MX2007001100A - Encapsulated active material with reduced formaldehyde potential. - Google Patents

Abstract

The invention in its various embodiments provides a microcapsule product with reduced levels of formaldehyde. Formaldehyde levels are reduced by the inclusion of a formaldehyde scavenger. The microcapsules provided are well suited for rinse-off applications associated with personal care and cleaning products.

Description

PROCEDURE FOR PREPARING ACTIVE ENCAPSULATED MATERIAL WITH REDUCED FORMALDEHYDE POTENTIAL STATUS OF RELATED REQUESTS This application is a continuation in part of our previous request from E.U.A. serial number 11 / 304,089, filed on December 15, 2005, the contents of which are incorporated in the present invention as references and are set forth in their entirety.

FIELD OF THE INVENTION The present invention relates to active materials that are encapsulated within a polymeric material exhibiting reduced levels of formaldehyde. Encapsulated fragrance materials are suitable for rinsing applications associated with personal care and cleaning products.

BACKGROUND OF THE INVENTION Fragrance chemicals are used in numerous products to improve a consumer's pleasure for a product. Fragrance chemicals are added to consumer products such as laundry detergents laundry, fabric softeners, soaps, detergents, personal care products, such as shampoos, products for body washes, deodorants and the like, as well as numerous other products. In order to improve the effectiveness of the fragrance materials for the user, various technologies have been employed to improve the administration of the fragrance materials at the desired time. A widely used technology is the encapsulation of the fragrance material in a protective coating. Frequently, the protective coating is a polymeric material. The polymeric material is used to protect the fragrance material from evaporation, reaction, oxidation or from other elements that dissipate the odor before use. A brief review of the encapsulated polymeric fragrance materials is described in the following US Patents: The US Patent. No. 4,081, 384 discloses a softener or anti-static forming core coated by a polycondensate suitable for use in a fabric conditioner; the Patent of E.U.A. No. 5,112,688 discloses selected fragrance materials having the appropriate volatility to be coated by coacervation with microparticles in a wall that can be activated for use in fabric conditioning; the Patent of E.U.A. No. 5,145,842 describes a solid core of a fatty alcoholic, ester, or other solid plus a fragrance coated by an aminoplast shell; and the U.S. Patent. No. 6,248,703 discloses various agents including fragrance in an aminoplast shell being included in a bar soap extruder. The patents of E.U.A. The aforementioned are incorporated herein by reference as if they were established in their entirety. Pastes watered in fragrance microcapsules consist of a core of a fragrance surrounded by a crosslinked polymeric wall, dispersed in an aqueous medium. The wall is often made of natural or synthetically derived homopolymers or copolymers containing the amide, amine, carboxyl, hydroxyl, thiol and mercaptan functional groups. These polymers are crosslinked with aminoplast type crosslinkers. These crosslinkers are based on melamine-formaldehyde, urea-formaldehyde, glycouryl-formaldehyde, benzoguanamine-formaldehyde, ethylene-formaldehyde, dihydroxyethylene-formaldehyde, hydroxyl (alkoxy) alkyleneurea. A by-product of the cross-linking reaction is formaldehyde, which remains dissolved in the watery paste medium (water). The watery paste is used "as it is" if no attempt to purify it. Therefore, the formaldehyde produced in the reaction contributes to the level of formaldehyde in the slurry. In addition, formaldehyde is used in the process of making the crosslinkers, in which typically no purification is carried out either. Therefore this level also contributes to the final levels of the watery paste. Formaldehyde is a colorless gas that dissolves easily in water. Aqueous formaldehyde solutions have strong, unpleasant odors. Formaldehyde is considered an industrial pollutant and is has observed that it is carcinogenic based on laboratory tests. It is also an irritant and skin sensitizer. Frequently, it is necessary to reduce formaldehyde levels in watered microcapsule fragrance pastes for processing and end-use benefits. There are several methods that can reduce the levels of free formaldehyde in the fragrance microcapsules. The first method is to remove the existing free formaldehyde from the watery paste. This can be done by several methods. One way is to spray-dry the capsules so that the formaldehyde evaporates. This could result in a dry product instead of a watery paste, which may or may not be desirable, depending on the application. Free formaldehyde can also be removed by spraying with an inert gas or steam. A final way to oxidize or derive (eliminate) free formaldehyde, rendering it inactive. This can be followed by the removal of the derivative by evaporation or adsorption. All these methods are aimed at the existence of formaldehyde levels but are inefficient in reducing future formaldehyde levels that may increase after aging. It has been observed that after resting, the levels of free formaldehyde can be increased gradually, presumably due to the residual cure or to the hydrolysis of the functional group that are carried out. This phenomenon is easily observed more frequently in the product formulations, for example, after the slurry of the capsule has been added to a formulation of the final product. Therefore, it is desirable to have an established system that also reduces or eliminates this "future" free formaldehyde. This can be achieved by elimination. By adding excess levels of a scavenger to the slurry, the existing free formaldehyde can be reduced and the free formaldehyde that is subsequently generated can also be reduced. Eliminators bind with free formaldehyde resulting in a benign complex. The scavengers that have been reported for the purpose of microencapsulation include ammonium chloride, ammonium hydroxide, and urea. Ammonia-based scavengers can impart an undesirable ammonia odor to watered pastes. Urea-based scavengers are inefficient, requiring the addition of a large molar excess for effective removal. In addition, the elimination reaction only occurs at certain temperatures and pH. If these conditions can not be achieved under the storage conditions of slurry or other products then the scavengers are inefficient. Under other conditions the elimination reactions are reversible, resulting in the generation of additional formaldehyde. In addition, traces of free formaldehyde generated over time from unreacted crosslinkers in aged slurry are not eliminated because the disposal conditions are no longer favorable.

In addition, formaldehyde reducers known in the art while working to reduce formaldehyde levels are not as effective when added to low or high pH product bases. The adducted formaldehyde scavengers that are formed are unstable under low pH conditions in such products as rinse conditioners, and "ball" antiperspirant antiperspirants. As such, formaldehyde is released due to the hydrolysis of these adducts over time. Therefore, there is a need in the art to provide a formaldehyde reductant whose adducts or products formed are stable to hydrolysis at a low and high pH, such that free formaldehyde concentrations remain low in the final product for consumption. during the shelf life. Up to now, the prior art has not described a free formaldehyde reductant whose adduct or reaction product is stable to hydrolysis in the final consumer product.

BRIEF DESCRIPTION OF THE INVENTION It is an object of the present invention to provide a process for the preparation of a product containing microcapsules with reduced levels of formaldehyde and potentially reducing the generation of formaldehyde incorporated within a final product formulation, which comprises: a) providing an aqueous slurry of a plurality of microcapsules having a polymeric wall and a core comprising an active material, wherein the microcapsule comprises a crosslinked network of polymers of a crosslinked copolymer of acrylamide-substituted or unsubstituted acrylic acid with a polymer selected from melamine-formaldehyde, a precondensate of urea-formaldehyde and mixtures thereof; b) providing from about 0.01 times to about 100 times the molar amount of all the formaldehyde added in the form of an aminoplast crosslinker (bound and free formaldehyde) of a formaldehyde scavenger selected from the group consisting of β-dicarl compounds , amides, imines, acetal formers, sulfur-containing compounds, activated car ammonium, organic amines, an oxidizing agent and mixtures; c) mixing the microcapsules and the eliminator d) providing a microcapsule product with reduced levels of formaldehyde. In another embodiment of the invention, the scavenger may be provided either before, during or after curing. In another modality, a combination of eliminators can be selected to minimize formaldehyde levels while maintaining the performance of the capsule.

In another embodiment, formaldehyde scavengers can be immobilized on insoluble solid supports. In yet another embodiment, polymeric scavengers containing eliminating portions can be used to reduce formaldehyde levels. In yet another embodiment of the invention, the formaldehyde scavenger can be used with microcapsules that cure at temperatures greater than 90 ° C. In another embodiment of the invention, the microcapsule product prepared according to the present invention can be added to a product for consumption. In a further embodiment of the present invention, the formaldehyde scavenger can directly provide the consumer product containing the microcapsules comprising formaldehyde. In even a further embodiment of the invention, formaldehyde levels are reduced to levels less than about 1000 ppm, more preferably less than about 500 ppm, even more preferably less than about 250 ppm and more preferably less than about 100 ppm and less, such as less than about 10 ppm.

DETAILED DESCRIPTION OF THE INVENTION In the present invention several series of formaldehyde scavengers are described, each reacting with formaldehyde by a different mechanism. It is understood by this invention that formaldehyde scavengers include formaldehyde scavengers and reducers and these terms can be used interchangeably. According to one embodiment, the formaldehyde scavenger can be used from trace quantities effective up to 100 times the stoichiometric amount. The stoichiometric amount is the amount of scavenger required to theoretically bind or react all of the added formaldehyde in the form of an aminoplast interlayer (bound and free formaldehyde). This amount of scavenger can be added either to the slurry or subsequently to the formulation of the final product. For example, a watery paste removed can be added to the formulation, followed by a certain amount of the scavenger. The particular amount of the formaldehyde-based crosslinker that is used to create the slurry paste for the capsule contains a percentage of free formaldehyde and bound formaldehyde. The combined total moles of free and bound formaldehyde will determine the amount of moles of the scavenger that are needed to react with all of the formaldehyde. To direct this reaction to its term we would have to add approximately a molar excess of 10x, preferably a molar excess about 5x eliminator. By moles, it is intended that here we understand moles of eliminating groups. Thus, if the eliminating molecule is multifunctional (for example polymeric), it is necessary to add less moles of this molecule. This is the maximum eliminator level necessary based on the amount of crosslinker used. The minimum level of eliminator required is that amount that removes only the free formaldehyde in the slurry. This level is determined-analytically. The minimum amount of moles of the scavenger required is equal to the moles of formaldehyde measured (1: 1). The reason for determining this minimum level is because the procedure can affect the level of free formaldehyde in the final waxy paste. Again, if the scavenger molecule is multifunctional (eg polymeric) less moles of this molecule are needed. In a further embodiment, the formaldehyde scavengers described throughout the specification can be added directly to a product for consumption. The additional scavenger can be added from about 0.01 times to about 00 times the molar amount of all the formaldehyde in the product for consumption. The additional scavenger maintains reduced levels of formaldehyde that are subsequently generated during storage by reaction with the scavenger, especially in consumer products with a pH less than 3 such as a fabric softener.

In the case of multifunctional scavengers such as scavenger polymers and solid supports, the moles of scavenger in the aforementioned specifications are determined by the number of moles of scavenger groups added via the polymer or solid support. In accordance with the present invention, the β-dicarbonyl compounds are effective formaldehyde scavengers. The β-dicarbonyl compounds of the present invention have an acidic hydrogen that gives rise to a nucleophilic atom can be reacted with formaldehyde. The β-dicarbonyl compounds contemplated by the present invention are represented by the following structures: Structure 1 a Structure 1 b wherein X, X3 and? ß can be selected from the group consisting of H; (1) a C1-22, straight-chained, branched or cyclic hydrocarbon or an aromatic portion selected from phenyl, phenylene, naphthalene or other polyaromatic hydrocarbons, followed by a polar group or 1 -3 halogens. The groups X, X3 and X6 can be chemically associated to form cyclic or heterocyclic structures; (2) a halogen on its own; (3) a polar group followed by H or a straight chain, branched or cyclic hydrocarbon or cyclic hydrocarbon or an aromatic portion selected from phenyl, phenylene, naphthalene or other polyaromatic hydrocarbon; and (4) a polar group on its own. The halogen described in the aforementioned options can be selected from F, Cl, Br and I. The polar group described in the aforementioned options can be selected from a group O, OH, COOH, carbonyl, amide, amine , thiol, ethoxy or propoxy quaternary nitrogen, or combinations thereof; and where and X4 is any C, N, S, or P; and wherein X2 and X5 can be selected from the group consisting of H; (1) a C1-22 straight chain, branched or cyclic hydrocarbon or an aromatic portion selected from phenyl, phenylene, naphthalene or other polyaromatic hydrocarbons, followed by a polar group or from about 1 to about 3 halogens; (2) a halogen on its own; (3) a polar group followed by H or a straight chain, branched or cyclic hydrocarbon or cyclic hydrocarbon or an aromatic portion selected from phenyl, phenylene, naphthalene or other polyaromatic hydrocarbon; Y (4) a polar group on its own. The halogen described in the aforementioned options can be selected from F, Cl, Br and I. The polar group described in the above-mentioned options can be selected from O, OH, COOH, carbonyl, amide, amine, thiol , ethoxy or propoxy nitrogen quaternary group and combinations thereof. The β-dicarbonyl scavengers react with formaldehyde by the following reaction scheme: 7-16 can be selected independently from the group consisting of H; (1) a C1-22 straight chain, branched or cyclic hydrocarbon or an aromatic portion selected from phenyl, phenylene, naphthalene and other polyaromatic hydrocarbons, followed by a polar group and from about 1 to about 3 halogens; (2) a halogen on its own; (3) a polar group followed by H or a straight-chain, branched or cyclic hydrocarbon of C1-22 or a cyclic hydrocarbon or a portion aromatic selected from phenyl, phenylene, naphthalene or other polyaromatic hydrocarbon; and (4) a polar group on its own. The halogen described in the aforementioned options can be selected from F, Cl, Br and I. The polar group described in the above-mentioned options can be selected from O, OH, COOH, carbonyl, amide, amine, ~ thiol, ethoxy or propoxy nitrogen quaternary group and combinations thereof. Initially an equivalent of the eliminator reacts with an equivalent of formaldehyde resulting in a methylol compound. Another equivalent of the scavenger reacts with the methylolol carbon to form the stable, disubstituted adduct. Preferred β-dicarbonyl compounds are acetoacetamide (BKB (Eastman)), ethyl acetoacetate (EAA (Eastman)), N, N-dimethylenacetamide (DMAA (Eastman)), acetoacetone, dimethyl-1,3-acetonadicarboxylate, acid 1, 3 acetonadicarboxylic acid, malonic acid, resorcinol, 1,3-cyclohexadione, barbituric acid, 5,5-dimethyl-1,3-cyclohexanedione (dimedone), 2,2-dimethyl-1,3-dioxane-4,6-dione ( Meldrum acid), salicylic acid, methyl acetoacetate (MAA (Eastman)), ethyl-2-methyl acetoacetate, 3-methyl-acetoacetone, dimethyl malonate, diethyl malonate, 1,3-dimethyl barbituric acid, resorcinol, phloroglucinol, orcinol, 2,4-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, malonamide and ß-dicarbonyl eliminator listed in US Patents Us 5,194,674 and 5,446,195 as well as in Tomasino et al. Textile Chemist and Colorist, volume 16, No. 12 (1984), which are incorporated herein by reference. Mono and diamine scavengers can also be used as effective formaldehyde reducers. The diamine eliminators are represented by the following structures: Structure 2 wherein X 7 and X19 can be independently selected from the group consisting of H; (1) a C1-22 straight chain, branched or cyclic hydrocarbon or an aromatic portion selected from phenyl, phenylene, naphthalene or other polyaromatic hydrocarbons, followed by a polar group or 1 -3 halogens; (2) a halogen on its own; (3) a polar group followed by H or a C1-22 hydrocarbon (straight chain, branched or cyclic) or an aromatic portion (phenyl, phenylene, naphthalene or other polyaromatic hydrocarbon); and (4) a polar group on its own. The halogen described in the aforementioned options can be selected from F, Cl, Br and I.

In accordance with the present invention, the diamine scavengers react with fornnaldehyde through nitrogen and form the following adducts as depicted in the reaction scheme below: wherein Xi7-26 can be independently selected from the group consisting of H; (1) a straight, branched or cyclic C 1 -22 hydrocarbon or an aromatic portion selected from phenyl, phenylene, naphthalene or other polyaromatic hydrocarbons, followed by a polar group or 1 -3 halogens; (2) a halogen on its own; (3) a polar group followed by H or a straight, branched or cyclic straight-chain C1-22 hydrocarbon or an aromatic portion selected from phenyl, phenylene, naphthalene or other polyaromatic hydrocarbons; and (4) a polar group on its own. The halogen described in the aforementioned options can be selected from F, Cl, Br and I. The initial mechanism is similar to that of the β-dicarbonyl compounds described above. Depending on the functionality of the urea, any disubstituted or polymeric adduct is formed. Examples of preferred effective mono and diamine scavengers are urea, ethyleneurea, propyleneurea, e-caprolactam, glycouril, hydantoin, 2-oxazolidinone, 2-pyrrolidinone, uracil, barbituric acid, thymine, uric acid, allantoin, polyamides, 4,5-dihydroxyethyleneurea, monomethylol-4-hydroxy-4-methoxy -5,5-dimethyl-propylurea, nylon 2-hydroxyethyl ethyleneurea (SR-511; SR-512 (Sartomer)), 2-hydroxyethylurea (Hydrovance (National Starch)), L-citrulline, biotin, N-methyl urea, N-ethyl urea, N-phenyl urea, 4,5-dimethoxy ethyleneurea and succinimide. Another class of compounds that are effective eliminators of formaldehyde are amines which form mines by reaction with formaldehyde as represented by the following reaction schemes: O - NH2 + X X28 - N = CH2 rl H Y wherein X27-30 can be independently selected from the group consisting of H; (1) a C1-22 straight chain, branched or cyclic hydrocarbon or an aromatic portion selected from phenyl, phenylene, naphthalene or other polyaromatic hydrocarbons, followed by a polar group or from about 1 to about 3 halogens; (2) a halogen on its own; (3) a polar group followed by H or a straight, branched or cyclic straight-chain C1-22 hydrocarbon or an aromatic portion selected from phenyl, phenylene, naphthalene or other polyaromatic hydrocarbon; and (4) a polar group on its own. The halogen described in the aforementioned options can be selected from F, Cl, Br and I. Depending on the amine, similar but different products can be obtained. Preferred amines contemplated by this invention include, but are not limited to, poly (vinylamine) (Lupamin (BASF)), arginine, lysine, asparagine, proline, tryptophan, 2-amino-2-methyl-1-propanol (AMP); proteins such as casein, gelatin, collagen, whey protein, soy protein, and albumin; melamine, benzoguanamine, 4-aminobenzoic acid (PABA), 3-aminobenzoic acid, 2-aminobenzoic acid (anthranilic acid), 2-aminophenol, 3-aminophenol, 4-aminophenol, creatine, 4-aminosalicylic acid, 5-aminosalicylic acid, methyl anthranilate, methoxylamine HCl, anthranilamide, 4-aminobenzamide, p-toluidine, p-anisidine, sulphanilic acid, sulfanilamide, methyl 4-aminobenzoate, ethyl-4-aminobenzoate (benzocaine), beta-diethylaminoethyl-4-aminobenzoate (procaine), 4-aminobenzamide, 3,5-diaminobenzoic acid and 2,4-diaminophenol. Other amines as described in the co-pending privilege patents of E.U.A. for Patent Application Number 11 / 23,898 and E.U.A. 6,261, 483, and those mentioned in Tomasino et al, Textile Chemist and Colorist, volume 16, No. 12 (1984), are also contemplated by the present invention and therefore are incorporated by reference. Hydrazines such as 2,4-dinitrophenylhydrazine can also react with formaldehyde by the first method to produce hydrazones. The reaction is dependent on the irreversible pH. Other preferred amines may be selected from a non-limiting list of 1,2-phenylenediamine, 1,3-phenylenediamine, and 1,3-phenylenediamine. In addition, aromatic amines, triamines, and aliphatic polyamine can also be used. Examples of these amines may include, but are not limited to, aniline, hexamethylenediamine, bis-hexamethylenetriamine, triethyleneaminetriamine, poly (popilenoxide) triamine, and poly (propylene glycol) diamines.

Another class of formaldehyde reducers provided by the present invention is acetal forming compounds such as they are represented by the following structures: Structure 3 wherein X31 and X32 can be independently selected from the group consisting of H; (1) a C1-22 straight chain, branched or cyclic hydrocarbon or an aromatic portion selected from phenyl, phenylene, naphthalene or other polyaromatic hydrocarbons, followed by a polar group or 1 -3 halogens; (2) a halogen on its own; (3) a polar group followed by H or a straight, branched or cyclic straight-chain C1-22 hydrocarbon or an aromatic portion selected from phenyl, phenylene, naphthalene or other polyaromatic hydrocarbons; and (4) a polar group on its own. The halogen described in the aforementioned options can be selected from F, Cl, Br and I. Preferred compounds that form acetal include, but are not limited to, diethylene glycol, saccharides such as D-sorbitol and sucrose, tannins / acid tannic, and polysaccharides such as starches, guar, xanthan, pectin, chemically modified cellulose, chitosan, ascorbic acid, dextrose and mixtures thereof. Also suitable are suitable aliphatic alcohols listed in Tomasino et al, Textile Chemist and Colorist, vol. 16, No. 12 (1984), which is incorporated herein by reference. In addition, polymers with alcohol functional groups such as polyvinylalcohol can also be selected. The complex that forms acetal reacts with formaldehyde in accordance with the following general reaction scheme: wherein X33-36 can be independently selected from the group consisting of H; (1) a straight, branched or cyclic C 1 -22 hydrocarbon or an aromatic portion selected from phenyl, phenylene, naphthalene or other polyaromatic hydrocarbons, followed by a polar group or 1 -3 halogens; (2) a halogen on its own; (3) a polar group followed by H or a straight-chain, branched or cyclic C1-22 hydrocarbon or an aromatic portion selected from phenyl, phenylene, naphthalene or other polyaromatic hydrocarbon; and (4) a polar group on its own. The halogen described in the aforementioned options can be selected from F, Cl, Br and I.

Similar to the amines described above, the reaction is pH dependent and reversible.

Sulfur-containing compounds are also capable of react with a formaldehyde scavenger. There are two modes of reaction. The first reaction is with a bisulfide: O O NaO-S-OH + ^ QO - S- G-- OH H H in this case the formaldehyde reacts with the oxygen bound to the sulfur that forms a stable addition compound. The compounds Preferred sulfur containing compounds are, but are not limited to, 1, 3,5-triazine-2,4,6-trithiol (TAICROS TMT; TMT 15 (DeGussa)) and glutathione. The other mode of reaction is similar to the mechanism of the aforementioned acetal, with the sulfur groups taking the place of the oxygens.

A unique case is with the amino acid cysteine which has groups neighboring sulfur and nitrogen and is illustrated in the following reaction scheme: Cysteine forms a stable complex with formaldehyde. Cysteine-containing proteins can also participate in this reaction.

Removers immobilized on solid supports In accordance with one embodiment of the invention, the eliminating portions can be attached to the surfaces of the solid supports. Solid supports are defined as substances that are insoluble in the slurry in capsule, the base product containing the slurry in capsule and the base product in use. The scavengers in the solid support can be added to the slurry in capsule or to capsules containing a commercial product to reduce formaldehyde levels. The formaldehyde becomes permanently attached to the solid support and results in an adduct that is inert and benign. Suitable solid supports can be polymeric or inorganic in nature. Examples of polymeric supports are polyolefins such as polyethylene, polystyrene, polyvinylacetate, polysaccharides such as dextran, polyesters, polyamides, polyurethanes, polyacrylates and polyureas. The polymers can be straight chain, branched or crosslinked. The surfaces of the supports can be further processed to allow the attachment of the eliminating portions. An example of such treatment is plasma oxidation. Examples of inorganic supports are clays, alumina, silica, zeolite and titanium dioxide. The supports can have a range in size from submicrons to millimeters in dimension. The binding eliminative portions that are effective are aromatic amines, thiol, thiourea, urea and beta-dicarbonyl. The eliminators can exist being directly linked to the or attached to the linker molecule that is attached directly to the support. A commercial example of a resin with a thiol functional group is Amberlite / Duolite GT-73 (Rohm &Haas). Commercial examples of resins with thiourea functional groups are Lewatit MonoPlus TP-214 (Lanxess) and lonac SR-3 (Lanxess). Beta-dicarbonyl, aromatic amine and thiol functional group resins are sold by Sigma-Aldrich.

Polymeric eliminators In another embodiment of the invention, the polymeric scavengers can be added to the slurry in capsule or to the basic product to remove the formaldehyde. Polymeric scavengers are defined as macromolecular species containing scavenger moieties. Additionally, the polymeric eliminators are soluble in the gummy paste in capsule, the base product containing the gum paste in capsule and the base product in use. The scavenger portions can be attached to the polymer base structures either as terminal groups or as pendant groups. Alternatively, the polymeric base structure may contain eliminating moieties. The advantage of a polymeric scavenger is that the scavenger and the formaldehyde scavenging adduct are macromolecular and therefore typically are more inert and benign. Stable polymeric base structures which can be modified with eliminating end groups are based on vinyl, acrylic, olefin, saccharide, alkylene oxide, amine, urea, urethane, carbonate chemistries, ester, and amide / petida. The polymer molecular weights may have a size range of 100 to 10,000,000 Daltons (more preferably 500 to 1,000,000 Daltons). The polymers can be straight chain, branched, crosslinked and networked in structure. The eliminating portions can be attached to all or some of the terminal chains. The terminal group removal moieties which are effective may be selected from, but not limited to, amides, ureas, thiols, sulfites, aromatic amines and beta-dicarbonyl. Examples of polymeric terminal group scavengers are poly (1,4-butanediol) -bis- (4-aminobenzoate) and poly (ethylene glycol) diacetoacetate. The stripping portions may be present in the polymer from 0.1 to 100 weight percent. There are two types of hanging pendant groups. A type is when the existing pending group has an inherent elimination capacity. This could be when the pending group ends with a portion N, O, or S. Suitable polymeric base structures are those based on vinyl amine, vinyl alcohol, vinyl mercaptan and allylamine. Other pendant eliminating portions that are effective are, but are not limited to, aromatic amines, ureas, thiols and beta-dicarbonyls. The polymer molecular weights may have a size range of 100 to 10,000,000 Daltons and more preferably 500 to 1,000,000 Daltons. The polymers can be straight chain, branched, or crosslinked or networked in the structure. Examples of outstanding polymeric scavengers are poly (vinyl amine) (Lupamin (BASF)) and poly (vinyl alcohol).

Another type of pendant eliminator group is when the existing pendant functional group is further functionalized by reaction to produce pendant groups with scavenger capacity. In this way, a polymer with pendant groups that lacks scavenging activity can be converted to an effective scavenger. Suitable polymeric base structures are those based on acrylic acid, methacrylic acid, maleic anhydride, maleic acid, itaconic acid, acrylamide, vinyl amide, vinyl alcohol, vinyl mercaptan, saccharides, peptides, and allylamine. The molecular weights of the polymer can range in size from 100 to 10,000,000 Daltons (more preferably from 500 to 1,000,000 Daltons). The polymers can be straight chain, branched, or crosslinked or networked in the structure. The eliminating portions may be attached to all or some of the pendant groups. The eliminators may exist directly attached to the pendant group or linked to a linker molecule which is then directly attached to the pendant group. Suitable stripping portions are selected from, but not limited to, amines, amides / ureas, thiols, and beta-dicarbonyls. Those skilled in the art can determine the specific reaction pathway for the attachment of these eliminating moieties to the pendant groups. In addition to the aforementioned formaldehyde reducers, formaldehyde can also be removed (eg, removal or absorption) to achieve partial and complete removal of the formaldehyde. As stated above, the formaldehyde scavenger can be used from trace amounts up to 100 times the stoichiometric amount. The stoichiometric amount is the amount of scavenger required to bind theoretically or react with all of the formaldehyde added in the form of an aminoplast crosslinker (bound and free formaldehyde). The material can be added either during the process of making the capsule, after the capsules have been formed or in both procedures. The processing conditions affect the efficiency of the elimination reaction. This pH should be selected from about 1 to about 9, more preferably from about 2 to about 8, more preferably from about 2 to about 6. Optimal conditions, such as pH and temperature, are highly dependent on the elimination chemistry. However, frequently the most suitable pH conditions are found above and below 7. In addition, frequently higher temperature conditions may be favorable. The stability of the capsules can be affected when eliminators are used. One way to minimize this effect is to use a combination of scavengers such as, but not limited to, the combination of urea and ethyleneurea to keep formaldehyde levels and stability low. For such eliminator combinations, which may be 2 or more, each of the individual eliminators may be present at 0.1- 99. 9% of the total amount of the added eliminator (the combination as a whole). For example, a suitable combination could be urea and ethyleneurea in the ratio of 1: 3 to 3: 1. Said combinations include the option of having a eliminator or eliminating combination used in the gummy paste of the capsule as well as a different eliminator or combination of eliminators that is added to the final product for consumption. Another embodiment of this invention is to remove the formaldehyde or adducts from the formaldehyde scavenger from the slurry of the capsule using a solid support such as commercially available active carbon. This is surprising, since formaldehyde is very soluble in water. The activated carbon can be washed and reused. The activated carbon can be selected from any commercial sources prepared from a wide range of processes using coal, wood and coconut. Granular activated carbon is preferred over powder samples for ease of handling. Some non-limiting examples are TIGG 5D 1240, TIGG 5DR 0840, TIGG 5D 2050, TIGG 5WCS-G, and TIGG 5DAW 1240 from TIGG Corporation (Bridgeville, PA); GC 8x30, GC 8x30AW, GC 8x30S, GC 2x40SAW from General Coal Corp., (Paterson, NJ 07501); and CAL® 12x40, FILTRASORB® 100 &200, and FILTERSOB 300 &400® from Calgon Coal (Pittsburgh, PA). A more extensive list can be found in the technical brochures published by the manufacturers. The activated carbon can be added to the formaldehyde solution at the same time that the formaldehyde adduct is formed. This can also be added in the last stage.

In a variant of the aforementioned embodiment, the formaldehyde can be removed by ammonization and the adducts formed can subsequently be adsorbed with activated carbon. According to this embodiment, formaldehyde reacts with ammonium in an alkaline medium to form hemethyleneteramine which can then be adsorbed by activated carbon. Another embodiment of the invention is to remove the formaldehyde from the slurry of the capsule by direct oxidation: (1) to produce formic acid. The formaldehyde was removed after oxidation to formic acid with hydrogen peroxide in an alkaline base to form a formic acid / salt complex. (2) for carbon dioxide. In the present invention, formaldehyde is oxidized to carbon dioxide by exhaustive chemical oxidation and is thus removed from the slurry of the capsule. This can be achieved by the oxidation of formaldehyde by H2O2 in acid medium. Optionally, discoloration activators and / or decolorization catalysts (including oxidizing enzymes) can be used to accelerate oxidation. The detailed options for this application are listed below. The oxidation reaction of formaldehyde can be facilitated by the use of a transition metal ion such as iron (II) or iron (III) as a catalyst. Ions of the active Redox transition metal such such as Cu (I) and Mn (II) can also be used. Enzymes such as oxidase can also be employed. It is also possible to remove formaldehyde by chemical oxidation using manganese oxide (MnO2). The formaldehyde can be oxidized by MnO2 in acid medium and thus removed from the slurry of the capsule. Other inorganic or organic oxidant may be included, but is not limited to, ruthenium oxide (Ru02), vanadium oxide (V2O5), sodium percarbonate, permanganate, sodium perborate. The amount of oxidant must be sufficient to react in a stoichiometric manner with the amount of formaldehyde originally present in the gumpaste not removed. This level of formaldehyde in slurry not removed depends on the level of formaldehyde added to the slurry via the aminoplast crosslinker. In order to optimize oxidation, various sources of discoloration can be used. These can be optionally accelerated and activated using discoloration activators and catalysts (synthetic and enzymatic). The options are listed below.

Sources of discoloration Hydrogen peroxide (H2O2), hypochlorite, chlorine, peracids, oxygen, ozone, and chlorine dioxygen.

Sources of H2O2 Sources of hydrogen peroxide are listed in Kirk Othmer's Encyclopedia of Chemical Technology, 4th Ed (1992, John Wiley &Sons), vol. 4, pp. 271-300"Bleaching Agents (Survey)". Some of the sources of hydrogen peroxide are sodium perborate, sodium percarbonate, sodium carbonate peroxyhydrate, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, or the present invention can use sodium peroxide. Another useful source of available oxygen is persulfate for discoloration (for example, OXONE, manufactured by DuPont).

Discoloration activators These materials can activate the release of peroxide. Examples of these are: TAED (tetraacetylethylenediamine). Other activators are listed in the U.S. Patent. No. 4,915,854, filed on April 10, 1990 to Mao et al, and Patent of E.U.A. No. 4,412,932. Also, nonanoyloxybenzene sulfonate (NOBS) or acyl lactam activators can be used, and mixtures thereof can also be used with TAED. Conventional decolorization activators are listed in the U.S. Patent. No. 4,634,551. Another class of discoloration activators are the amido-derived discoloration activators which are described in the U.S. Patent. No. 4,634,551. Also, the discoloration activators comprising the benzoxazine type activators described by Hoge et al in the US Patent may be used. No. 4,966,723. In addition, they can be use the decolorization activators of the class of acyl lactam activators such as octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl valerolactam, 3, 5,5-trimethylhexanoyl valerolactam and mixtures thereof. Finally, the quaternary substituted discoloration activators can be used such as those described in the U.S. Patent Applications. No. 298,903, 298,650, 298,906 and 298,904, incorporated in the present invention as references.

Discoloration catalysts Discoloration catalysts can be used to further catalyze the discoloration / oxidation reaction. Examples of said catalysts are: salts of the transition metal cation and complexes with organic reagents; metal salts that are manganese, cobalt, copper, iron, titanium, ruthenium, tungsten, and molybdenum. The catalysts of the cobalt complex are described in EP 408,131. Lower metal catalysts (described in U.S. Patent No. 4,430,243) can also be used. Manganese-based complexes described in the Patents of E.U.A. Nos. 5,246,621 and 5,244,594, Application EP 549,272, and Patent of E.U.A. No. 5,194,416.

Complexes with other ligands such as 1, 5,9-trimethyl-1, 5,9-triazacyclododecane, 2-methyl-1, 4,7-triazacyclononane, 2-methyl-1, 4,7-triazacyclononane, and mixtures thereof. same. Metal salt complexes with a polyhydroxy non-carboxylate compound having at least three consecutive C-OH groups, such as those described in the U.S. Patent. No. 5,114,606. For example, complexes of manganese (II), (III), and / or (IV) with sorbitol, iditol, dulsitol, mannitol, xylitol, arabitol, adonitol, mesoerythritol, mesoinositol, lactose, and mixtures thereof. Discoloration catalysts of the type described in the U.S. Patent. No. 5,114,611. Examples are decolorization catalysts comprising Co, Cu, Mn, Fe, bispyridylmethane and bispyridylamine complexes such as Co (2,2'-bispyridylamine) Cl 2, Di (isothiocyanato) bispyridylamine-cobalt (II), trispyridylamine-cobalt (II ) perchlorate, Co (2,2-bispyridylamine) 2 02 CIO4, Bis- (2,2'-bispyridylamine) copper (II) perchlorate, tris (di-2-pyridylamine) iron (II) perchlorate, and mixtures thereof. Mn gluconate, Mn (CF3 S03) 2, Co (NH3) 5 Cl, and the binuclear Mn complex with ligands tetra-N-dentate and bi-N-dentate, including N4 Mn1"(uO) 2 Mnl N4) + y [ Bipi2 Mn1"(uO) 2 Mnlv bipi2] - (CIO4) 3. Metallo-porphyrin catalysts such as those described in EP Applications Nos. 384,503, and 306,089. Catalysts absorbed on mineral supports such as those described in the Patents of E.U.A. No. 4,601, 845 and 4,711, 748.

The discoloration catalysts described in the Patents of E.U.A. Nos. 4,728,455, 4,711, 748, 4,626,373, 4,119,557, 4,430,243, 4,728,455 and DE Patent No. 2,054,019. Another group of discoloration catalysts that can be used are polyoxymethalates.

Oxidizing enzymes: Oxidizing enzymes such as horseradish peroxidase, haloperoxidases, amine oxidase, amino acid oxidase, cholesterol oxidase, uric acid oxidase, xanthine oxidase, glucose oxidase, galactose oxidase and alcohol oxidase can also be used to oxidize formaldehyde. The necessary concentration of oxidant can be calculated by the concentration of the formaldehyde used. The molar ratio of the peroxide to formaldehyde can vary from 1 to 20, preferably from 1 to 10. The amount of catalyst can be used at the level where a reasonable ratio is reached. A preferable ratio will be from eleventh to 1% with respect to that of the peroxide. It is appreciated by those skilled in the art that the formaldehyde scavengers described above can be used alone or in combination with the formaldehyde absorbers described above. The ratio of formaldehyde absorbers (active carbon) to the slurry is determined by the level of formaldehyde present. This means that prior to the absorption of formaldehyde, one skilled in the art should evaluate the binding capacity of the absorbent of the Formaldehyde and you must be sure that the capacity for formaldehyde absorption is in excess with respect to the amount of formaldehyde in the watery paste of the capsule not eliminated. The pH of the process and the temperature conditions for the use of the oxidizing agents depends on the type of discoloration source. More moderate conditions are possible when discoloration activators and catalysts (synthetic or enzymes) are used. In another embodiment of the invention, the formaldehyde scavengers described in the present invention can be used in a process to increase the stability of a microcapsule product by curing the microcapsules at higher temperatures. The retention capabilities of the microcapsule product are improved when the crosslinked network of polymers containing active materials is cured at temperatures above 90 ° C. In a more preferred embodiment, the retention capabilities of the microcapsule product are improved when the cure temperature is greater than 110 ° C. In a more preferred embodiment, the retention capabilities of the microcapsule product are improved when the cure temperature is greater than 120 ° C. In a further embodiment the crosslinked polymer network containing active materials can be cured for periods of time greater than 1 hour and more preferably greater than two hours. The term "high stability" refers to the ability of a microcapsule product to retain active materials in bases that have a tendency to promote discoloration of the active material away from the microcapsule product towards the base. For example, there is a relationship between a higher concentration of the surfactants in the consumer product base and an increased decolorization effect of the active materials encapsulated outside the microcapsules and towards the base. Bases that are primarily non-aqueous in nature, for example, those based on alcohols, or volatile silicones can also discolor active materials from capsules over time. Volatile silicones such as but not limited to cyclomethicone are exemplified by SF 256 Cyclopentasiloxane, SF1257 Cyclopentasiloxane are registered trademarks of General Electric Company. Volatile silicones are found in many personal care products, such as antiperspirants, deodorants, hair sprays, cleansing creams, skin creams, lotions and bar products, bath oils, sunscreen and shaving products, varnishes and polishes Of nails. In these types of product, the same base solvent solubilizes the active material.

Encapsulated active materials The active material suitable for use in the present invention can be a wide variety of materials in which one wishes to administer in a controlled release manner on the surfaces to be treated with the present compositions or within the environment surrounding the surfaces . Non-limiting examples of active materials include perfumes, flavoring agents, fungicides, brighteners, antistatic agents, agents for the control of wrinkles, active fabric softeners, active ingredients for cleaning hard surfaces, skin and / or hair conditioning agents, antimicrobial actives, agents UV protectors, insect repellents, animal / pest repellents, flame retardants, and the like. In a preferred embodiment, the active material is a fragrance, in which the microcapsules containing fragrance provide a controlled release aroma on the surface to be treated or within the environment surrounding the surface. In this case, the fragrance may be comprised of numerous unpurified fragrance materials known in the art, such as essential oils, botanical extracts, synthetic fragrance materials, and the like. The level of fragrance in the encapsulated fragrance coated with cationic polymers ranges from about 5 about 95 percent by weight, preferably from about 40 to about 95, and more preferably from about 50 to about 90 percent by weight on a dry basis. In addition to the fragrance, other agents may be used in conjunction with the fragrance and it is understood that they may be included. As mentioned above, the fragrance can also be combined with a variety of solvents which serve to increase the compatibility of the various materials, increase the general hydrophobicity of the mixture, influence the vapor pressure of the materials, or serve to structure the mixture. Solvents that carry out these functions are well known in the art and include mineral oils, triglyceride oils, silicone oils, fats, waxes, fatty alcohols, diisodecyl adipate, and diethyl phthalate among others. As described in the present invention, the present invention is suitable for use in a variety of well-known consumer products such as laundry detergents and fabric softeners, liquid dishwashing detergents, automatic dishwashing detergents, as well as hair shampoos and conditioners. These products employ surfactants and emulsifying systems that are well known. For example, fabric softener systems are described in US Patents. Nos. 6,335,315, 5,674,832, 5,759,990, 5,877,145, 5,574,179; 5,562,849, 5,545,350, 5,545,340, 5,411, 671, 5,403,499, 5,288,419, and 4,767,547, 4,424,134. Liquid dishwashing detergents are described in US Patents. Nos. 6,069,122 and 5,990,065; Automatic dishwashing detergent products are described in US Patents. Nos. 6,020,294, 6,017,871, 5,968,881, 5,962,386, 5,939,373, 5,914,307, 5,902,781, 5,705,464, 5,703,034, 5,703,030, 5,679,630, 5,597,936, 5,581, 005, 5,559,261, 4,515,705, 5,169,552, and 4,714,562. Laundry liquid detergents that can utilize the present invention include those systems described in U.S. Pat. Nos. 5,929,022, 5,916,862, 5,731, 278, 5,565,145, 5,470,507, 5,466,802, 5,460,752, 5,458,810, 5,458,809, 5,288,431, 5,194,639, 4,968,451, 4,597,898, 4,561, 998, 4,550,862, 4,537,707, 4,537,706, 4,515,705, 4,446,042, and 4,318,818. Shampoos and conditioners that can employ the present invention include those described in U.S. Pat. Nos. 6,162,423, 5,968,286, 5,935, 561, 5,932,203, 5,837,661, 5,776,443, 5,756,436, 5,661, 1 18, 5,618,523, 5,275,755, 5,085,857, 4,673,568, 4,387,090 and 4,705,681. All Patents of E.U.A. previously mentioned.

Capsule Technology Encapsulation of active materials such as fragrance is known in the art, see for example US Patents. Nos. 2,800,457, 3, 870, 542, 3, 516, 941, 3, 415, 758, 3, 041, 288, 5, 1 12, 688, 6, 329, 057, and 6, 261, 483. Another discussion of the fragrance encapsulation is found in the Kirk-Othmer Encyclopedia. Preferred encapsulating polymers include those formed from melamine formaldehyde or urea formaldehyde condensates, as well as similar types of aminoplast. Additionally, microcapsules made via simple or complex coacervation of gelatin are also preferred for use with the coating. Microcapsules having cover walls comprising polyurethane, polyamide, polyolefin, polysaccharide, protein, silicone, lipid, modified cellulose, gums, polyacrylate, polystyrene, and polyesters or combinations of these materials are also functional.

A representative procedure used for encapsulation in aminoplast is described in the U.S. Patent. No. 3,516,941 although it is recognized that many variations are possible with respect to the materials and process steps. A representative procedure used for gelatin encapsulation is described in the U.S. Patent. No. 2,800,457 although it is recognized that many variations are possible with respect to the materials and process steps. Both methods are discussed in the context of fragrance encapsulation for use in consumer products in the U.S. Patents. Nos. 4,145,184 and 5,112,688 respectively. Well-known materials such as solvents, surfactants, emulsifiers, and the like can be used in addition to the polymers described throughout the invention to encapsulate the active materials such as fragrances without departing from the scope of the present invention. It is understood that the term encapsulated means that the active material is substantially fully covered. The encapsulation can provide empty pores or interstitial openings depending on the encapsulation technique employed. Most preferably the entire portion of active material of the present invention is encapsulated. The fragrance capsules known in the art consist of a core of various radii of fragrance and solvent materials, a wall or shell comprising a three-dimensional crosslinked network of an aminoplast resin, more specifically an acrylic acid polymers substituted or unsubstituted or crosslinked copolymer with a pre-condensate of urea-formaldehyde or a pre-condensate of melamine-formaldehyde. The microcapsule formation using mechanisms similar to the foregoing mechanisms, using (i) pre-condensates of melamine-formaldehyde or urea-formaldehyde and (ii) polymers containing substituted vinyl monomer units having portions of proton donor functional groups (eg Examples of sulfonic acid groups or carboxylic acid anhydride groups linked together are described in the US Pat. No. 4,406,816 (2-acrylamido-2-methyl-propane sulfonic acid groups), Patent Application Published in UK GB 2,062,570 A (styrenesulfonic acid groups) and Patent Application Published in UK GB 2,006,709 A (anhydride groups of the carboxylic acid). The wall precursor for polymer microcapsule cover of the crosslinkable acrylic acid or copolymer has a plurality of carboxylic acid moieties, with: and preferably it is one or a mixture of the following: (i) an acrylic acid polymer; (ii) a methacrylic acid polymer; (iii) a copolymer of acrylic acid-methacrylic acid; (iv) an acrylamide-acrylic acid copolymer; (v) a methacrylamide-acrylic acid copolymer; (vi) an acrylamide-methacrylic acid copolymer; (vii) a methacrylamide-methacrylic acid copolymer; (viii) an alkyl copolymer of CrC4 acrylate-acrylic acid; (ix) an alkyl C 4 acrylate-methacrylic acid copolymer; (x) a C 1 -C 4 alkyl methacrylate-acrylic acid copolymer; (xi) a C 1 -C 4 alkyl methacrylate-methacrylic acid copolymer; (xii) an alkyl C 4 C acrylate-acrylic acid-acrylamide copolymer; (xiii) an alkyl C4-acrylate-methacrylic acid-acrylamide copolymer; (xiv) an alkyl copolymer of C-1-C4 methacrylate-acrylic acid-acrylamide; (xv) an alkyl C4-methacrylate-methacrylic acid-acrylamide copolymer; (xvi) an alkyl C 4 C acrylate-acrylic acid-methacrylamide copolymer; (xvii) an alkyl copolymer of CrC4 acrylate-methacrylic-methacrylamide acid; (xviii) an alkyl C4-methacrylate-acrylic acid-methacrylamide copolymer; Y (xix) an alkyl C4-methacrylate-methacrylic acid-methacrylamide copolymer; and more preferably, a copolymer of acrylic acid-acrylamide. When substituted or unsubstituted acrylic acid copolymers are used in the practice of the invention, in the case of the use of a copolymer having two different monomer units, for example, monomeric acrylamide units and monomeric units of acrylic acid, the molar ratio of the first monomeric unit with respect to the second monomeric unit is in the range of from about 1: 9 to about 9: 1, preferably from about 3: 7 to about 7: 3. In the case of the use of a copolymer having three different monomer units, for example ethyl methacrylate, acrylic acid and acrylamide, the molar ratio of the first monomeric unit with respect to the second monomeric unit with respect to the third monomeric unit is found in the range from 1: 1: 8 to about 8: 8: 1, preferably from about 3: 3: 7 to about 7: 7: 3. The molecular weight range of the substituted or unsubstituted acrylic acid polymers or copolymers useful in the practice of the invention is from about 5000 to about 1,000,000, preferably from about 10,000 to about 100,000. Substituted or unsubstituted acrylic acid polymers or copolymers are useful in practice of the invention can be branched, linear, star-shaped, dendrite-shaped or can be a block polymer or copolymer, or mixtures of any of the aforementioned polymers or copolymers. Said substituted or unsubstituted acrylic acid polymers or copolymers should be prepared in accordance with any procedures known to those skilled in the art, for example, De ~ E: U.A. No. 6,545,084. The precursors of the cover wall of the urea-formaldehyde and melamine-formaldehyde precondensate microcapsule were prepared by the reaction of urea or melamine with formaldehyde where the molar ratio of melamine or urea to formaldehyde was is in the range of from about 10: 1 to about 1: 6, preferably from about 1: 2 to about 1: 5. For purposes of the practice of the invention, the resulting materials have a molecular weight in the range of about 156 to 3000. The resulting materials to be used "as is" as a crosslinking agent for the polymer or copolymer of the substituted acrylic acid or unsubstituted or can be further reacted with a C 1 -C 6 alkanol, for example methanol, ethanol, 2-propanol, 3-propanol, 1-butanol, 1-pentanol or 1-hexanol, thus forming a partial ether in where the molar ratio of melamine or urea: formaldehyde: alkanol is in the range of 1: (0.1-6): (0.1-6). The resulting product that contains the portion ether can be used "as-is" as a cross-linking agent for the polymer or copolymer of the aforementioned substituted or unsubstituted acrylic acid, or it can be self-condensed to form dimers, trimers and / or tetramers which can also be used as crosslinking agents for the aforementioned substituted or unsubstituted acrylic polymers or copolymers. The methods for the formation of said pre-condensates of melamine-formaldehyde and urea-formaldehyde are set forth in the patent of E.U.A. No. 3,516,846, U.S. Patent. No. 6,261, 483, and Lee et al. J. Microencapsulation, 2002, Vol. 19, No. 5, pp. 559-569, "Microencapsulation of fragrant oil via in situ polymerization: effects of pH and melamine-formaldehyde molar ratio". Examples of urea-formaldehyde pre-condensates useful in the practice of the invention are URAC 180 and URAC 186, trademarks of Cytec Technology Corp. of Wilmington, Delaware 19801, E.U.A. Examples of melamine-formaldehyde pre-condensates useful in the practice of the invention are CYMEL U-60, CYMEL U-64 and CYMEL U-65, trademarks of Cytec Technology Corp. of Wilmington, Delaware 19801, E.U.A. In the practice of the invention it is preferable to use the pre-condensates to crosslink the polymer or copolymer of substituted or unsubstituted acrylic acid. The melamine-formaldehyde precondensate has the structure: where each of the R groups are the same or different and each represents hydrogen or lower C 1 -C 6 alkyl, for example methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2- methyl-1-propyl, 1-pentyl, 1-hexyl and / or 3-methyl-1-pentyl. In the practice of the invention, the range of molar ratios of pre-condensate of urea-formaldehyde or precondensate of melamine-formaldehyde: polymer or copolymer of substituted or unsubstituted acrylic acid is in the range of about 9: 1 to about 1: 9 , preferably from about 5: 1 to about 1: 5 and more preferably from about 2: 1 to about 1: 2. Once the fragrance material is encapsulated, a cationically charged water soluble polymer can optionally be applied to the encapsulated fragrance polymer. This water-soluble polymer can also be an amphoteric polymer with a ratio of cationic and anionic functionalities resulting in a total net charge of zero and positive, for example, cationic. Those skilled in the art would appreciate that the Loading of these polymers can be adjusted by changing the pH, depending on the product in which this technology is used. Any suitable method can be used for coating the cationically charged materials on the encapsulated fragrance materials. The nature of the suitable cationically charged polymers to aid in the administration of the capsule to the interfaces depends on the compatibility with the chemistry of the capsule wall since there has to be some association with the capsule wall. This association can be through physical interactions, such as hydrogen bonds, ionic interactions, hydrophobic interactions, electron transfer interactions or, alternatively, the polymeric coating can be chemically grafted (covalently) to the capsule or surface of the molecule. particle. Chemical modification of the capsule or the surface of the particle is another way to optimize the anchoring of the polymeric coating to the capsule or to the surface of the particle. In addition, the capsule and the polymer need to move to the desired interface and, therefore, needs to be compatible with the chemistry (polarity, for example) of that interface. Therefore, depending on which capsule and interface chemistry is used (eg, cotton, polyester, hair, skin, wool), the cationic polymer can be selected from one or more polymers with a zero general charge (amphoteric: cationic and anionic functional groups) or net positive charge, based on the following polymer base structures: polysaccharides, polypeptides, polycarbonates, polyesters, polyolefin (vinyl, acrylic, acrylamide, polydiene), polyester, polyether, polyurethane, polyoxazoline, polyamine, silicone, polyphosphazine, oliaromatic, polyheterocyclic, or polyionne, with molecular weight (MW) in a range from about 1,000 to about 1,000,000,000, preferably from about 5,000 to approximately 10,000,000. As used in the present invention, the molecular weight is provided as the weight average molecular weight. Optionally, these cationic polymers can be used in combination with nonionic and anionic polymers and surfactants, possibly through the formation of preservatives. A more detailed list of the cationic polymers that can be used to coat the incarcerated fragrance is provided below: polysaccharides include but are not limited to guar, alginates, starch, xanthan, chitosan, cellulose, dextrans, gum arabic, carrageenan, hyaluronate. These polysaccharides can be used with: (a) cationic modification and cationic alkoxy modifications, such as cationic hydroxyethyl, cationic hydroxy propyl. For example, the cationic reagents of choice are 3-chloro-2-hydroxypropyl trimethylammonium chloride or its epoxy version. Another example is the inserted polyDADMAC copolymers on the cellulose-like element in Celquat L-200 (Polyquaternium-4), Polyquaternium-10 and Polyquaternium-24, commercially available from National Starch, Bridgewater, N.J .; (b) aldehyde, carboxyl, succinate, acetate, alkyl, amide, sulfonate, ethoxy, propoxy, butoxy, and combinations of these functionalities.

Any combination of amylose and milopectin and general molecular weight of the polysaccharide; and (c) any hydrophobic modification (as compared to the polarity of the base structure of the polysaccharide). The aforementioned modifications described in (a), (b) and (c) may be in any relationship and degree of functionalization until the replacement of all functional groups is completed, as long as the theoretical net charge of the polymer is zero (mixture of cationic and anionic functional groups) or preferably positive. In addition, up to 5 different types of functional groups can be linked to the polysaccharides. Also, the chains infected with the polymer can be modified differently from the base structure. The counterions can be any halide ion or organic counterion. Patent of E.U.A. No. 6,297,203 and Patent of E.U.A. No. 6,200,554. Another source of cationic polymers contains protonatable amine groups so that the overall net charge is zero (amphoteric: mixture of cationic and anionic functional groups) or positive. The pH during use will determine the overall net charge of the polymer. Examples are silk protein, zein, gelatin, keratin, collagen and any polypeptide, such as polylysine. Additional cationic polymers include polyvinyl polymers, with up to 5 different types of monomers, having the generic formula of the monomer -C (R2) (R1) -CR2R3-. It can also be used any co-polymer from the types listed in this specification. The general polymer will have a theoretical positive charge net or equal to zero (mixture of cationic and anionic functional groups). Although R1 is any alkanes from C1-C25 or H; the number of double bonds in a range of 0-5. In addition, R 1 may be an alkoxylated fatty alcohol with any carbon alkoxy length, number of alkoxy groups and length of the C 1 -C 25 alkyl chain. R1 may also be a liquid crystalline portion that can be returned to the polymer with thermoplastic liquid crystalline properties, or the selected alnes may result in the fusion of side chains. In the aforementioned formula R2 is H or CH3; and R3 is -Cl, -NH2 (for example, polyvinylamine or its copolymers with N-vinylformamide, these are sold under the name Lupamin 9095 by BASF Corporation), -NHR1, -NR1 R2, -NR1 R2 R6 (wherein R6 = R1, R2, or -CH2-COOH or its salt), -NH-C (O) -H, -C (O) -NH2 (amide), -C (O) -N (R2) (R2 ') ( R2"), -OH, styrene sulfonate, pyridine, pyridine-N-oxide, quaternized pyridine, imidazolinium halide, imidazolinium halide, imidazole, piperidine, pyrrolidone, substituted alkyl pyrrolidone, caprolactam or pyridine, phenyl-R4 or naphthalene- R5 wherein R4 and R5 are R1, R2, R3, sulphonic acid or its alkali salt -COOH, alkali salt -COO-, ethoxy sulfate or any other organic counterion Any mixture of these R3 groups can be used. further containing hydroxyalkylvinylamine units, as described in U.S. Patent No. 6,057,404.

Another class of materials are the polyacrylates, with up to 5 different types of monomers, which have the generic monomer formula: -CH (R1) -C (R2) (CO-R3-R4) -. Any co-monomer can also be used from the types listed in this specification. The general polymer will have a theoretical positive net charge or zero (mixture of cationic and anionic functional groups). In the above-mentioned formula R1 is any alkane from C1-C25 or H with a number of double bonds of 0-5, aromatic portions, polysiloxane, or mixture thereof. In addition, R 1 can be an alkoxylated fatty alcohol with any length of any carbon alkoxy length, number of alkoxy groups and length of the C 1 -C 25 alkyl chain. R1 may also be a liquid crystalline portion that can be returned to the polymer with liquid crystalline thermoplastic properties, or the selected alkanes can result in the fusion of side chains. R2 is H or CH3; and R3 is-C1-25 alkyl alcohol or an alkylene oxide with any number of double bonds, or R3 may be absent such that the C = O bond is (via the C atom) directly connected with R4. R4 can be: -NH2, -NHR1, -NR1 R2 R6 (wherein R6 = R1, R2, or -CH2-COOH or its salt), -NH-C (O) -H, sulfo betaine, betaine, polyethylene, poly (ethylene oxide / propylene oxide / butylene oxide) grafts with any terminal group, H, OH, styrene sulfonate, pyridine, quaternized pyridine, substituted alkyl pyrrolidone or pyridine, pyridine-N-oxide, imidazolinium, imidazolinium halide, imidazole, piperidine, -OR1, -OH, alkali salt -COOH, sulfonate, ethoxy sulfonate, pyrrolidone, caprolactam, phenyl-R4 or naphthalene-R5 wherein R 4 and R 5 are R 1, R 2, R 3, sulfonic acid or its alkali salt or organic counter ion. Any mixture of these R3 groups can be used. Also, glyoxylated cationic polyacrylamides can be used. Typical polymers of choice are those which contain the cationic monomer of dimethylaminoethyl methacrylate (DMAEMA) or methacrylamidopropyltrimethyl ammonium chloride (MAPTAC). DMAEMA can be found in Gafquat and Gaffix VC-713 polymers from ISP. MAPTAC can be found in Luviquat PQ11 PN of BASF and Gafquat HS100 of ISP. Another group of polymers that can be used are those that contain cationic groups in the main chain or in the base structure. Included in this group are the: (1) polyalkylene compounds such as polyethylene mine, commercially available as Lupasol from BASF. Any molecular weight and any degree of crosslinking of this polymer can be used in the present invention; (2) ions having the general formula stated as - [N (+) R1 R2-A1-N (R5) -XN (R6) -A2-N (+) R3R4] n-2Z-, as described in US patents Nos. 4,395,541 and 4,597,962; (3) adipic acid / dimethylamino hydroxypropyl diethylene triamine copolymers, such as Cartaretin F-4 and F-23, commercially available from Sandoz; (4) polymers of the general formula - [N (CH3) 2- (CH2) x-NH- (CO) -NH- (CH2) y- (CH3) 2) - (CH2) zO- (CH2) p] n-, with x, y, z, p = 1-12, and n of conformity with the molecular weight requirements. Examples of Polyquaternium 2 (Mirapol A-15), Polyquaternium-17 (Mirapol AD-1), and Polyquaternium-18 (Mirapol AZ-1). Other polymers include cationic polysiloxanes and cationic polysiloxanes with carbon-based grafts with a network with a theoretical charge positive or zero (mixture of cationic and anionic functional groups). This includes functionalized silicones in the cationic end group (for example Polyquaternium-80). Silicones with general structure: - [- Si (R1) (R2) -O- [Si (R3) (R2) -0-] y- where R1 is an alkane from C1-25 or H with a number of 0-5 double bonds, aromatic portions, polysiloxane grafts, or mixtures thereof. R1 may also be a liquid crystalline portion of may be returned to the polymer with liquid crystalline thermotropic properties, or the selected alkanes may result in side chain fusion. R2 can be H or CH3 and R3 can be -R1-R4, wherein R4 can be -NH2, -NHR1, -NR1 R2, -NR1 R2R6 (where R6 = R1, R2, or -CH2-COOH or its salt ), -NH-C (O) -, -COOH, -COO alkali salt, any C1-25 alcohol, -C (O) -NH2 (amide), -C (O) N (R2) (R2 ') (R2"), sulfo betaine, betaine, polyethylene oxide, grafts of poly (ethylene oxide / propylene oxide / butylene oxide) with any terminal group, H, -OH, styrene sulfonate, pyridine, quaternized pyridine, pyrrolidone or substituted alkyl pyridine, pyridine-N-oxide, imidazolinium halide, imidazolium halide, imidazole, piperidine, pyrrolidone, caprolactam, -COOH, -COO alkali salt, sulfonate, ethoxysulfatophenyl-R5 or naphthalene-R6 wherein R5 and R6 are R1, R2, R3, acid sulphonic or its alkaline salt or organic counterion. R3 can also be - (CH2) x -O-CH2-CH (OH) -CH2-N (CH3) 2-CH2-COOH and their salts. It can select any mixture of these R3 groups. x and y can always vary and when the theoretical net charge of the polymer is zero (amphoteric) or positive.

In addition, polysiloxanes containing up to 5 types can be used different from monomer units. The examples of polysiloxanes suitable are found in the Patents of E.U.A. Nos. 4,395,541, 4,597,962 and U.S. Patent. 6,200,554. Another group of polymers that can use to improve the capsule / particle deposition are the Phospholipids are modified with cationic polysiloxanes. The examples of these Polymers are found in the U.S. Patent. No. 5,849,313, Application for Patent WO 9518096A1 and European Patent EP0737183B1.

In addition, the silicone copolymers and polysaccharides and proteins (commercially available as the products CRODASONE brand).

Another class of polymers include oxide polymers polyethylene-copropylene oxide-butadiene oxide of any ratio of ethylene oxide / propylene oxide / butylene oxide with cationic groups which result in a theoretical net charge positive or equal to zero (amphoteric). The general structure is R3 - (BuO) z "(PO) and" (EO) x "\ / (EO) x (PO) and (BuO) z-R1 (R5) N - (CH2) and N (R6) R4 - (BuO) z '"(PO) and'" (EO) x "7 \ (EO) x '(PO) and' (BuO) z '- R2 wherein R1, 2, 3, 4, is -NH2, -N (R) 3X +, R with R being H or any alkyl group. R5.6 is -CH3 or H. The counterion is any halide ion or organic counterion. X, Y, can be any integer, with any distribution with an average and a standard deviation and all 12 can be different. Examples of such polymers are commercially available TETRONIC brand polymers. Suitable polyheterocyclic polymers (the different molecules appear in the base structure) include the copolymers with a piperazine-alkylene backbone described in Ind. Eng. Chem. Fundam., (1986), 25, pp. 120-125, by Isamu Kashiki and Akira Suzuki. Also suitable for use in the present invention are copolymers containing monomers with cationic charge in the primary polymer chain. Up to 5 different types of monomers can be used. Any co-monomer can also be used from the types listed in this specification. Examples of such polymers are poly diallyl dimethyl ammonium halides (PolyDADMAC) copolymers of DADMAC with vinyl pyrrolidone, acrylamides, imidazoles, imidazolinium halides, and the like. These polymers are described in Henkel EP 0327927A2 and PCT Patent Application 01 / 62376A1. Also suitable are Polyquaternium-6 (Merquat 100), Polyquaternium-7 (Merquat S, 550, and 2200), Polyquaternium-22 (Merquats 282 these 95) and Polyquaternium-39 (Merquat Plus 3330), available from Ondeo Nalco .

Polymers containing non-nitrogen cationic monomers of the general type -CH2-C (R1) (R2-R3-R4) - can be used with: R1 being a -H or C1-20 hydrocarbon. R2 is a disubstituted benzene ring or an ester, ether, or amide bond. R3 is C1-20 hydrocarbon, preferably C1-C10 hydrocarbon, more preferably C1-C4 hydrocarbon. R4 may be a trialkylphosphonium, dialkylsulfonium, or a benzopyryl group, each with a counterion of halide. The alkyl groups for R4 are C1-C20 hydrocarbon, more preferably methyl and t-butyl. These monomers can be copolymerized with up to 5 different types of monomers. Any comonomer can also be used from the types listed in this specification. The substantivity of these polymers can be further improved through the formulation with cationic, amphoteric and nonionic surfactants and emulsifiers, or by the formation of preservatives between the surfactants and the polymers or between different polymers. Combinations of the polymer systems (including those previously mentioned) can be used for this purpose as well as those described in EP 1995/000400185. In addition, the polymerization of the monomers listed above within a block, graft or star polymers (with several arms) can frequently increase the substantivity towards the various surfaces. The monomers in the various blocks, grafts and arms are can be selected from the various polymer classes listed in this specification and the sources below: Encyclopedia of Polymers and Thickeners for Cosmetics, Robert Lochhead and William From, in Cosmetics & Toiletries, Vol. 108, May 1993, pp. 95-138; Modified Starches: Properties & Uses, O.B. Wurzburg, CRC Press, 1986. Specifically, chapters 3, 8, and 10; Patents of E.U.A. Nos. 6,190,678 and 6,200,554; and PCT Patent Application WO 01 / 62376A1 assigned to Henkel. The polymers, or mixtures of the following polymers: (a) polymers comprising reaction products between polyamides and (chloromethyl) oxirane or (bromomethyl) oxirane. The polyamides being 2 (R1) N - [- R2-N (R1) -] n-R2-N (R1) 2, 2 NH-R1-NH2, 2 NH-R2-N (R1) 2 and 1 H-imidazole. Also, the polyamine can be melamine. R1 in the polyamine being H or methyl. R2 being C1-C20 alkylene groups or phenylene groups. Examples of such polymers are known under CAS numbers 67953-56-4 and 68797-57-9. The ratio of (chloromethyl) oxirane to the polyamine in the ranges of the cationic polymers are from 0.05-0.95. (b) polymers comprising the reaction products of alkanedioic acids, polyamides and (chloromethyl) oxirane or (bromomethyl) oxirane. Alkane groups in C0-C20 alkanedioic acids. The polyamine structures are as mentioned in (a). Additional reagents for the polymer are dimethyl amine, aziridine and polyalkylene oxide (of any molecular weight but at least dihydroxy terminated, the alkylene group being C1-20, preferably C2-4). Polyalkylene oxide polymers that can also be used are the Tetronics series. Examples of polymers mentioned in the present invention are known under CAS numbers 68583-79-9 (the additional reagent being dimethyl amine), 96387-48-3 (the additional reagent being urea), and 167678-45-7 (the additional reagents being polyethylene oxide and aziridine). These reagents can be used in any relationship. (c) the polyamide amine and polyaminoamide-epichlorohydrin resins are described by David Devore and Stephen Fisher in Tappi Journal, vol. 76, No. 8, pp. 121-128 (1993). Also referred to in the present invention as "Polyamide-polyamine-epichlorohydrin resins" by W.W. Moyer and R.A. Stagg in Wet-Strenght in Paper and Paperboard, Tappi Monograph Series Monograph Series No. 29, Tappi Press (1965), chapter 3, 33-37. The preferred cationically charged materials comprise reaction products of polyamines and (chloromethyl) oxirane. In particular, the reaction products of 1 H-imidazole and (chloromethyl) oxirane, are known under CAS No. 68797-57-9. Also preferred are polymers comprising reaction products of 1,6-hexanediamine, N- (6-aminohexyl) and (chloromethyl) oxirane, known under CAS No. 67953-56-4. The preferred weight ratio of the imidazole polymer and the hexanediamine, amino hexyl polymer is from about 5:95 to about 95: 5 by weight percent and preferably from about 25:75 to about 75:25.

The level of the external cationic polymer is from about 1% to about 3000%, preferably from about 5% to about 1000% and more preferably from about 10% to about 500% of the compositions containing the fragrance, based on a relationship with the Fragrance on a daily basis. The weight ratio of the encapsulating polymer to the fragrance is from about 1: 25 to about 1: 1. Preferred products have had a variation of the weight ratio of the encapsulating polymer with respect to the fragrance from about 1: 10 to about 4:96. For example, if a mixture of the capsule has 20% by weight of fragrance and 20% by weight of polymer, the ratio of the polymer could be (20/20) multiplied by 100 (%) = 100%. In the present invention, the encapsulated fragrance is suitable for washing products. As the washing products are understood those products that are applied for a given period of time and then removed. These products are common in areas such as laundry products, and include detergents, fabric conditioners, and the like; as well as personal care products which include shampoos, hair rinses, body washes, soaps and the like. As described herein, the present invention is suitable for use in a variety of well-known consumer products such as laundry detergent and fabric softeners, liquid dishwashing detergents, automatic dishwashing detergents, as well as shampoos for hair and conditioners. These products employ surfactants and emulsifying systems that are well known. For example, fabric softener systems are described in US Patents. Nos. 6, 335, 315, 5, 674, 832, 5, 759, 990, 5, 877, 145, 5, 574, 179, 5, 562, 849, 5, 545, 350, 5, 545, 340, 5, 41 1, 671, 5, 403, 499, 5, 288, 417, 4, 767, 547 and 4, 424, 134. Liquid dishwashing detergents are described in 6, 069, 122 and 5, 990, 065; automatic dishwashing detergent products are described in 6, 020, 294, 6, 017, 871, 5, 968, 881, 5, 962,386, 5, 939, 373, 5, 914, 307, 5, 902, 781, 5 , 705, 464, 5, 703, 034, 5, 703, 030, 5, 679, 630, 5, 597, 936, 5, 581, 005, 5, 559, 261, 4, 515, 705, 5, 169 , 552, and 4, 714, 562. Liquid laundry detergents that can utilize the present invention include those systems described in 5, 929, 022, 5, 916, 862, 5, 731, 278, 5, 565, 145, 5, 470, 507, 5, 466, 802, 5, 460, 752, 5, 458, 810, 5, 458, 809, 5, 288, 431, 5, 194, 639, 4, 968, 451, 4, 597, 898, 4, 561, 998, 4, 550, 862, 4, 537, 707, 4, 537, 706, 4, 515, 705, 4, 446, 042, and 4, 318, 818. The shampoo and Conditioners that can employ the present invention include 6, 162, 423, 5, 968,286, 5, 935, 561, 5, 932, 203, 5, 837, 661, 5, 776, 443, 5, 756, 436, 5, 661, 1 18, 5, 618, 523, 5, 275, 755, 5, 085, 857, 4, 673, 568, 4, 387, 090, 4, 705, 681.

All patents of E.U.A. and patent applications cited in the present invention are incorporated by reference as if they were established in their entirety. These and further modifications and improvements of the present invention may also be apparent to those skilled in the art. It is intended that the particular combinations of elements described and illustrated in the present invention only represent a certain embodiment of the present invention and are not intended to serve as limitations of alternative articles within the spirit and scope of the invention. All materials are reported in percentage weight unless otherwise stated. As used in the present invention it is understood that all percentages are by weight percentage. The ASTM test method (American Standards and Testing Methods) was used in the following examples to determine the level of formaldehyde present in the slurries of the capsule. This standard is provided under the fixed designation D 5910-96.

EXAMPLES The following fragrance composition was prepared to use the following examples: EXAMPLE l Formaldehyde levels of capsules not eliminated A reactor was charged with 34 g of a solution of acrylic acid-acrylamide copolymer, 18 g of a melamine-formaldehyde precondensate and 293 g of water. This mixture was stirred until a clear solution with a pH of about 6.3 was obtained. Acetic acid was added until reaching pH 5. This mixture was then stirred for 1 hour at 23 ° C at which time 210 g of the fragrance core consisting of 105 g of accord fragrance and 105 g of Neobee M oil were added. -5 and the mixture was subjected to high shear until a mean droplet size of 8 μ? T was achieved. The temperature was raised to 80 ° C for 2 hours to cure the microcapsules.

After 2 hours, 40 g of water was added and the mixture was cooled. After cooling, a white wash was obtained with a pH of 5-6. Formaldehyde analysis by ASTM indicates formaldehyde levels in the slurry of 1500-3000 ppm.

EXAMPLE II Removal of formaldehyde after curing with an amide type eliminator After healing and while it was still hot, they were added 25 g of solid ethyleneurea and 15 g of water to a batch of 560 g of fragrance microcapsules and the mixture was cooled. After cooling, a white wash was obtained with a pH of 5-6. Formaldehyde analysis by ASTM indicates formaldehyde levels in the slurry of 50 ppm.

EXAMPLE III Removal of formaldehyde after curing with a β-dicarbonyl type eliminator After curing a batch of 560 g of fragrance microcapsules, and while it was still hot, 30 g of 1,3-cyclohexanedione and 10 g of water were added and the mixture was cooled. After cooling, a white wash was obtained with a pH of 5-6. The analysis of formaldehyde by ASTM indicates formaldehyde levels in the slurry of < 1 ppm.

EXAMPLE IV Removal of formaldehyde after curing with an amine type eliminator After curing a batch of 560 g of the fragrance microcapsules, and while still hot, 40 g of Lupamin 1595 (poly (vinylamine)) was added, and the mixture was cooled. After cooling, a white gouache with a pH of 5-8 was obtained. Formaldehyde analysis by ASTM S 5910-96 indicates formaldehyde levels in the slurry of 200 ppm. The aforementioned scavengers can also be added to various stages in the capsule manufacturing process, as opposed to the last typical step.

EXAMPLE V Partial removal of formaldehyde using activated carbon 20 g of prewetted activated carbon grains [Tiggs Corporation, Bridgeville, PA] were mixed with 80 g of slurry from the capsule. The mixture was incubated at 45 ° C overnight. Charcoal activated was filtered and the watery paste analyzed. The formaldehyde concentration was found to be 1200 ppm. Analysis of the same slurry without activated carbon produced a formaldehyde level value of 1520 ppm. It is quite evident that the use of activated carbon has reduced the formaldehyde concentration by approximately 21%. The pH of the final product was approximately 5.5.

EXAMPLE VI Removal of formaldehyde, the synergistic use of 1,4-phenylenediamine 10 g of a solution of 1,4-phenylenediamine (1%) were mixed with 10 g of slurry from the capsule and 4 g of activated carbon supplied by Tiggs Corporation [Bridgeville, PA]. The mixture was incubated at 45 ° C overnight. The water paste was analyzed and the amount of formaldehyde was found to be less than 1 ppm. Analysis of the same slurry without 1, 4-phenylenediamine and activated carbon yielded a formaldehyde level value of 1500 ppm. The use of both 1,4-phenylenediamine and activated carbon reduced the formaldehyde concentration by 99.9%. This significant reduction clearly demonstrates that complete removal of formaldehyde can be achieved by the present invention. The pH of the final slurry was 5.5.

EXAMPLE VII Removal of formaldehyde using manganese oxide An amount of 1 g of Mn02 was obtained mixed with 20 g of slurry from the capsule. Mn02 was obtained from Aldrich Chemicals, Miiwaukee, Wisconsin, E.U.A. The mixture was incubated at 45 ° C overnight. The slurry was analyzed and the amount of formaldehyde was found to be less than 4 ppm. Analysis of the same slurry without the addition of MnO2 yielded a formaldehyde level value of 1500 ppm. As can be seen, the addition of Mn02 reduced the formaldehyde concentration one thousand times. This significant reduction clearly demonstrates that almost complete removal of formaldehyde can be achieved by the present invention. The pH at the end was 5.5.

EXAMPLE VIII Removal of formaldehyde using hydrogen peroxide 100 g of the slurry of the capsule was mixed with 4.3 g of a 30% hydrogen peroxide solution obtained from Aldrich Chemicals, Miiwaukee, Wisconsin, E.U.A. In addition, 2 g of a solution of Fe (III), 1000 ppm in HNO3, was added as a catalyst. The mixture was left at room temperature overnight. The watery paste is analyzed and found that the amount of formaldehyde was 1500 ppm. The formaldehyde was reduced by 74%. The pH at the end was 5.5.

EXAMPLE IX Adding the pre-procedure eliminator One reactor was charged with 34 g of a solution of the acrylic acid-acrylamide copolymer, 18 g of a melamine-formaldehyde precondensate, 293 g of water and 25 g of solid ethyleneurea. This mixture was stirred until a clear solution with a pH of about 6.3 was obtained. Acetic acid was added until reaching pH 5. This mixture was then stirred for 1 hour at 23 ° C at which time 210 g of the fragrance core consisting of 105 g of accord fragrance and 105 g of Neobee M oil were added. -5 and the mixture was subjected to high shear until a mean droplet size of 8 μ was achieved. The temperature was raised to 80 ° C for 2 hours to cure the microcapsules. After 2 hours the mixture was cooled. After cooling, a white wash was obtained. Formaldehyde analysis by AST indicates formaldehyde levels in the slurry of 50 ppm. The pH of the final slurry was 5.5.

EXAMPLE X Adding the pre-cure eliminator After high shear stress, 210 g of the fragrance core was added into an acidified mixture of 34 g of a solution of acrylic acid-acrylamide copolymer, 18 g of a melamine-formaldehyde precondensate, and 293 g of water to form an emulsion, and 25 g of ethyleneurea were added. The temperature was raised to 80 ° C for 2 hours to cure the microcapsules. After 2 hours the mixture was cooled. After cooling, a white wash was obtained. Formaldehyde analysis by ASTM indicates formaldehyde levels in the slurry of 50 ppm. The pH of the final slurry was 5.5.

EXAMPLE XI Adding the post-procedure eliminator The removal can be carried out to existing the watery paste of the fragrance microcapsules. After 560 g of the lot of the fragrance microcapsules had been established for 1 week, 25 g of solid ethyleneurea and 15 g of water were added and the mixture was stirred. Formaldehyde analysis by ASTM indicates formaldehyde levels in the slurry of 50 ppm. The pH of the final slurry was 5.5.

EXAMPLE XII Preparation of the control and of the microcapsules containing fragrance with high stability with different concentrations of urea and ethyleneurea as the formaldehyde scavenger 80 parts by weight of the fragrance mentioned at the beginning of this example section were mixed with 20 parts by weight of the solvent NEOBEE-M5 thus forming a "fragrance / solvent composition". The uncoated capsules were prepared by creating a polymeric wall to encapsulate the droplets of the fragrance / solvent composition. To make the watery pastes from the capsule, a copolymer of acrylamide and acrylic acid was first dispersed in water together with a methylated melamine-formaldehyde resin. These two components were allowed to react under acidic conditions. The fragrance / solvent composition was then added into the solution and the desired droplet size was achieved by high shear homogenization. For the slurry of the control microcapsule, the curing of the polymeric layer around the droplets of the fragrance composition of Example A / solvent was carried out at 80 ° C. For the slurry of the microcapsule A with high stability (HS-microcapsules A), the curing of the polymeric layer around the droplets of the fragrance composition of Example A / solvent was at 90 ° C. Urea and ethyleneurea were added respectively within the aqueous paste of the microcapsule at molar concentrations equivalent to 3 times and 2 times of formaldehyde available in the slurry. Slurry pulp products containing urea / ethyleneurea combinations at molar concentrations equivalent to 3 times / 1.5 times and 1.5 times / 1.5 times of formaldehyde available in the slurry were also prepared for use in Example 15. The slurry paste of the The resulting microcapsule contained approximately 55% water, and approximately 45% of the filled microcapsules (35% of the core consisting of 80% fragrance oil, and 20% NEOBEE M-5 and 10% of the microcapsule wall) . The pH of the final slurry was 5.5.

EXAMPLE XIII Preparation of the fabric conditioner samples containing the control microcapsules and the microcapsules with high stability In this example, a non-fragrance model fabric conditioner containing approximately 24% by weight of cationic quaternary surfactants was used. Both microcapsules control and microcapsules with high stability (HS-A) having cover walls composed of an acrylamide-acrylic acid copolymer crosslinked with melamine-formaldehyde resin as described in example XII were mixed with the fabric conditioner model separately using an agitator raised to 300 rpm until it is homogeneous. the basis of Finished fabric conditioner contained 0.5% by weight of encapsulated fragrance oil, mentioned at the beginning of this examples section, was used for the washing experiment in example XIV. A reference fabric conditioner base containing 0.5% by weight of pure fragrance oil of Example I was also prepared. All samples of fabric conditioner stored refrigerated at 4 ° C, 37 ° C, and 43 ° C for 4 hours. weeks EXAMPLE XIV Sensory performance and formaldehyde concentration of microcapsules containing fabric conditioners For the sensory performance evaluation, the samples of the fabric conditioner (pH 2-4) (90 grams per sample) with reference to the aforementioned example I, were introduced inside a Sears washing machine, Roebuck and Co. KENMORE (brand Registered by Sears Brands of Hoffman Estafes, Illinois (USA) 60179 during the rinsing cycle of the same to condition 22 hand towels weighing a total of approximately 2400 gm. Samples of fabric conditioner of 4 weeks of age were used. contained 0.5 percent by weight of the fragrance from the capsules After rinsing, each of the hand towels, which weighed 10 grams each, was dried in line for two days followed by the sensitive evaluation of 8 towels randomly selected The 8 dry towels selected at random were evaluated in this way by a panel of 10 people using the classification magnitude scale (LMS) from 0 to 99, where: 3 = "scarcely detectable"; 7 = "weak", 16 = "moderate", and 32 = "strong". Sensitive evaluations were recorded before and after each of the eight randomly selected towels in a separate polyethylene bag were rubbed by hand. Each rubbing test was carried out using 5 time intervals at 2 seconds for intervals of time for a total rubbing time of 10 seconds. The corresponding fabric conditioner samples used for the evaluation of sensory performance were subjected to liquid chromatography for the determination of formaldehyde concentration.

TABLE 1 TABLE 2 Type of Concentration Temperature of HCHO HCHO storage molar capsule (ppm) in (ppm) in ethyleneurea with product to product at 2 o'clock 4 HCHO week weeks Fragrance N / A 37 ° C 0.9 0.9 pure Microcapsules 3 times 37 ° C 4.7 5.0 HS-A Microcapsules 2 times 37 ° C 10.6 10.9 HS-A Microcapsules 3 times 37 ° C 3.5 6.1 control Microcapsules 2 times 37 ° C 10.5 13.8 control Microcapsules 3 times 4 ° C 3.5 4.0 control As seen from table 1, the fabric conditioner containing the HS-A high stability microcapsules developed a flavor that has a higher intensity pre-rubbing and post-rubbing than the fabric conditioner containing the control capsules in each corresponding concentration of ethyleneurea. The data indicate the use of both ethyleneurea at a 2-fold equivalent molar concentration of available formaldehyde and an increased concentration of ethyleneurea (2-fold to 3-fold) in the control microcapsules resulting in a noticeable decline in sensory performance after aging. the sample. With HS-A high stability microcapsules regardless of the concentration of ethyleneurea, the sensory performance, both in the pre-rubbing and post-rubbing intensities, after the aging of the sample was almost equivalent to that of the control capsules stored at 4 hours. ° C. The data in Table 2 suggest that microcapsules with high stability HS-A produced comparable concentrations of formaldehyde (HCHO) in the fabric conditioner compared to the control microcapsules at each corresponding concentration of ethyleneurea. Therefore, it was concluded that microcapsules with high stability is the most optimal option when using ethyleneurea eliminators or other highly efficient eliminators at the same time that they have a detrimental effect with respect to sensory performance.

EXAMPLE XV Sensory performance and formaldehyde concentration of microcapsules containing fabric conditioners This example illustrates the benefit of using the urea / ethyleneurea combination to obtain a reasonably low concentration of formaldehyde in the microcapsules containing fabric conditioner while maintaining its sensitive performance after storage at 37 ° C.

TABLE 3 As will be seen from Table 3, mentioned above, the fabric conditioner containing ethyleneurea at a molar concentration of 2 times with respect to formaldehyde results in a reduction of about 33% in the concentration of formaldehyde in the fabric conditioner when compared to that which contains any urea / ethylene combinations of 1.5 times / 1.5 times or 3 times / 1.5 times. Even, the data suggest that the control capsules contained a 2-fold ethyleneurea yield producing the fabric conditioner with a minimal sensory benefit compared to the pure fragrance after 7 weeks of storage at 43 ° C. The microcapsules containing the urea / ethylene urea combination advantageously performed superiorly to the control capsules containing 2 times of ethylene, in both pre-rubbing and post-rubbing intensities. These data clearly demonstrate that the optimal concentration of formaldehyde-performance of the sensitive stability from the microcapsules can be achieved by the intelligent selection of combinations of urea / ethyleneurea as the formaldehyde scavenger.

EXAMPLE XVI Solid support with eliminating surface groups After curing and while it was still hot, 40 g of Amberlite GT-73 (Rohm &Haas) was added to 560 g of the batch of the fragrance microcapsules, and the mixture was cooled. After cooling, a slurry with a pH of 5-6 was obtained. Formaldehyde analysis by ASTM indicates formaldehyde levels in the 300 ppm diluted paste.

EXAMPLE XVII Polymer with eliminating end groups After curing a batch of 560 g of the fragrance microcapsules, and while it was still hot, 30 g of Poly (1,4-butanediol) -bis- (4-aminobenzoate) (Sigma-Aldrich) were added. g of water, and the mixture was cooled. After cooling, a white gouache with a pH of 5-6 was obtained. Formaldehyde analysis by ASTM indicates formaldehyde levels in the slurry of 750 ppm.

EXAMPLE XVIII Polymer pending functionality 500 g of Lupamin 9095 (poly (vinylamine)) and 40 g of diethyl carbonate were refluxed for 5 hours. Then the solution was evaporated to dry at an elevated temperature. After cooling, a solid mass was obtained which was equivalent to poly (propyleneurea). This solid was dissolved in water and used in Example XIX. Alternatively, poly (propyleneurea) was obtained by substitution of urea with the ethylcarbonate.

EXAMPLE XIX Polymer with pending deleter groups After curing a batch of 560 g of the fragrance microcapsules, and while still hot, 40 g of Lupamin 1595 (poly (vinylamine)) was added, and the mixture was cooled. After cooling, a slurry with a pH of 5-8 was obtained. Formaldehyde analysis by ASTM D 5910-96 indicates formaldehyde levels in the 200 ppm waxy paste. The aforementioned scavengers can also be added at various stages in the capsule manufacturing process, as opposed to the last typical step.

Claims (99)

1. NOVELTY OF THE INVENTION CLAIMS 1. - A process for the preparation of a microcapsule product with reduced levels of formaldehyde, which comprises: a) providing an aqueous slurry paste of a plurality of microcapsules having a polymeric wall and a core comprising an active material, wherein the microcapsule comprises a crosslinked network of polymers of a crosslinked copolymer of acrylamide-acrylic acid substituted or unsubstituted with a polymer selected from melamine-formaldehyde, a precondensate of urea-formaldehyde and mixtures thereof; b) providing a stoichiometric excess of a formaldehyde scavenger selected from the group consisting of ß-dicarbonyl compounds, amides, mines, acetal formers, sulfur-containing compounds, activated carbon, ammonium, organic amines, an oxidizing agent and mixtures; c) mixing the microcapsules and the eliminator; d) provide a microcapsule product with reduced levels of formaldehyde. 2. The process according to claim 1, further characterized in that the amount of scavenger is present from a trace amount effective to approximately 10 times the molar excess of the molar equivalence of the potential formaldehyde present in the slurry. 3. The process according to claim 1, further characterized in that the β-dicarbonyl compound is selected from the group consisting of acetoacetamide, ethyl acetoacetate, N, N-dimethylene acetamide, acetoacetone, dimethyl-1,3-acetonadicarboxylate, acid 1,3-acetonadicarboxylic acid, resorcinol, 1,3-cyclohexadione, barbituric acid, salicylic acid, 5,5-dimethyl-1,3-cyclohexanedione (dimedone), 2,2-dimethyl-1,3-dioxane-4,6 -Diona and mixtures thereof. 4. The process according to claim 1, further characterized in that the amide compound is selected from the group consisting of urea, ethyleneurea, propyleneurea, e-caprolactam, glycuryl, hydantoin, 2-oxazolidinone, 2-pyrrolidinone, Uracil, barbituric acid, thymine, uric acid, allantoin, 4,5-dihydroxyethyleneurea, monomethylol-4-hydroxy-4-methoxy-5,5-dimethyl-propylurea, polyamides, nylon and mixtures thereof. 5. The process according to claim 4, further characterized in that the amide compound is ethyleneurea. 6. The process according to claim 1, further characterized in that the amide compound is selected from the group consisting of poly (vinyl) amine, arginine, lysine, lysine-containing proteins and asparagine, hydrazines, aromatic amines, aromatic diamines, aminobenzoic acid derivatives, amine phenols, melamine, 2-amino-2-methyl-1-propanol, benzoguanamine and mixtures thereof. 7. - The method according to claim 6, further characterized in that the proteins are selected from casein, gelatin, gluten, whey protein, soy protein, collagen and mixtures thereof. 8. The process according to claim 6, further characterized in that the hydrazine is 2,4-dinitrophenylhydrazine. 9. The process according to claim 1, further characterized in that the acetal-forming compound is selected from the group consisting of diethylene glycol, saccharides, polysaccharides and mixtures thereof. 10. The process according to claim 9, further characterized in that the saccharides are selected from glucose, D-sorbitol, sucrose, tannins / tannic acid and mixtures thereof. 11. - The method according to claim 9, further characterized in that the polysaccharide is selected from pectin, starch and mixtures thereof. 12. - The method according to claim 1, further characterized in that the sulfur-containing compound is selected from the group consisting of bisulfite, cysteine and mixtures thereof. 13. The process according to claim 1, further characterized in that the oxidizing agent is selected from the group consisting of manganese oxide, hydrogen peroxide (H2O2), hypochlorite, chlorine, peracids, oxygen, ozone, chlorine dioxygen, sodium percarbonate, sodium perborate and mixtures thereof. 14. The process according to claim 13, further characterized in that it additionally comprises tetraacetylethylenediamine, transition metal complexes, metalloporphyrins, peroxidases and mixtures thereof. 15. - The method according to claim 1, further characterized in that the crosslinked network of polymers comprises a copolymer of melamine-formaldehyde: acrylamide-acrylic acid wherein the molar ratio is in the range of 9: 1 to 1: 9 . 16. The process according to claim 15, further characterized in that the molar ratio of the melamine-formaldehyde: acrylamide-acrylic acid copolymer is in the range of 5: 1 to 1: 5. 17. The process according to claim 15, further characterized in that the molar ratio of the melamine-formaldehyde: acrylamide-acrylic acid copolymer is in the range of 2: 1 to 1: 2. 18. The method according to claim 1, further characterized in that the crosslinked polymer network containing an active material is cured at a temperature above 90 ° C. 19. - The method according to claim 1, further characterized in that the crosslinked polymer network containing an active material is cured at a temperature above 110 ° C. 20. - The method according to claim 1, further characterized in that the crosslinked polymer network containing an active material is cured at a temperature above 120 ° C. 21. - The method according to claim 1, further characterized in that the crosslinked polymer network containing an active material is cured at a temperature above 180 ° C. 22. The method according to claim 1, further characterized in that the crosslinked polymer network containing an active material is cured for more than 1 hour. 23. - The method according to claim 1, further characterized in that the crosslinked polymer network containing an active material is cured for more than 2 hours. 24. - The method according to claim 1, further characterized in that the pH of the slurry is from about 1 to about 9. 25. The process according to claim 24, further characterized in that the pH of the slurry is from about 2 to about 8. 26. The process according to claim 24, further characterized in that the pH of the slurry is from about 2 to about 6. 27. The process according to claim 1, further characterized in that the scavenger comprises a combination of ethyleneurea and urea. 28. - The method according to claim 1, further characterized in that the microcapsule product is additionally covered by a cationic copolymer. 29. The process according to claim 28, further characterized in that the cationic polymer is selected from polysaccharides, cationically modified starch and cationically modified guar, polysiloxanes, poly diallyl dimethyl ammonium halides, poly diallyl dimethyl ammonium chloride copolymers and vinyl pyrrolidone, acrylamides, imidazoles, imidazolinium halides, imidazolium halides and mixtures. 30. The method according to claim 28, further characterized in that the cationic polymer is selected from a cationically modified starch, cationically modified guar and mixtures thereof. 31. A method for imparting an effective olfactory amount of a fragrance within a consumer product that comprises incorporating at least 0.25% by weight of the capsules according to claim 1 into a consumer product. 32. - The method according to claim 31, further characterized in that the consumer product is selected from the group consisting of detergent for laundry, fabric softeners, discoloration products, sheets for drum dryer, liquid dishwashing detergents, detergents for washing automatic dishwashers, hair shampoos, hair conditioners, toothpastes, mouthwashes, oral care products, liquid soaps, body wash products, lotions, creams, hair gels, antiperspirants, deodorants, shaving products , cologne water, products for body washes, compositions for automatic dishwashers, food products, beverages and mixtures thereof. 33. - A microcapsule product produced in accordance with the method according to claim 1. 34. - A consumer product selected from the group consisting of laundry detergent, fabric softeners, discoloration products, sheets for dryer of drum, liquid dishwashing detergents, automatic dishwashing detergents, hair shampoos, hair conditioners, toothpastes, mouthwashes, oral care products, liquid soaps, body wash products, lotions, creams, hair gels, anti-perspirants, deodorants, shaving products, cologne, products for body washes, automatic dishwashing compositions, food products, beverages and mixtures thereof included in the product in a microcapsule according to the method according to claim 1. 35. The consumer product according to claim 34, further characterized in that it additionally comprises a stoichiometric excess of formaldehyde scavenger selected from the group consisting of β-dicarbonyl, amides, imines, acetal formers, sulfur-containing compounds, activated carbon, ammonium, organic amines, an oxidizing agent and mixtures thereof. 36. - The consumer product according to claim 35, further characterized in that the eliminator is ethyleneurea. 37. - The consumer product according to claim 34, further characterized in that the eliminator is a combination of ethyleneurea and urea. 38. - The consumer product according to claim 34, further characterized in that the pH is less than 3. 39. - The consumer product according to claim 34, further characterized in that the pH is less than 4. 40. - The consumer product according to claim 34, further characterized in that the pH is less than 5. 41.- A process for the preparation of a consumer product with reduced levels of formaldehyde, which comprises: a) providing a product of consumption; b) providing a plurality of microcapsules having a polymeric wall and a core comprising a material active, wherein the microcapsule comprises formaldehyde; c) mixing the consumer product and the microcapsules; d) providing the stoichiometric excess of the formaldehyde scavenger selected from the group consisting of β-dicarbonyl compounds, amides, mines, acetal formers, sulfur-containing compounds, activated carbon, ammonium, organic amines, an oxidizing agent and mixtures thereof; e) mix the consumer product and the eliminator; f) provide a consumer product with reduced levels of formaldehyde. 42.- The method according to claim 41, further characterized in that the consumer product is selected from the group consisting of laundry detergent, fabric softeners, discoloration products, sheets for tumble dryer, liquid dishwashing detergents, automatic dishwashing detergents, hair shampoos, hair conditioners, toothpastes, mouthwashes, oral care products, liquid soaps, products for body washes, lotions, creams, hair gels, antiperspirants, deodorants, products for shaving, cologne, products for body washes, compositions for automatic dishwashers, food products, beverages and mixtures thereof. 43.- The method according to claim 41, further characterized in that the eliminator is ethyleneurea. 44. - The method according to claim 41, further characterized in that the scavenger is a combination of ethyleneurea and urea. 45. - The method according to claim 41, further characterized in that the consumer product has a lower pH of 3. 46. - The method according to claim 41, further characterized in that the consumer product has a pH less than 4. 47. The method according to claim 41, further characterized in that the consumer product has a lower pH of 5. 48.- A process for the preparation of a microcapsule product with reduced levels of free formaldehyde, which comprises: a) providing a plurality of microcapsules having a polymeric wall and a core comprising an active material, wherein the microcapsule comprises formaldehyde; b) providing a stoichiometric excess of a formaldehyde scavenger selected from the group consisting of a small molecule scavenger, a polymeric scavenger, a scavenging moiety immobilized on an insoluble polymer scaffold and mixtures thereof; c) mixing the microcapsules and the eliminator; d) provide a microcapsule product with reduced levels of formaldehyde. 49. The process according to claim 48, further characterized in that the amount of formaldehyde scavenger is present from a trace amount effective up to about 100 times the molar excess of the molar equivalence of the potential formaldehyde present in the slurry. 50. The process according to claim 48, further characterized in that the amount of formaldehyde scavenger is present from about 0.01 times to about 10 times the molar excess of the molar equivalence of the potential formaldehyde present in the slurry. 51. - The method according to claim 48, further characterized in that the formaldehyde levels are reduced to less than about 000 ppm. 52. - The method according to claim 48, further characterized in that the formaldehyde levels are reduced to less than about 750 ppm. 53. - The method according to claim 48, further characterized in that the formaldehyde levels are reduced to less than about 500 ppm. 54.- The method according to claim 48, further characterized in that the formaldehyde levels are reduced to less than about 250 ppm. 55. - The method according to claim 48, further characterized in that the formaldehyde levels are reduced to less than about 100 ppm. 56. The method according to claim 48, further characterized in that the formaldehyde levels are reduced to less than about 50 ppm. 57. - The method according to claim 48, further characterized in that the formaldehyde levels are reduced to less than about 10 ppm. 58.- The method according to claim 48, further characterized in that the formaldehyde levels are reduced to less than about 5 ppm. 59. - The method according to claim 48, further characterized in that the encapsulating polymer is selected from a vinyl polymer; an acrylate polymer, melamine-formaldehyde; urea formaldehyde and mixtures thereof. 60. - The method according to claim 48, further characterized in that the formaldehyde scavenger is a molecule selected from ß-dicarbonyl compounds, amides, mines, acetal formers, sulfur-containing compounds, activated carbon, ammonium, organic amines, and oxidizing agent and mixtures thereof. 61. - The method according to claim 60, further characterized in that the β-dicarbonyl compound is selected from from the group consisting of acetoacetamide, ethyl acetoacetate, N, N-dimethylenacetamide, acetoacetone, dimethyl-1,3-acetonadicarboxylate, 1,3-acetonadicarboxylic acid, resorcinol, 1,3-cyclohexadione, barbituric acid, salicylic acid, 5, 5-dimethyl-1,3-cyclohexanedione (dimedone), 2,2-dimethyl-1,3-dioxane-4,6-dione and mixtures thereof. 62. The process according to claim 61, further characterized in that the amide compound is selected from the group consisting of urea, ethyleneurea, propyleneurea, e-caprolactam, glycouryl, hydantoin, 2-oxazolindinone, 2-pyrrolidinone, Uracil, barbituric acid, thymine, uric acid, allantoin, 4,5-dihydroxyethyleneurea, monomethylol-4-hydroxy-4-methoxy-5,5-dimethyl-propylurea, polyamides, nylon and mixtures thereof. 63. - The method according to claim 62, further characterized in that the amide compound is ethyleneurea. 64.- The method according to claim 60, further characterized in that the amine compound is selected from the group consisting of poly (vinyl) amine, arginine, lysine, proteins containing lysine and asparagine, hydrazines, aromatic amines, aromatic diamines, aminobenzoic acid derivatives, amine phenols, melamine, 2-amino-2-methyl-1-propanol, benzoguanamine and mixtures thereof. 65.- The method according to claim 64, further characterized in that the protein is selected from casein, gelatin, gluten, whey protein, soy protein, collagen and mixtures thereof. 66.- The method according to claim 64, further characterized in that the hydrazine is 2,4-dinitrophenylhydrazine. 67.- The method according to claim 60, further characterized in that the acetal-forming compound is selected from the group consisting of diethylene glycol, saccharides, polysaccharides and mixtures thereof. 68. - The method according to claim 67, further characterized in that the saccharide is selected from glucose, D-sorbitol, sucrose, tannins / tannic acid and mixtures thereof. 69. - The method according to claim 67, further characterized in that the polysaccharide is selected from pectin, starch and mixtures thereof. The process according to claim 60, further characterized in that the sulfur-containing compound is selected from the group consisting of bisulfide, cysteine and mixtures thereof. 71.- The method according to claim 60, further characterized in that the oxidizing agent is selected from the group consisting of manganese oxide, hydrogen peroxide (H2O2), hypochlorite, chlorine, peracids, oxygen, ozone, chlorine dioxygen , sodium percarbonate, sodium perborate and mixtures thereof. 72. The process according to claim 71, further characterized in that it additionally comprises tetraacetylethylenediamine, transition metal complexes, metalloporphyrins, peroxidases and mixtures thereof. 73.- The method according to claim 48, further characterized in that the formaldehyde scavenger is polymeric. 74. - The method according to claim 73, further characterized in that the polymeric scavenger is selected from the group consisting of methacrylic acid, maleic anhydride, maleic acid, itaconic acid, acrylamide, vinylamine, vinyl alcohol, vinyl mercaptan, saccharides , peptides, allylamine, acrylic acid, olefin, alkylene oxide, amine, urea, urethane, carbonate, ester, amides, proteins and mixtures thereof. 75. The process according to claim 74, further characterized in that the terminal groups of the polymeric scavenger are modified with functional groups selected from the group consisting of ß-dicarbonyl compounds, amides, imines, acetal formers, compounds which they contain sulfur, activated carbon, ammonium, organic amines and mixtures thereof. 76. The process according to claim 75, further characterized in that the polymeric eliminator modified with functional end groups is selected from the group consisting of poly (1,4-butanediol) -bis- (4-aminobenzoate) and poly (ethylene glycol) diacetoacetate. 77. The process according to claim 73, further characterized in that the pendant groups of the polymer are modified with functional groups selected from the group consisting of ß-dicarbonyl compounds, amides, mines, acetal formers, sulfur-containing compounds , activated carbon, ammonium, organic amines and mixtures thereof. 78. - The method according to claim 48, further characterized in that the solid support is selected from the group consisting of polyolefins such as polyethylene and polystyrene, polyvinylacetate, polysaccharides such as dextran, polyesters, polyamides, polyurethanes, polyacrylates, polyureas , inorganic supports are clays, alumina, silica, zeolite and titanium dioxide. 79. - The method according to claim 78, further characterized in that the scavenging portion immobilized on the solid support is selected from the group consisting of ß-dicarbonyl compounds, amides, mines, acetal formers, compounds containing sulfur, activated carbon, ammonium and organic amines. 80. The method according to claim 48, further characterized in that the encapsulating polymer is a crosslinked polymer network comprising a copolymer of melamine-formaldehyde: acrylamide-acrylic acid wherein the molar ratio is in the range of about 9. : 1 to 1: 9. 81. The process according to claim 80, further characterized in that the molar ratio of the melamine-formaldehyde: acrylamide-acrylic acid copolymer is in the range of about 5: 1 to about 1: 5. 82. The process according to claim 80, further characterized in that the molar ratio of the melamine-formaldehyde: acrylamide-acrylic acid copolymer is in the range of from about 2: 1 to about 1: 2. 83. - The method according to claim 48, further characterized in that the encapsulating polymer is cured at a temperature greater than about 90 ° C. 84. - The method according to claim 48, further characterized in that the encapsulating polymer is cured at a temperature greater than about 110 ° C. 85.- The method according to claim 48, further characterized in that the encapsulating polymer is cured at a temperature greater than about 120 ° C. 86. - The method according to claim 48, further characterized in that the encapsulating polymer is cured for up to about one hour. 87. - The method according to claim 48, further characterized in that the encapsulating polymer is cured for up to about two hours. 88. - The method according to claim 48, further characterized in that the encapsulating polymer is cured for more than about two hours. 89. - The method according to claim 48, further characterized in that the pH of the product in microcapsule is from about 1 to about 9. 90. - The method according to claim 89, further characterized in that the pH of the product in microcapsule is from about 2 to about 8. 91.- The method according to claim 89, further characterized in that the pH of the microcapsule product is from about 3 to about 6. 92. - The method according to claim 48, characterized in addition, because the microcapsule product is additionally covered by a cationic polymer. 93. - The method according to claim 91, further characterized in that the cationic polymer is selected from polysaccharides, cationically modified starch and cationically modified guar, polysiloxanes, poly diallyl dimethyl ammonium halides, poly diallyl dimethyl ammonium chloride copolymers and vinyl pyrrolidone, acrylamides, imidazoles, imidazolinium halides, imidazolium halides and mixtures. 94. - The method according to claim 93, further characterized in that the cationic polymer is selected from a cationically modified starch, cationically modified guar and mixtures thereof. 95. A method for imparting an effective olfactory amount of a fragrance within a consumer product comprising incorporating at least about 0.25% by weight of the capsules according to claim 48 into a consumer product. 96. - The method according to claim 95, further characterized in that the consumer product is selected from the group consisting of laundry detergent, fabric softeners, discoloration products, sheets for tumble dryer, liquid dishwashing detergents, automatic dishwashing detergents, hair shampoos, hair conditioners, toothpastes, mouthwashes, oral care products, liquid soaps, products for body washes, lotions, creams, hair gels, antiperspirants, deodorants, products for shaving, cologne, products for body washes, compositions for automatic dishwashers, food products, beverages and mixtures thereof. 97. - A microcapsule product produced according to the method according to claim 48. 98.- A consumer product selected from the group consisting of laundry detergent, fabric softeners, discoloration products, sheets for dryer Drum, liquid dishwashing detergents, automatic dishwashing detergents, hair shampoos, hair conditioners, toothpastes, mouthwashes, oral care products, liquid soaps, products for body washes, lotions, creams, hair gels, anti-perspirants, deodorants, shaving products, cologne, laundry products body, compositions for automatic dishwashers, food products, beverages and mixtures thereof comprising the product in microcapsule according to the method according to claim 48. 99.- The consumer product according to claim 98, further characterized because it additionally comprises from about 0.01 times to about 100 times the molar amount of all formaldehyde in the consumer product of the formaldehyde scavenger selected from the group consisting of β-dicarbonyl compounds, amides, mines, acetal formers, compounds containing sulfur, activated carbon, ammonium, amines or Rganic agents, an oxidizing agent, a polymeric scavenger, a scavenging moiety immobilized on an insoluble polymer support and mixtures thereof.