CA2918844A1 - Microcapsule-containing detergent or cleaning agent - Google Patents

Abstract

The invention relates to consumer products, including detergents or cleaning agents which comprise capsules that are low in formaldehydes and/or free from formaldehyde, are storage stable and thus prevent a contamination of the detergent or cleaning agent with formaldehyde, comprising microcapsules, the capsule wall of which contains a resin which is obtained by reacting at least one aromatic alcohol or ether or derivative thereof and at least one aldehydic component which comprises at least two c-atoms per molecule, and optionally at least one (meth)acrylate polymer, and builders and/or surfactants. Said detergent or cleaning agents enable, during application, a targeted and durable release of liquid active substances, such as, in particular scents, to the treated objects.

Description

MICROCAPSULE-CONTAINING DETERGENT OR CLEANING AGENT
FIELD OF INVENTION
The invention relates to microcapsules, methods of making and using same as well as consumer products comprising such microcapsules and methods of making and using same.
BACKGROUND OF THE INVENTION
Many consumer products, for example, cleaning and/or treatment composition contain sensitive ingredients. It is disadvantageous that such ingredients, which are used in such agents, frequently lose their activity, or at a minimum their activity is greatly reduced, during storage and/or before the desired date of application, for example by chemical reactions resulting from interaction with other components of the consumer product and/or through physical influences.
For this reason, certain ingredients such as perfumes are encapsulated.
Microcapsules that are free or nearly free of formaldehyde free are desired for use in consumer products as the use of formaldehyde scavengers can be avoided or minimized.
Thus, the use of microcapsules having a shell that comprises the reaction product of a material that comprises an aromatic alcohol moiety and a material that comprises an aldehyde moiety for use in laundry applications has been proposed. Unfortunately, such capsules can discolor a consumer product, fail to provide a benefit across all consumer touch points and may fail to deliver a sufficient amount of their core when subjected to external stimuli like temperature, infrared radiation, visible light, and/or ultraviolet radiation.
Surprisingly, it was found that the source of the discoloration was, in large part, due to the capsule's color intensity bleeding through the consumer product and the diffusion of unreacted capsule components into the formulation rather than simply the reaction of the capsules with other formulation ingredients and that combination of such microcapsules with judiciously selected materials solve such problem. In addition, Applicants recognized that when the proper di-aldehyde is employed, release that is triggered by electromagnetic radiation can be obtained.

2 SUMMARY OF THE INVENTION
The invention relates to microcapsules, methods of making and using same as well as consumer products comprising such microcapsules and methods of making and using same.
DETAILED DESCRIPTION OF THE INVENTION
Definitions As used herein "consumer product" means baby care, beauty care, fabric & home care, family care, feminine care, health care, snack and/or beverage products or devices generally intended to be used or consumed in the form in which it is sold. Such products include but are not limited to diapers, bibs, wipes; products for and/or methods relating to treating hair (human, dog, and/or cat), including, bleaching, coloring, dyeing, conditioning, shampooing, styling;
deodorants and antiperspirants; personal cleansing; cosmetics; skin care including application of creams, lotions, and other topically applied products for consumer use including fine fragrances;
and shaving products, products for and/or methods relating to treating fabrics, hard surfaces and any other surfaces in the area of fabric and home care, including: air care including air fresheners and scent delivery systems, car care, dishwashing, fabric conditioning (including softening and/or freshing), laundry detergency, laundry and rinse additive and/or care, hard surface cleaning and/or treatment including floor and toilet bowl cleaners, and other cleaning for consumer or institutional use; products and/or methods relating to bath tissue, facial tissue, paper handkerchiefs, and/or paper towels; tampons, feminine napkins; products and/or methods relating to oral care including toothpastes, tooth gels, tooth rinses, denture adhesives, tooth whitening;
over-the-counter health care including cough and cold remedies, pain relievers, RX
pharmaceuticals, pet health and nutrition; processed food products intended primarily for consumption between customary meals or as a meal accompaniment (non-limiting examples include potato chips, tortilla chips, popcorn, pretzels, corn chips, cereal bars, vegetable chips or crisps, snack mixes, party mixes, multigrain chips, snack crackers, cheese snacks, pork rinds, corn snacks, pellet snacks, extruded snacks and bagel chips); and coffee.
As used herein, the term "cleaning and/or treatment composition" is a subset of consumer products that includes, unless otherwise indicated, beauty care, fabric & home care products.
Such products include, but are not limited to, products for treating hair (human, dog, and/or cat), including, bleaching, coloring, dyeing, conditioning, shampooing, styling;
deodorants and antiperspirants; personal cleansing; cosmetics; skin care including application of creams, lotions, and other topically applied products for consumer use including fine fragrances; and shaving

3 products, products for treating fabrics, hard surfaces and any other surfaces in the area of fabric and home care, including: air care including air fresheners and scent delivery systems, car care, dishwashing, fabric conditioning (including softening and/or freshing), laundry detergency, laundry and rinse additive and/or care, hard surface cleaning and/or treatment including floor and toilet bowl cleaners, granular or powder-form all-purpose or "heavy-duty"
washing agents, especially cleaning detergents; liquid, gel or paste-form all-purpose washing agents, especially the so-called heavy-duty liquid types; liquid fine-fabric detergents; hand dishwashing agents or light duty dishwashing agents, especially those of the high-foaming type;
machine dishwashing agents, including the various tablet, granular, liquid and rinse-aid types for household and institutional use; liquid cleaning and disinfecting agents, including antibacterial hand-wash types, cleaning bars, mouthwashes, denture cleaners, dentifrice, car or carpet shampoos, bathroom cleaners including toilet bowl cleaners; hair shampoos and hair-rinses; shower gels , fine fragrances and foam baths and metal cleaners; as well as cleaning auxiliaries such as bleach additives and "stain-stick" or pre-treat types, substrate-laden products such as dryer added sheets, dry and wetted wipes and pads, nonwoven substrates, and sponges; as well as sprays and mists all for consumer or/and institutional use; and/or methods relating to oral care including toothpastes, tooth gels, tooth rinses, denture adhesives, tooth whitening.
As used herein, the term "fabric and/or hard surface cleaning and/or treatment composition" is a subset of cleaning and treatment compositions that includes, unless otherwise indicated, granular or powder-form all-purpose or "heavy-duty" washing agents, especially cleaning detergents; liquid, gel or paste-form all-purpose washing agents, especially the so-called heavy-duty liquid types; liquid fine-fabric detergents; hand dishwashing agents or light duty dishwashing agents, especially those of the high-foaming type; machine dishwashing agents, including the various tablet, granular, liquid and rinse-aid types for household and institutional use; liquid cleaning and disinfecting agents, including antibacterial hand-wash types, cleaning bars, car or carpet shampoos, bathroom cleaners including toilet bowl cleaners; and metal cleaners, fabric conditioning products including softening and/or freshing that may be in liquid, solid and/or dryer sheet form ; as well as cleaning auxiliaries such as bleach additives and "stain-stick" or pre-treat types, substrate-laden products such as dryer added sheets, dry and wetted wipes and pads, nonwoven substrates, and sponges; as well as sprays and mists.
All of such products which are applicable may be in standard, concentrated or even highly concentrated form even to the extent that such products may in certain aspect be non-aqueous.

4 As used herein, articles such as "a" and "an" when used in a claim, are understood to mean one or more of what is claimed or described.
As used herein, the terms "include", "includes" and "including" are meant to be non-limiting.
As used herein, the term "solid" includes granular, powder, bar and tablet product forms.
As used herein, the term "fluid" includes liquid, gel, paste and gas product forms.
As used herein, the term "situs" includes paper products, fabrics, garments, hard surfaces, hair and skin.
Unless otherwise noted, all component or composition levels are in reference to the active portion of that component or composition, and are exclusive of impurities, for example, residual solvents or by-products, which may be present in commercially available sources of such components or compositions.
All percentages and ratios are calculated by weight unless otherwise indicated. All percentages and ratios are calculated based on the total composition unless otherwise indicated.
It should be understood that every maximum numerical limitation given throughout this specification includes every lower numerical limitation, as if such lower numerical limitations were expressly written herein. Every minimum numerical limitation given throughout this specification will include every higher numerical limitation, as if such higher numerical limitations were expressly written herein. Every numerical range given throughout this specification will include every narrower numerical range that falls within such broader numerical range, as if such narrower numerical ranges were all expressly written herein.
Compositions A composition comprising i) surfactants and/or builders, as well as ii) microcapsules comprising a wall having an exterior surface and a core, said wall encapsulating said core, said wall comprising a resin which can be obtained by reacting a) at least one aromatic alcohol or its ether or derivatives with b) at least one aldehydic component which comprises at least two carbon atoms per molecule, and c) optionally in the presence of at least one (meth)acrylate polymer iii) a material selected from the group consisting of a hueing dye, a structurant, a density balancing agent, a deposition aid, a perfume delivery system in addition to said microcapsules, a fabric softener and mixtures thereof is disclosed.

5 In one aspect, said microcapsules comprise a deposition aid comprising a material selected from the group consisting of poly(meth)acrylate, poly(ethylene-maleic anhydride), polyamine, wax, polyvinylpyrrolidone, polyvinylpyrrolidone co-polymers, polyvinylpyrrolidone-ethyl acrylate, polyvinylpyrrolidone- vinyl acrylate, polyvinylpyrrolidone methylacrylate, polyvinylpyrrolidone/vinyl acetate, polyvinyl acetal, polyvinyl butyral, polysiloxane, poly(propylene maleic anhydride), maleic anhydride derivatives, co-polymers of maleic anhydride derivatives, polyvinyl alcohol, styrene-butadiene latex, gelatin, gum Arabic, carboxymethyl cellulose, carboxymethyl hydroxyethyl cellulose, hydroxyethyl cellulose, other modified celluloses, sodium alginate, chitosan, casein, pectin, modified starch, polyvinyl acetal, polyvinyl butyral, polyvinyl methyl ether/maleic anhydride, polyvinyl pyrrolidone and its co polymers, poly(vinyl pyrrolidone/methacrylamidopropyl trimethyl ammonium chloride), polyvinylpyrrolidone/vinyl acetate, polyvinyl pyrrolidone/dimethylaminoethyl methacrylate, polyvinyl amines, polyvinyl formamides, polyallyl amines and copolymers of polyvinyl amines, polyvinyl formamides, and polyallyl amines and mixtures thereof, said deposition aid coating the exterior of said microcapsules' wall.
In one aspect, a) said structurant comprising a material selected from the group consisting of castor oil, hydrogenated castor oil, polysaccharides, modified celluloses, modified proteins, inorganic salts, quaternized polymeric materials, imidazoles;
nonionic polymers having a pKa less than 6.0, polyurethanes, plant cellulose, bacterial cellulose, coated bacterial cellulose, non-polymeric crystalline hydroxyl-functional materials, polymeric structuring agents, di-amido gellants and mixtures thereof;
b) said hueing dye is selected from the group consisting of small molecule dyes, polymeric dyes, dye-clay conjugates, and organic and inorganic pigments, in one aspect, said hueing dye comprises a chromophore selected from one or more of the following: acridine, anthraquinone, azine, azo, azulene, benzodifurane and benzodifuranone, carotenoid, coumarin, cyanine, diazahemicyanine, diphenylmethane, formazan, hemicyanine, indigoids, methane, naphthalimides,

6 naphthoquinone, nitro and nitroso, oxazine, phthalocyanine, pyrazoles, stilbene, styryl, triarylmethane, triphenylmethane, xanthenes and mixtures thereof, in one aspect said fabric hueing agent may be selected from the fabric hueing agents described in the section titled "Fabric Hueing Agents" which is found in the Adjunct Materials section of this specification;
c) said additional perfume delivery comprises a material selected from the group consisting of a second microcapsule, a polymer assisted delivery system; a molecule-assisted delivery system; a fiber-assisted delivery system; a cyclodextrin delivery system; a starch encapsulated accord; and/or an inorganic carrier delivery system; and d) said fabric softener comprises from 1% to 49% by weight of the composition of a bis-(2-hydroxypropy1)-dimethylammonium methylsulphate fatty acid ester having a molar ratio of fatty acid moieties to amine moieties of from 1.85 to 1.99, an average chain length of the fatty acid moieties of from 16 to 18 carbon atoms and an iodine value of the fatty acid moieties, calculated for the free fatty acid, of from 0.5 to 60.
Said second microcapsule, is of different type than said microcapsules obtained by reacting at least one aromatic alcohol or its ether or derivatives with at least one aldehydic component which comprises at least two carbon atoms per molecule, and optionally in the presence of at least one (meth)acrylate polymer. In one aspect, said second microcapsule may be a acrylate microcapsule and/or aminoplast microcapsule such as a melamine formaldehyde microcapsule.
In one aspect, the at least one aromatic alcohol (ii)(a) is chosen from phenols, o-cresol, m-cresol, p-cresol, a-naphthol, 13-naphthol, thymol, catechol, resorcin, hydroquinone and 1,4-naphthohydroquinone, phloroglucin, pyrogallol and hydroxy hydroquinone, and is in particular resorcinol and/or phloroglucin.
In one aspect, the aldehydic component (ii)(b) is chosen from azobenzene-4,4'-dicarboxaldehyde, valeraldehyde, capronaldehyde, caprylaldehyde, decanal, succindialdehyde, cyclohexanecarbaldehyde, cyclopentanecarbaldehyde, 2-methyl-l-propanal, 2-methylproprionaldehyde, acetaldehyde, acrolein, aldosterone, antimycin A, 8'-apo-13-carotene-8'-al, benzaldehyde, butanal, chloral, citral, citronellal, crotonaldehyde, dimethylaminobenzaldehyde, folinic acid, fosmidomycin, furfural, glutaraldehyde, glycerin aldehyde, glycol aldehyde, glyoxal, glyoxylic acid, heptanal, 2- hydroxybenzaldehyde, 3-hydroxy butanal, hydroxy methyl furfural, 4-

7 hydroxynonenal, isobutanal, isobutyraldehyde, methacrolein, 2-methylundecanal, mucochloric acid, N-methylformamide, 2-nitrobenzaldehyde, nonanal, octanal, oleocanthal, orlistate, pentanal, phenyl ethanal, phycocyanin, piperonal, propanal, propenal, protocatechualdehyde, retinal, salicylaldehyde, secologanin, streptomycin, strophanthidin, tylosin, vanillin, and cinnamic aldehyde, but preferably has at least two free aldehyde groups per molecule, in particular glutar-and/or succindialdehyde.
In one aspect, the (meth)acrylate polymer is a homo- or copolymer of a polar functionalized (meth)acrylate monomer, preferably one containing a sulfonic acid group, wherein the (meth)acrylate polymer is in particular a copolymer of 2-acrylamido-2-methyl propanesulfonic acid or its salts along with one or more other (meth)acrylate monomers, chosen from the group of (meth)acrylates, vinyl compounds, unsaturated di- or polycarboxylic acids and the salts of amyl compounds or allyl compounds.
In one aspect, said microcapsules are present in said composition in amounts of 0.0001 to 50 wt %, 0.01 to 20 wt %, 0.05 to 5%, 0.1 to 5 wt %, or 0.1 to 2%, based on the product as a whole.
In one aspect, said composition contains, based on total composition weight, 0.05 wt %
to 50 wt %, advantageously 1 to 40 wt %, 3 to 30 wt % or 5 wt % to 20 wt %
surfactant selected from the groups of anionic surfactants, nonionic surfactants, cationic, zwitterionic and/or amphoteric surfactants.
In one aspect, said composition contains, based on total composition weight, a nonionic surfactant, in one aspect, said composition contains, based on total composition weight, from 0.01 to 25 wt %, from 1 to 20 wt %, or from 3 to 15 wt %, nonionic surfactant.
In one aspect, said composition contains, based on total composition weight, from 0.1 to 80 wt %, 1 to 60 wt %, or 5 to 50 wt % builders.
In one aspect, said composition contains a soluble builder system, in one aspect, said soluble builder system comprises soda, silicate, citrate and/or polycarboxylates.
In one aspect, said microcapsules contain aromatic substances.
In one aspect, said benefit agent delivery particles may have any combination of the aforementioned parameters as listed in the aforementioned aspects.
In one aspect, a method for manufacturing a liquid composition, comprising stirring in a microcapsule dispersion comprising microcapsules, the capsule walls of which contain a resin, which can be obtained by reacting a) at least one aromatic alcohol or its ether or derivatives with

8 b) at least one aldehydic component that has at least two carbon atoms per molecule, and c) optionally in the presence of at least one (meth)acrylate polymer in a liquid composition or by continuously adding said microcapsule dispersion into a liquid composition and mixing the ingredients by means of static mixing elements, in one aspect, the microcapsule dispersion is mixed with surfactant beforehand is disclosed.
In one aspect, a method for manufacturing a solid composition, selected from the group consisting of (a) by mixing a microcapsule dispersion comprising microcapsules, the capsule walls of which contain a resin which can be obtained by reacting:
(i) at least one aromatic alcohol or its ether or derivatives with (ii) at least one aldehydic component that has at least two C atoms per molecule, and (iii)optionally in the presence of at least one (meth)acrylate polymer into a solid composition;
(b) by mixing said microcapsules in granulated or supported form into a solid composition;
or (c) by mixing said microcapsules in dried form into the solid composition is disclosed.
In one aspect, the use of a composition described herein in a washing or cleaning process to deposit microcapsules on the treated object to enable the targeted release of, in one aspect, liquid active substances such as, in particular, aromatic substances, onto the objects by mechanical stimulus is disclosed.
In one aspect, the use of a composition described herein in a washing or cleaning process to deposit microcapsules on the treated object to enable the long-lasting release of, in one aspect, liquid active substances such as, in particular, aromatic substances, onto the objects by diffusion is disclosed.
In one aspect, compositions of the present invention, for example shampoos, may include the following components:
A. Detersive Surfactant The composition of the present invention may include a detersive surfactant.
The detersive surfactant component may comprise anionic detersive surfactant, zwitterionic or amphoteric detersive surfactant, or a combination thereof. The concentration of the anionic surfactant component in the composition should be sufficient to provide the desired cleaning and

9 lather performance, and generally range from about 5% to about 50%.
Anionic surfactants suitable for use in the compositions are the alkyl and alkyl ether sulfates. Other suitable anionic detersive surfactants are the water-soluble salts of organic, sulfuric acid reaction products conforming to the formula R1--S03-M where R1-is a straight or branched chain, saturated, aliphatic hydrocarbon radical having from about 8 to about 24, or about 10 to about 18, carbon atoms; and M is a cation described hereinbefore.
Still other suitable anionic detersive surfactants are the reaction products of fatty acids esterified with isethionic acid and neutralized with sodium hydroxide where, for example, the fatty acids are derived from coconut oil or palm kernel oil; sodium or potassium salts of fatty acid amides of methyl tauride in which the fatty acids, for example, are derived from coconut oil or palm kernel oil.
Other anionic detersive surfactants suitable for use in the compositions are the succinnates, examples of which include disodium N-octadecylsulfosuccinnate;
disodium lauryl sulfosuccinate; diammonium lauryl sulfosuccinate; tetrasodium N-(1,2-dicarboxyethyl)-N-octadecylsulfosuccinnate; diamyl ester of sodium sulfosuccinic acid; dihexyl ester of sodium sulfosuccinic acid; and dioctyl esters of sodium sulfosuccinic acid.
Other suitable anionic detersive surfactants include olefin sulfonates having about 10 to about 24 carbon atoms. In addition to the true alkene sulfonates and a proportion of hydroxy-alkanesulfonates, the olefin sulfonates can contain minor amounts of other materials, such as alkene disulfonates depending upon the reaction conditions, proportion of reactants, the nature of the starting olefins and impurities in the olefin stock and side reactions during the sulfonation process.
Another class of anionic detersive surfactants suitable for use in the compositions is the beta-alkyloxy alkane sulfonates. These surfactants conform to the formula oR2 R1 ___________________________________________ so3m H
where R1- is a straight chain alkyl group having from about 6 to about 20 carbon atoms, R2 is a lower alkyl group having from about 1 to about 3 carbon atoms, or even 1 carbon atom, and M is a water-soluble cation.

B. Cationic Surfactant System The composition of the present invention may comprise a cationic surfactant system. The cationic surfactant system can be one cationic surfactant or a mixture of two or more cationic surfactants. If present, the cationic surfactant system is included in the composition at a level by 5 weight of from about 0.1% to about 10%, from about 0.5% to about 8%, from about 1% to about 5%, or even from about 1.4% to about 4%, in view of balance among ease-to-rinse feel, rheology and wet conditioning benefits.
A variety of cationic surfactants including mono- and di-alkyl chain cationic surfactants can be used in the compositions of the present invention. Examples of suitable materials include

10 mono-alkyl chain cationic surfactants in view of the desired gel matrix and wet conditioning benefits. The mono-alkyl cationic surfactants are those having one long alkyl chain which has from 12 to 22 carbon atoms, from 16 to 22 carbon atoms, or a C18-C22 alkyl group, in view of providing balanced wet conditioning benefits. The remaining groups attached to nitrogen are independently selected from an alkyl group of from 1 to about 4 carbon atoms or an alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, aryl or alkylaryl group having up to about 4 carbon atoms. Such mono-alkyl cationic surfactants include, for example, mono-alkyl quaternary ammonium salts and mono-alkyl amines. Mono-alkyl quaternary ammonium salts include, for example, those having a non-functionalized long alkyl chain. Mono-alkyl amines include, for example, mono-alkyl amidoamines and salts thereof.
Mono-long alkyl quaternized ammonium salts useful herein are those having the formula (II):
(II) R75 76 1 a 78 xe R -N -R

wherein one of R75, R76, R77 and R78 is selected from an alkyl group of from 12 to 30 carbon atoms or an aromatic, alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, aryl or alkylaryl group having up to about 30 carbon atoms; the remainder of R75, R76, R77 and R78 are independently selected from an alkyl group of from 1 to about 4 carbon atoms or an alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, aryl or alkylaryl group having up to about 4 carbon atoms; and X- is a salt-forming anion such as those selected from halogen, (e.g. chloride, bromide), acetate, citrate, lactate, glycolate, phosphate, nitrate, sulfonate, sulfate, alkylsulfate, and alkyl sulfonate radicals. The alkyl groups can contain, in addition to carbon and hydrogen atoms, ether and/or ester linkages, and other groups such as amino groups. The longer chain

11 alkyl groups, e.g., those of about 12 carbons, or higher, can be saturated or unsaturated. In one aspectõ one of R75, R76, R77 and R78 is selected from an alkyl group of from

12 to 30 carbon atoms, in another aspect, from 16 to 22 carbon atoms, in another aspect, from 18 to 22 carbon atoms, or even 22 carbon atoms; the remainder of R75, R76, R77 and R78 are independently selected from CH3, C2H5, C2H4OH, and mixtures thereof; and X is selected from the group consisting of Cl, Br, CH30S03, C2H50S03, and mixtures thereof.
Examples of suitable mono-long alkyl quaternized ammonium salt cationic surfactants include: behenyl trimethyl ammonium salt; stearyl trimethyl ammonium salt;
cetyl trimethyl ammonium salt; and hydrogenated tallow alkyl trimethyl ammonium salt. Among them, highly useful materials are behenyl trimethyl ammonium salt and stearyl trimethyl ammonium salt.
Mono-alkyl amines are also suitable as cationic surfactants. Primary, secondary, and tertiary fatty amines are useful. Particularly useful are tertiary amido amines having an alkyl group of from about 12 to about 22 carbons. Exemplary tertiary amido amines include:
stearamidopropyldimethylamine, stearamidopropyldiethylamine, stearamidoethyldiethylamine, s tearamidoethyldimethyl amine, palmitamidopropyldimethylamine, palmitamidopropyldiethylamine, palmitamidoethyldiethylamine, palmitamidoethyldimethyl amine, behenamidopropyldimethylamine, behenamidopropyldiethylamine, behenamidoethyldiethylamine, behenamidoethyldimethylamine, arachidamidopropyldimethylamine, arachidamidoprop yldiethyl amine, arachidamidoethyldiethylamine, arachidamidoethyldimethylamine, diethylaminoethylstearamide.
These amines can also be used in combination with acids such as t-glutamic acid, lactic acid, hydrochloric acid, malic acid, succinic acid, acetic acid, fumaric acid, tartaric acid, citric acid, t-glutamic hydrochloride, maleic acid, and mixtures thereof; in one aspect, t-glutamic acid, lactic acid, citric acid are highly useful. In one aspect, amines herein are partially neutralized with any of the acids at a molar ratio of the amine to the acid of from about 1 : 0.3 to about 1 : 2, or even from about 1: 0.4 to about 1: 1.
Although the mono-alkyl chain cationic surfactants are useful, other cationic surfactants such as di-alkyl chain cationic surfactants may also be used alone, or in combination with the mono-alkyl chain cationic surfactants. Such di-alkyl chain cationic surfactants include, for example, dialkyl (14-18) dimethyl ammonium chloride, ditallow alkyl dimethyl ammonium chloride, dihydrogenated tallow alkyl dimethyl ammonium chloride, distearyl dimethyl ammonium chloride, and dicetyl dimethyl ammonium chloride.

C. High Melting Point Fatty Compound The composition of the present invention may include a high melting point fatty compound. The high melting point fatty compound useful herein has a melting point of 25 C or higher, and is selected from the group consisting of fatty alcohols, fatty acids, fatty alcohol derivatives, fatty acid derivatives, and mixtures thereof. It is understood by the artisan that the compounds disclosed in this section of the specification can in some instances fall into more than one classification, e.g., some fatty alcohol derivatives can also be classified as fatty acid derivatives. However, a given classification is not intended to be a limitation on that particular compound, but is done so for convenience of classification and nomenclature.
Further, it is understood by the artisan that, depending on the number and position of double bonds, and length and position of the branches, certain compounds having certain required carbon atoms may have a melting point of less than 25 C. Such compounds of low melting point are not intended to be included in this section.
Among a variety of high melting point fatty compounds, fatty alcohols are used in one aspect the present invention. The fatty alcohols useful herein are those having from about 14 to about 30 carbon atoms, or even from about 16 to about 22 carbon atoms. These fatty alcohols are saturated and can be straight or branched chain alcohols. In one aspect, fatty alcohols include, for example, cetyl alcohol, stearyl alcohol, behenyl alcohol, and mixtures thereof.
High melting point fatty compounds of a single compound of high purity are typically used. In one aspect, single compounds of pure fatty alcohols selected from the group of pure cetyl alcohol, stearyl alcohol, and behenyl alcohol are employed. By "pure"
herein, what is meant is that the compound has a purity of at least about 90%, or even at least about 95%. These single compounds of high purity provide good rinsability from the hair when the consumer rinses off the composition.
The high melting point fatty compound is included in the composition at a level of from about 0.1% to about 40%, from about 1% to about 30%, from about 1.5% to about 16% by weight of the composition, or even from about 1.5% to about 8% in view of providing improved conditioning benefits such as slippery feel during the application to wet hair, softness and moisturized feel on dry hair.

13 D. Cationic Polymers The compositions of the present invention may contain a cationic polymer.
Concentrations of the cationic polymer in the composition typically range from about 0.05% to about 3%, in another embodiment from about 0.075% to about 2.0%, and in yet another embodiment from about 0.1% to about 1.0%. Suitable cationic polymers will have cationic charge densities of at least about 0.5 meq/gm, in another embodiment at least about 0.9 meq/gm, in another embodiment at least about 1.2 meq/gm, in yet another embodiment at least about 1.5 meq/gm, but in one embodiment also less than about 7 meq/gm, and in another embodiment less than about 5 meq/gm, at the pH of intended use of the composition, which pH
will generally range from about pH 3 to about pH 9, in one embodiment between about pH 4 and about pH 8.
Herein, "cationic charge density" of a polymer refers to the ratio of the number of positive charges on the polymer to the molecular weight of the polymer. The average molecular weight of such suitable cationic polymers will generally be between about 10,000 and 10 million, in one embodiment between about 50,000 and about 5 million, and in another embodiment between about 100,000 and about 3 million.
Suitable cationic polymers for use in the compositions of the present invention contain cationic nitrogen-containing moieties such as quaternary ammonium or cationic protonated amino moieties. The cationic protonated amines can be primary, secondary, or tertiary amines (in one aspect, secondary or tertiary), depending upon the particular species and the selected pH of the composition. Any anionic counterion can be used in association with the cationic polymers so long as the polymers remain soluble in water, in the composition, or in a coacervate phase of the composition, and so long as the counterions are physically and chemically compatible with the essential components of the composition or do not otherwise unduly impair product performance, stability or aesthetics. Non limiting examples of such counterions include halides (e.g., chloride, fluoride, bromide, iodide), sulfate and methyl sulfate.
Non limiting examples of suitable cationic polymers include copolymers of vinyl monomers having cationic protonated amine or quaternary ammonium functionalities with water soluble spacer monomers such as acrylamide, methacrylamide, alkyl and dialkyl acrylamides, alkyl and dialkyl methacrylamides, alkyl acrylate, alkyl methacrylate, vinyl caprolactone or vinyl pyrrolidone.
Suitable cationic protonated amino and quaternary ammonium monomers, for inclusion in the cationic polymers of the composition herein, include vinyl compounds substituted with dialkylaminoalkyl acrylate, dialkylaminoalkyl methacrylate, monoalkylaminoalkyl acrylate,

14 monoalkylaminoalkyl methacrylate, trialkyl methacryloxyalkyl ammonium salt, trialkyl acryloxyalkyl ammonium salt, diallyl quaternary ammonium salts, and vinyl quaternary ammonium monomers having cyclic cationic nitrogen-containing rings such as pyridinium, imidazolium, and quaternized pyrrolidone, e.g., alkyl vinyl imidazolium, alkyl vinyl pyridinium, alkyl vinyl pyrrolidone salts.
Other suitable cationic polymers for use in the compositions include copolymers of 1-vinyl-2-pyrrolidone and 1-vinyl-3-methylimidazolium salt (e.g., chloride salt) (referred to in the industry by the Cosmetic, Toiletry, and Fragrance Association, "CTFA", as Polyquaternium-16);
copolymers of 1-viny1-2-pyrrolidone and dimethylaminoethyl methacrylate (referred to in the industry by CTFA as Polyquaternium-11); cationic diallyl quaternary ammonium-containing polymers, including, for example, dimethyldiallylammonium chloride homopolymer, copolymers of acrylamide and dimethyldiallylammonium chloride (referred to in the industry by CTFA as Polyquaternium 6 and Polyquaternium 7, respectively); amphoteric copolymers of acrylic acid including copolymers of acrylic acid and dimethyldiallylammonium chloride (referred to in the industry by CTFA as Polyquaternium 22), terpolymers of acrylic acid with dimethyldiallylammonium chloride and acrylamide (referred to in the industry by CTFA as Polyquaternium 39), and terpolymers of acrylic acid with methacrylamidopropyl trimethylammonium chloride and methyl acrylate (referred to in the industry by CTFA as Polyquaternium 47). In one aspect, cationic substituted monomers may be the cationic substituted dialkylaminoalkyl acrylamides, dialkylaminoalkyl methacrylamides, and combinations thereof. Such monomers conform the to the formula X
R2- N+ - R4 (CH2)n NH
C=0 -[-CH2 C

wherein R1 is hydrogen, methyl or ethyl; each of R2, R3 and R4 are independently hydrogen or a short chain alkyl having from about 1 to about 8 carbon atoms, from about 1 to about 5 carbon atoms, or even from about 1 to about 2 carbon atoms; n is an integer having a value of from about 1 to about 8, or even from about 1 to about 4; and X is a counterion.
The nitrogen attached to R2, R3 and R4 may be a protonated amine (primary, secondary or tertiary), but is in one aspect, a quaternary ammonium wherein each of R2, R3 and R4 are alkyl groups a non limiting example of which is polymethacrylamidopropyl trimonium chloride, available under the trade name Polycare 133, from Rhone-Poulenc, Cranberry, N.J., U.S .A.

Other suitable cationic polymers for use in the composition include polysaccharide polymers, such as cationic cellulose derivatives and cationic starch derivatives. Suitable cationic polysaccharide polymers include those which conform to the formula A-0-(R-N+-R'õ
X) I

wherein A is an anhydroglucose residual group, such as a starch or cellulose anhydroglucose residual; R is an alkylene oxyalkylene, polyoxyalkylene, or hydroxyalkylene group, or combination thereof; R1, R2, and R3 independently are alkyl, aryl, alkylaryl, arylalkyl, alkoxyalkyl, or alkoxyaryl groups, each group containing up to about 18 carbon atoms, and the total number of carbon atoms for each cationic moiety (i.e., the sum of carbon atoms in R1, R2 and R3) is typically about 20 or less; and X is an anionic counterion as described in hereinbefore.

15 Useful cationic cellulose polymers include salts of hydroxyethyl cellulose reacted with trimethyl ammonium substituted epoxide, referred to in the industry (CTFA) as Polyquaternium 10 and available from Amerchol Corp. (Edison, N.J., USA) in their UcareTm Polymer LR, UcareTm Polymer JR, and UcareTm Polymer KG series of polymers. Other suitable types of cationic cellulose include the polymeric quaternary ammonium salts of hydroxyethyl cellulose reacted with lauryl dimethyl ammonium-substituted epoxide referred to in the industry (CTFA) as Polyquaternium 24. These materials are available from Amerchol Corp. under the trade name UcareTm Polymer LM-200.
Other suitable cationic polymers include cationic guar gum derivatives, such as guar hydroxypropyltrimonium chloride, specific examples of which include the Jaguar series commercially available from Rhone-Poulenc Incorporated and the NHance series commercially available from Aqualon Division of Hercules, Inc. Other suitable cationic polymers include quaternary nitrogen-containing cellulose ethers. Other suitable polymers include synthetic polymers. Other suitable cationic polymers include copolymers of etherified cellulose, guar and starch. When used, the cationic polymers herein are either soluble in the composition or are soluble in a complex coacervate phase in the composition formed by the cationic polymer and the anionic, amphoteric and/or zwitterionic detersive surfactant component

16 described hereinbefore. Complex coacervates of the cationic polymer can also be formed with other charged materials in the composition.
E. Nonionic polymers The composition of the present invention may include a nonionic polymer.
Polyalkylene glycols having a molecular weight of more than about 1000 are useful herein. Useful are those having the following general formula:
H(OCH2CH)OH
1x R"
wherein R95 is selected from the group consisting of H, methyl, and mixtures thereof.
Polyethylene glycol polymers useful herein are PEG-2M (also known as Polyox WSR N-10, which is available from Union Carbide and as PEG-2,000); PEG-5M (also known as Polyox WSR N-35 and Polyox WSR N-80, available from Union Carbide and as PEG-5,000 and Polyethylene Glycol 300,000); PEG-7M (also known as Polyox WSR N-750 available from Union Carbide); PEG-9M (also known as Polyox WSR N-3333 available from Union Carbide);
and PEG-14 M (also known as Polyox WSR N-3000 available from Union Carbide).
F. Conditioning agents Conditioning agents, and in particular silicones, may be included in the composition.
Conditioning agents include any material which is used to give a particular conditioning benefit to hair and/or skin. In hair treatment compositions, suitable conditioning agents are those which deliver one or more benefits relating to shine, softness, compatibility, antistatic properties, wet-handling, damage, manageability, body, and greasiness. The conditioning agents useful in the compositions of the present invention typically comprise a water insoluble, water dispersible, non-volatile, liquid that forms emulsified, liquid particles. Suitable conditioning agents for use in the composition are those conditioning agents characterized generally as silicones (e.g., silicone oils, cationic silicones, silicone gums, high refractive silicones, and silicone resins), organic conditioning oils (e.g., hydrocarbon oils, polyolefins, and fatty esters) or combinations thereof, or those conditioning agents which otherwise form liquid, dispersed particles in the aqueous surfactant matrix herein. Such conditioning agents should be physically and chemically compatible with the essential components of the composition, and should not otherwise unduly impair product stability, aesthetics or performance.
The concentration of the conditioning agent in the composition should be sufficient to provide the desired conditioning benefits, and as will be apparent to one of ordinary skill in the

17 art. Such concentration can vary with the conditioning agent, the conditioning performance desired, the average size of the conditioning agent particles, the type and concentration of other components, and other like factors.
1. Silicones The conditioning agent of the compositions of the present invention can be an insoluble silicone conditioning agent. The silicone conditioning agent particles may comprise volatile silicone, non-volatile silicones, or combinations thereof. In one aspect, non-volatile silicones conditioning agents are employed. If volatile silicones are present, it will typically be incidental to their use as a solvent or carrier for commercially available forms of non-volatile silicone materials ingredients, such as silicone gums and resins. The silicone conditioning agent particles may comprise a silicone fluid conditioning agent and may also comprise other ingredients, such as a silicone resin to improve silicone fluid deposition efficiency or enhance glossiness of the hair.
The concentration of the silicone conditioning agent typically ranges from about 0.01%
to about 10%, from about 0.1% to about 8%, from about 0.1% to about 5%, or even from about 0.2% to about 3%. The silicone conditioning agents for use in the compositions of the present invention typically have a viscosity, as measured at 25 C, from about 20 centistokes to about 2,000,000 centistokes ("cst"), from about 1,000 cst to about 1,800,000 cst, from about 50,000cst to about 1,500,000 cst, or even from about 100,000 cst to about 1,500,000 csk.
The dispersed silicone conditioning agent particles typically have a number average particle diameter ranging from about 0.011.tm to about 50 m. For small particle application to hair, the number average particle diameters typically range from about 0.01 m to about 4i.tm, from about 0.01 m to about 2i.tm, or even from about 0.01 m to about 0.5 m.
For larger particle application to hair, the number average particle diameters typically range from about 4jim to about 50 ,m, from about 6i.tm to about 30 ,m, from about 9i.tm to about 20 ,m, or even from about 121.tm to about 18 m.
a. Silicone oils Silicone fluids may include silicone oils, which are flowable silicone materials having a viscosity, as measured at 25 C, less than 1,000,000 cst, from about 5 cst to about 1,000,000 cst, or even from about 100 cst to about 600,000 cst. Suitable silicone oils for use in the compositions of the present invention include polyalkyl siloxanes, polyaryl siloxanes, polyalkylaryl siloxanes, polyether siloxane copolymers, and mixtures thereof.
Other insoluble, non-volatile silicone fluids having hair conditioning properties may also be used.

18 b. Amino and Cationic silicones Compositions of the present invention may include an aminosilicone.
Aminosilicones, as provided herein, are silicones containing at least one primary amine, secondary amine, tertiary amine, or a quaternary ammonium group. Useful aminosilicones may have less than about 0.5%
nitrogen by weight of the aminosilicone, less than about 0.2%, or even less than about 0.1%.
Higher levels of nitrogen (amine functional groups) in the amino silicone tend to result in less friction reduction, and consequently less conditioning benefit from the aminosilicone. It should be understood that in some product forms, higher levels of nitrogen are acceptable in accordance with the present invention.
In one aspect, the aminosilicones used in the present invention have a particle size of less than about 5011 once incorporated into the final composition. The particle size measurement is taken from dispersed droplets in the final composition. Particle size may be measured by means of a laser light scattering technique, using a Horiba model LA-930 Laser Scattering Particle Size Distribution Analyzer (Horiba Instruments, Inc.).
In one embodiment, the aminosilicone typically has a viscosity of from about 1,000 cst (centistokes) to about 1,000,000 cst, from about 10,000 to about 700,000 cst, from about 50,000 cst to about 500,000 cst, or even from about 100,000 cst to about 400,000 cst.
This embodiment may also comprise a low viscosity fluid, such as, for example, those materials described below in Section F.(1). The viscosity of aminosilicones discussed herein is measured at 25 C.
In another embodiment, the aminosilicone typically has a viscosity of from about 1,000 cst to about 100,000 cst, from about 2,000 cst to about 50,000 cst, from about 4,000 cst to about 40,000 cst, or even from about 6,000 cst to about 30,000 cs.
The aminosilicone typically is contained in the composition of the present invention at a level by weight of from about 0.05% to about 20%, from about 0.1% to about 10%, and or even from about 0.3% to about 5%.
c. Silicone gums Other silicone fluids suitable for use in the compositions of the present invention are the insoluble silicone gums. These gums are polyorganosiloxane materials having a viscosity, as measured at 25 C, of greater than or equal to 1,000,000 csk. Specific non-limiting examples of silicone gums for use in the compositions of the present invention include polydimethylsiloxane, (polydimethylsiloxane) (methylvinylsiloxane) copolymer, poly(dimethylsiloxane) (diphenyl siloxane)(methylvinylsiloxane) copolymer and mixtures thereof.

19 d. High refractive index silicones Other non-volatile, insoluble silicone fluid conditioning agents that are suitable for use in the compositions of the present invention are those known as "high refractive index silicones,"
having a refractive index of at least about 1.46, at least about 1.48, m at least about 1.52, or even at least about 1.55. The refractive index of the polysiloxane fluid will generally be less than about 1.70, typically less than about 1.60. In this context, polysiloxane "fluid" includes oils as well as gums.
The high refractive index polysiloxane fluid includes those represented by general Formula (III) above, as well as cyclic polysiloxanes such as those represented by Formula (VIII) below:
wherein R is as defined above, and n is a number from about 3 to about 7, or even from about 3 to about 5.
e. Silicone resins Silicone resins may be included in the conditioning agent of the compositions of the present invention. These resins are highly cross-linked polymeric siloxane systems. The cross-linking is introduced through the incorporation of trifunctional and tetrafunctional silanes with monofunctional or difunctional, or both, silanes during manufacture of the silicone resin.
Silicone materials and silicone resins in particular, can conveniently be identified according to a shorthand nomenclature system known to those of ordinary skill in the art as "MDTQ" nomenclature. Under this system, the silicone is described according to presence of various siloxane monomer units which make up the silicone. Briefly, the symbol M denotes the monofunctional unit (CH3)35i00 5; D denotes the difunctional unit (CH3)25i0; T
denotes the trifunctional unit (CH3)SiOi 5; and Q denotes the quadra- or tetra-functional unit 5i02. Primes of the unit symbols (e.g. M', D', T', and Q') denote substituents other than methyl, and must be specifically defined for each occurrence.
In one aspect, silicone resins for use in the compositions of the present invention include, but are not limited to MQ, MT, MTQ, MDT and MDTQ resins. In one aspect, Methyl is a highly suitable silicone substituent. In another aspect, silicone resins are typically MQ resins, wherein the M:Q ratio is typically from about 0.5:1.0 to about 1.5:1.0 and the average molecular weight of the silicone resin is typically from about 1000 to about 10,000.
f. Modified silicones or silicone copolymers 5 Other modified silicones or silicone copolymers are also useful herein.
Examples include silicone-based quaternary ammonium compounds (Kennan quats), end-terminal quaternary siloxanes; silicone aminopolyalkyleneoxide block copolymers; hydrophilic silicone emulsions;
and polymers made up of one or more crosslinked rake or comb silicone copolymer segments.
In alternative embodiments of the present invention, the above-noted silicone-based 10 quaternary ammonium compounds may be combined with the silicone polymers.
2. Organic conditioning oils The compositions of the present invention may also comprise from about 0.05%
to about 3%, from about 0.08% to about 1.5%, or even from about 0.1% to about 1%, of at least one organic conditioning oil as the conditioning agent, either alone or in combination with other 15 conditioning agents, such as the silicones (described herein). Suitable conditioning oils include hydrocarbon oils, polyolefins, and fatty esters. Suitable hydrocarbon oils include, but are not limited to, hydrocarbon oils having at least about 10 carbon atoms, such as cyclic hydrocarbons, straight chain aliphatic hydrocarbons (saturated or unsaturated), and branched chain aliphatic hydrocarbons (saturated or unsaturated), including polymers and mixtures thereof. Straight chain

20 hydrocarbon oils are typically from about C12 to about C19. Branched chain hydrocarbon oils, including hydrocarbon polymers, typically will contain more than 19 carbon atoms. Suitable polyolefins include liquid polyolefins, liquid poly-cc-olefins, or even hydrogenated liquid poly-cc-olefins. Polyolefins for use herein may be prepared by polymerization of C4 to about C14 or even C6 to about C12. Suitable fatty esters include, but are not limited to, fatty esters having at least 10 carbon atoms. These fatty esters include esters with hydrocarbyl chains derived from fatty acids or alcohols (e.g. mono-esters, polyhydric alcohol esters, and di-and tri-carboxylic acid esters). The hydrocarbyl radicals of the fatty esters hereof may include or have covalently bonded thereto other compatible functionalities, such as amides and alkoxy moieties (e.g., ethoxy or ether linkages, etc.).
3. Other conditioning agents Also suitable for use in the compositions herein are the conditioning agents.

21 G. Anti-dandruff Actives The compositions of the present invention may also contain an anti-dandruff agent.
Suitable, non-limiting examples of anti-dandruff actives include:
antimicrobial actives, pyridinethione salts, azoles, selenium sulfide, particulate sulfur, keratolytic acid, salicylic acid, octopirox (piroctone olamine), coal tar, and combinations thereof. In one aspect, the anti-dandruff actives typically are pyridinethione salts. Such anti-dandruff particulate should be physically and chemically compatible with the essential components of the composition, and should not otherwise unduly impair product stability, aesthetics or performance.
It is contemplated that when ZPT is used as the anti-dandruff particulate in the compositions herein, that the growth or re-growth of hair may be stimulated or regulated, or both, or that hair loss may be reduced or inhibited, or that hair may appear thicker or fuller.
H. Humectant The compositions of the present invention may contain a humectant. The humectants herein are selected from the group consisting of polyhydric alcohols, water soluble alkoxylated nonionic polymers, and mixtures thereof. The humectants, when used herein, are typically used at levels of from about 0.1% to about 20%, or even from about 0.5% to about 5%.
I. Suspending Agent The compositions of the present invention may further comprise a suspending agent at concentrations effective for suspending water-insoluble material in dispersed form in the compositions or for modifying the viscosity of the composition. Such concentrations range from about 0.1% to about 10%, or even from about 0.3% to about 5.0%.
Suspending agents useful herein include anionic polymers and nonionic polymers. Useful herein are vinyl polymers such as cross linked acrylic acid polymers with the CTFA name Carbomer, cellulose derivatives and modified cellulose polymers such as methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, nitro cellulose, sodium cellulose sulfate, sodium carboxymethyl cellulose, crystalline cellulose, cellulose powder, polyvinylpyrrolidone, polyvinyl alcohol, guar gum, hydroxypropyl guar gum, xanthan gum, arabia gum, tragacanth, galactan, carob gum, guar gum, karaya gum, carrageenan, pectin, agar, quince seed (Cydonia oblonga Mill), starch (rice, corn, potato, wheat), algae colloids (algae extract), microbiological polymers such as dextran, succinoglucan, pulleran, starch-based polymers such as carboxymethyl starch, methylhydroxypropyl starch, alginic acid-based polymers such as sodium alginate, alginic acid propylene glycol esters, acrylate polymers such as sodium polyacrylate, polyethylacrylate, polyacrylamide, polyethyleneimine, and inorganic water

22 soluble material such as bentonite, aluminum magnesium silicate, laponite, hectonite, and anhydrous silicic acid.
Commercially available viscosity modifiers highly useful herein include Carbomers with trade names Carbopol 934, Carbopol 940, Carbopol 950, Carbopol 980, and Carbopol 981, all available from B. F. Goodrich Company, acrylates/steareth-20 methacrylate copolymer with trade name ACRYSOLTm 22 available from Rohm and Hass, nonoxynyl hydroxyethylcellulose with trade name AmercellTm POLYMER HM-1500 available from Amerchol, methylcellulose with trade name BENECEL , hydroxyethyl cellulose with trade name NATROSOL , hydroxypropyl cellulose with trade name KLUCEL , cetyl hydroxyethyl cellulose with trade name POLYSURF 67, all supplied by Hercules, ethylene oxide and/or propylene oxide based polymers with trade names CARBOWAX PEGs, POLYOX WASRs, and UCON FLUIDS, all supplied by Amerchol. Other optional suspending agents include crystalline suspending agents which can be categorized as acyl derivatives, long chain amine oxides, and mixtures thereof.
These suspending agents include ethylene glycol esters of fatty acids in one aspect having from about 16 to about 22 carbon atoms. In one aspect, useful suspending agents include ethylene glycol stearates, both mono and distearate, but in one aspect, the distearate containing less than about 7% of the mono stearate. Other suitable suspending agents include alkanol amides of fatty acids, having from about 16 to about 22 carbon atoms, or even about 16 to 18 carbon atoms, examples of which include stearic monoethanolamide, stearic diethanolamide, stearic monoisopropanolamide and stearic monoethanolamide stearate. Other long chain acyl derivatives include long chain esters of long chain fatty acids (e.g., stearyl stearate, cetyl palmitate, etc.); long chain esters of long chain alkanol amides (e.g., stearamide diethanolamide distearate, stearamide monoethanolamide stearate); and glyceryl esters (e.g., glyceryl distearate, trihydroxystearin, ..................................................... a commercial example of which is Thixin R available from Rheox, Inc. Long chain acyl derivatives, ethylene glycol esters of long chain carboxylic acids, long chain amine oxides, and alkanol amides of long chain carboxylic acids in addition to the materials listed above may be used as suspending agents.
Other long chain acyl derivatives suitable for use as suspending agents include N,N-dihydrocarbyl amido benzoic acid and soluble salts thereof (e.g., Na, K), particularly N,N-di(hydrogenated) C16, C18 and tallow amido benzoic acid species of this family, which are commercially available from Stepan Company (Northfield, Ill., USA).
Examples of suitable long chain amine oxides for use as suspending agents include alkyl dimethyl amine oxides, e.g., stearyl dimethyl amine oxide.

23 Other suitable suspending agents include primary amines having a fatty alkyl moiety having at least about 16 carbon atoms, examples of which include palmitamine or stearamine, and secondary amines having two fatty alkyl moieties each having at least about 12 carbon atoms, examples of which include dipalmitoylamine or di(hydrogenated tallow)amine. Still other suitable suspending agents include di(hydrogenated tallow)phthalic acid amide, and crosslinked maleic anhydride-methyl vinyl ether copolymer.
J. Aqueous Carrier The formulations of the present invention can be in the form of pourable liquids (under ambient conditions). Such compositions will therefore typically comprise an aqueous carrier, which is present at a level of from about 20% to about 95%, or even from about 60% to about 85%. The aqueous carrier may comprise water, or a miscible mixture of water and organic solvent, and in one aspect may comprise water with minimal or no significant concentrations of organic solvent, except as otherwise incidentally incorporated into the composition as minor ingredients of other essential or optional components.
The carrier useful in the present invention includes water and water solutions of lower alkyl alcohols and polyhydric alcohols. The lower alkyl alcohols useful herein are monohydric alcohols having 1 to 6 carbons, in one aspect, ethanol and isopropanol. The polyhydric alcohols useful herein include propylene glycol, hexylene glycol, glycerin, and propane diol.
K. Dispersed Particles The compositions may optionally comprise particles. The particles may be dispersed water-insoluble particles. The particles may be inorganic, synthetic, or semi-synthetic. In one embodiment, the particles have an average mean particle size of less than about 300 m.
L. Gel Matrix The above cationic surfactants, together with high melting point fatty compounds and an aqueous carrier, may form a gel matrix in the composition of the present invention.
The gel matrix is suitable for providing various conditioning benefits such as slippery feel during the application to wet hair and softness and moisturized feel on dry hair. In view of providing the above gel matrix, the cationic surfactant and the high melting point fatty compound are contained at a level such that the weight ratio of the cationic surfactant to the high melting point fatty compound is in the range of, from about 1:1 to about 1:10, or even from about 1:1 to about 1:6.
The detergents or cleaning agents according to the invention have the advantage that they have, at most, a very low formaldehyde content, because they are manufactured, at most, with very little

24 formaldehyde introduced or, in particular, with no formaldehyde introduced at all. The detergents or cleaning agents according to the invention enable the targeted release of active substances, in particular aromatic substances that are stored in the capsules. The capsules are stable within the detergent or cleaning agent matrix and can be opened by targeted stimulation, in particular mechanical force. During use of the detergent or cleaning agent, for example when washing laundry, the microcapsules are deposited on the item to be cleaned, and after the item is dried, they can be easily opened, for example through friction. In this manner a targeted release of active substance is achieved, increasing the performance profile of the product as a whole. In so doing, the fragrance effect acquires a particular importance, because in many cases the consumer judges product performance in proportion to the pleasant scent. However, the release of the active substances, in particular fragrances, can be accomplished in a diffuse manner, in which the active substances, in particular fragrances, migrate through the polymer shell material and then are slowly released. The present detergent or cleaning agent enables in particular a long-lasting release of active substance, in particular a durable scenting of the items to be cleaned, as well as a targeted release of active substance, in particular release of scent, even after long periods of time, through the use of microencapsulated active substances, in particular fragrances.
The microcapsules that can be used according to the invention are contained in the detergent or cleaning agent in amounts of preferably 0.0001 to 50 wt%, advantageously 0.001 to 40 wt%, more advantageously 0.005 to 30 wt%, even more advantageously 0.01 to 20 wt%, in a further advantageous manner 0.05 to 10 wt%, and in particular 0.1 to 5 wt%, based on the product as a whole.
The microcapsules contain, in particular, liquids, preferably comprising i. aromatic substances (perfume oils) ii. liquid detergent and cleaning agent ingredients, such as, preferably, surfactants, in particular nonionic surfactants, silicone oils, paraffins iii liquid non-pharmaceutical additives or active substances, for example oils such as, for example, almond oil or cooling substances, and mixtures of the above.
However, it is most preferable if aromatic substances (perfume oils) are contained in the microcapsules. In the context of this invention, the terms "aromatic substances" and "fragrances"
are used synonymously.

In the following, first the microcapsules that can be used are described in detail.
In the context of the present invention, aryl oxy alkanols, aryl alkanols and oligoalkanol aryl ethers 5 are preferred as aromatic alcohols (ii)(a). Also preferred are aromatic compounds in which at least one free hydroxy group; particularly preferred at least two free hydroxy groups are directly aromatically bound; it is particularly preferred if at least two free hydroxy groups are directly bound to an aromatic ring, and most particularly preferred are arranged in meta position to one another. It is preferred that the aromatic alcohols are chosen from phenols, cresols, (o-, m- and p-10 cresol), naphthols (a- and 13-naphthol) and thymol, as well as from ethyl phenols, propyl phenols, fluorophenols and methoxyphenols.
Aromatic alcohols preferred according to the invention are also those that are used to manufacture polycarbonate plastics (e.g. for compact discs, plastic bowls, baby bottles) and 15 epoxy resin finishes (e.g. for coatings of cans and foil packages), in particular 2,2-bis-(4-hydroxyphenyl) propane (Bisphenol A).
It is particularly preferred if the aromatic alcohol is chosen from phenols with two or more hydroxy groups, preferably from catechol, resorcin, hydroquinone, and 1,4-20 naphthohydroquinone, phloroglucin, pyrogallol, or hydroxy-hydroquinone;
resorcin and/or phloroglucin being particularly preferred as aromatic alcohols.
In summary, compositions according to the invention are preferred in which the at least one aromatic alcohol (ii)(a) is chosen from phenols, cresols (o-, m- and p-cresol), naphthols (a- and

25 13-naphthol), thymol, catechol, resorcin, hydroquinone and 1,4-naphthohydroquinone, phloroglucin, pyrogallol and hydroxy-hydroquinone.
In another embodiment of the present invention, the detergents or cleaning agents contain microcapsules, in the manufacture of which aromatic alcohol is used in the form of ether, the ether being a derivative of each free form of the aromatic alcohol to be converted according to the invention. The free alcohol can also be present at the same time; there is then, accordingly, a mixture. For this case, the molar ratio between the free form of the aromatic alcohol to be

26 converted according to the invention and the named additional components (ether form of an aromatic alcohol) can be between 0:100, preferably 1: 1 or 1:2 or 1:4.
The advantage of the mixture of aromatic alcohol with an ether form is that it can be used to influence the reactivity of the system. In particular, with a suitable choice of the ratio, a system can be created, the reactivity of which stands in a balanced ratio to the storage stability of the system. Esters are preferred as derivatives of the aromatic alcohols.
According to the present invention, preferred as aldehydes (ii)(b) with at least two C atoms are both aliphatic and aromatic aldehydes. Particularly preferred aldehydes are one or more aldehydeschosen from the following group: azobenzene-4,4'-dicarboxaldehyde, valeraldehyde, capronaldehyde, caprylaldehyde, decanal, succindialdehyde, cyclohexanecarbaldehyde, cyclopentanecarbaldehyde, 2-methyl- 1-propanal, 2-methyl-propionaldehyde, acetaldehyde, acrolein, aldosterone, antimycin A, 8'-apo-13-carotene-8'-al, benzaldehyde, butanal, chloral, citral, citronellal, crotonaldehyde, dimethylaminobenzaldehyde, folinic acid, fosmidomycin, furfural, glutaraldehyde, glycerin aldehyde, glycol aldehyde, glyoxal, glyoxylic acid, heptanal, 2-hydroxy-benzaldehyde, 3-hydroxy-butanal, hydroxy-methyl-furfural, 4-hydroxy-nonenal, isobutanal, isobutyraldehyde, methacrolein, 2-methyl-undecanal, mucochloric acid, N-methyl formamide, 2-nitrobenzaldehyde, nonanal, octanal, oleocanthal, orlistate, pentanal, phenyl ethanol, phycocyanine, piperonal, propanal, propenal, protcatechualdehyde, retinal, salicylic aldehyde, secologanin, streptomycin, strophanthidin, tylosin, vanillin, and cinnamic aldehyde.
For the purposes of the present invention, the aldehydic components can have one or two, particularly preferably two, three or four, in particular two free aldehyde groups per molecule, preference being given to at least glyoxal, glutardialdehyde and/or succindialdehyde being present as the aldehydic component; particular preference being given to glutardialdehyde.
In the microcapsules that can be used according to the invention, the molar ratio of (a) the at least one aromatic alcohol (or ether or derivative thereof) to (b) the at least one aldehydic component is generally between 1: 1 and 1: 5, particularly preferably between 1 to 2 and 1 to 3 and most particularly preferably for resorcin at approximately 1 to 2.6. The weight ratio of components (a) + (b) to (c), i.e. the ratio of the sum weight of (a) + (b) to the weight of component (c) is generally between 1: 1 and 1: 0.01, particularly preferably between 1: 0.2 and 1: 0.05.

27 In summary, preferred compositions according to the invention are those in which the aldehydic component (ii)(b) is chosen from valeraldehyde, capronaldehyde, caprylaldehyde, decanal, succindialdehyde, cyclohexanecarbaldehyde, cyclopentanecarbaldehyde, 2-methyl-l-propanal, 2-methylproprionaldehyde, acetaldehyde, acrolein, aldosterone, antimycin A, 8'-apo-13-carotene-8'-al, benzaldehyde, butanal, chloral, citral, citronellal, crotonaldehyde, dimethylaminobenzaldehyde, folinic acid, fosmidomycin, furfural, glutaraldehyde, glycerinaldehyde, glycol aldehyde, glyoxal, glyoxylic acid, heptanal, 2- hydroxybenzaldehyde, 3-hydroxybutanal, hydroxymethylfurfural, 4-hydroxynonenal, isobutanal, isobutyraldehyde, methacrolein, 2-methylundecanal, mucochloric acid, N-methylformamide, 2-nitrobenzaldehyde, nonanal, octanal, oleocanthal, orlistate, pentanal, phenylethanal, phycocyanin, piperonal, propanal, propenal, protocatechualdehyde, retinal, salicylaldehyde, secologanin, streptomycin, strophanthidin, tylosin, vanillin, and cinnamic aldehyde.
The optionally used (meth)acrylate polymers can be homo- or copolymers of methacrylate monomers and/or acrylate monomers. In this invention, the term "(meth)acrylate" refers to both methacrylates and acrylates. (Meth)acrylate polymers are, for example, homo-or copolymers, preferably copolymers, of one or more polar functionalized (meth)acrylate monomers, such as (meth)acrylate monomers containing sulfonic acid groups, carboxylic acid groups, phosphoric acid groups, nitrile groups, phosphonic acid groups, ammonium groups, amine groups or nitrate groups. The polar groups can also be present in salt form. (Meth)acrylate polymers are suitable as protective colloids and can be used advantageously in the manufacture of microcapsules.
(Meth)acrylate copolymers can consist, for example, of two or more (meth)acrylate monomers (e.g. acrylate + 2-acrylamido-2-methyl propanesulfonic acid) or of one or more (meth)acrylate monomers and one or more monomers that are different from meth(acrylate) monomers (e.g.
methacrylate + styrene).
Examples of (meth)acrylate polymers include homopolymers of (meth)acrylates containing sulfonic acid groups (e.g. 2-acrylamido-2-methyl propanesulfonic acid or its salts (AMPS), which is commercially available as Lupasol PA 140, BASF) or their copolymers, copolymers of acrylamide and (meth)acrylic acid, copolymers of alkyl (meth)acrylates and N-vinylpyrrolidone (commercially available as Luviskol K15, K30 or K90, BASF), copolymers of (meth)acrylates

28 with polycarboxylates or polystyrene sulfonates, copolymers of (meth)acrylates with vinyl ethers and/or maleic acid anhydride, copolymers of (meth)acrylates with ethylene and/or maleic acid anhydride, copolymers of (meth)acrylates with isobutylene and/or maleic acid anhydride, or copolymers of (meth)acrylates with styrene maleic acid anhydride.
Preferred (meth)acrylate polymers are homo- or copolymers, preferably copolymers, of 2-acrylamido-2-methyl propanesulfonic acid or its salts (AMPS). Preferred are copolymers of 2-acrylamido-2-methyl propanesulfonic acid or its salts, for example copolymers with one or more comonomers from the group of the (meth)acrylates; vinyl compounds, such as vinyl esters or styrenes; unsaturated di- or polycarboxylic acids, such as maleic acid ester;
or the salts of amyl compounds or allyl compounds. Listed below are preferred comonomers for AMPS;
however, these comonomers can also be copolymerized with other polar functionalized (meth)acrylate monomers:
(1) Vinyl compounds, for example vinyl esters such as vinyl acetate, vinyl laurate, vinyl propionate or vinyl esters of neononanoic acid, or aromatic vinyl compounds such as styrene comonomers, for example styrene, alpha-methyl styrene or polar functionalized styrenes such as styrenes containing hydroxy groups, amino, nitrile or carboxylic acid groups, phosphonic acid or phosphoric acid groups, nitro or sulfonic acid groups and their salts; the styrenes preferably being polar functionalized in para position.
(2) Unsaturated di- or polycarboxylic acids, for example maleic acid esters such as dibutyl maleinate or diocytyl maleinate, as salts of allyl compounds, for example sodium allyl sulfonate, and as salts of amyl derivatives, for example sodium amyl sulfonate.
(3) (Meth)acrylate comonomers; these are esters of acrylic acid and methacrylic acid, wherein the ester groups are, for example, saturated or unsaturated, straight-chained, branched or cyclic hydrocarbon groups which can contain one or more heteroatoms such as N, 0, S, P, F, Cl, Br, or I.
Examples of such hydrocarbon groups are straight-chained, branched or cyclic alkyl; straight-chained, branched or cyclic alkenyl; aryls such as phenyl; or heterocylyls such as tetrahydrofurfuryl.

29 Possible (meth)acrylate comonomers, preferably for AMPS, include:
(a) acrylic acid, CrCn-alkyl acrylic acid, such as methacrylic acid;
(b) (meth)acrylamides such as acrylamide, methacrylamide, diacetone acrylamide, diacetone methacrylamide, N-butoxymethyl acrylamide, N-iso-butoxymethyl acrylamide, N-butoxymethyl methacrylamide, N-iso-butoxymethyl methacrylamide, N-methylol acrylamide and N-methylol methacrylamide;
(c) heterocyclyl (meth)acrylates such as tetrahydrofurfuryl acrylate and tetrahydrofurfuryl methacrylate or carbocyclic (meth)acrylates such as isobornyl acrylate and isobornyl methacrylate.
(d) urethane (meth)acrylates such as diurethane diacrylate and diurathane methacrylate (CAS:
72869-86-4);
(e) CrCn-alkyl acrylates such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, hexyl (e.g. n-hexyl, isohexyl or cyclohexyl), heptyl, octyl (e.g. 2-ethyl hexyl), nonyl, decyl (e.g. 2-propylheptyl or isodecyl), undecyl, dodecyl, tridecyl (e.g.
isotridecyl) and tetradecyl acrylate; the alkyl groups can optionally be substituted with one or more halogen atoms (e.g. fluorine, chlorine, bromine or iodine), for example trifluoroethyl acrylate, or with one or more amino groups, for example diethylaminoethyl acrylate, or with one or more alkoxy groups such as methoxy propyl acrylate, or with one or more aryloxy groups such as phenoxy ethyl acrylate.
(0 C2-C14 alkenyl acrylates such as ethenyl, n-propenyl, isopropenyl, n-butenyl, sec-butenyl, isobutenyl, tert-butenyl, n-pentenyl, isopentenyl, hexenyl (e.g. n-hexenyl, isohexenyl or cyclohexenyl), heptenyl, octenyl (e.g. 2-ethyl hexenyl), nonenyl, decenyl (e.g. 2-propenyl heptyl or isodecenyl), undecenyl, dodecenyl, tridecenyl (e.g. isotridecenyl) and tetradecenyl acrylate, and their epoxides such as glycidyl acrylate, or aziridines such as aziridine acrylate.
(g) Ci-C14hydroxyalkyl acrylates such as hydroxymethyl, hydroxyethyl, hydroxy-n-propyl, hydroxy isopropyl, hydroxy-n-butyl, hydroxy-sec-butyl, hydroxy isobutyl, hydroxy-tert-butyl, hydroxy-n-pentyl, hydroxy isopentyl, hydroxy hexyl (e.g. hydroxy-n-hexyl, hydroxy isohexyl or hydroxy cyclohexyl), hydroxy heptyl, hydroxy octyl (e.g. 2-ethyl hexyl), hydroxy nonyl, hydroxy decyl (e.g.
hydroxy-2-propyl heptyl or hydroxy isodecyl), hydroxy undecyl, hydroxy dodecyl, hydroxy tridecyl (e.g. hydroxy isotridecyl) and hydroxy tetradecyl acrylate; the hydroxy groups preferably being 5 located in the terminal position (w-position) (e.g. 4-hydroxy-n-butyl acrylate) or in the (03-1) position (e.g. 2-hydroxy-n-propylacrylate) of the alkyl group;
(h) alkylene glycol acrylates containing one or more alkylene glycol units.
Examples include (i) monoalkylene glycol acrylates, such as acrylates of ethylene glycol, propylene glycol (e.g. 1,2- or 10 1,3-propanediol), butylene glycol (e.g. 1,2- or 1,3- or 1,4-butanediol), pentylene glycol (e.g. 1,5-pentanediol) or hexylene glycol (e.g. 1,6-hexanediol), in which the second hydroxy group is etherified or esterified, for example by sulfuric acid, phosphoric acid, acrylic acid or methacrylic acid; or (ii) polyalkylene glycol acrylates such as polyethylene glycol acrylates, polypropylene glycol acrylates, polybutylene glycol acrylates, polypentylene glycol acrylates or polyhexylene glycol 15 acrylates, the second hydroxy group of which can optionally be etherified or esterified, for example by sulfuric acid, phosphoric acid, acrylic acid or methacrylic acid;
Examples of (poly)alkylene glycol units containing etherified hydroxy groups are CrCn-alkyloxy (poly)alkylene glycols (e.g. CrCn-alkyloxy polyalkylene glycol acrylates);
examples of 20 (poly)alkylene glycol units containing esterified hydroxy groups are sulfonium (poly)alkylene glycols (e.g. sulfonium (poly)alkylene glycol acrylates) and their salts, (poly)alkylene glycol diacrylates such as 1,4-butanediol diacrylate or 1,6-hexanediol diacrylate or (poly)alkylene glycol methacrylate acrylates such as 1,4-butanediol methacrylate acrylate or 1,6-hexanediol methacrylate acrylate;
Polyalkylene glycol acrylates can carry an acrylate group (e.g. polyethylene glycol monoacrylate, polypropylene glycol monoacrylate, polybutylene glycol monoacrylate, polypentylene glycol monoacrylate or polyhexylene glycol monoacrylate) or they can carry two or more, preferably two, acrylate groups such as polyethylene glycol diacrylate, polypropylene glycol diacrylate, polybutylene glycol diacrylate, polypentylene glycol diacrylate or polyhexylene glycol diacrylate;

Polyalkylene glycol acrylates can also contain two or more different polyalkylene glycol blocks, for example blocks of polymethylene glycol and polyethylene glycol or blocks of polyethylene glycol and polypropylene glycol.
The degree of polymerization of the polyalkylene glycol units or polyalkylene glycol blocks generally ranges from 1 to 20, preferably from 3 to 10, and particularly preferably from 3 to 6.
(i) Ci-C14-alkyl methacrylates such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, hexyl (e.g. n-hexyl, isohexyl or cyclohexyl), heptyl, octyl (e.g. 2-ethyl hexyl), nonyl, decyl (e.g. 2-propylheptyl or isodecyl), undecyl, dodecyl, tridecyl (e.g. isotridecyl) and tetradecyl methacrylate; the alkyl groups can optionally be substituted with one or more halogen atoms (e.g. fluorine, chlorine, bromine or iodine), for example trifluoroethyl methacrylate, or with one or more amino groups, for example diethylaminoethyl methacrylate, or with one or more alkoxy groups such as methoxy propyl methacrylate, or with one or more aryloxy groups such as phenoxyethyl methacrylate.
(j) C2-C14 alkenyl methacrylates such as ethenyl, n-propenyl, isopropenyl, n-butenyl, sec-butenyl, isobutenyl, tert-butenyl, n-pentenyl, isopentenyl, hexenyl (e.g. n-hexenyl, isohexenyl or cyclohexenyl), heptenyl, octenyl (e.g. 2-ethyl hexenyl), nonenyl, decenyl (e.g. 2-propenyl heptyl or isodecenyl), undecenyl, dodecenyl, tridecenyl (e.g. isotridecenyl) and tetradecenyl methacrylate, and their epoxides such as glycidyl methacrylate, or aziridines such as aziridine methacrylate.
(k) Ci-C14 hydroxyalkyl methacrylates such as hydroxymethyl, hydroxyethyl, hydroxy-n-propyl, hydroxy isopropyl, hydroxy-n-butyl, hydroxy sec-butyl, hydroxy isobutyl, hydroxy tert-butyl, hydroxy-n-pentyl, hydroxy isopentyl, hydroxy hexyl (e.g. hydroxy-n-hexyl, hydroxy isohexyl or hydroxy cyclohexyl), hydroxy heptyl, hydroxy octyl (e.g. 2-ethyl hexyl), hydroxy nonyl, hydroxy decyl (e.g. hydroxy-2-propyl heptyl or hydroxy isodecyl), hydroxy undecyl, hydroxy dodecyl, hydroxy tridecyl (e.g. hydroxy isotridecyl) and hydroxytetradecyl methacrylate; the hydroxy groups preferably being located in the terminal position (w-position) (e.g. 4-hydroxy-n-butyl methacrylate) or in the (03-1) position (e.g. 2-hydroxy-n-propyl methacrylate) of the alkyl group;

(1) alkylene glycol methacrylates containing one or more alkylene glycol units. Examples include (i) monoalkylene glycol methacrylates, such as methacrylates of ethylene glycol, propylene glycol (e.g. 1,2- or 1,3-propanediol), butylene glycol (e.g. 1,2- or 1,3- or 1,4-butanediol), pentylene glycol (e.g. 1,5-pentanediol) or hexylene glycol (e.g. 1,6-hexanediol), in which the second hydroxy group is etherified or esterified, for example by sulfuric acid, phosphoric acid, acrylic acid or methacrylic acid; or (ii) polyalkylene glycol methacrylates such as polyethylene glycol methacrylates, polypropylene glycol methacrylates, polybutylene glycol methacrylates, polypentylene glycol methacrylates or polyhexylene glycol methacrylates, the second hydroxy group of which can optionally be etherified or esterified, for example by sulfuric acid, phosphoric acid, acrylic acid or methacrylic acid;
Examples of (poly)alkylene glycol units containing etherified hydroxy groups are Ci-C14-alkyloxy (poly)alkylene glycols (e.g. Ci-C14-alkyloxy polyalkylene glycol methacrylates).
Examples of (poly)alkylene glycol units containing esterified hydroxy groups are sulfonium (poly)alkylene glycols (e.g. sulfonium (poly)alkylene glycol methacrylates) and their salts, or (poly)alkylene glycol dimethacrylates such as 1,4-butanediol dimethacrylate;
The polyalkylene glycol methacrylates can carry a methacrylate group (e.g.
polyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate, polybutylene glycol monomethacrylate, polypentylene glycol monomethacrylate or polyhexylene glycol monomethacrylate) or they can carry two or more, preferably two, methacrylate groups, such as polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, polybutylene glycol dimethacrylate, polypentalene glycol dimethacrylate or polyhexylene glycol dimethacrylate;
The polyalkylene glycol methacrylates can also contain two or more different polyalkylene glycol blocks, for example blocks of polymethylene glycol and polyethylene glycol or blocks of polyethylene glycol and polypropylene glycol (e.g. Bisomer PEM63PHD (Cognis) 75-9);
The degree of polymerization of the polyalkylene glycol units or polyalkylene glycol blocks generally ranges from 1 to 20, preferably from 3 to 10, and particularly preferably from 3 to 6.

Examples of preferred (meth)acrylate comonomers include 4-hydroxy butyl acrylate, 2-hydroxy propyl methacrylate, ammonium sulfatoethyl methacrylate, pentapropylene glycol methacrylate, acrylic acid, hexaethylene glycol methacrylate, hexapropylene glycol acrylate, hexaethylene glycol acrylate, hydroxy ethyl methacrylate, polyalkylene glycol methacrylate (CAS No. 589-75-9), Bisomer PEM63PHD, methoxy polyethylene glycol methacrylate, 2-propylheptyl acrylate (2-PHA), 1,3-butanediol dimethacrylate (BDDMA), triethylene glycol dimethacrylate (TEGDMA), hydroxy ethyl acrylate (HEA), 2-hydroxy propyl acrylate (HPA), ethylene glycol dimethacrylate (EGDMA), glycidyl methacrylate (GMA) and/or allyl methacrylate (ALMA).
The AMPS copolymers generally have a proportion of AMPS units greater than 50 mol%, preferably in the range of 60 to 95 mol%, particularly preferably 80 to 90 mol%; the proportion of comonomers is generally less than 50 mol%, preferably in the range of 5 to 40 mol%, and particularly preferably from 1 to 20 mol%.
The copolymers can be obtained by methods known per se, for example in a batch or semi-batch method. For example, first, the appropriate amounts of water and monomers are fed into a temperature-controllable reactor and placed in an inert gas atmosphere. The contents are then stirred, brought to reaction temperature (preferably ranging from approximately 70 to 80 C) and initiator is added, preferably in the form of an aqueous solution. Suitable initiators are known initiators for radical polymerization, for example sodium, potassium or ammonium peroxodisulfate, or H202 based mixtures, for example mixtures of H202 and citric acid. The heat is allowed to build up until it reaches the maximum temperature, and as soon as the temperature in the reactor drops, either (a) the remaining monomers are added and then a post-reaction takes place (semi-batch method), or (b) the post-reaction takes place immediately (batch method). The obtained reaction mixture is then cooled to room temperature and the copolymer is isolated from the aqueous solution, for example by extraction with organic solvents such as hexane or methylene chloride and then the solvent is distilled off. The copolymer can then be washed with organic solvent and dried.
The obtained reaction mixture can also be processed further directly; in this case it is advantageous to add a preservative to the aqueous copolymer solution.
The AMPS copolymers are suitable as protective colloids in the manufacture of the microcapsules that can be used according to the present invention.

In summary, preference is given to compositions according to the invention in which the (meth)acrylate polymer is a copolymer of 2-acrylamido-2-methyl propanesulfonic acid or its salts, with one or more additional (meth)acrylate monomers chosen from the group consisting of (meth)acrylates, vinyl compounds, unsaturated di- or polycarboxylic acids and the salts of amyl compounds or allyl compounds.
In compositions particularly preferred according to the invention, the molar ratio of the at least one aromatic alcohol (ii)(a) to the at least one aldehydic component (ii)(b), which has at least two C atoms per molecule, is between 1 to 2 and 1 to 3.5, preferably between 1 to 2.4 and 1 to 2.8, and particularly preferably 1 to 2.6.
Preferred detergents or cleaning agents according to the invention contain microcapsules having the following components (ii)(a), (ii)(b) and (ii)(c):
Phloroglucin, glutardialdehyde, AMPS/hydroxyethyl methacrylate copolymer;
Phloroglucin, succindialdehyde, AMPS/hydroxyethyl methacrylate copolymer;
Phloroglucin, glyoxal, AMPS/hydroxyethyl methacrylate copolymer;
Phloroglucin, glutardialdehyde, AMPS/hydroxyethyl acrylate copolymer;
Phloroglucin, succindialdehyde, AMPS/hydroxyethyl acrylate copolymer;
Phloroglucin, glyoxal, AMPS/hydroxy ethylacrylate copolymer;
Phloroglucin, glutardialdehyde, AMPS/hydroxypropyl methacrylate copolymer;
Phloroglucin, succindialdehyde, AMPS/hydroxypropyl methacrylate copolymer;
Phloroglucin, glyoxal, AMPS/hydroxypropyl methacrylate copolymer;
Phloroglucin, glutardialdehyde, AMPS/hydroxypropyl acrylate copolymer;
Phloroglucin, succindialdehyde, AMPS/hydroxypropyl acrylate copolymer;
Phloroglucin, glyoxal, AMPS/hydroxypropyl acrylate copolymer;
Phloroglucin, glutardialdehyde, AMPS/hydroxybutyl methacrylate copolymer;
Phloroglucin, succindialdehyde, AMPS/hydroxybutyl methacrylate copolymer;
Phloroglucin, glyoxal, AMPS/hydroxybutyl methacrylate copolymer;

Phloroglucin, glutardialdehyde, AMPS/hydroxybutyl acrylate copolymer;
Phloroglucin, succindialdehyde, AMPS/hydroxybutyl acrylate copolymer;
Phloroglucin, glyoxal, AMPS/hydroxybutyl acrylate copolymer;
5 Phloroglucin, glutardialdehyde, AMPS/polyethylene glycol monomethacrylate copolymer;
Phloroglucin, succindialdehyde, AMPS/polyethylene glycol monomethacrylate copolymer;
Phloroglucin, glyoxal, AMPS/polyethylene glycol monomethacrylate copolymer;
Phloroglucin, glutardialdehyde, AMPS/polyethylene glycol monoacrylate copolymer;
10 Phloroglucin, succindialdehyde, AMPS/polyethylene glycol monoacrylate copolymer;
Phloroglucin, glyoxal, AMPS/polyethylene glycol monoacrylate copolymer;
Phloroglucin, glutardialdehyde, AMPS/polypropylene glycol monomethacrylate copolymer;
Phloroglucin, succindialdehyde, AMPS/polypropylene glycol monomethacrylate copolymer;
15 Phloroglucin, glyoxal, AMPS/polypropylene glycol monomethacrylate copolymer;
Phloroglucin, glutardialdehyde, AMPS/polypropylene glycol monoacrylate copolymer;
Phloroglucin, succindialdehyde, AMPS/polypropylene glycol monoacrylate copolymer;
Phloroglucin, glyoxal, AMPS/polypropylene glycol monoacrylate copolymer;
Phloroglucin, glutardialdehyde, AMPS/methoxy polyethylene glycol monomethacrylate copolymer;
Phloroglucin, succindialdehyde, AMPS/methoxy polyethylene glycol monomethacrylate copolymer;
Phloroglucin, glyoxal, AMPS/methoxy polyethylene glycol monomethacrylate copolymer;
Phloroglucin, glutardialdehyde, AMPS/methoxy polyethylene glycol monoacrylate copolymer;
Phloroglucin, succindialdehyde, AMPS/methoxy polyethylene glycol monoacrylate copolymer;
Phloroglucin, glyoxal, AMPS/methoxy polyethylene glycol monoacrylate copolymer;
Resorcin, glutardialdehyde, AMPS/hydroxyethyl methacrylate copolymer;
Resorcin, succindialdehyde, AMPS/hydroxyethyl methacrylate copolymer;
Resorcin, glyoxal, AMPS/hydroxyethyl methacrylate copolymer;

Resorcin, glutardialdehyde, AMPS/hydroxyethyl acrylate copolymer;
Resorcin, succindialdehyde, AMPS/hydroxyethyl acrylate copolymer;
Resorcin, glyoxal, AMPS/hydroxyethyl acrylate copolymer;
Resorcin, glutardialdehyde, AMPS/hydroxypropyl methacrylate copolymer;
Resorcin, succindialdehyde, AMPS/hydroxypropyl methacrylate copolymer;
Resorcin, glyoxal, AMPS/hydroxypropyl methacrylate copolymer;
Resorcin, glutardialdehyde, AMPS/hydroxypropyl acrylate copolymer;
Resorcin, succindialdehyde, AMPS/hydroxypropyl acrylate copolymer;
Resorcin, glyoxal, AMPS/hydroxypropyl acrylate copolymer;
Resorcin, glutardialdehyde, AMPS/hydroxybutyl methacrylate copolymer;
Resorcin, succindialdehyde, AMPS/hydroxybutyl methacrylate copolymer;
Resorcin, glyoxal, AMPS/hydroxybutyl methacrylate copolymer;
Resorcin, glutardialdehyde, AMPS/hydroxybutyl acrylate copolymer;
Resorcin, succindialdehyde, AMPS/hydroxybutyl acrylate copolymer;
Resorcin, glyoxal, AMPS/hydroxybutyl acrylate copolymer;
Resorcin, glutardialdehyde, AMPS/polyethylene glycol monomethacrylate copolymer;
Resorcin, succindialdehyde, AMPS/polyethylene glycol monomethacrylate copolymer;
Resorcin, glyoxal, AMPS/polyethylene glycol monomethacrylate copolymer;
Resorcin, glutardialdehyde, AMPS/polyethylene glycol monoacrylate copolymer;
Resorcin, succindialdehyde, AMPS/polyethylene glycol monoacrylate copolymer;
Resorcin, glyoxal, AMPS/polyethylene glycol monoacrylate copolymer;
Resorcin, glutardialdehyde, AMPS/polypropylene glycol monomethacrylate copolymer;
Resorcin, succindialdehyde, AMPS/polypropylene glycol monomethacrylate copolymer;
Resorcin, glyoxal, AMPS/polypropylene glycol monomethacrylate copolymer;

Resorcin, glutardialdehyde, AMPS/polypropylene glycol monoacrylate copolymer;
Resorcin, succindialdehyde, AMPS/polypropylene glycol monoacrylate copolymer;
Resorcin, glyoxal, AMPS/polypropylene glycol monoacrylate copolymer;
Resorcin, glutardialdehyde, AMPS/methoxy polyethylene glycol monomethacrylate copolymer;
Resorcin, succindialdehyde, AMPS/methoxy polyethylene glycol monomethacrylate copolymer;
Resorcin, glyoxal, AMPS/methoxy polyethylene glycol monomethacrylate copolymer;
Resorcin, glutardialdehyde, AMPS/methoxy polyethylene glycol monoacrylate copolymer;
Resorcin, succindialdehyde, AMPS/methoxy polyethylene glycol monoacrylate copolymer;
Resorcin, glyoxal, AMPS/methoxy polyethylene glycol monoacrylate copolymer;
In another embodiment of the invention, one or more nitrogen-containing or silica-containing agents can be used in addition to manufacture the microcapsules that can be used according to the invention. The nitrogen-containing agents can be polymerized into the resin (e.g. in order to round off the property profile of the resin) or for after-treatment.
For this purpose, preference is given to the use of heterocyclic compounds having at least one nitrogen atom as the heteroatom, which is adjacent either to an amino-substituted carbon atom or to a carbonyl group like, for example, pyridazine, pyrimidine, pyrazine, pyrrolidone, aminopyridine, and compounds derived therefrom. Advantageous compounds of this type are aminopyridine and compounds derived therefrom. Suitable in principle are all aminopyridines, for example melamine, 2,6-diaminopyridine, substituted and dimeric aminopyridines and mixtures made from these compounds. Also advantageous are polyamides and dicyandiamide, urea and its derivatives, as well as pyrrolidone and compounds derived therefrom, for example hydantoin, the derivatives of which are particularly advantageous. Particularly advantageous of these compounds are allantoin and its derivatives. Also particularly advantageous are triamino-1,3,5-triazine (melamine) and its derivatives.
It should be emphasized in particular that the after-treatment is "purely" an after-treatment of the surface undertaken to arrive at this preferred embodiment of the microcapsules that can be used according to the invention. In other words: in this preferred embodiment, the stated nitrogen-containing agent is not uniformly involved in the composition of the entire capsule wall, but instead is concentrated primarily on the outside surface of the capsule walls. The after-treatment can also be effected with silica gel (in particular amorphous hydrophobic silica gel) or aromatic alcohols (a), which are preferably used in the form of slurries.
The microcapsules that can be used according to the invention are introduced into the detergent or cleaning agent according to the invention in particular in the form of microcapsule dispersions that contain one or more of the microcapsules that can be used according to the invention.
The microcapsules contained in the detergents or cleaning agents according to the invention are preferably manufactured by combining and reacting together, optionally in the presence of at least one (meth)acrylate polymer and if necessary in the presence of at least one substance to be encapsulated (the core material), the at least one aromatic alcohol to be reacted according to the invention and the at least one aldehydic component having at least two C atoms per molecule to be reacted according to the invention, and by subsequently hardening the capsules by increasing the temperature. In so doing, it is particularly preferred that the pH is increased over the course of the process.
During such a process, preferably first (a) the at least one aromatic alcohol and/or its derivative or ether and the at least one aldehydic component and, optionally, at least one (meth)acrylate polymer and at least one substance to be encapsulated are combined at a temperature of 40 to 65 C
and a pH between 6 and 9, preferably 7 and 8.5, and (b) in a later method step the pH is raised at a temperature of 40 to 65 C
to more than 9, preferably between 9.5 and 11, (c) the capsules later being hardened by increasing the temperature to 60 C up to 110 C, preferably 70 C up to 90 C, in particular 80 C.
However, if phloroglucin is used as the alcohol component, it is more advantageous to harden the capsules in the acidic range; preferably the pH is then no higher than 4, particularly preferably between 3 and 4, for example between 3.2 and 3.5.
The yield and quality of the microcapsules or microcapsule dispersions that can be used according to the invention are influenced by the chosen parameters of temperature, pH
and/or stirring speed. In particular, a too-low temperature can lead to a less-thick capsule wall. This is apparent to the person skilled in the art in a reduced yield as well as precipitation of core material as condensate in the filter of the dryer. On the other hand, it should be made sure that the reaction speed is not too high, because otherwise there will be only a little wall material around the capsules or there will be too much free wall material outside the capsules. This free wall material may then be present in particles that are larger than the capsules.
Alkalinity can also be important for the quality of the microcapsules that can be used according to the invention. In addition, within the scope of process control, the pH
influences the tendency of the preparation to gel. If particles are formed (step (b), above) at a pH of 9 or lower, the preparation could gel. In one embodiment of the described method, an alkali salt, preferably alkali carbonate, in particular sodium carbonate, is used to adjust the alkalinity.
Sodium carbonate is preferred because it reduces the risk of gelling.
In terms of the method presented here, at the beginning of the reaction (method step (a)) of the aromatic alcohol with the aldehydic component stirring can take place; the stirring speed can be from 500 to 2,500 rpm, in particular from 1,000 to 2,000 rpm. With regard to the pre-condensate obtained, optionally the (meth)acrylate polymer and the substance to be encapsulated can then be added.
Preferably, later and immediately before or during the raising of the alkalinity (method step (b)), the stirring speed is increased; it can then be from 3,000 to 5,000 rpm, in particular from 3,500 to 4,500 rpm, and particularly 4,000 rpm. Preferably, the stirring speed increased in this manner is maintained until the viscosity values of the mixture drop, and when the reduction in viscosity starts, the stirring speed is lowered preferably to 500 to 2,500 rpm, particularly preferably to 1,000 to 2,000 rpm.
Reducing the stirring speed earlier can likewise lead to unwanted gelling of the preparation.
Preferably, at least 20 minutes after the start of the described reduction in viscosity, particularly preferably between 30 and 180 minutes, the mixture is stirred again at a stirring speed from 1,000 to 2,000 rpm and at a temperature from 40 to 65 C before the hardening of the capsules is effected in method step (c) by increasing the temperature. In the present invention, this phase after the start of the described reduction in viscosity and before the capsules are hardened is also called the "dwell phase."
The dwell phase can preferably serve to achieve the pre-formation of sufficiently stable capsule walls or, in other words, render the capsule walls sufficiently stable that core material can no longer escape.
It is also possible to manufacture solid spheres, i.e. capsules that do not surround any core material. These solid spheres can even have a diameter of less than 500 nm (preferably between 300 and 400 nm). These can preferably be monodisperse solid spheres. In one embodiment, phloroglucin can be used to manufacture these solid spheres.
The microcapsules generally have diameters ranging from 1 to 1,000 lam. For the purposes of the 5 present invention, the term "microcapsule" also comprises nanocapsules, i.e. capsules with a diameter < 1 lam. However, the capsules preferably have diameters ranging from 1 to 100 lam, preferably from 2 to 50 lam. The wall thickness can be, for example, 0.05 to 10 lam.
The choice of protective colloids, as well as bases and acids, for successful encapsulation covers a 10 large range; in the case of the bases, preference is given to those that generate catalytic effects during the reaction of the aromatic alcohols with the aldehydes. This enables both the formation of resoles and the formation of novolak-analogous capsule walls.
The capsules can generally be loaded with gaseous, liquid and solid substances. Preference is 15 given to the use of hydrophobic materials. Particularly preferred, however, are liquid substances, in particular aromatic substances, liquid detergent and cleaning agent ingredients, such as preferably surfactants, in particular nonionic surfactants, silicone oils, paraffins, liquid non-pharmaceutical additives or active substances, for example oils such as, for example, almond oil, and mixtures of the above. However, it is most preferred that aromatic substances 20 (perfume oils) are contained in the microcapsules.
All substances and mixtures known for that purpose can be used as fragrances or aromatic substances or perfume oils. For the purposes of this invention, the terms "aromatic substance(s),"
"fragrances" and "perfume oil(s)" are used synonymously. This means in particular all substances 25 or mixtures thereof that humans and animals perceive as smells, in particular those that humans perceive as pleasant smells. The fragrance components used can be perfumes, perfume oils or perfume oil components. According to the invention, perfume oils and fragrances can be individual aromatic substance compounds, for example the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons. Aromatic substance compounds of the ester type

30 include benzyl acetate, phenoxy ethyl isobutyrate, p-tert.-butyl cyclohexyl acetate, linalyl acetate, dimethyl benzyl carbinyl acetate (DMBCA), phenyl ethyl acetate, benzyl acetate, ethyl methyl phenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate, benzyl salicylate, cyclohexyl salicylate, floramate, melusate and jasmecyclate. The ethers include, for example, benzyl ethyl ether and ambroxan; the aldehydes include, for example, linear alkanals containing 8 to 18 C
atoms, citral, citronellal, citronellyloxy acetaldehyde, cyclamen aldehyde, lilial and bourgeonal.
The ketones include, for example, the jonones, alpha-isomethyl ionone and methyl cedryl ketone;
the alcohols include anethol, citronellol, eugenol, geraniol, linalool, phenyl ethyl alcohol and terpineol; the hydrocarbons include mainly terpenes such as pinene. However, preference is given to the use of mixtures of various aromatic substances that together produce a pleasing fragrance.
Such perfume oils can also contain mixtures of natural aromatic substances, like those accessible from plant-based sources, for example pine, citrus, jasmine, patchouli, rose or ylang-ylang oil. Also suitable are muscatel sage oil, chamomile oil, clove oil, melissa oil, mint oil, cinnamon leaf oil, linden-blossom oil, juniper-berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil, as well as orange blossom oil, neroli oil, orange peel oil and sandalwood oil.
Aromatic substances that can be used according to the invention include essential oils such as angelica root oil, anise oil, arnica blossom oil, basil oil, bay oil, bergamot oil, champaca blossom oil, silver fir oil, silver fir cone oil, elemi oil, eucalyptus oil, fennel oil, pine needle oil, galbanum oil, geranium oil, ginger grass oil, guaiac wood oil, gurjun balm oil, helichrysum oil, ho oil, ginger oil, iris oil, cajeput oil, calamus oil, chamomile oil, camphor oil, canago oil, cardamom oil, cassia oil, pine needle oil, copaiba balsam oil, coriander oil, spearmint oil, caraway oil, cumin oil, lavender oil, lemongrass oil, lime oil, mandarin orange oil, melissa oil, musk grain oil, myrrh oil, clove oil, neroli oil, naiouli oil, olibanum oil, orange oil, origanum oil, palmarosa oil, patchouli oil, peru balsam, petitgrain oil, pepper oil, peppermint oil, allspice oil, pine oil, rose oil, rosemary oil, sandalwood oil, celery oil, lavender spike oil, star anise oil, turpentine oil, thuja oil, thyme oil, verbena oil, vetiver oil, juniper berry oil, wormwood oil, wintergreen oil, ylang-ylang oil, hyssop oil, cinnamon oil, cinnamon leaf oil, citronella oil and cypress oil. However, higher boiling or solid aromatic substances of natural or synthetic origin can also be used for the purposes of the present invention as adhesive aromatic substances or mixtures of aromatic substances, i.e. fragrances.
These compounds include the following compounds or mixtures thereof:
ambrettolide, a-amyl cinnamic aldehyde, anethole, anise aldehyde, anise alcohol, anisole, anthranilic acid methyl ester, acetophenone, benzyl acetone, benzaldehyde, benzoic acid ethyl ester, benzophenone, benzyl alcohol, benzyl acetate, benzyl benzoate, benzyl formate, benzyl valerianate, borneol, bornyl acetate, a-bromostyrene, n-decyl aldehyde, n-dodecyl aldehyde, eugenol, eugenol methyl ether, eucalyptol, farnesol, fenchone, fenchyl acetate, geranyl acetate, geranyl formate, heliotropin, heptin carboxylic acid methyl ester, heptaldehyde, hydroquinone dimethyl ether, hydroxy cinnamic aldehyde, hydroxy cinnamic alcohol, indole, iran, isoeugenol, isoeugenol methyl ether, isosafrol, jasmone, camphor, carvacrol, carvone, p-cresol methyl ether, coumarin, p-methoxy acetophenone, methyl-n-amyl ketone, methyl anthranilic acid methyl ester, p-methyl acetophenone, methyl chavicol, p-methyl quinoline, methyl-13-naphthyl ketone, methyl-n-nonyl acetaldehyde, methyl-n-nonyl ketone, muscone, 13-naphthol ethyl ether, 13-naphthol methyl ether, neroli, nitrobenzene, n-nonyl aldehyde, nonyl alcohol, n-octyl aldehyde, p-oxy acetophenone, pentadecanolide, 13-phenyl ethyl alcohol, phenyl acetaldehyde dimethyl acetal, phenyl acetic acid, pulegone, safrole, salicylic acid isoamyl ester, salicylic acid methyl ester, salicylic acid hexyl ester, salicylic acid cyclohexyl ester, santalol, scatole, terpineol, thyme, thymol, y-undecalactone, vanillin, veratrum aldehyde, cinnamic aldehyde, cinnamic alcohol, cinnamic acid, cinnamic acid ethyl ester, and cinnamic acid benzyl ester.
Highly volatile aromatic substances include in particular lower boiling aromatic substances of natural or synthetic origin that can be used alone or in mixtures. Examples of highly volatile aromatic substances include alkyl isothiocyanates (alkyl mustard oils), butanedione, limonene, linalool, linalyl acetate and linalyl propionate, menthol, menthone, methyl-n-heptenone, phellandrene, phenyl acetaldehyde, terpinyl acetate, citral, and citronellal.
Aromatic substance compounds that can be preferably used (in particular aromatic substances to be encapsulated) of the aldehyde type include hydroxy citronellal (CAS 107-75-05), helional (CAS 1205-17-0), citral (5392-40-5), bourgeonal (18127-01-0), triplal (CAS 27939-60-2), ligustral (CAS
68039-48-5), vertocitral (CAS 68039-49-6), florhydral (CAS 125109-85-5), citronellal (CAS
106-23-0), citronellyl oxyacetaldehyde (CAS 7492-67-3).
It is also preferred that the perfume to be encapsulated does not contain any 2-methyl-undecanal, decanal, benzene acetaldehyde or 3-phenylprop-2-enal.
The microcapsules can also preferably contain one or more (preferably liquid) skin-care and/or skin-protecting active ingredients. Skin-care active ingredients are all active ingredients that provide the skin a sensory and/or cosmetic benefit. Skin-care active ingredients are preferably chosen from the following substances:
a) waxes such as, for example, carnauba, spermaceti, beeswax, lanolin and/or derivatives of the same and others;
b) hydrophobic plant extracts;

c) hydrocarbons such as, for example, squalene and/or squalane;
d) higher fatty acids, preferably those containing at least 12 carbon atoms, for example lauric acid, stearic acid, behenic acid, myristic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, isostearic acid and/or polyunsaturated fatty acids and others;
e) higher fatty alcohols, preferably those containing at least 12 carbon atoms, for example lauryl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, behenyl alcohol, cholesterol and/or 2-hexadecanaol and others;
f) esters, preferably those such as cetyl octanoate, lauryl lactate, myristyl lactate, cetyl lactate, isopropyl myristate, myristyl myristate, isopropyl palmitate, isopropyl adipate, butyl stearate, decyl oleate, cholesterol isostearate, glycerol monostearate, glycerol distearate, glycerol tristearate, alkyl lactate, alkyl citrate and/or alkyl tartrate and others;
g) lipids such as, for example, cholesterol, ceramides and/or sucrose esters and others;
h) vitamins such as, for example, vitamins A, C and E, vitamin alkyl esters, including vitamin C
alkyl ester and others;
i) sunscreens;
j) phospholipids;
k) derivatives of alpha hydroxy acids;
1) germicides for cosmetic use, both synthetic such as, for example, salicylic acid and/or others, as well as natural such as, for example, neem oil and/or others;
m) silicones;
n) natural oils, for example almond oil;
as well as mixtures of any of the above components.
The detergent or cleaning agent according to the invention contains, in addition to the described microcapsules, other ingredients, namely, at a minimum, surfactants and/or builders.
Described in greater detail below are other possible ingredients of the detergents or cleaning agents.
However, it should first be made clear that for the purposes of this invention, the term "detergent"
comprises in particular detergents or cleaning agents as well as after-treatment agents (such as, preferably, fabric softeners, fragrant rinses, conditioning sheets for use in clothes dryers, hygiene rinses, etc.). Fabric detergent is the term for the formulations needed for washing fabrics, for example present in the form of powders, granules, pearls, tablets, pastes, gels, sheets, portions or liquids, which are preferably used in aqueous solutions, in particular in washing machines. Fabric softeners are fabric after-treatment agents for the treatment of fabrics and preferably contain active substances that make the treated fabric feel softer, in particular cationic active substances (preferably cationic surfactants, for example quaternary ammonium compounds), fatty acid derivatives and/or silicone oils. Fragrant rinses are fabric after-treatment agents containing perfume to treat fabrics; they give the fabrics a particularly appealing fragrance. Conditioning sheets for use in clothes dryers are nonwovens or sheets containing active substances (in particular fabric softeners). Hygiene rinses are fabric after-treatment agents for treating fabrics that contain at least one antimicrobial active substance, for example quaternary ammonium compounds such as, for example, benzalkonium chloride, and help reduce the laundry's bacterial load. The term "cleaning agent" comprises all clean(s)ers for hard or soft surfaces, but preferably hard surfaces, in particular dishwashing detergents (including dishwashing liquids and machine dishwashing detergents), all-purpose cleaners, toilet-bowl cleaners, bathroom cleaners and glass cleaners. All detergents or cleaning agents can be, for example, in the form of powders, granules, pearls, tablets, pastes, gels, sheets, portions or liquids.
They can be single-phase or multi-phase. They can also be present in single-serve packages, so-called "pouches," wherein in one variant, the microcapsules are embedded in the film materials used for the pouch, for example PVA.
The detergents or cleaning agents according to the invention contain, in addition to microcapsules, surfactants and/or builders as necessary components.
Possible surfactants include, in particular, anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants and/or amphoteric surfactants, However, it is particularly preferred if the detergent or cleaning agent according to the invention contains anionic, nonionic and/or cationic surfactants. Particularly advantageous is the use of a mixture of anionic and nonionic surfactants. The detergent or cleaning agent according to the invention preferably contains 0.05 wt% to 50 wt%, advantageously 1 to 40 wt%, more advantageously 3 to 30 wt%, and in particular 5 wt% to 20 wt% surfactant(s), in particular from the groups of anionic surfactants, nonionic surfactants, cationic, zwitterionic and/or amphoteric surfactants.
This corresponds to a preferred embodiment of the invention and enables optimum cleaning performance.
It is particularly preferred if the detergent or cleaning agent according to the invention contains anionic surfactant, advantageously in amounts from 0.1 to 25 wt%, more advantageously 1 to 20 wt%, and in particular in amounts of 3 to 15 wt%, based on the product as a whole. This corresponds to a preferred embodiment of the invention and enables particularly advantageous cleaning performance. One particularly suitable anionic surfactant is alkyl benzene sulfonate, preferably linear alkyl benzene sulfonate (LAS). If the detergent or cleaning agent according to the invention contains alkyl benzene sulfonate, advantageously in amounts of 0.1 to 25 wt%, more 5 advantageously 1 to 20 wt%, and in particular in amounts of 3 to 15 wt%, based on the product as a whole, this constitutes a preferred embodiment of the invention.
Other particularly suitable anionic surfactants are alkyl sulfates, in particular fatty alcohol sulfates (FAS) such as, for example, C12-C18 fatty alcohol sulfate. C8-C18 alkyl sulfates can preferably be 10 used; particularly preferred are C13 alkyl sulfate and C13-C15 alkyl sulfate and C13-C17 alkyl sulfate, advantageously branched, in particular alkyl-branched C13-C17 alkyl sulfate.
Particularly suitable fatty alcohol sulfates can be derived from lauryl and myristyl alcohol; i.e. fatty alcohol sulfates containing 12 or 14 carbon atoms. Long-chained FAS types (C16 to C18) are very suitable for washing laundry at higher temperatures. Other preferred anionic surfactants that can be used include alkane sulfonates 15 (e.g. secondary C13-C18 alkane sulfonate), methyl ester sulfonates (e.g.
C12-C18 methyl ester sulfonate) and a-olefin sulfonates (e.g. C14-C18 olefin sulfonate) and alkyl ether sulfates (e.g. C12-C14 fatty alcohol-2E0 ether sulfate) and/or soaps. Other suitable anionic surfactants will be described further below. However, particularly suitable are FAS and/or LAS.
20 The anionic surfactants, including the soaps, can be in the form of their sodium, potassium or ammonium salts, as well as soluble salts of organic bases such as mono-, di-or triethanolamine.
Preferably, the anionic surfactants are present in the form of their sodium or potassium salts, in particular in the form of sodium salts.
It is particularly preferred if the detergent or cleaning agent according to the invention contains 25 nonionic surfactants, advantageously in amounts of 3 to 15 wt %, more advantageously 1 to 20 wt %, and in particular in amounts of 3 to 15 wt %, based on the product as a whole. This corresponds to one preferred embodiment of the invention. Particularly preferred is the use of alkyl polyglycol ethers, in particular in combination with anionic surfactant, such as, preferably, LAS. Other suitable nonionic surfactants are alkyl phenol polyglycol ether (APEO), (ethoxylated) sorbitan fatty 30 acid ester (sorbitans), alkyl polyglucosides (APG), fatty acid glucamides, fatty acid ethoxylates, amine oxides, ethylene oxide propylene oxide block polymers, polyglycerol fatty acid ester, and/or fatty acid alkanol amides. Other suitable nonionic surfactants will be described further below.
Sugar-based nonionic surfactants, such as, in particular, APG, are particularly preferred.

For the purposes of the invention, builders include in particular zeolites, polycarboxylates, citrates (such as, for example, sodium citrate, soda, sodium hydrogen carbonate, phosphates, sodium silicates (soluble glass), phosphonates, alkaline amorphous disilicates, and crystalline layered silicates. Builders are contained in the detergent or cleaning agent according to the invention preferably in amounts of 0.1 to 80 wt %, advantageously 1 to 60 wt %, and more advantageously 5 to 50 wt %. In addition, it is most particularly preferred that the detergent or cleaning agent according to the invention contain a builder system (i.e. at least two substances having a builder effect), preferably a builder system containing zeolite, preferably comprising zeolite in amounts > 1 wt %, advantageously > 5 wt %, more advantageously > 10 wt %, in particular? 15 wt %, wt % based on the product as a whole. A useful maximum amount can be 40 wt %, 30 wt % or 20 wt %, based on the product as a whole. This corresponds to a preferred embodiment of the invention. A combination of zeolite and soda is preferred.
It is also particularly preferred if the detergent or cleaning agent according to the invention contains a soluble builder system, preferably comprising soda, silicate, citrate and/or polycarboxylates, advantageously in amounts of 0.1 to 50 wt %, based on the product as a whole.
This corresponds to a preferred embodiment of the invention. If such a soluble builder system is contained in the product, it is most preferable if the product contains only minor amounts of insoluble builders, such as, in particular, zeolite, for example < 5 wt % to 0.1 wt %, and in particular, if the product in such cases contains no insoluble builder at all.
It is also possible for the detergent or cleaning agent according to the invention to contain phosphates. Phosphate is preferably contained in amounts of 1 to 40 wt %, in particular 5 to 30 wt %, based on the product as a whole. However, according to another preferred embodiment, the detergent or cleaning agent according to the invention is free of phosphates.
The detergents or cleaning agents according to the invention, which, for example, can be present as, in particular, solids in powder form, in passivated particle form, as homogenous solutions or suspensions, can also in principle contain all known ingredients that are customary in such products. The products according to the invention can, as was already shown, contain in particular builder substances, surfactants, also bleaching agents, bleach activators, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators, and other additives such as optical brighteners, fluorescing agents, anti-redeposition agents, shrinkage blockers, anti-creasing agents, color-transfer inhibitors, antimicrobial active substances, germicides, fungicides, antioxidants, preservatives, corrosion inhibitors, glass corrosion inhibitors, disintegrating agents, static inhibitors, bitters, ironing aids, water-repellent and impregnating agents, swelling and anti-slip agents, neutral filling salts, as well as UV absorbers, foam regulators, as well as colorants and aromatic substances.
The detergents and cleaning agents according to the invention can additionally also contain so-called "free," non-microencapsulated perfume oils (aromatic substances). This corresponds to a particularly preferred embodiment of the invention. The composition of these perfume oils can be the same as or different from the perfume oils to be encapsulated. Based on the detergent or cleaning agent as a whole, preferably 0.0001 to 15 wt %, advantageously 0.001 to 10 wt %, and in particular 0.01 to 5 wt % aromatic substances can be contained therein.
Another subject matter of the invention is a method for manufacturing a solid detergent or cleaning agent, characterized (a) by mixing a microcapsule dispersion comprising microcapsules, the capsule walls of which include a resin which can be obtained by reacting a) at least one aromatic alcohol or its ether or derivatives with b) at least one aldehydic component that has at least two C atoms per molecule, and c) optionally in the presence of at least one (meth)acrylate polymer into the remaining detergent or cleaning agent matrix, or (b) by mixing the above microcapsules in granulated or supported form into the remaining detergent or cleaning agent matrix, or (c) by mixing the above microcapsules in dried form into the remaining detergent or cleaning agent matrix.
To manufacture products according to the invention with increased bulk weight, in particular ranging from 650 g/L to 950 g/L, a method having an extrusion step and granulation are preferred.
To manufacture products according to the invention in tablet form, which can be single-phase or multiphase, monochromatic or polychromatic, and which can in particular consist of one layer or of several (in particular two) layers, preferably one starts by mixing all the components ¨ if necessary one layer at a time ¨ together in a mixer and pressing the mixture by means of conventional tablet presses, for example eccentric presses or rotary presses. In particular in the case of multi-layered tablets, it can be advantageous if at least one layer is pressed beforehand.
In this way, unbreakable tablets are obtained without difficulty, which nevertheless dissolve sufficiently rapidly during use.
The tablets can be of any shape, round, oval or square; intermediate forms are also possible. It is advantageous to round off corners and edges.
Liquid or pasty products according to the invention in the form of solutions containing typical solvents are generally manufactured by mixing ingredients that can be placed as a substance or solution in an automatic mixer. The microcapsules according to the invention can then be suspended, for example afterwards, in the otherwise "finished" composition.
Another subject matter of the invention is a method for manufacturing a liquid detergent or cleaning agent, characterized by stirring a microcapsule dispersion comprising microcapsules, the capsule walls of which contain a resin which can be obtained by reacting a) at least one aromatic alcohol or its ether or derivatives with b) at least one aldehydic component that has at least two C atoms per molecule, and c) optionally in the presence of at least one (meth)acrylate polymer in the liquid detergent or cleaning agent matrix or by continuously adding the microcapsule dispersion into a liquid detergent or cleaning agent matrix and mixing the ingredients by means of static mixing elements; the microcapsule dispersion preferably having been mixed with surfactant beforehand.
When manufacturing the detergents or cleaning agents according to the invention, whether solid or liquid, it is generally advantageous to introduce the microcapsules to be introduced in the form of a microcapsule slurry (aqueous dispersion of microcapsules). For that purpose, it has proved very advantageous to mix the microcapsule slurry with surfactant to stabilize it; the surfactant used being cationic, anionic and/or nonionic surfactant, preferably nonionic surfactant; ethoxylated oxo alcohol being particularly suitable. Such stabilized microcapsule slurries are easier to work with. Otherwise, the workability of the microcapsule slurry may be complicated by a reversible flocculation.

Anionic surfactants are advantageously used in the method in amounts of 1 to 40 wt %, for example 2 to 30 wt % and in particular 3 to 20 wt %, to stabilize the dispersions (wt % based on the dispersion as a whole). Cationic surfactants can be advantageously used in amounts of 0.001 to 4 wt %, for example 0.01 to 3 wt % and in particular 0.1 to 2 wt %, to stabilize the dispersions (wt %
based on the dispersion as a whole). Nonionic surfactants can be advantageously used in amounts of 0.01 to 20 wt %, for example 0.1 to 15 wt % and in particular 1 to 10 wt %, to stabilize the dispersions (wt % based on the dispersion as a whole). Suitable anionic surfactants include alkyl benzene sulfonates, preferably secondary Cio-C13-n-alkyl benzene sulfonate, alkane sulfonates, methyl ester sulfonates, a-olefin sulfonates, alkyl sulfates, preferably fatty alcohol sulfate, alkyl ether sulfates, preferably fatty alcohol ether sulfate and sulfosuccinates.
Suitable cationic surfactants include quaternary ammonium compounds, in particular quaternary ammonium compounds with one or two hydrophobic alkyl groups, quaternary phosphonium salts or tertiary sulfonium salts. Particularly preferred are so-called "esterquats." Esterquat is the collective name for cationic surface-active compounds containing, preferably, two hydrophobic groups that are linked by ester bonds having a quaternized di(tri)ethanol amine or an analogous bond.
The use of nonionic surfactants to stabilize aqueous microcapsule dispersions has proved to be particularly advantageous. Advantageously usable compounds include in particular fatty alcohol ethoxylates, oxo alcohol ethoxylates, alkyl phenol polyglycol ethers, fatty acid ethoxylates, fatty amine ethoxylates, ethoxylated triacylglycerols and mixed ethers (polyethylene glycol ethers alkylated on both sides) as well as alkyl polyglucosides, sucrose esters, sorbitan esters, fatty acid glucamides and amine oxides.
However, the use of oxo alcohol ethoxylates is particularly advantageous in terms of the desired stabilization of the aqueous microcapsule dispersions. They enable the best results for the purposes of the invention. Preferred oxo alcohol ethoxylates are derived from oxo alcohols containing 9 to 15 carbon atoms, to which preferably 3 to 15 mol ethylene oxide are attached.
One particularly preferred oxo alcohol ethoxylate for the purposes of the invention is C13-C15 oxo alcohol, to which 7 mol ethylene oxide are attached. A suitable commercial product is, for example, Lutensol AO 7 from BASF. The use of oxo alcohol ethoxylates can completely repress the reversible flocculation.

The above-described stabilized microcapsule dispersions are particularly advantageous for the manufacture of liquid detergents or cleaning agents. A method according to the invention, in which a liquid detergent or cleaning agent is mixed with a microcapsule dispersion, as described above, preferably by stirring the microcapsule dispersion into the detergent or cleaning agent 5 matrix or by continuously adding it into a liquid detergent or cleaning agent and mixing the ingredients by means of static mixing elements, therefore is a preferred embodiment of the invention.
Stabilized microcapsule dispersions are just as advantageous for the manufacture of solid 10 detergents or cleaning agents. A method according to the invention, in which a solid detergent or cleaning agent is mixed with a microcapsule dispersion, as described above, for example by spraying the microcapsule dispersion onto the solid detergent or cleaning agent matrix or onto detergent or cleaning agent granules, therefore is a preferred embodiment of the invention.
15 Also particularly advantageous is a method for manufacturing a solid detergent or cleaning agent in which the microcapsule dispersion is granulated before it is mixed with a detergent or cleaning agent.
Another subject matter of the invention is a method for washing fabrics that uses a detergent or 20 cleaning agent according to the invention (as described above), preferably in an automatic washing machine, wherein the washing temperature is < 60 C, preferably < 40 C.
Fabric after-treatment agents are preferred detergents or cleaning agents according to the invention.
These fabric after-treatment agents, as well, contain the microcapsules used according to the 25 invention, as well as surfactants and/or builders. They are preferably fabric softeners, i.e. fabric after-treatment agents, containing a cationic surfactant. Preferred contained cationic surfactants are esterquats. Esterquats are quaternary ammonium compounds containing, preferably, two hydrophobic groups, each of which contains an ester group as a so-called "predetermined breaking point" for easier biodegradability. The amount of cationic surfactant is preferably 2 to 80 wt %, 30 advantageously 4 to 40 wt %, further preferred 6 to 20 wt % and in particular 8 to 15 wt % in each instance based on the product as a whole. Polyquaternized polymers (e.g.
Luviquat Care from BASF) and cationic chitin-based biopolymers and their derivatives, for example the polymer sold under the trade name Chitosan (manufacturer: Cognis) can also be used as cationic surfactants.

Another subject matter of the invention is a fabric conditioning method that uses a fabric after-treatment agent according to the invention (as described above) in the rinse cycle of an automatic washing machine.
Another subject matter of the invention is a fabric drying method that uses a detergent or cleaning agent according to the invention in an automatic clothes dryer.
Another subject matter of the invention is a fabric conditioning method that uses a fabric after-treatment agent according to the invention in the form of a conditioning substrate in an automatic clothes dryer.
Another subject matter of the invention is the use of a fabric after-treatment agent according to the invention to condition fabrics.
For the purposes of the invention, preferred products are also cleaning agents, in particular cleansers for hard surfaces. These, as well, contain the microcapsules used according to the invention as well as surfactants and/or builders. Also included as cleaning additives in connection with automatic dishwasher detergents are, for the purposes of the invention, fragrance delivery systems that comprise a container and particles for the deodorizing and scenting of automatic dishwashers; said particles comprising microcapsules that contain aromatic substances.
If the cleaning agent according to the invention is chosen from the group consisting of dishwashing liquids, machine dishwashing detergents, toilet-bowl cleaners and bathroom cleaners, pipe cleaners and drain cleaners, universal or all-purpose cleaners, sanitary cleaners, oven cleaners and grill cleaners, metal cleaning agents, glass cleaners and window cleaners, cleaning aids, floor cleaners and special cleaning agents, this constitutes a preferred embodiment of the invention.
Also in connection with cleaning agents, an advantage of the invention lies in that it enables a retarded and/or targeted release of liquids, for example fragrances, from the microcapsules containing them. This makes possible an often strived-for slow-release effect or long-lasting effect and/or a carefully targeted release of active substance. The cleaned surface, for example a floor, is uniformly scented over a long period of time or fragrances are released when the deposited microcapsules are broken up by mechanical stress. Other incorporated liquids, for example liquids containing antimicrobial agents, germicides, fungicides or other active substances, can also be released in a retarded and/or targeted manner, for example by the action of mechanical force.
Another subject matter of the present invention is a particulate detergent or cleaning agent additive comprising the previously described microcapsules that can be used according to the invention, as well as surfactants and/or builders.
It has now been found that through the use of these particles according to the invention, as described above, if they contain aromatic substance, a particularly advantageous olfactory impression (increased appeal / higher intensity / better longevity) can be obtained during washing or cleaning of surfaces, in particular of fabrics. Retarded and/or targeted release of fragrance is made possible.
Another subject matter of the invention is the use of a detergent or cleaning agent according to the invention in a washing or cleaning process to deposit microcapsules on the treated objects (surfaces) in order to enable the targeted release of, preferably, liquid active substances such as, in particular, aromatic substances, on the objects by mechanical stimulus.
Another subject matter of the invention is the use of a detergent or cleaning agent according to the invention in a washing or cleaning process to deposit microcapsules on the treated objects (surfaces) in order to enable the long-lasting release of, preferably, liquid active substances such as, in particular, aromatic substances, on the objects by diffusion.
Adjunct Materials The disclosed compositions may include additional adjunct ingredients that include:
fabric hueing agents, bleach activators, surfactants, builders, chelating agents, dye transfer inhibiting agents, dispersants, enzymes, and enzyme stabilizers, catalytic metal complexes, polymeric dispersing agents, clay and soil removal/anti-redeposition agents, brighteners, suds suppressors, dyes, additional perfumes and perfume delivery systems, structure elasticizing agents, fabric softeners, carriers, hydrotropes, processing aids and/or pigments. Other embodiments of Applicants' compositions do not contain one or more of the following adjuncts materials: fabric hueing agents, bleach activators, surfactants, builders, chelating agents, dye transfer inhibiting agents, dispersants, enzymes, and enzyme stabilizers, catalytic metal complexes, polymeric dispersing agents, clay and soil removal/anti-redeposition agents, brighteners, suds suppressors, dyes, additional perfumes and perfume delivery systems, structure elasticizing agents, fabric softeners, carriers, hydrotropes, processing aids and/or pigments. The precise nature of these additional components, and levels of incorporation thereof, will depend on the physical form of the composition and the nature of the operation for which it is to be used.
However, when one or more adjuncts are present, such one or more adjuncts may be present as detailed below. The following is a non-limiting list of suitable additional adjuncts.
Fabric Hueing Agents - The composition may comprise a fabric hueing agent (sometimes referred to as shading, bluing or whitening agents). Typically the hueing agent provides a blue or violet shade to fabric. Hueing agents can be used either alone or in combination to create a specific shade of hueing and/or to shade different fabric types. This may be provided for example by mixing a red and green-blue dye to yield a blue or violet shade.
Hueing agents may be selected from any known chemical class of dye, including but not limited to acridine, anthraquinone (including polycyclic quinones), azine, azo (e.g., monoazo, disazo, trisazo, tetrakisazo, polyazo), including premetallized azo, benzodifurane and benzodifuranone, carotenoid, coumarin, cyanine, diazahemicyanine, diphenylmethane, formazan, hemicyanine, indigoids, methane, naphthalimides, naphthoquinone, nitro and nitroso, oxazine, phthalocyanine, pyrazoles, stilbene, styryl, triarylmethane, triphenylmethane, xanthenes and mixtures thereof.
Suitable fabric hueing agents include dyes, dye-clay conjugates, and organic and inorganic pigments. Suitable dyes include small molecule dyes and polymeric dyes.
Suitable small molecule dyes include small molecule dyes selected from the group consisting of dyes falling into the Colour Index (C.I.) classifications of Acid, Direct, Basic, Reactive or hydrolysed Reactive, Solvent or Disperse dyes for example that are classified as Blue, Violet, Red, Green or Black, and provide the desired shade either alone or in combination. In another aspect, suitable small molecule dyes include small molecule dyes selected from the group consisting of Colour Index (Society of Dyers and Colourists, Bradford, UK) numbers Direct Violet dyes such as 9, 35, 48, 51, 66, and 99, Direct Blue dyes such as 1, 71, 80 and 279, Acid Red dyes such as 17, 73, 52, 88 and 150, Acid Violet dyes such as 15, 17, 24, 43, 49 and 50, Acid Blue dyes such as 15, 17, 25, 29, 40, 45, 75, 80, 83, 90 and 113, Acid Black dyes such as 1, Basic Violet dyes such as 1, 3, 4, 10 and 35, Basic Blue dyes such as 3, 16, 22, 47, 66, 75 and 159, Disperse or Solvent dyes US
8,268,016 B2, or dyes as disclosed in US 7,208,459 B2, and mixtures thereof.
In another aspect, suitable small molecule dyes include small molecule dyes selected from the group consisting of C. I. numbers Acid Violet 17, Acid Blue 80, Acid Violet 50, Direct Blue 71, Direct Violet 51, Direct Blue 1, Acid Red 88, Acid Red 150, Acid Blue 29, Acid Blue 113 or mixtures thereof.
Suitable polymeric dyes include polymeric dyes selected from the group consisting of polymers containing covalently bound (sometimes referred to as conjugated) chromogens, (dye-polymer conjugates), for example polymers with chromogens co-polymerized into the backbone of the polymer and mixtures thereof. Polymeric dyes include those described in US 7,686,892 B2.
In another aspect, suitable polymeric dyes include polymeric dyes selected from the group consisting of fabric-substantive colorants sold under the name of Liquitint (Milliken, Spartanburg, South Carolina, USA), dye-polymer conjugates formed from at least one reactive dye and a polymer selected from the group consisting of polymers comprising a moiety selected from the group consisting of a hydroxyl moiety, a primary amine moiety, a secondary amine moiety, a thiol moiety and mixtures thereof. In still another aspect, suitable polymeric dyes include polymeric dyes selected from the group consisting of Liquitint Violet CT, carboxymethyl cellulose (CMC) covalently bound to a reactive blue, reactive violet or reactive red dye such as CMC conjugated with C.I. Reactive Blue 19, sold by Megazyme, Wicklow, Ireland under the product name AZO-CM-CELLULOSE, product code S-ACMC, alkoxylated triphenyl-methane polymeric colourants, alkoxylated thiophene polymeric colourants, and mixtures thereof.
Suitable dye clay conjugates include dye clay conjugates selected from the group comprising at least one cationic/basic dye and a smectite clay, and mixtures thereof. In another aspect, suitable dye clay conjugates include dye clay conjugates selected from the group consisting of one cationic/basic dye selected from the group consisting of C.I. Basic Yellow 1 through 108, C.I. Basic Orange 1 through 69, C.I. Basic Red 1 through 118, C.I. Basic Violet 1 through 51, C.I. Basic Blue 1 through 164, C.I. Basic Green 1 through 14, C.I.
Basic Brown 1 through 23, CI Basic Black 1 through 11, and a clay selected from the group consisting of Montmorillonite clay, Hectorite clay, Saponite clay and mixtures thereof. In still another aspect, suitable dye clay conjugates include dye clay conjugates selected from the group consisting of:
Montmorillonite Basic Blue B7 C.I. 42595 conjugate, Montmorillonite Basic Blue B9 C.I. 52015 conjugate, Montmorillonite Basic Violet V3 C.I. 42555 conjugate, Montmorillonite Basic Green G1 C.I. 42040 conjugate, Montmorillonite Basic Red R1 C.I. 45160 conjugate, Montmorillonite C.I. Basic Black 2 conjugate, Hectorite Basic Blue B7 C.I. 42595 conjugate, Hectorite Basic Blue B9 C.I. 52015 conjugate, Hectorite Basic Violet V3 C.I. 42555 conjugate, Hectorite Basic Green G1 C.I. 42040 conjugate, Hectorite Basic Red R1 C.I. 45160 conjugate, Hectorite C.I.
Basic Black 2 conjugate, Saponite Basic Blue B7 C.I. 42595 conjugate, Saponite Basic Blue B9 C.I. 52015 conjugate, Saponite Basic Violet V3 C.I. 42555 conjugate, Saponite Basic Green G1 C.I. 42040 conjugate, Saponite Basic Red R1 C.I. 45160 conjugate, Saponite C.I. Basic Black 2 5 conjugate and mixtures thereof.
The hueing agent may be incorporated into the detergent composition as part of a reaction mixture which is the result of the organic synthesis for a dye molecule, with optional purification step(s). Such reaction mixtures generally comprise the dye molecule itself and in addition may comprise un-reacted starting materials and/or by-products of the organic synthesis route.

Suitable polymeric hueing agents may be alkoxylated. As with all such alkoxylated compounds, the organic synthesis may produce a mixture of molecules having different degrees of alkoxylation. Such mixtures may be used directly to provide the hueing agent, or may undergo a purification step to increase the proportion of the target molecule.Suitable pigments include pigments selected from the group consisting of flavanthrone, indanthrone, chlorinated 15 indanthrone containing from 1 to 4 chlorine atoms, pyranthrone, dichloropyranthrone, monobromodichloropyranthrone, dibromodichloropyranthrone, tetrabromopyranthrone, perylene-3,4,9,10-tetracarboxylic acid diimide, wherein the imide groups may be unsubstituted or substituted by Cl-C3 -alkyl or a phenyl or heterocyclic radical, and wherein the phenyl and heterocyclic radicals may additionally carry substituents which do not confer solubility in water, 20 anthrapyrimidinecarboxylic acid amides, violanthrone, isoviolanthrone, dioxazine pigments, copper phthalocyanine which may contain up to 2 chlorine atoms per molecule, polychloro-copper phthalocyanine or polybromochloro-copper phthalocyanine containing up to 14 bromine atoms per molecule and mixtures thereof. In another aspect, suitable pigments include pigments selected from the group consisting of Ultramarine Blue (C.I. Pigment Blue 29), Ultramarine 25 Violet (C.I. Pigment Violet 15), Monastral Blue and mixtures thereof.
The aforementioned fabric hueing agents can be used in combination (any mixture of fabric hueing agents can be used).
Deposition Aid - In one aspect, the fabric treatment composition may comprise from about 0.01% to about 10%, from about 0.05 to about 5%, or from about 0.15 to about 3% of a 30 deposition aid. In one aspect, the deposition aid may be a cationic or amphoteric polymer. In another aspect, the deposition aid may be a cationic polymer. Cationic polymers in general and their method of manufacture are known in the literature. In one aspect, the cationic polymer may have a cationic charge density of from about 0.005 to about 23 meq/g, from about 0.01 to about 12 meq/g, or from about 0.1 to about 7 meq/g, at the pH of the composition.
For amine-containing polymers, wherein the charge density depends on the pH of the composition, charge density is measured at the intended use pH of the product. Such pH will generally range from about 2 to about 11, more generally from about 2.5 to about 9.5. Charge density is calculated by dividing the number of net charges per repeating unit by the molecular weight of the repeating unit. The positive charges may be located on the backbone of the polymers and/or the side chains of polymers.
In another aspect, the deposition aid may comprise a cationic acrylic based polymer. In a further aspect, the deposition aid may comprise a cationic polyacrylamide. In another aspect, the deposition aid may comprise a polymer comprising polyacrylamide and polymethacrylamidopropyl trimethylammonium cation. In another aspect, the deposition aid may comprise poly(acrylamide- N-dimethyl aminoethyl acrylate) and its quaternized derivatives.
In another aspect, the deposition aid may be selected from the group consisting of cationic or amphoteric polysaccharides. In one aspect, the deposition aid may be selected from the group consisting of cationic and amphoteric cellulose ethers, cationic or amphoteric galactomannan, cationic guar gum, cationic or amphoteric starch, and combinations thereof Another group of suitable cationic polymers may include alkylamine-epichlorohydrin polymers which are reaction products of amines and oligoamines with epichlorohydrin. Another group of suitable synthetic cationic polymers may include polyamidoamine-epichlorohydrin (PAE) resins of polyalkylenepolyamine with polycarboxylic acid. The most common PAE resins are the condensation products of diethylenetriamine with adipic acid followed by a subsequent reaction with epichlorohydrin.
The weight-average molecular weight of the polymer may be from about 500 Daltons to about 5,000,000 Daltons, or from about 1,000 Daltons to about 2,000,000 Daltons, or from about 2,500 Daltons to about 1,500,000 Daltons, as determined by size exclusion chromatography relative to polyethylene oxide standards with RI detection. In one aspect, the MW of the cationic polymer may be from about 500 Daltons to about 37,500 Daltons.
Surfactants: Surfactants utilized can be of the anionic, nonionic, zwitterionic, ampholytic or cationic type or can comprise compatible mixtures of these types.
Anionic and nonionic surfactants are typically employed if the fabric care product is a laundry detergent. On the other hand, cationic surfactants are typically employed if the fabric care product is a fabric softener.

In addition to the anionic surfactant, the fabric care compositions of the present invention may further contain a nonionic surfactant. The compositions of the present invention can contain up to about 30%, alternatively from about 0.01% to about 20%, more alternatively from about 0.1% to about 10%, by weight of the composition, of a nonionic surfactant. In one embodiment, the nonionic surfactant may comprise an ethoxylated nonionic surfactant. Suitable for use herein are the ethoxylated alcohols and ethoxylated alkyl phenols of the formula R(0C2H4)n OH, wherein R is selected from the group consisting of aliphatic hydrocarbon radicals containing from about 8 to about 20 carbon atoms and alkyl phenyl radicals in which the alkyl groups contain from about 8 to about 12 carbon atoms, and the average value of n is from about 5 to about 15.
Suitable nonionic surfactants are those of the formula R1(0C2H4)n0H, wherein R1 is a Cio -C16 alkyl group or a C8 -C12 alkyl phenyl group, and n is from 3 to about 80. In one aspect, particularly useful materials are condensation products of C9-C15 alcohols with from about 5 to about 20 moles of ethylene oxide per mole of alcohol.
The fabric care compositions of the present invention may contain up to about 30%, alternatively from about 0.01% to about 20%, more alternatively from about 0.1% to about 20%, by weight of the composition, of a cationic surfactant. For the purposes of the present invention, cationic surfactants include those which can deliver fabric care benefits. Non-limiting examples of useful cationic surfactants include: fatty amines; quaternary ammonium surfactants;
and imidazoline quat materials.
Non-limiting examples of fabric softening actives are N, N-bis(stearoyl-oxy-ethyl) N,N-dimethyl ammonium chloride, N,N-bis(tallowoyl-oxy-ethyl) N,N-dimethyl ammonium chloride, N,N-bis(stearoyl-oxy-ethyl) N-(2 hydroxyethyl) N-methyl ammonium methylsulfate; 1, 2 di (stearoyl-oxy) 3 trimethyl ammoniumpropane chloride;
dialkylenedimethylammonium salts such as dicanoladimethylammonium chloride, di(hard)tallowdimethylammonium chloride dicanoladimethylammonium methylsulfate;
1-methyl-1- stearoylamidoethy1-2-stearoylimidazolinium methylsulfate; 1-tallowylamidoethy1-2-tallowylimidazoline; N,N" -dialkyldiethylenetriamine ;the reaction product of N-(2-hydroxyethyl)-1,2-ethylenediamine or N-(2-hydroxyisopropy1)-1,2-ethylenediamine with glycolic acid, esterified with fatty acid, where the fatty acid is (hydrogenated) tallow fatty acid, palm fatty acid, hydrogenated palm fatty acid, oleic acid, rapeseed fatty acid, hydrogenated rapeseed fatty acid;
polyglycerol esters (PGEs), oily sugar derivatives, and wax emulsions and a mixture of the above.

It will be understood that combinations of softener actives disclosed above are suitable for use herein.
Builders - The compositions may also contain from about 0.1% to 80% by weight of a builder. Compositions in liquid form generally contain from about 1% to 10% by weight of the builder component. Compositions in granular form generally contain from about 1% to 50% by weight of the builder component. Detergent builders are well known in the art and can contain, for example, phosphate salts as well as various organic and inorganic nonphosphorus builders.
Water-soluble, nonphosphorus organic builders useful herein include the various alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates and polyhydroxy sulfonates. Examples of polyacetate and polycarboxylate builders are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylene diamine tetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, and citric acid. Other polycarboxylate builders are the oxydisuccinates and the ether carboxylate builder compositions comprising a combination of tartrate monosuccinate and tartrate disuccinate. Builders for use in liquid detergents include citric acid.
Suitable nonphosphorus, inorganic builders include the silicates, aluminosilicates, borates and carbonates, such as sodium and potassium carbonate, bicarbonate, sesquicarbonate, tetraborate decahydrate, and silicates having a weight ratio of 5i02 to alkali metal oxide of from about 0.5 to about 4.0, or from about 1.0 to about 2.4. Also useful are aluminosilicates including zeolites.
Dispersants ¨ The compositions may contain from about 0.1%, to about 10%, by weight of dispersants Suitable water-soluble organic materials are the homo- or co-polymeric acids or their salts, in which the polycarboxylic acid may contain at least two carboxyl radicals separated from each other by not more than two carbon atoms. The dispersants may also be alkoxylated derivatives of polyamines, and/or quaternized derivatives.
Enzymes ¨ The compositions may contain one or more detergent enzymes which provide cleaning performance and/or fabric care benefits. Examples of suitable enzymes include hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, B-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase, and amylases, or mixtures thereof. A
typical combination may be a cocktail of conventional applicable enzymes like protease, lipase, cutinase and/or cellulase in conjunction with amylase. Enzymes can be used at their art-taught levels, for example at levels recommended by suppliers such as Novozymes and Genencor.
Typical levels in the compositions are from about 0.0001% to about 5%. When enzymes are present, they can be used at very low levels, e.g., from about 0.001% or lower; or they can be used in heavier-duty laundry detergent formulations at higher levels, e.g., about 0.1% and higher.
In accordance with a preference of some consumers for "non-biological" detergents, the compositions may be either or both enzyme-containing and enzyme-free.
Dye Transfer Inhibiting Agents - The compositions may also include from about 0.0001%, from about 0.01%, from about 0.05% by weight of the compositions to about 10%, about 2%, or even about 1% by weight of the compositions of one or more dye transfer inhibiting agents such as polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof.
Chelant ¨ The compositions may contain less than about 5%, or from about 0.01%
to about 3% of a chelant such as citrates; nitrogen-containing, P-free aminocarboxylates such as EDDS, EDTA and DTPA; aminophosphonates such as diethylenetriamine pentamethylenephosphonic acid and, ethylenediamine tetramethylenephosphonic acid; nitrogen-free phosphonates e.g., HEDP; and nitrogen or oxygen containing, P-free carboxylate-free chelants such as compounds of the general class of certain macrocyclic N-ligands such as those known for use in bleach catalyst systems.
Brighteners ¨ The compositions may also comprise a brightener (also referred to as "optical brightener") and may include any compound that exhibits fluorescence, including compounds that absorb UV light and reemit as "blue" visible light. Non-limiting examples of useful brighteners include: derivatives of stilbene or 4,4' -diaminostilbene, biphenyl, five-membered heterocycles such as triazoles, pyrazolines, oxazoles, imidiazoles, etc., or six-membered heterocycles (coumarins, naphthalamide, s-triazine, etc.). Cationic, anionic, nonionic, amphoteric and zwitterionic brighteners can be used. Suitable brighteners include those commercially marketed under the trade name Tinopal-UNPA-GX by Ciba Specialty Chemicals Corporation (High Point, NC).

Bleach system ¨ Bleach systems suitable for use herein contain one or more bleaching agents. Non-limiting examples of suitable bleaching agents include catalytic metal complexes;
activated peroxygen sources; bleach activators; bleach boosters;
photobleaches; bleaching 5 enzymes; free radical initiators; H202; hypohalite bleaches; peroxygen sources, including perborate and/or percarbonate and combinations thereof. Suitable bleach activators include perhydrolyzable esters and perhydrolyzable imides such as, tetraacetyl ethylene diamine, octanoylcaprolactam, benzoyloxybenzenesulphonate, nonanoyloxybenzene¨isulphonate, benzoylvalerolactam, dodecanoyloxybenzenesulphonate. Other bleaching agents include metal 10 complexes of transitional metals with ligands of defined stability constants.
Stabilizer - The compositions may contain one or more stabilizers and thickeners. Any suitable level of stabilizer may be of use; exemplary levels include from about 0.01% to about 20%, from about 0.1% to about 10%, or from about 0.1% to about 3% by weight of the 15 composition. Non-limiting examples of stabilizers suitable for use herein include crystalline, hydroxyl-containing stabilizing agents, trihydroxystearin, hydrogenated oil, or a variation thereof, and combinations thereof. In some aspects, the crystalline, hydroxyl-containing stabilizing agents may be water-insoluble wax-like substances, including fatty acid, fatty ester or fatty soap. In other aspects, the crystalline, hydroxyl-containing stabilizing agents may be 20 derivatives of castor oil, such as hydrogenated castor oil derivatives, for example, castor wax.
The hydroxyl containing stabilizers are disclosed in US Patents 6,855,680 and 7,294,611. Other stabilizers include thickening stabilizers such as gums and other similar polysaccharides, for example gellan gum, carrageenan gum, and other known types of thickeners and rheological additives. Exemplary stabilizers in this class include gum-type polymers (e.g.
xanthan gum), 25 polyvinyl alcohol and derivatives thereof, cellulose and derivatives thereof including cellulose ethers and cellulose esters and tamarind gum (for example, comprising xyloglucan polymers), guar gum, locust bean gum (in some aspects comprising galactomannan polymers), and other industrial gums and polymers.

Silicones - Suitable silicones comprise Si-0 moieties and may be selected from (a) non-functionalized siloxane polymers, (b) functionalized siloxane polymers, and combinations thereof. The molecular weight of the organosilicone is usually indicated by the reference to the viscosity of the material. In one aspect, the organosilicones may comprise a viscosity of from about 10 to about 2,000,000 centistokes at 25 C. In another aspect, suitable organosilicones may have a viscosity of from about 10 to about 800,000 centistokes at 25 C.
Suitable organosilicones may be linear, branched or cross-linked.
In one aspect, the organosilicone may comprise a cyclic silicone. The cyclic silicone may comprise a cyclomethicone of the formula RCH3)25i0l11 where n is an integer that may range from about 3 to about 7, or from about 5 to about 6.
In one aspect, the organosilicone may comprise a functionalized siloxane polymer.
Functionalized siloxane polymers may comprise one or more functional moieties selected from the group consisting of amino, amido, alkoxy, hydroxy, polyether, carboxy, hydride, mercapto, sulfate phosphate, and/or quaternary ammonium moieties. These moieties may be attached directly to the siloxane backbone through a bivalent alkylene radical, (i.e., "pendant") or may be part of the backbone. Suitable functionalized siloxane polymers include materials selected from the group consisting of aminosilicones, amidosilicones, silicone polyethers, silicone-urethane polymers, quaternary ABn silicones, amino ABn silicones, and combinations thereof.
In one aspect, the functionalized siloxane polymer may comprise a silicone polyether, also referred to as "dimethicone copolyol." In general, silicone polyethers comprise a polydimethylsiloxane backbone with one or more polyoxyalkylene chains. The polyoxyalkylene moieties may be incorporated in the polymer as pendent chains or as terminal blocks. In another aspect, the functionalized siloxane polymer may comprise an aminosilicone.
In one aspect, the organosilicone may comprise amine ABn silicones and quat ABn silicones. Such organosilicones are generally produced by reacting a diamine with an epoxide.
In another aspect, the functionalized siloxane polymer may comprise silicone-urethanes.
These are commercially available from Wacker Silicones under the trade name SLM-21200 .
Perfume: The optional perfume component may comprise a component selected from the group consisting of (1) a perfume microcapsule, or a moisture-activated perfume microcapsule, comprising a perfume carrier and an encapsulated perfume composition, wherein said perfume carrier may be selected from the group consisting of cyclodextrins, starch microcapsules, porous carrier microcapsules, and mixtures thereof; and wherein said encapsulated perfume composition may comprise low volatile perfume ingredients, high volatile perfume ingredients, and mixtures thereof;
(2) a pro-perfume;

(3) a low odor detection threshold perfume ingredients, wherein said low odor detection threshold perfume ingredients may comprise less than about 25%, by weight of the total neat perfume composition; and (4) mixtures thereof; and Porous Carrier Microcapsule - A portion of the perfume composition can also be absorbed onto and/or into a porous carrier, such as zeolites or clays, to form perfume porous carrier microcapsules in order to reduce the amount of free perfume in the multiple use fabric conditioning composition.
Pro-perfume - The perfume composition may additionally include a pro-perfume.
Pro-perfumes may comprise nonvolatile materials that release or convert to a perfume material as a result of, e.g., simple hydrolysis, or may be pH-change-triggered pro-perfumes (e.g. triggered by a pH drop) or may be enzymatically releasable pro-perfumes, or light-triggered pro-perfumes.
The pro-perfumes may exhibit varying release rates depending upon the pro-perfume chosen.
Examples I. Synthesis examples:
Example 1.1: Manufacture of copolymers a) AMPS hydroxybutyl acrylate For 1,500 g preparation, 891 g demineralized water together with 585 g AMPS
(50% aqueous solution) and 7.5 g 4-hydroxy butyl acrylate (HBA) are filled into the reactor and placed in an inert gas atmosphere. The reaction mixture is heated to 75 C while stirring (400 rpm). 0.03 g of the water-soluble initiator sodium peroxodisulfate are dissolved in 15 g water and injected by means of a syringe into the reactor when the reaction temperature is reached.
An hour of post-reaction starts after the maximum temperature is reached. The preparation is then cooled to room temperature and mixed with 1.5 g preservative.
The aqueous solution is characterized in terms of its viscosity, solids content and pH. The viscosity is 540 mPas (measured at 20 rpm Brookfield), the solids content is 21% and the pH is 3.3. 3 g copolymers are placed on a petri dish and dried for 24 hours at 160 C
in a drying cabinet.
The end weight is 0.69 g, which equals a yield of 21.6%.
b) AMPS polyalkylene glycol monomethacrylate The ingredients provided consist of 912 g of demineralized water, 240 g AMPS
and 7.5 g poly(ethylene or propylene)glycol monomethacrylate (Bisomer PEM 63P HD from Cognis, CAS
No. 589-75-9).
The mixture is placed in an inert gas atmosphere. The reaction mixture is heated to 75 C while stirring (400 rpm). 1.5 g sodium peroxodisulfate are dissolved in 15 g water and transferred by means of a syringe into the reactor. After the temperature has reached a maximum in the reactor and starts to drop, 240 g AMPS is dispensed by means of a peristaltic pump along with 83 g PEM
63P over a period of one hour. A half-hour post-reaction then takes place. The preparation is then cooled to room temperature and mixed with 1.5 g preservative.
The aqueous solution is characterized in terms of its viscosity, solids content and pH. The viscosity is 110 mPas (measured at 20 rpm Brookfield), the solids content is 23% and the pH is 3.1. 3 g copolymers are placed on a petri dish and dried for 24 hours at 160 C
in a drying cabinet.
The end weight is 0.68 g, which equals a yield of 21.6%.
Example 1.2: Resorcin capsule In a 400 mL beaker, 5.5 g resorcin are dissolved in water while stirring (stirring speed:
approximately 1,500 rpm) and then mixed with 2.0 g sodium carbonate solution (20 wt %), upon which the pH is 7.9. The solution is heated to a temperature of approximately 52 C. 25.5 g glutardialdehyde are then added.
The mixture is stirred for approximately an additional 10 minutes at a stirring speed of approximately 1,500 rpm and a temperature of approximately 52 C (pre-condensation time).
Afterward, approximately 20 g water are added and approximately 2 minutes later, 1 g of one of the protective colloids (a) copolymer 1.1a, (b) copolymer 1.1b and (c) poly-AMPS (AMPS
homopolymer) is added and approximately another 2 minutes later 55 g butyl phenylacetate (CAS No. 122-43-0; aromatic substance with a honey-like aroma) are added.
Immediately afterward, the stirring speed is increased to approximately 4,000 rpm and at approximately the same time, 20.0 g sodium carbonate solution (20 wt %) are added. Afterward the pH of the mixture is approximately 9.7. Subsequently, the viscosity and the volume of the mixture increase.
Stirring is continued at a stirring speed of approximately 4,000 rpm until the viscosity drops again. Only then is the stirring speed reduced to approximately 1,500 rpm. The preparation is stirred for an additional approximately 60 minutes at a temperature of approximately 52 C and at a roughly constant stirring speed. This phase is also called the dwell phase.
The mixture is then heated to approximately 80 C and the capsules are hardened at this temperature for a period of 3 hours.
Capsule size distribution ¨ D (90) 5 to 10 pm; encapsulation efficiency approx. 90%;
Drying yield > 90%; solids of the slurry approximately 40 wt %.
The capsules produced are formaldehyde-free and can be processed without any problems from the aqueous slurry into a dry, free-flowing powder as stable core/shell microcapsules.
The capsules can also be loaded with other gaseous, liquid or solid hydrophobic materials and substance classes instead of with butyl phenyl acetate, in particular with aromatic substances and/or perfume oils.
In addition to the butyl-phenyl-acetate-containing resorcin microcapsules of Example 1, additional microcapsules were produced according to analogous methods:
- Example 1.3: hydroxycitronellal-containing resorcin microcapsules;
- Example 1.4: helional-containing resorcin microcapsules;
- Example 1.5: citral-containing resorcin microcapsules;
- Example 1.6: bourgeonal-containing resorcin microcapsules;
- Example 1.7: triplal-containing resorcin microcapsules;
- Example 1.8: ligustral-containing resorcin microcapsules;
- Example 1.9: vertocitral-containing resorcin microcapsules;
- Example 1.10: florhydral-containing resorcin microcapsules;
- Example 1.11: citronellal-containing resorcin microcapsules;
- Example 1.12: citronellyl-oxyacetaldehyde-containing resorcin microcapsules.
In another series of examples, phloroglucin microcapsules were produced.
Analogously to the method according to Example 1.2, the 5.5 g resorcin that were used there were completely replaced by 6.3 g phloroglucin, in this manner obtaining:
- Example 1.13: butyl-phenyl-acetate-containing phloroglucin microcapsules;
- Example 1.14: citronellal-containing phloroglucin microcapsules;
- Example 1.15: helional-containing phloroglucin microcapsules;
- Example 1.16: citral-containing phloroglucin microcapsules;
- Example 1.17: bourgeonal-containing phloroglucin microcapsules;

- Example 1.18: triplal-containing phloroglucin microcapsules;
- Example 1.19: ligustral-containing phloroglucin microcapsules;
- Example 1.20: vertocitral-containing phloroglucin microcapsules;
- Example 1.21: florhydral-containing phloroglucin microcapsules;
5 - Example 1.22: citronellal-containing phloroglucin microcapsules;
- Example 1.23: citronellyl-oxyacetaldehyde-containing phloroglucin microcapsules.
In the two series of examples, 1.3 through 1.12 (resorcin) and 1.13 through 1.23 (phloroglucin), 25.5 g glutardialdehyde can be replaced by 21.9 g succindialdehyde during the synthesis of the 10 microcapsules. Such resorcin and phloroglucin microcapsules based on succinaldehyde were produced in example series 1.24 through 1.34 (resorcin and glutardialdehyde) and 1.35 through 1.45 (phloroglucin and glutardialdehyde).
II. Examples of use 11.1 Granular laundry detergent compositions for hand washing or washing machines, typically top-loading washing machines.
A B C D E F
(wt %) (wt %) (wt %) (wt %) (wt %) (wt %) Linear alkylbenzenesulfonate 20 22 20 15 19.5 20 C12-14 Dimethylhydroxyethyl ammonium chloride 0.7 0.2 1 0.6 0.0 0 AE3S 0.9 1 0.9 0.0 0.4 0.9 AE7 0.0 0.0 0.0 1 0.1 3 Sodium tripolyphosphate 5 0.0 4 9 2 0.0 Zeolite A 0.0 1 0.0 1 4 1 1.6R Silicate (5i02:Na20 at ratio 1.6:1) 7 5 2 3 3 5 Sodium carbonate 25 20 25 17 18 19 Polyacrylate MW 4500 1 0.6 1 1 1.5 1 Random graft copolymerl 0.1 0.2 0.0 0.0 0.05 0.0 Carboxymethyl cellulose 1 0.3 1 1 1 1 Stainzyme (20 mg active/g) 0.1 0.2 0.1 0.2 0.1 0.1 Protease (Savinase , 32.89 nrq active/g) 0.1 0.1 0.1 0.1 0.1 Amylase - Natalase (8.65 mg active/g) 0.1 0.0 0.1 0.0 0.1 0.1 Lipase - Lipex (18 mg active /g) 0.03 0.07 0.3 0.1 0.07 0.4 Fluorescent Brightener 1 0.06 0.0 0.06 0.18 0.06 0.06 Fluorescent Brightener 2 0.1 0.06 0.1 0.0 0.1 0.1 DTPA 0.6 0.8 0.6 0.25 0.6 0.6 MgSO4 1 1 1 0.5 1 1 Sodium Percarbonate 0.0 5.2 0.1 0.0 0.0 0.0 Sodium Perborate Monohydrate 4.4 0.0 3.85 2.09 0.78 3.63 NOBS 1.9 0.0 1.66 0.0 0.33 0.75 TAED 0.58 1.2 0.51 0.0 0.015 0.28 Sulphonated zinc phthalocyanine 0.0030 0.0 0.0012 0.0030 0.0021 0.0 S-ACMC 0.1 0.0 0.0 0.0 0.06 0.0 Direct Violet Dye (DV9 or DV99 or DV66) 0.0 0.0 0.0003 0.0001 0.0001 0.0 Additional Neat Perfume (1) 0.5 0.5 0.5 0.5 0.5 0.5 Microcapsules (2) 0.7 1.0 2.3 0.5 1.2 0.8 Sulfate/Moisture Balance (1) Optional.
(2) Microcapsules of the present invention comprising a core that comprise perfume.
11.2 Granular laundry detergent compositions typically for front-loading automatic washing machines. The typical pH is about 10 A E F
(wt B C D (wt%) (wt%) %) (wt%) (wt%) (wt%) Linear alkylbenzenesulfonate 8 7.1 7 6.5 7.5 7.5 AE3S 0 4.8 1.0 5.2 4 4 C12-14 Alkylsulfate 1 0 1 0 0 0 AE7 2.2 0 2.2 0 0 0 C10-12 Dimethyl 0 0 hydroxyethylammonium chloride 0.75 0.94 0.98 0.98 Crystalline layered silicate (8- 0 0 Na2Si205) 4.1 0 4.8 0 Zeolite A 5 0 5 0 2 2 Citric Acid 3 5 3 4 2.5 3 Sodium Carbonate 15 20 14 20 23 23 Silicate 2R (5i02:Na20 at ratio 2:1) 0.08 0 0.11 0 0 0 Soil release agent 0.75 0.72 0.71 0.72 0 0 Acrylic Acid/Maleic Acid 2.6 3.8 Copolymer 1.1 3.7 1.0 3.7 Carboxymethylcellulose 0.15 1.4 0.2 1.4 1 0.5 Protease - Purafect (84 mg active/g) 0.2 0.2 0.3 0.15 0.12 0.13 Amylase - Stainzyme Plus (20 mg 0.15 0.15 active/g) 0.2 0.15 0.2 0.3 Lipase - Lipex (18.00 mg active/g) 0.05 0.15 0.1 0 0 0 Amylase - Natalase (8.65 mg 0.15 0.15 active/g) 0.1 0.2 0 0 Cellulase - CellucleanTM (15.6 mg 0.1 0.1 active/g) 0 0 0 0 TAED 3.6 4.0 3.6 4.0 2.2 1.4 Percarbonate 13 13.2 13 13.2 16 14 Na salt of Ethylenediamine-N,N'- 0.2 0.2 disuccinic acid, (S,S) isomer (EDDS) 0.2 0.2 0.2 0.2 Hydroxyethane di phosphonate 0.2 0.2 (HEDP) 0.2 0.2 0.2 0.2 MgSO4 0.42 0.42 0.42 0.42 0.4 0.4 Perfume 0.5 0.6 0.5 0.6 0.6 0.6 Suds suppressor agglomerate 0.05 0.1 0.05 0.1 0.06 0.05 Soap 0.45 0.45 0.45 0.45 0 0 Sulphonated zinc phthalocyanine 0.00 0 0 (active) 07 0.0012 0.0007 0 S-ACMC 0.01 0.01 0 0.01 0 0 Direct Violet 9 (active) 0 0 0.0001 0.0001 0 0 Additional Neat Perfume (1) 0.5 0.5 0.5 0.5 0.5 0.5 Perfume Microcapsules (2) 2.0 1.5 0.9 2.2 1.5 0.8 Sulfate/ Water & Miscellaneous Balance (1) Optional.
(2) Microcapsules of the present invention comprising a core that comprise perfume.
11.3 Heavy Duty Liquid laundry detergent compositions A B C D E F G
(wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) AES C12-15 alkyl ethoxy (1.8) sulfate 11 10 4 6.32 0 0 0 AE3S 0 0 0 0 2.4 0 0 Linear alkyl benzene sulfonate/sulfonic acid 1.4 4 8 3.3 5 8 19 HSAS 3 5.1 3 0 0 0 0 Sodium formate 1.6 0.09 1.2 0.04 1.6 1.2 0.2 Sodium hydroxide 2.3 3.8 1.7 1.9 1.7 2.5 2.3 To pH
Monoethanolamine 1.4 1.49 1.0 0.7 0 0 8.2 Diethylene glycol 5.5 0.0 4.1 0.0 0 0 0 AE9 0.4 0.6 0.3 0.3 0 0 0 AE8 0 0 0 0 0 0 20.0 AE7 0 0 0 0 2.4 6 0 Chelant (HEDP) 0.15 0.15 0.11 0.07 0.5 0.11 0.8 Citric Acid 2.5 3.96 1.88 1.98 0.9 2.5 0.6 C12-14 dimethyl Amine Oxide 0.3 0.73 0.23 0.37 0 0 0 C12-18 Fatty Acid 0.8 1.9 0.6 0.99 1.2 0 15.0 4-formyl-phenylboronic acid 0 0 0 0 0.05 0.02 0.01 Borax 1.43 1.5 1.1 0.75 0 1.07 0 Ethanol 1.54 1.77 1.15 0.89 0 3 7 A compound having the following general structure:
bis((C2H50)(C2H40)n)(CH3)-N+-CM2x-N -(CH3)-bis((C2H50)(C2H40)n), wherein n = from 20 to 30, and x = from 3 to 8, or sulphated or sulphonated variants thereof 0.1 0 0 0 0 0 2.0 Ethoxylated (E015) tetraethylene pentamine 0.3 0.33 0.23 0.17 0.0 0.0 0 Ethoxylated Polyethylenimine 0 0 0 0 0 0 0.8 Ethoxylated hexamethylene diamine 0.8 0.81 0.6 0.4 1 1 1,2-Propanediol 0.0 6.6 0.0 3.3 0.5 2 8.0 Fluorescent Brightener 0.2 0.1 0.05 0.3 0.15 0.3 0.2 Hydrogenated castor oil derivative 0.1 0.1 structurant 0 0 0 0 0 Perfume 1.6 1.1 1.0 0.8 0.9 1.5 1.6 Protease (40.6 mg active/g) 0.8 0.6 0.7 0.9 0.7 0.6 1.5 Mannanase: Mannaway@ (25 mg active/g) 0.07 0.05 0.045 0.06 0.04 0.045 0.1 Amylase: Stainzyme@ (15 mg active/g) 0.3 0 0.3 0.1 0 0.4 0.1 Amylase: Natalase@ (29 mg active/g) 0 0.2 0.1 0.15 0.07 0 0.1 Xyloglucanase (Whitezyme@, 0.2 20mg active/g) 0.2 0.1 0 0 0.05 0.05 Lipex (18 mg active/g) 0.4 0.2 0.3 0.1 0.2 0 0 Additional Neat Perfume (1) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Perfume Microcapsules (2) 0.25 3.2 2.5 4.0 2.5 1.4 0.8 *Water, dyes & minors Balance * Based on total cleaning and/or treatment composition weight, a total of no more than 12%
water (1) Optional.
(2) Microcapsules of the present invention comprising a core that comprise perfume.
Examples 11.4 Unit Dose Compositions Example of Unit Dose detergents A B
C14_ 15 alkyl poly ethoxylate (8) 12 -C12 - 14 alkyl poly ethoxylate (7) 1 14 C12 - 14 alkyl poly ethoxylate (3) sulfate Mono 8.4 9 EthanolAmine salt Linear Alkylbenzene sulfonic acid 15 16 Citric Acid 0.6 0.5 C1218 Fatty Acid 15 17 Enzymes 1.5 1.2 Diethylene triamine penta methylene 1.3 _ phosphonic acid or HEDP
Fluorescent brightener 0.2 0.3 Hydrogenated Castor Oil 0.2 0.2 1, 2 propanediol 16 12 Glycerol 6.2 8.5 Sodium hydroxide - 1 Mono Ethanol Amine 7.9 6.1 Dye Present Present PDMS - 2.7 Potassium sulphite 0.2 0.2 Perfume Microcapsules (1) 1.5 0.9 Up to Up to Water 100p 100 (1) Microcapsules of the present invention comprising a core that comprise perfume.

Raw Materials and Notes For Composition Examples LAS is linear alkylbenzenesulfonate having an average aliphatic carbon chain length C9-C15 supplied by Stepan, Northfield, Illinois, USA or Huntsman Corp. (HLAS is acid form).
C12-14 Dimethylhydroxyethyl ammonium chloride, supplied by Clariant GmbH, Germany 5 AE3S is C12-15 alkyl ethoxy (3) sulfate supplied by Stepan, Northfield, Illinois, USA
AE7 is C12-15 alcohol ethoxylate, with an average degree of ethoxylation of 7, supplied by Huntsman, Salt Lake City, Utah, USA
AES is C10-18 alkyl ethoxy sulfate supplied by Shell Chemicals.
AE9 is C12-13 alcohol ethoxylate, with an average degree of ethoxylation of 9, supplied by 10 Huntsman, Salt Lake City, Utah, USA
HSAS or HC1617HSAS is a mid-branched primary alkyl sulfate with average carbon chain length of about 16-17 Sodium tripolyphosphate is supplied by Rhodia, Paris, France Zeolite A is supplied by Industrial Zeolite (UK) Ltd, Grays, Essex, UK
15 1.6R Silicate is supplied by Koma, Nestemica, Czech Republic Sodium Carbonate is supplied by Solvay, Houston, Texas, USA
Polyacrylate MW 4500 is supplied by BASF, Ludwigshafen, Germany Carboxymethyl cellulose is Finnfix V supplied by CP Kelco, Arnhem, Netherlands Suitable chelants are, for example, diethylenetetraamine pentaacetic acid (DTPA) 20 supplied by Dow Chemical, Midland, Michigan, USA or Hydroxyethane di phosphonate (HEDP) supplied by Solutia, St Louis, Missouri, USA Bagsvaerd, Denmark Savinase , Natalase , Stainzyme , Lipex , CellucleanTM, Mannaway and Whitezyme are all products of Novozymes, Bagsvaerd, Denmark.
Proteases may be supplied by Genencor International, Palo Alto, California, USA (e.g.
25 Purafect Prime(D) or by Novozymes, Bagsvaerd, Denmark (e.g. Liquanase , Coronase ).
Fluorescent Brightener 1 is Tinopal AMS, Fluorescent Brightener 2 is Tinopal CBS-X, Sulphonated zinc phthalocyanine and Direct Violet 9 is Pergasol Violet BN-Z all supplied by Ciba Specialty Chemicals, Basel, Switzerland Sodium percarbonate supplied by Solvay, Houston, Texas, USA
30 Sodium perborate is supplied by Degussa, Hanau, Germany NOBS is sodium nonanoyloxybenzenesulfonate, supplied by Future Fuels, Batesville, USA

TAED is tetraacetylethylenediamine, supplied under the Peractive brand name by Clariant GmbH, Sulzbach, Germany S-ACMC is carboxymethylcellulose conjugated with C.I. Reactive Blue 19, sold by Megazyme, Wicklow, Ireland under the product name AZO-CM-CELLULOSE, product code S-ACMC.
Soil release agent is Repel-o-tex PF, supplied by Rhodia, Paris, France Acrylic Acid/Maleic Acid Copolymer is molecular weight 70,000 and acrylate:maleate ratio 70:30, supplied by BASF, Ludwigshafen, Germany Na salt of Ethylenediamine-N,N'-disuccinic acid, (S,S) isomer (EDDS) is supplied by Octel, Ellesmere Port, UK
Hydroxyethane di phosphonate (HEDP) is supplied by Dow Chemical, Midland, Michigan, USA
Suds suppressor agglomerate is supplied by Dow Corning, Midland, Michigan, USA

HSAS is mid-branched alkyl sulfate as disclosed in US 6,020,303 and US
6,060,443 C12_14 dimethyl Amine Oxide is supplied by Procter & Gamble Chemicals, Cincinnati, USA
Random graft copolymer is a polyvinyl acetate grafted polyethylene oxide copolymer having a polyethylene oxide backbone and multiple polyvinyl acetate side chains. The molecular weight of the polyethylene oxide backbone is about 6000 and the weight ratio of the polyethylene oxide to polyvinyl acetate is about 40:60 and no more than 1 grafting point per 50 ethylene oxide units.
Ethoxylated polyethyleneimine is polyethyleneimine (MW = 600) with 20 ethoxylate groups per -NH.
Cationic cellulose polymer is LK400, LR400 and/or JR3OM from Amerchol Corporation, Edgewater NJ
Note: all enzyme levels are expressed as % enzyme raw material EXAMPLE 5. Microcapsules in Shampoo A subset of the capsules from the above examples is formulated into a rinse-off Shampoo formulation as follows: to 90.0 grams of shampoo formulation (with a typical formulation given below) is added an appropriate amount of microcapsule slurry to deliver a fragrance usage level of 0.5wt%. The microcapsules and water are added on top of the shampoo formulation, then the contents are mixed using a SpeedMixer by Hauschild DAC 400FVZ mixer, at 1850 RPM for 1 minute.

Typical composition of shampoo formulations are given in the examples below.
EXAMPLE COMPOSITION I II III
- =
In Water q.s. q.s. q.s.
Polyquaternium 76' 2.50 Guar, Hydroxylpropyl 0.25 Trimonium Chloride Polyquaterium 6 3 0.79 Sodium Laureth Sulfate 21.4 21.4 (SLE3S) 4 3 3 21.43 Sodium Lauryl Sulfate (SLS) 20.6 20.6 20.69 Silicone 6 0.75 1.00 0.5 Cocoamidopropyl Betaine 7 3.33 3.33 3.33 Cocoamide MEA 8 1.0 1.0 1.0 Ethylene Glycol Distearate 9 1.50 1.50 1.50 Sodium Chloride 1 0.25 0.25 0.25 Fragrance 0.70 0.70 0.70 Fragrance Microcapsule 1.2 1.2 1.2 Up Up Up to Preservatives, pH adjusters to to 1%
1% 1%
1 Mirapol AT-1, Copolymer of Acrylamide(AM) and TRIQUAT, MW=1,000,000;
CD= 1.6 meq./gram; 10% active ; Supplier Rhodia 2 Jaguar C500, MW - 500,000, CD=0.7, supplier Rhodia 3 Mirapol 100S, 31.5% active, supplier Rhodia 4 Sodium Laureth Sulfate, 28% active, supplier: P&G
5 Sodium Lauryl Sulfate, 29% active supplier: P&G
6 Glycidol Silicone VC2231-193C
7 Tegobetaine F-B, 30% active supplier: Goldschmidt Chemicals 8 Monamid CMA, 85% active, supplier Goldschmidt Chemical 9 Ethylene Glycol Distearate, EGDS Pure, supplier Goldschmidt Chemical Sodium Chloride USP (food grade), supplier Morton; note that salt is an adjustable ingredient, higher or lower levels may be added to achieve target viscosity.
EXAMPLE COMPOSITION IV V VI
Ingredient Water q.s. q.s. q.s.
Silicone A 1 1.0 Silicone B 2 0.5 Silicone C 3 0.5 Cyclopentasiloxane 4 0.61 1.5 Behenyl trimethyl 2.25 2.25 2.25 ammonium chloride 5 Isopropyl alcohol 0.60 0.60 0.60 Cetyl alcohol 6 1.86 1.86 1.86 Stearyl alcohol 7 4.64 4.64 4.64 Disodium EDTA 0.13 0.13 0.13 NaOH 0.01 0.01 0.01 Benzyl alcohol 0.40 0.40 0.40 Methylchloroisothiazolinone/ 0.000 0.000 0.0005 5 Methylisothiazolinone 8 5 Panthenol 9 0.10 0.10 0.10 Panthenyl ethyl ether 1 0.05 0.05 0.05 Fragrance 0.35 0.35 0.35 Fragrance Microcapsules 1.2 1.2 1.2 1 Glycidol Silicone VC2231-193 2 Glycidol Silicone VC2231-193F
3 Glycidol Silicone VC2231-193A
4 Cyclopentasiloxane: SF1202 available from Momentive Performance Chemicals Behenyl trimethyl ammonium chloride/Isopropyl alcohol: Genamin ril \II KMP
available from Clariant 6 Cetyl alcohol: Konol ril \II series available from Shin Nihon Rika 7 Stearyl alcohol: Konol TM series available from Shin Nihon Rika 8 Methylchloroisothiazolinone/Methylisothiazolinone: Kathon TM CG available from Rohm & Haas 9 Panthenol: Available from Roche Panthenyl ethyl ether: Available from Roche EXAMPLE COMPOSITION VII VIII
Ingredient Sodium Laureth Sulfate 10.00 10.00 Sodium Lauryl Sulfate 1.50 1.50 Cocamidopropyl betaine 2.00 2.00 Guar Hydroxypropyl trimonium chloride (1) 0.40 Guar Hydroxypropyl trimonium chloride (2) 0.40 Dimethicone (3) 2.00 2.00 Gel Network (4) 27.27 Ethylene Glycol Distearate 1.50 1.50 5-Chloro-2-methyl-4-isothiazolin-3-one, Kathon 0.0005 0.0005 CG
Sodium Benzoate 0.25 0.25 Disodium EDTA 0.13 0.13 Perfume 0.70 0.70 Fragrance Microcapsules of Example 3 1.0 1.0 Citric Acid/ Sodium Citrate Dihydrate pH QS pH QS
Sodium Chloride/ Ammonium Xylene Sulfonate Visc. Visc.
QS QS
Water QS QS
(1) Jaguar C17 available from Rhodia (2) N-Hance 3269 (with Mol. W. of -500,000 and 0.8meq/g) available from Aqulaon/Hercules (3) Viscasil 330M available from General Electric Silicones (4) Gel Networks; See Composition below. The water is heated to about 74 C
and the Cetyl Alcohol, Stearyl Alcohol, and the SLES Surfactant are added to it. After incorporation, this mixture is passed through a heat exchanger where it is cooled to about 35 C.
As a result of this cooling step, the Fatty Alcohols and surfactant crystallized to form a crystalline gel network.
Ingredient Wt. %
Water 86.14%
Cetyl Alcohol 3.46%
Steary Alcohol 6.44%
Sodium laureth-3 sulfate (28% Active) 3.93%
5-Chloro-2-methyl-4-isothiazolin-3-one, Kathon CG 0.03%
EXAMPLE 6. Microcapsules in Lotion Example I II III
PHASE A
DC-9040 1 8.60 3.00 5.00 Dimethicone 4.09 4.00 4.00 Polymethylsilsesquioxane 2 4.09 4.00 4.00 Cyclomethicone 11.43 0.50 11.33 KSG-210 3 5.37 5.25 5.40 Polyethylene wax 4 3.54 2.05 DC-2503 Cosmetic Wax 5 7.08 10.00 3.77 Hydrophobic TiO2 0.50 Iron oxide coated Mica 0.65 TiO2 Coated Mica 1.00 1.00 Fragrance Particles 1.00 1.00 1.00 PHASE B
Glycerin 10.00 10.00 10.00 Dexpanthenol 0.50 0.50 0.50 Pentylene Glycol 3.00 3.00 3.00 Hexamidine Diisethionate 6 0.10 0.10 0.10 Niacinamide 7 5.00 5.00 5.00 Methylparaben 0.20 0.20 0.20 Ethylparaben 0.05 0.05 0.05 Sodium Citrate 0.20 0.20 0.20 Citric Acid 0.03 0.03 0.03 Sodium Benzoate 0.05 0.05 0.05 Sodium Chloride 0.50 0.50 0.50 FD&C Red #40 (1%) 0.05 0.05 0.05 q.s to q.s to q.s to Water 100 100 100 Hardness at 21 C (g) 33.3 15.4 14.2 Hardness at 33 C (g) 6.4 0.7 4.0 1. 12.5% Dimethicone Crosspolymer in Cyclopentasiloxane. Available from Dow CorningTM.
2. E.g., TospearlTm 145A or Tospearl 2000. Available from GE Toshiba SiliconeTM.
3. 25% Dimethicone PEG-10/15 Crosspolymer in Dimethicone. Available from Shin-EtsijTM.
4. JeenateTm 3H polyethylene wax from JeenTM
5 5. Stearyl Dimethicone. Available from Dow Corning.
6. Hexamidine diisethionate, available from Laboratoires Serobiologiques.
7. Additionally or alternatively, the composition may comprise one or more other skin care actives, their salts and derivatives, as disclosed herein, in amounts also disclosed herein as would be deemed suitable by one of skill in the art.
For the examples above, in a suitable container, combine the ingredients of Phase A. In a separate suitable container, combine the ingredients of Phase B. Heat each phase to 73 C-78 C
while mixing each phase using a suitable mixer (e.g., Anchor blade, propeller blade, or IKA T25) until each reaches a substantially constant desired temperature and is homogenous. Slowly add Phase B to Phase A while continuing to mix Phase A. Continue mixing until batch is uniform.
Pour product into suitable containers at 73-78 C and store at room temperature. Alternatively, continuing to stir the mixture as temperature decreases results in lower observed hardness values at 21 and 33 C.
Example 7 di-Aldehyde functional diazobenzene synthesis a) 4,4' -dibromoazobenzene synthesis 50 g. of p-bromoaniline (available from Sigma-Aldrich) and 1 liter of anhydrous benzene is added to a round bottom flask with stirring. 258 grams of finely powdered lead tetraacetate is added slowly over 3 hours. After one additional hour the lead diacetate is filtered off and the filtrate is washed thoroughly with 3 liters of water. After separating the benzene and aqueous layers, the benzene solution is concentrated to a volume of 100 ml.
The concentrate on cooling in ice yields 31 g. of a solid material that on sublimation in vacuum (0.001 mm.) within the temperature range of 200-250" (air-bath) gives 20 grams of 4,4'-dibromoazobenzene. The product is recrystallized from chloroform.
b) di-Aldehyde functional diazobenzene synthesis A solution of 10 grams of 4,4' -dibromo-azobenzene from the example above and 50 ml of diethyl ether (available from Sigma-Aldrich) is added dropwise to a dispersion of 2 grams of magnesium (available from Sigma-Aldrich) in 25m1 of diethyl ether in a round bottom flask equipped with nitrogen gas. After 3 hours at 25C, a solution of 3 grams of paraformaldehyde (available from Sigma-Aldrich) dissolved in 30 ml of diethyl ether is added dropwise over a 30 minute period. After stirring for an additional 8 hours, the solution is acidified with an aqueous solution of 0.1N HC1 (available from Sigma-Aldrich).
The ether solution is filtered from the solids and extracted with 0.1N sodium bicarbonate solution, followed by extractions with water. The ether layer is vacuum dried and 2 grams of the product is dissolved into 50m1 of acetonitrile. A solution of 5 grams of sodium periodate (NaI04) in 10 milliliters of water and this is added to the product from the previous step dissolved in acetonitrile. The reaction mixture is diluted with 200 mL of methylene chloride and filtered. The resin is thoroughly washed with methylene chloride and combined washings and filtrates are purified on silica-gel plates or silica-gel column.
IR and 1H NMR spectral data confirm the identity of the product.
c) Re s orcin capsule In a 400 mL beaker, 5.5 g resorcin are dissolved in water while stirring (stirring speed:
approximately 1,500 rpm) and then mixed with 2.0 g sodium carbonate solution (20 wt %), upon which the pH is 7.9. The solution is heated to a temperature of approximately 52 C. 20 g glutardialdehyde are then added.
The mixture is stirred for approximately an additional 10 minutes at a stirring speed of approximately 1,500 rpm and a temperature of approximately 52 C (pre-condensation time).
Afterward, approximately 20 g water are added and approximately 2 minutes later, 1 g of one of the protective colloids (a) copolymer 1.1a, (b) copolymer 1.1b and (c) poly-AMPS (AMPS
homopolymer) is added and approximately another 2 minutes later 55 g butyl phenylacetate (CAS No. 122-43-0; aromatic substance with a honey-like aroma) and 5.5 g of di-Aldehyde functional diazobenzene are added. Immediately afterward, the stirring speed is increased to approximately 4,000 rpm and at approximately the same time, 20.0 g sodium carbonate solution (20 wt %) are added. Afterward the pH of the mixture is approximately 9.7.
Subsequently, the viscosity and the volume of the mixture increase. Stirring is continued at a stirring speed of approximately 4,000 rpm until the viscosity drops again. Only then is the stirring speed reduced to approximately 1,500 rpm. The preparation is stirred for an additional approximately 60 minutes at a temperature of approximately 52 C and at a roughly constant stirring speed. This phase is also called the dwell phase. The mixture is then heated to approximately 80 C and the capsules are hardened at this temperature for a period of 3 hours.
Capsule size distribution ¨ D (90) 5 to 10 pm; encapsulation efficiency approx. 90%;
Drying yield > 90%; solids of the slurry approximately 40 wt %.

The capsules produced are formaldehyde-free and can be processed without any problems from the aqueous slurry into a dry, free-flowing powder as stable core/shell microcapsules.
The capsules can also be loaded with other gaseous, liquid or solid hydrophobic materials and substance classes instead of with butyl phenyl acetate, in particular with aromatic substances and/or perfume oils. One aliquot of capsules are subjected to pressure and a second aliquot are subjected to electromagnetic radiation both aliquots demonstrate trigger release of their core materials.
The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as "40 mm" is intended to mean "about 40 mm."
Every document cited herein, including any cross referenced or related patent or application and any patent application or patent to which this application claims priority or benefit thereof, is hereby incorporated herein by reference in its entirety unless expressly excluded or otherwise limited. The citation of any document is not an admission that it is prior art with respect to any invention disclosed or claimed herein or that it alone, or in any combination with any other reference or references, teaches, suggests or discloses any such invention.
Further, to the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in this document shall govern.
While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.

Claims (15)

78What is claimed is:

1. A composition comprising i) surfactants and/or builders, as well as ii) microcapsules comprising a wall having an exterior surface and a core, said wall encapsulating said core, said wall comprising a resin which can be obtained by reacting a) at least one aromatic alcohol or its ether or derivatives with b) at least one aldehydic component which comprises at least two c-atoms per molecule, and c) optionally in the presence of at least one (meth)acrylate polymer iii) a material selected from the group consisting of a hueing dye, a structurant, a density balancing agent, a deposition aid, a perfume delivery system in addition to said microcapsules, a fabric softener and mixtures thereof.

2. The composition of Claim 1 wherein said microcapsules comprise a deposition aid comprising a material selected from the group consisting of poly(meth)acrylate, poly(ethylene-maleic anhydride), polyamine, wax, polyvinylpyrrolidone, polyvinylpyrrolidone co-polymers, polyvinylpyrrolidone-ethyl acrylate, polyvinylpyrrolidone- vinyl acrylate, polyvinylpyrrolidone methylacrylate, polyvinylpyrrolidone/vinyl acetate, polyvinyl acetal, polyvinyl butyral, polysiloxane, poly(propylene maleic anhydride), maleic anhydride derivatives, co-polymers of maleic anhydride derivatives, polyvinyl alcohol, styrene-butadiene latex, gelatin, gum Arabic, carboxymethyl cellulose, carboxymethyl hydroxyethyl cellulose, hydroxyethyl cellulose, other modified celluloses, sodium alginate, chitosan, casein, pectin, modified starch, polyvinyl acetal, polyvinyl butyral, polyvinyl methyl ether/maleic anhydride, polyvinyl pyrrolidone and its co polymers, poly(vinyl pyrrolidone/methacrylamidopropyl trimethyl ammonium chloride), polyvinylpyrrolidone/vinyl acetate, polyvinyl pyrrolidone/dimethylaminoethyl methacrylate, polyvinyl amines, polyvinyl formamides, polyallyl amines and copolymers of polyvinyl amines, polyvinyl formamides, and polyallyl amines and mixtures thereof, said deposition aid coating the exterior of said microcapsules' wall.

3. The composition according to any preceding claims wherein:
a) said structurant comprising a material selected from the group consisting of castor oil, hydrogenated castor oil, polysaccharides, modified celluloses, modified proteins, inorganic salts, quaternized polymeric materials, imidazoles;
nonionic polymers having a pKa less than 6.0, polyurethanes, plant cellulose, bacterial cellulose, coated bacterial cellulose, non-polymeric crystalline hydroxyl-functional materials, polymeric structuring agents, di-amido gellants and mixtures thereof;
b) said hueing dye is selected from the group consisting of small molecule dyes, polymeric dyes, dye-clay conjugates, and organic and inorganic pigments, in one aspect, said hueing dye comprises a chromophore selected from one or more of the following: acridine, anthraquinone, azine, azo, azulene, benzodifurane and benzodifuranone, carotenoid, coumarin, cyanine, diazahemicyanine, diphenylmethane, formazan, hemicyanine, indigoids, methane, naphthalimides, naphthoquinone, nitro and nitroso, oxazine, phthalocyanine, pyrazoles, stilbene, styryl, triarylmethane, triphenylmethane, xanthenes and mixtures thereof;
c) said additional perfume delivery comprises a material selected from the group consisting of a second microcapsule, a polymer assisted delivery system; a molecule-assisted delivery system; a fiber-assisted delivery system; a cyclodextrin delivery system; a starch encapsulated accord; and/or an inorganic carrier delivery system;
d) said fabric softener comprises from 1% to 49% by weight of the composition of a bis-(2-hydroxypropyl)-dimethylammonium methylsulphate fatty acid ester having a molar ratio of fatty acid moieties to amine moieties of from 1.85 to 1.99, an average chain length of the fatty acid moieties of from 16 to 18 carbon atoms and an iodine value of the fatty acid moieties, calculated for the free fatty acid, of from 0.5 to 60.

4. The composition according to any preceding claim, wherein the at least one aromatic alcohol (ii)(a) is chosen from phenols, o-cresol, m-cresol, p-cresol, a-naphthol, 13-naphthol, thymol, catechol, resorcin, hydroquinone and 1,4-naphthohydroquinone, phloroglucin, pyrogallol and hydroxy hydroquinone, and is in particular resorcinol and/or phloroglucin.

5. The composition according to any preceding claim, characterized in that the aldehydic component (ii)(b) is chosen from valeraldehyde, capronaldehyde, caprylaldehyde, decanal, succindialdehyde, cyclohexanecarbaldehyde, cyclopentanecarbaldehyde, 2-methyl-1-propanal, 2-methylproprionaldehyde, acetaldehyde, acrolein, aldosterone, antimycin A, 8'-apo-.beta.-carotene-8'-al, benzaldehyde, butanal, chloral, citral, citronellal, crotonaldehyde, dimethylaminobenzaldehyde, folinic acid, fosmidomycin, furfural, glutaraldehyde, glycerin aldehyde, glycol aldehyde, glyoxal, glyoxylic acid, heptanal, 2- hydroxybenzaldehyde, 3-hydroxy butanal, hydroxy methyl furfural, 4-hydroxynonenal, isobutanal, isobutyraldehyde, methacrolein, 2-methylundecanal, mucochloric acid, N-methylformamide, 2-nitrobenzaldehyde, nonanal, octanal, oleocanthal, orlistate, pentanal, phenyl ethanal, phycocyanin, piperonal, propanal, propenal, protocatechualdehyde, retinal, salicylaldehyde, secologanin, streptomycin, strophanthidin, tylosin, vanillin, and cinnamic aldehyde, but preferably has at least two free aldehyde groups per molecule, in particular glutar-and/or succindialdehyde.

6. The composition according to any preceding claim, characterized in that the (meth)acrylate polymer is a homo- or copolymer of a polar functionalized (meth)acrylate monomer, preferably one containing a sulfonic acid group, wherein the (meth)acrylate polymer is in particular a copolymer of 2-acrylamido-2-methyl propanesulfonic acid or its salts along with one or more other (meth)acrylate monomers, chosen from the group of (meth)acrylates, vinyl compounds, unsaturated di- or polycarboxylic acids and the salts of amyl compounds or allyl compounds.

7. The composition according to any preceding claim, characterized in that it contains the microcapsules named in Claim 1 in amounts of 0.0001 to 50 wt %, preferably 0.01 to 20 wt %, 0.05 to 5%, 0.1 to 5 wt %, or 0.1 to 2%, based on the product as a whole.

8. The composition according to any preceding claim, characterized in that it contains 0.05 wt % to 50 wt %, advantageously 1 to 40 wt %, preferably 3 to 30 wt % and in particular wt % to 20 wt % surfactant(s) chosen from the groups of anionic surfactants, nonionic surfactants, cationic, zwitterionic and/or amphoteric surfactants, the wt %
based on the product as a whole, preferably it contains nonionic surfactant, advantageously in amounts from 0.01 to 25 wt %, more advantageously from 1 to 20 wt %, and in particular in amounts from 3 to wt %, based on the product as a whole.

9. The composition according to any preceding claim, characterized in that it contains from 0.1 to 80 wt %, advantageously 1 to 60 wt %, and more advantageously 5 to 50 wt % builders, based on the product as a whole.

10. The composition according to any preceding claim, characterized in that it contains a soluble builder system, preferably comprising soda, silicate, citrate and/or polycarboxylates.

11. The composition according to any preceding claim, characterized in that the microcapsules contain aromatic substances.

12. A method for manufacturing a liquid composition, characterized by stirring in a microcapsule dispersion comprising microcapsules, the capsule walls of which contain a resin, which can be obtained by reacting a) at least one aromatic alcohol or its ether or derivatives with b) at least one aldehydic component that has at least two C atoms per molecule, and c) optionally in the presence of at least one (meth)acrylate polymer in a liquid composition or by continuously adding said microcapsule dispersion into a liquid composition and mixing the ingredients by means of static mixing elements, wherein the microcapsule dispersion was in each instance preferably mixed with surfactant beforehand.

13. A method for manufacturing a solid composition, selected from the group consisting of (a) by mixing a microcapsule dispersion comprising microcapsules, the capsule walls of which contain a resin which can be obtained by reacting:
(i) at least one aromatic alcohol or its ether or derivatives with (ii) at least one aldehydic component that has at least two C atoms per molecule, and (iii) optionally in the presence of at least one (meth)acrylate polymer into a solid composition;
(b) by mixing said microcapsules in granulated or supported form into a solid composition;
or (c) by mixing said microcapsules in dried form into the solid composition.

14. Use of a product according to any of Claims 1 through 11 in a washing or cleaning process to deposit microcapsules on the treated object to enable the targeted release of, preferably, liquid active substances such as, in particular, aromatic substances, onto the objects by mechanical stimulus.

15. Use of a product according to any of Claims 1 through 11 in a washing or cleaning process to deposit microcapsules on the treated object to enable the long-lasting release of, preferably, liquid active substances such as, in particular, aromatic substances, onto the objects by diffusion.