Systems, Inc. (Totowa, New York), employing perforated drums with 1 mm apertures and 2.5 mm spacing. This equipment deposits the lozenges on a smooth surface drum that is coated with a layer of silicone oil and heated to about 30°C. When the drum is one quarter covered with pastilles, stop turning. The lozenges were dried with a hot air heater until the surface of the lozenges was dry to the touch. The resulting particles were then scraped off and collected.

EXAMPLE 2 Process for preparing foam articles of the present invention in the form of tablets, pellets or granules Equipment: microbalance, 100 ml measuring cup, Kenwood "chef" brand food processor with stirrer and mixing cup, glass or plastic molds, spatula . Chemicals: polyvinyl alcohol (Aldrich Chemical Company, weight average molecular weight Mw=30-70k), glycerin (99%, Aldrich Chemical Company), citric acid (Aldrich, citric acid, USP anhydrous), distilled water, dry ice (or solid CO ₂ ), insulated box. process:

1. Weigh 50±0.2g of PVA and 30±0.2g of glycerin.

2. Mix the PVA and glycerin with a mixer at low speed (2nd setting; low shear).

3. Gradually add 50±1 ml of water to the dry mixture and keep mixing mechanically for 2 minutes. Obtain a homogeneous colloid.

4. Increase the mixing shear speed to the highest gear (8 gears). Add 10-20ml of water until the PVA foam forms. Maintain high shear mixing for 3 minutes.

5. Gradually add active ingredients, such as 2-10 g of enzymes, to the foam, maintaining mechanical mixing to obtain a uniform active foam.

6. Stop mixing. Spread the PVA foam inside the mould, avoiding any structural damage.

7. Place the filled molds in an insulated box 1/3 filled with dry ice. Let it freeze for 5 hours.

8. Quickly put the frozen sample into a vacuum freeze dryer (Edward XX) and keep it for 24 hours.

9. Remove the dry sample from the mold.

Any active ingredient may be added in step 5 in any amount, generally up to about 50 g, eg fabric softener, bleach, nonionic surfactant.

Any stabilizer may be added in step 5 in any amount, generally up to about 50 g, eg, bovine serum albumin, ammonium sulfate, sucrose, and styrenated phenol.

Example 3

Process for the preparation of elastic articles of the invention in the form of tablets, beads or granules

Device: Same as in the example above.

Chemicals: polyvinyl alcohol (Aldrich Chemical Company, weight average molecular weight _Mw =30-70k), glycerin (99%, Aldrich Chemical Company), citric acid (Aldrich, citric acid, USP anhydrous), sodium carbonate (Aldrich, Anhydrous), lauryl sulfate surfactant (Aldrich), distilled water, Petri dish (diameter 90mm), oven (set at 45°C±2°C). Process:

1. Weigh 50±0.2g of PVA, 30±0.2g of glycerin, 20±0.2g of sodium carbonate and 2±0.2g of sodium lauryl sulfate.

2. Mix PVA, glycerin and sodium lauryl sulfate with a mixer at low speed (2 gear).

3. Gradually add 50±1ml of water to the dry mixture and maintain mechanical stirring for 2 minutes. Obtain a homogeneous colloid.

4. Add the active ingredients eg 5g enzyme and sodium carbonate and stir the mixture vigorously for 30 seconds until a fully expanded foam is obtained.

5. Spread the foam on a Petri dish to form a non-uniform coating 1 cm thick.

6. Put the Petri dish in an oven at 40°C for 24 hours.

7. Remove the dry foam film from the mold.

Any active ingredient may be added in step 4 in any amount, typically up to about 50 g, eg fabric softener, bleach, nonionic surfactant.

Repeat this process with 55% by weight of polycarboxylate polymer, 20% by weight of anhydrous sodium carbonate and 25% by weight of enzyme and softening clay; and with 45% by weight of polycarboxylate polymer, 15% by weight of polyethylene glycol Alcohol, 20% by weight of anhydrous sodium carbonate and 20% by weight of enzymes and softened clay etc. Repeat this process.

Claims (15)

1. An elastic product comprising: a) an active ingredient; and b) a foam matrix formed from at least one polymeric material and a plasticizer; and c) a stabilizer; wherein said article is capable of releasing said active ingredient into a liquid environment. 2. The elastic article according to claim 1, wherein said active ingredient is active in an aqueous environment, and wherein said article is water-dispersible, water-disintegrable or water-soluble, preferably water-soluble. 3. An elastic article according to any preceding claim, wherein 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. An elastic article according to any preceding claim, wherein said matrix has a modulus of elasticity of less than 1 GN.m ^-2 , preferably less than 0.1 GN.m ^-2 , or even less than 0.01 GN.m ^-2 . 5. An elastic article according to any preceding claim, wherein said stabilizer comprises a foam stabilizer. 6. An elastic article according to any preceding claim, wherein said active ingredient is a cleaning product ingredient, fabric care ingredient, pharmaceutical or cosmetic ingredient, preferably selected from the group consisting of enzymes, surfactants, brighteners, dyes, suds suppressors bleaches, bleach activators, fabric softeners, fabric conditioners, antibacterials, effervescent systems and mixtures thereof. 7. An elastic article according to any preceding claim, wherein said active ingredient comprises at least one enzyme, and wherein said stabilizer comprises an enzyme stabilizer, preferably said stabilizer is an enzyme stabilizer. 8. An elastic article according to any preceding claim, wherein said polymeric material comprises a water soluble polymer, preferably water soluble polyvinyl alcohol. 9. An elastic article according to any preceding claim in the form of particles having a volume average particle size of 50-4000 microns, preferably 100-1500 microns. 10. An elastic article according to any preceding claim, which has a relative density of 0.05-0.9, preferably 0.3-0.7. 11. An elastic article according to any preceding claim, wherein said matrix forms a series of closed and open cells, wherein the ratio of the number of closed cells to open cells is preferably at least 1:1. 12. An elastic article according to claim 7 obtainable by a process comprising the steps of: a) preparing a mixture of polymer material and plasticizer, preferably water and another plasticizer; and b) chemically or physically introducing a gas into said mixture; and c) bringing the active ingredient into contact with said mixture before, and/or simultaneously, and/or after step b); and d) contacting a stabilizer with said mixture before, and/or simultaneously, and/or after step c); and e) shaping the resulting mixture into an article; Wherein it is preferred to remove part of the water, if any, after or simultaneously with one or more of the steps a) to e). 13. An elastic article according to claim 12, wherein said active ingredient is contacted with said stabilizer prior to contacting said active ingredient with said mixture of polymeric material and plasticizer. 14. Use of an elastic article according to any one of claims 1-13 to release an active ingredient into an aqueous environment, preferably the active ingredient is a detersive active ingredient, preferably an enzyme, and preferably the aqueous environment is wash water. 15. Use of an elastic article according to any one of claims 1-13 in a cleaning composition, a fabric care composition, a personal care composition, a cosmetic composition or a pharmaceutical composition, preferably wherein Active ingredients: enzymes, fragrances, surfactants, brighteners, dyes, suds suppressors, bleaches, bleach activators, fabric softeners, antimicrobials, effervescent systems and mixtures thereof.