WO2007128326A1

WO2007128326A1 - Perfume delivery system for cleaners

Info

Publication number: WO2007128326A1
Application number: PCT/EP2006/004108
Authority: WO
Inventors: Felix Müller; Jörg Peggau; Herbert Schramm
Original assignee: Evonik Goldschmidt Gmbh
Priority date: 2006-05-03
Filing date: 2006-05-03
Publication date: 2007-11-15

Abstract

Perfume delivery systems, comprising insoluble carrier par ticles with surface silanols, which have been grafted with an organosilane and carry amino functional groups, a poly mer with positively charged functional groups added to said carrier particles and a fragrance adsorbed to or absorbed into the carrier particles. The perfume delivery systems impart a long lasting fragrance to hard surfaces treated with compositions containing the perfume delivery system.

Description

Perfume Delivery System for Cleaners

Field of the invention

The invention relates to perfume delivery systems, comprising insoluble carrier particles with surface silanols, which have been grafted with an organosilane and which carry amino groups, a polymer carrying positively charged functional groups and a fragrance adsorbed to or absorbed into the carrier particles. The perfume delivery systems impart a long lasting fragrance to surfaces treated with compositions containing the perfume delivery system.

Background of the invention

Household care products such as cleaners or dish washing liquids usually contain a perfume. The perfume does not only mask unpleasant odors of some of the components of the product but also impart surfaces treated with the product with a pleasing fragrance.

Perfumes are among the most expensive ingredients of household care products and therefore it is desirable to have as much as possible of the perfume contained in the product remain on the surface treated. For these products there is a need for perfume delivery systems that are substantive on surfaces. Such a perfume delivery system should also provide a delayed release of perfume to impart the treated surface with a long lasting fragrance, starting with a moderate level of fragrance intensity that is not perceived as offensive. In the fabric care area, some technologies are already known .

GB 1 306 924 discloses finely divided silica and finely divided silica gel as carrier particles for perfume oils. With these carrier particles, liquid perfume oils can be formulated as free flowing powders comprising up to 70 wt. -% of the perfume oil.

US 5,840,668 discloses perfumed laundry detergent powders. The disclosed detergents contain a perfume on carrier system comprising amorphous silica as the carrier. The experiments described in column 7, line 58 to column 9, line 26 demonstrate that perfume adsorbed onto carrier particles of silica is rapidly released into an aqueous wash liquor in the presence of only small amounts of surfactants. Therefore, such a perfume delivery system will not be efficient in delivering a perfume to a fabric treated with the disclosed detergent.

US 4,954,285 discloses the incorporation of such silica particles having a perfume adsorbed thereon into solid dryer-activated fabric softener compositions . The document discloses in column 4, lines 53 to 55 that the perfumed silica particles will release perfume when they are wetted with an aqueous fluid. In accordance with this teaching, the document discloses particles of the fabric softener composition comprising perfumed silica particles having an additional water insoluble coating for the application of the fabric softener in an aqueous process.

US 4,954,285 discloses a perfume containing carrier consisting of particles of . a smectite type clay or a zeolite with a perfume absorbed into the particle, having a coating of a fabric adhesive agent, which is preferably a quaternary ammonium compound. The perfume delivery system is used in a laundry detergent and the document discloses an increased level of fragrance .for fabrics washed with such a laundry detergent compared to fabrics washed with a laundry detergent containing the perfume without a carrier system. However, the perfume delivery system disclosed in US 4,536,315 still has the drawback that surfactants or dis- persants can easily remove the coating of the particles during the process of treating the fabrics, which will diminish the efficiency of perfume delivery.

US 5,476,660 discloses compositions for depositing an active substance, such as a perfume, onto a target surface, such as a fabric, containing carrier particles with a cati- onic surface, having positively charged organocarbyl groups, and an active substance absorbed or adsorbed by the carrier particles . The carrier particles can be made by coating a solid material like porous silica, zeolite or Ia- tex particles with a polymer, which has pendant positively charged groups. An alternative way of making the carrier particles is by grafting a solid material, which has surface reactive groups, with one or more polymers containing difunctional organocarbyl groups.

US 6,020,302 discloses color care compositions comprising a polymer with a polyamine backbone modified via quaterniza- tion, substitution or oxidation and optionally a perfume protected by carrier materials such as zeolites, starch, cyclodextrin or wax. The document contains no teaching on the fragrance intensity of fabrics treated with such compositions . It has now been found that a perfume delivery system, comprising insoluble carrier particles, a polymer carrying positively charged functional groups and a fragrance adsorbed to or absorbed into the carrier particles, can be improved by using carrier particles with surface silanols and grafting the surface silanols with at least one or- ganosilane which carries amino groups . Such perfume delivery systems comprising carrier particles grafted with an organosilane with amino groups surprisingly impart a stronger and longer lasting fragrance to hard surfaces treated with compositions containing the perfume delivery system compared to perfume delivery systems comprising carrier particles that are not grafted.

Summary of the invention

The present invention relates to a perfume delivery system comprising as a first component water insoluble carrier particles having surface silanol groups, wherein at least part of said silanol groups are substituted with organic residues by grafting with at least one organosilane and wherein at least part of said organic residues carry amino groups, as a second component at least one polymer which carries positively charged functional groups and as a third component a fragrance adsorbed to or absorbed into said carrier particles.

The invention also provides a process for making a perfume delivery system of the present invention comprising the steps reacting water insoluble carrier particles having surface silanol groups with an organosilane having at least one organic residue comprising at least one amino group to obtain carrier particles, wherein at least part of said silanol groups are substituted with organic residues carry- ing said amino groups, adding at least one polymer carrying positively charged functional groups to said carrier particles, and contacting the obtained particles with a fragrance to adsorb said fragrance onto said particles or absorb said fragrance into said particles.

The invention also provides compositions comprising the perfume delivery system of the present invention in practical use in carpet care or bathroom care.

Detailed description of the invention

I) Carrier Particles

The perfume delivery system of the invention comprises water insoluble carrier particles which initially have surface silanol groups. Such surface silanol groups are hydroxy groups directly bonded to a silicon atom of the carrier particles, which are accessible on the surface and can undergo condensation reactions. The carrier particles may be both inorganic materials or hybrid organic-inorganic polysiloxanes carrying surface silanol groups. Preferably, the carrier particles are inorganic particles selected from silicas, silica gels, silicates or aluminum silicates. The carrier particles of the perfume delivery system of the invention can also be mixtures of these materials. The silicates and aluminum silicates used as carrier particles for the invention preferably contain alkali metal ions or alkali earth metal ions to compensate any extra negative charge of the material. Preferably, negative charges are compensated by sodium ions .

In a preferred embodiment of the invention, the carrier particles are silicas, selected from the group comprising of precipitated silicas, fumed silicas and silica gels. In another preferred embodiment of the invention, the insoluble carrier particles are aluminum silicates with a zeolite structure. Most preferably, the zeolite is a large pore zeolite selected from the group comprising of zeolite X, zeolite Y and dealuminated zeolite Y.

The water insoluble carrier particles preferably have a high specific surface area of more than 30 m² /g and pref- erably more than 100 m²/g. The carrier particles may be porous particles, such as precipitated silicas, where the specific surface is largely due to the pores of the particles. The water insoluble carrier particles may also be non-porous particles, such as fumed silicas, where the par- tides are composed of small primary particles having a high geometric outer surface.

The insoluble carrier particles may be small size particles with a particle size in the range of 0.1 to 10 μm. Alter- natively, large size particles with a particle size in the range of 10 to 100 μm may be used, which are preferably attained by agglomeration of smaller size particles. Small size carrier particles are preferred, if the perfume delivery system is to be used in a liquid formulation having low viscosity, to avoid settling of the particles. Large size particles are preferred for a convenient handling of the perfume delivery system and to avoid dust formation during the handling.

The surface silanol groups of the insoluble carrier particles are partially or completely substituted with organic residue by a grafting reaction with at least one organosi- lane. The term organosilane here stands for a silicon compound that carries at least one organic residue bonded to a silicon atom through a silicon-carbon bond and which carries at least one reactive group bonded to silicon that is capable of reacting with a silanol group in a grafting reaction. A grafting reaction is a reaction that forms a covalent Si-O-Si linkage between a silicon atom of the carrier particle and a silicon atom of the organosilane . The grafting reaction leads to a permanent covalent bonding of the organic residue of the organosilane to the surface of the carrier particles.

The organosilanes used for grafting preferably comprise two or three functional groups that are reactive in the grafting reaction, such as chloride, alkoxide or hydroxide bonded to silicon, to enable the formation of multiple linkages between the organosilane and the particle surface in the grafting reaction-. Mixtures of two or more organosilanes may be used to obtain the desired composition of organic residue grafted to the carrier particle surface.

At least part of the organic residues grafted to the carrier particle surface carry amino groups. Preferably, at least part of these amino groups are primary amino groups. In a preferred embodiment, each of the organic residues carries at least one amino group. The organic residues may carry one amino group per residue or several amino groups per residue.

The amino group may already be comprised in the organosilane before the organosilane is reacted with the surface silanol groups of the carrier particles in the grafting reaction. In an alternative embodiment, the carrier particles are grafted with an organosilane which carries one or more functional groups other than amino groups which are converted to amino groups after the silane has been grafted onto the carrier particle surface. An example of this embodiment is a carrier particle, which is first grafted with an organosilane comprising one or more epoxy groups and which after the grafting reaction is reacted with a primary or secondary amine to convert at least part of the epoxy groups to the corresponding vicinal hydroxyamine groups .

The size and the composition of the organic residues grafted onto the surface of the carrier particles may be selected in a wide range, as long as at least part of the organic residues carry amino groups. Preferably, the organic residues comprise from 2 to 20 carbon atoms.

It is preferred to select the carrier particle and the at least one organosilane in such a manner as to provide, after grafting, a carrier particle that has a hydrophilic surface and therefore will be wetted when in contact with water. Carrier particles with a hydrophilic surface have the advantage of being easily dispersed in aqueous formulations .

II) Positively charged polymer

The perfume delivery system of the invention further comprises at least one polymer carrying positively charged functional groups, which is added to the carrier particles.

The term polymer as used in this invention stands for a molecule made up of one or more repetitive monomer units which comprises at least 10 identical repetitive monomer units. The term polymer encompasses both homopolymers made up of a single monomer unit or copolymers made up of two or more different monomer units. Such copolymers may be random copolymers with a statistical distribution of different monomer units, regular copolymers with alternating monomer units or block copolymers with alternating homopolymer blocks of different monomer units. The term polymer as used in this invention also encompasses any polymer that is modified by functional groups grafted onto the polymer molecule by covalent bonding.

The polymer used in the perfume carrier of the invention carries at least one kind of positively charged functional groups. Suitable positively charged functional groups are ammonium, phosphonium, sulfonium, amidinium, guanidinium or pyridinium functional groups. Preferably, the positively- charged functional groups are functional groups with a per- manent positive charge independent of the pH value of the medium surrounding the polymer. Most preferably, the positively charged functional groups are quaternary ammonium groups . The positive charges of the functional groups are conveniently compensated by counter ions such as chlo- ride, bromide, sulfate, phosphate, carbonate, hydrogencar- bonate, methylsulfate or the like.

Suitable polymers may be obtained by polymerizing one or more kinds of monomers carrying a positive charge, option- ally with one or more comonomers which do not carry a positive charge. A suitable example of a polymer composed of only one kind of monomer is poly-diallyldimethylammonium chloride, known as polyquaternium-6. Examples of suitable copolymers composed of both monomers carrying a positive charge and monomers not carrying a positive charge are polyquaternium-5, polyquaternium-7 and polyquaternium-22.

Alternatively, suitable polymers may be obtained by reacting a polymer, which does not contain a substantial num- ber of positively charged functional groups, with a reagent, which reacts with functional groups of the polymer to generate positively charged functional groups covalently linked to the polymer. Such polymers may be obtained for example by reacting a polymer comprising amino functional groups with an alkylating agent, such as dimethylsulfate, diethylsulfate, dimethylcarbonate, methyl chloride, methyl bromide or benzyl chloride. Alternatively, such polymers may be obtained by reacting a polymer comprising amino or hydroxy functional groups with a quaternary ammonium compound comprising an epoxy or chlorohydrin functional group, such as trimethyl-1- (2, 3-epoxypropyl) ammonium chloride or trimethyl-1- (3-chloro-2-hydroxypropyl) ammonium chloride. A further way of preparing such polymer is by reacting a polymer having easily abstractable hydrogen atoms with di- allyldimethylammonium chloride in the presence of a radical starter.

Preferably, the polymer carrying positively charged func- tional groups is composed of one or more carbohydrate monomer units, such as for example glucose, fructose, ara- binose, xylose, fucose, galactose, mannose, galacturonic acid, glucuronic acid, mannuronic acid, guluronic acid, galactosamine or glucoseamine . Most preferred are polymers obtained from starch, cellulose, guar gum or locust bean gum or from modified starches or celluloses, such as hy- droxymethyl starch, hydroxyethyl starch, carboxymethyl starch, hydroxymethyl cellulose, hydroxyethyl cellulose or carboxymethyl cellulose by reaction with a quaternary ammo- nium compound comprising an epoxy or chlorohydrin functional group, such as trimethyl-1- (2 , 3-epoxypropyl) ammonium chloride or trimethyl-1- (3-chloro-2-hydroxypropyl) ammonium chloride or by reaction with diallyldimethylammonium chloride in the presence of a radical starter. Starches from any kind of source, such as potato starch, corn starch, wheat starch, tapioka starch, sago starch or rice starch, can be used. An example of such a most preferred polymer is the reaction product of hydroxyethyl cellulose with trimethyl-1- (2, 3-epoxypropyl) ammonium chloride, known as polyquaternium-10, available from National Starch & Chemical under the trade name Celquat SC-240C. Another example is the reaction product of hydroxyethyl cellulose with diallyldimethylammonium chloride, known as polyquaternium-4 , available from National Starch & Chemical under the trade name Celquat H-IOO. The most preferred polymers obtained from modified starches or celluloses have the advantage of being readily biodegradable.

The polymer carrying positively charged functional groups preferably has a molecular weight in the range of from 1,000 to 10,000,000 g/mol and more preferably 5,000 to 5,000,000 g/mol.

The weight ratio of polymer to carrier particles is preferably selected to be from 0.001 to 0.5, more preferably from 0.005 to 0.2 and most preferably from 0.01 to 0.1.

Ill) Fragrance

The perfume delivery system of the invention further comprises a fragrance adsorbed to or absorbed into the water insoluble carrier particles. The fragrance comprises one or more fragrant compounds and may in addition comprise one or more suitable solvents and further additives, such as anti^¬ oxidants. The fragrance is applied to the carrier particles in a liquid state, either as such or as a solution in one or more suitable solvents. Application of the fragrance onto the carrier particles may be achieved by any suitable process, such as spraying the fragrance or a fragrance solution onto the carrier particles in a mixer or in a fluidized bed. If the perfume delivery system comprises nonporous carrier particles, the fragrance will be adsorbed to the surface of such carrier particles. If the perfume delivery system comprises porous carrier particles, most of the fragrance will be absorbed into the pores of the carrier particles. The composition of the fragrance and the nature of the fragrant compounds can be selected within a wide range and is not limited, as long as the fragrant compounds are sufficiently stable in contact with the material of the water insoluble carrier particles. If the perfume delivery system is intended to be used in an aqueous formulation or for applications in aqueous systems, the fragrant compounds contained in the fragrance are preferably selected from compounds having a low solubility in water.

Suitable fragrant compounds are for example adoxal (2, 6, lO-trimethyl-9-undecen-l-al) , amyl acetate, amyl salicylate, anisic aldehyde (4-methoxy benzaldehyde) , bacdanol (2-ethyl-4- (2,2, 3-trimethyl-3-cyclopenten-l-yl ) - 2-buten-l-ol) , benzaldehyde, benzophenone, benzyl acetate, benzyl salicylate, 3-hexen-l-ol, cetalox (dodecahydro- 3A, 6, 6, 9A-tetramethylnaphtho [2, IB] -furan) , cis-3-hexenyl acetate, cis-3-hexenyl salicylate, citronellol, coumarin, cyclohexyl salicylate, cymal (2-methyl-3-

(4-isopropylphenyl ) propionaldehyde) , decyl aldehyde, ethyl vanillin, ethyl-2-methyl butyrate, ethylene brassylate, eucalyptol, eugenol, exaltolide (cyclopentadecanolide) , florhydral (3- (3-isopropylphenyl) butanal), galaxolide

(1,3,4,6,7, 8-hexahydro-4, 6,6,7,8, 8-hexamethylcyclopenta- gamma-2-benzopyrane) , gamma-decalactone, gamma-do- decalactone, geraniol, geranyl nitrile, helional (alpha- methyl-3, 4- (methylenedioxy) hydrocinnamaldehyde) , heliotro- pin, hexyl acetate, hexyl cinnamic aldehyde, hexyl salicylate, hydroxyambran (2-cyclododecyl-propanol) , hydroxy- citronellal, iso E super (7-acetyl- 1,2,3,4,5,6,7, 8-octahydro-l, 1,6,7, tetramethyl naphthalene) , iso-eugenol, iso-jasmone, koavone (acetyl di-isoamylene) , lauric aldehyde, lrg 201 (2, 4-dihydroxy-3, 6-dimethyl benzoic acid methyl ester), lyral (4- (4-hydroxy-4-methyl-pen- tyl) -3-cylcohexene-l-carboxaldehyde) , majantol

(2, 2-dimethyl-3- (3-methylphenyl) -propanol) , mayol (4- (1-methylethyl) cyclohexane methanol), methyl anthranil- ate, methyl beta-naphthyl ketone, methyl cedrylone (methyl cedrenyl ketone), methyl chavicol ( l-methyloxy-4 , 2-propen- 1-yl benzene) , methyl dihydrojasmonate, methyl nonyl acet- aldehyde, musk indanone (4-acetyl-6-tert-butyl-l, 1-dimethy- lindane), nerol, nonalactone (4-hydroxynonanoic acid lactone), norlimbanol ( 1- (2 , 2, 6-trimethyl-cyclohexyl) -3-hexa- nol), P. T. bucinal (2-methyl-3 (4-tert-butylphenyl) propi- onaldehyde) , para-hydroxyphenylbutanone, patchouli, phenyl acetaldehyde, phenyl ethyl acetate, phenyl ethyl alcohol, phenyl ethyl phenyl acetate, phenyl hexanol/phenoxanol (3- methyl-5-phenylpentanol) , polysantol (3, 3-dimethyl-5-

(2, 2, 3-trimethyl-3-cyclopenten-l-yl) -4-penten-2-ol) , rosa- phen (2-methyl-5-phenyl-pentanol) , sandalwood, alpha-ter- pinene, tonalid/musk plus (7-acetyl-l, 1 , 3, 4 , 4 , 6-hexamethyl- tetralin) , undecalactone, undecavertol ( 4-methyl-3-decen-5- ol) , undecyl aldehyde, undecenylic aldehyde, vanillin, al- IyI amyl glycolate, allyl anthranilate, allyl benzoate, al- IyI butyrate, allyl caprate, allyl caproate, allyl cinnam- ate, allyl cyclohexane acetate, allyl cyclohexane butyrate, allyl cyclohexane propionate, allyl heptoate, allyl nonanoate, allyl salicylate, amyl cinnamyl acetate, amyl cinnamyl formate, cinnamyl formate, cinnamyl acetate, cy- clogalbanate, geranyl acetate, geranyl acetoacetate, geranyl benzoate, geranyl cinnamate, methallyl butyrate, methallyl caproate, neryl acetate, neryl butyrate, amyl cinnamyl formate, alpha-methyl cinnamyl acetate, methyl geranyl tiglate, mertenyl acetate, farnesyl acetate, fen- chyl acetate, geranyl anthranilate, geranyl butyrate, geranyl iso-butyrate, geranyl caproate, geranyl caprylate, geranyl ethyl carbonate, geranyl formate, geranyl furoate, geranyl heptoate, geranyl methoxy acetate, geranyl pelargo- nate, geranyl phenylacetate, geranyl phthalate, geranyl propionate, geranyl iso-propoxyacetate, geranyl valerate, geranyl iso-valerate, trans-2-hexenyl acetate, trans- 2-hexenyl butyrate, trans-2-hexenyl caproate, trans- 2-hexenyl phenylacetate, trans-2-hexenyl propionate, trans- 2-hexenyl tiglate, trans-2-hexenyl valerate, beta-pentenyl acetate, alpha-phenyl allyl acetate, prenyl acetate, tri- chloromethylphenylcarbinyl acetate, secondary-n-amyl acetate, ortho-tertiary-amyl-cyclohexyl acetate, isoamyl benzyl acetate, sec-n-amyl butyrate, amyl vinyl carbinyl acetate, amyl vinyl carbinyl propionate, cyclohexyl salicylate, dihydro-nor-cyclopentadienyl acetate, dihydro-nor-cy- clopentadienyl propionate, isobornyl acetate, isobornyl salicylate, isobornyl valerate, flor acetate, frutene, 2- methylbuten-2-ol-4-acetate, methyl phenyl carbinyl acetate, 2-methyl-3-phenyl propan-2-yl acetate, prenyl acetate, 4- tert-butyl cyclohexyl acetate, verdox (2-tert-butyl cyclo- hexyl acetate) , vertenex, (4-tert-butylcyclohexyl acetate) , Violiff (carbonic acid- 4-cycloocten-l-yl methyl ester), ethenyl-iso-amyl carbinylacetate, fenchyl acetate, fenchyl benzoate, fenchyl-n-butyrate, fenchyl isobutyrate, laevo- menthyl acetate, dl-menthyl acetate, menthyl anthranilate, menthyl benzoate, menthyl-iso-butyrate, menthyl formate, laevo-menthyl phenylacetate, menthyl propionate, menthyl salicylate, menthyl-iso-valerate, cyclohexyl acetate, cyclohexyl anthranilate, cyclohexyl benzoate, cyclohexyl butyrate, cyclohexyl-iso-butyrate, cyclohexyl caproate, cy- clohexyl cinnamate, cyclohexyl formate, cyclohexyl hep- toate, cyclohexyl oxalate, cyclohexyl pelargonate, cyclohexyl phenylacetate, cyclohexyl propionate, cyclohexyl thioglycolate, cyclohexyl valerate, cyclohexyl-iso-valer- ate, methyl amylacetate, methyl benzyl carbinyl acetate, methyl butyl cyclohexanyl acetate, 5-methyl-3-butyl-tetra- hydropyran-4-yl acetate, methyl citrate, methyl-iso-campho- late, 2-methyl cyclohexyl acetate, 4-methyl cyclohexyl acetate, 4-methyl cyclohexyl methyl carbinyl acetate, methyl ethyl benzyl carbinyl acetate, 2-methylheptanol-6-acetate, methyl heptenyl acetate, alpha-methyl-n-hexyl carbinyl formate, methyl-2-methylbutyrate, methyl nonyl carbinyl acetate, methyl phenyl carbinyl acetate, methyl phenyl carbinyl anthranilate, methyl phenyl carbinyl benzoate, methyl phenyl carbinyl-n-butyrate, methyl phenyl carbinyl-iso-bu- tyrate, methyl phenyl carbinyl caproate, methyl phenyl carbinyl caprylate, methyl phenyl carbinyl cinnamate, methyl phenyl carbinyl formate, methyl phenyl carbinyl phenylacetate, methyl phenyl carbinyl propionate, methyl phenyl car- binyl salicylate, methyl phenyl carbinyl-iso-valerate, 3- nonyl acetate, 3-nonenyl acetate, nonane diol-2 , 3-acetate, nonynol acetate, 2-octyl acetate, 3-octyl acetate, n-octyl acetate, secondary-octyl-iso-butyrate, beta-pentenyl acetate, alpha-phenyl ally! acetate, phenylethyl methyl car- binyl-iso-valerate, phenylethyleneglycol diphenylacetate, phenylethyl ethnyl carbinyl acetate, phenylglycol diace- tate, seconday-phenylglycol monoacetate, phenylglycol mono- benzoate, isopropyl caprate, isopropyl caproate, ispropyl caprylate, isopropyl cinnamate, para-isopropyl cyclohexyl acetate, propylglycol diacetate, propyleneglycol di-isobu- tyrate, propyleneglycol dipropionate, isopropyl-n-heptoate, isopropyl-n-hept-1-yne carbonate, isopropyl pelargonate, isopropyl propionate, isopropyl undecylenate, isopropyl- n-valerate, isopropyl-n-valerate, isopropyl-iso-valerate, isopropyl sebacinate, isopulegyl acetate, isopulegyl aceto- acetate, isopulegyl isobutyrate, isopulegyl formate, thymyl propionate, alpha-2, 4-trimethyl cyclohexane methylacetate, trimethyl cyclohexyl acetate, vanillin triacetate, vanil- lylidene diacetate, vanillyl vanillate, tert-amyl acetate, caryophyllene acetate, cedrenyl acetate, cedryl acetate, dihydromyrcenyl acetate, dihydroterpinyl acetate, dimethyl benzyl carbinyl acetate, dimethyl benzyl carbinyl isobutyrate, dimethyl heptenyl acetate, dimethyl heptenyl formate, dimethyl heptenyl propionate, dimethyl heptenyl-iso-bu- tyrate, dimethyl phenylethyl carbinyl acetate, dimethyl phenylethyl carbinyl-iso-butyrate, dimethyl phenylethyl carbinyl-iso-valerate, dihydro-nor-dicyclopentadienyl acetate, dimethyl benzyl carbinyl butyrate, dimethyl benzyl carbinyl formate, dimethyl benzyl carbinyl propionate, dimethyl phenylethyl carbinyl-n-butyrate, dimethyl phenylethyl carbinyl formate, dimethyl phenylethyl carbinyl propionate, elemyl acetate, ethinyl cyclohexylacetate, eu- desmyl acetate, eugenyl cinnamate, eugenyl formate, iso- eugenyl formate, eugenyl phenylacetate, iso-eugenyl phenyl- acetate, guaiyl acetate, hydroxycitronellyl ethylcarbonate, linallyl acetate, linallyl anthranilate, linallyl benzoate, linallyl butyrate, linallyl iosbutyrate, linallyl carpro- ate, linallyl caprylate, linallyl cinnamate, linallyl cit- ronellate, linallyl formate, linallyl heptoate, linallyl-N- methylanthranilate, linallyl methyltiglate, linallyl pelar- gonate, linallyl phenylacetate, linallyl propionate, linallyl pyruvate, linallyl salicylate, linallyl-n-valerate, Ii- nallyl-iso-valerate, methylcyclopentenolone butyrate, methyl cyclopentenolone propionate, methyl ethyl phenyl carbinyl acetate, methyl heptinyl carbonate, methyl nico- tinate, myrcenyl acetate-, myrcenyl formate, myrcenyl propionate, cis-ocimenyl acetate, phenyl salicylate, terpinyl acetate, terpinyl anthranilate, terpinyl benzoate, ter- pinyl-n-butyrate, terpinyl-iso-butyrate, terpinyl cinnam- ate, terpinyl formate, terpinyl phenylacetate, terpinyl propionate, terpinyl-n-valerate, terpinyl-iso-valerate, tributyl acetylcitrate, amyl vinyl carbinyl acetate, amyl vinyl carbinyl propionate, hexyl vinyl carbinyl acetate, 3-nonenyl acetate, 4-hydroxy-2-hexenyl acetate, linallyl anthranilate, linallyl benzoate, linallyl butyrate, linallyl iso-butyrate, linallyl carproate, linallyl caprylate, linallyl cinnamate, linallyl citronellate, linallyl for- mate, linallyl heptoate, linallyl-N-methylanthranilate, linallyl methyltiglate, linallyl pelargonate, linallyl phenylacetate, linallyl propionate, linallyl pyruvate, linallyl salicylate, linallyl-n-valerate, linallyl-iso-valer- ate, myrtenyl acetate, nerolidyl acetate, nerolidyl bu- tyrate, beta-pentenyl acetate, alpha-phenyl allyl acetate, acetylfuran, allethrolone, allyl-ionone, allyl-pulegone, amyl-cyclopentenone, benzylideneacetone, benzylideneaceto- phenone, alpha-iso-methyl-ionone, 4- (2, 6, 6-trimetyl-l- cyclohexen-1-yl) -3-buten-2-one, beta-damascone (1- (2,6,6- trimethylcyclohexen-1-yl) -2-buten-l-one) , damascenone (1-

(2,6, 6-trimethyl-l, 3-cyclohexadien-l-yl) -2-buten-l-one) , delta-damascone (1- (2, 6, 6-trimethyl-3-cyclo-hexen-l-yl) -2- buten-1-one) , alpha-ionone (4- (2 , 6, 6-trimethyl-l-cyclohex- enyl-1-yl) -3-buten-2-one) , beta-ionone (4- (2 , 6, 6-trimethyl- 1-cyclohexen-l-yl) -3-butene-2-one) , gamma-methylionone (4- (2, 6, δ-trimethyl-2-cyclohexyl-l-yl) -3-methyl-3-buten-2- one), pulegone, acetaldehyde benzyl-beta-methoxyethylace- tal, acetaldehyde di-iso-amylacetal, acetaldehyde di-penta- nediolacetal, acetaldehyde di-n-propylacetal, acetaldehyde ethyl-trans-3-hexenylacetal, acetaldehyde phenylethyle- neglycolacetal, acetaldehydephenylethyl n-propylacetal, cinnamic aldehyde dimethylacetal, acetaldehyde benzyl-beta- methoxyethylacetal, acetaldehyde di-iso-amylacetal, acetaldehyde diethylacetal, acetaldehyde di-cis-3-hexenylacetal, acetaldehyde di-pentanediolacetal, acetaldehyde di- n-propylacetal, acetaldehyde ethyl-trans-3-hexenylacetal, acetaldehyde phenylethyleneglycolacetal, acetaldehyde phen- ylethyl-n-propylacetal, acetylvanillin dimethylacetal, al- pha-amylcinnamic aldehyde di-iso-propylacetal, p-tert-amylphenoxyacetaldehyde diethylacetal, anisaldehyde diethylacetal, anisaldehyde dimethylacetal, iso-apiole, benzaldehyde diethylacetal, benzaldehyde di- (ethylenegly- colmonobutylether) acetal, benzaldehyde dimethylacetal, ben- zaldehyde ethyleneglycolacetal, benzaldehyde glycerylace- tal, benzaldehyde propyleneglycolacetal, cinnamic aldehyde diethylacetal, citral diethylacetal, citral dimethylacetal, citral propyleneglycolacetal, alpha-methylcinnamic aldehyde diethylacetal, alpha-cinnamic aldehyde dimethylacetal, phenylacetaldehyde 2, 3-butyleneglycolacetal, phenylacetal- dehyde citronellyl-methylacetal, phenylacetaldehyde dial- lylacetal, phenylacetaldehyde diamylacetal, phenylacetaldehyde dibenzylacetal, phenylacetaldehyde dibutylacetal, phenylacetaldehyde diethylacetal, phenylacetaldehyde diger- anylacetal, phenylacetaldehyde dimethylacetal, phenylacetaldehyde ethyleneglycolacetal, phenylacetalde glycerylace- tal, citronellal cyclomonoglycolacetal, citronellal di- ethylacetal, citronellal dimethylacetal, citronellal di- phenylethylacetal, geranoxyacetaldehyde diethylacetal, ace- tone diethylketal, acetone dimethylketal, acetophenone di- ethylketal, methyl-amyl-catechol ketal, methyl-butyl-cate- chol ketal, anisaldehyde methylanthranilate, aurantiol (hy- droxycitronellal methylanthranilate), verdantiol (4-tert- butyl-alpha-methyldihydrocinnamaldehyde methylanthrani- late), vertosine (2, 4-dimethyl-3-cyclohexene carbaldehyde) , hydroxycitronellal ethylanthranilate, hydroxycitronellal linallylanthranilate, methyl-N- (4- ( 4-hydroxy-4-methylpen- tyl) -3-cyclohexenyl-methylidene) anthranilate, methyl- naphthylketone methylanthranilate, methyl-nonyl-acetalde- hyde methylanthranilate, methyl-N- (3, 5, 5-trimethylhexy- lidene) anthranilate, vanillin methylanthranilate, amyl acetate, amyl propionate, anethol, anisic aldehyde, an- isole, benzaldehyde, benzyl acetate, benzyl acetone, benzyl alcohol, benzyl butyrate, benzyl formate, benzyl iso-valer- ate, benzyl propionate, camphor gum, carvacrol, laevo-car- veol, d-carvone, laevo-carvone, citral (neral) , citro- nellol, citronellyl acetate, citronellyl isobutyrate, cit- ronellyl nitrile, citronellyl propionate, para-cresol, para-cresyl methyl ether, cyclohexyl ethyl acetate, cuminic alcohol, cuminic aldehyde, cyclal C (3, 5-dimethyl- 3-cyclohexene-l-carboxaldehyde) , para-cymene, decyl aldehyde, dimethyl benzyl carbinol, dimethyloctanol, diphenyl oxide, dodecalactone, ethyl acetate, ethyl acetoacetate, ethyl amyl ketone, ethyl benzoate, ethyl butyrate, ethyl hexyl ketone, ethyl phenyl acetate, eucalyptol, eugenol, fenchyl alcohol, geraniol, geranyl nitrile, hexenol, beta- gamma-hexenol, hexenyl acetate, cis-3-hexenyl acetate, hex- enyl isobutyrate, cis-3-hexenyl tiglate, hexyl acetate, hexyl formate, hexyl neopentanoate, hexyl tiglate, hydra- tropic alcohol, hydroxycitronellal, indole, alpha-irone, isoamyl alcohol, isobutyl benzoate, isomenthone, isononyl acetate, isononyl alcohol, isobutyl quinoline, isomenthol, para-isopropyl phenylacetaldehyde, isopulegol, isopulegyl acetate, isoquinoline, cis-jasmone, lauric aldehyde (dode- canal) , ligustral (2, 4-dimethyl-3-cyclohexene-l-carboxalde- hyde) , linalool, linalool oxide, menthone, methyl acetophe- none, para-methyl acetophenone, methyl amyl ketone, methyl anthranilate, methyl benzoate, methyl benzyl acetate, methyl chavicol, methyl eugenol, methyl heptenone, methyl heptine carbonate, methyl heptyl ketone, methyl hexyl ketone, methyl nonyl acetaldehyde, methyl octyl acetaldehyde, methyl salicylate, myrcene, neral, nerol, gamma-nonalac- tone, nonyl acetate, nonyl aldehyde, allo-ocimene, octalac- tone, 2-octanol, octyl aldehyde, d-limonene, phenoxy etha- nol, phenyl acetaldehyde, phenyl ethyl acetate, phenyl ethyl alcohol, phenyl ethyl dimethyl carbinol, propyl bu- tyrate, rose oxide, 4-terpinenol, alpha-terpineol, terpi- nolene, tonalid ( 6-acetyl-l, 1, 3, 4, 4, 6-hexamethyltetrahydro- naphthalene) , undecenal, veratrol ( 1, 2-dimethoxybenzene) , ambrox ( 1, 5, 5, 9-tetramethyl-l, 3-oxatricyclotridecane) , ane- thole, bacdanol (2-ethyl-4- (2 , 2, 3-trimethyl-3-cyclopenten- 1-yl) -2-buten-l-ol) , benzyl acetone, benzyl salicylate, butyl anthranilate, calone, cetalox (2-ethyl-4- (2, 2 , 3-tri- methyl-3-cyclopenten-l-yl) -2-buten-l-ol) , cinnamic alcohol, coumarin, Cyclal .C (3, 5-dimethyl-3-cyclohexene- 1-carboxaldehyde) , cymal (2-methyl-3- ( 4-isopropylphenyl) - propionaldehyde) , 4-decenal, dihydroisojasmonate, gamma-do- decalactone, ebanol, ethyl anthranilate, ethyl-2-methyl bu- tyrate, ethyl vanillin, eugenol, florhydral (3- (3-isopropylphenyl) butanol) , fructone (ethyl-2-methyl- 1, 3-dioxolane-2-acetate) , heliotropin, herbavert (3, 3, 5-trimethylcyclohexyl ethyl ether), cis-3-hexenyl salicylate, indole, isocyclocitral, isoeugenol, alpha-iso- methylionone, keone, lilial (para-tert-butyl alpha-methyl hydrocinnamic aldehyde), linalool, lyral ( 4- (4-hydroxy-4- methyl-pentyl) -cylcohexene-1-carboxaldehyde) , methyl heptine carbonate, methyl anthranilate, methyl dihydrojas- monate, methyl-isobutenyl-tetrahydropyran, methyl beta- naphthyl ketone, methyl nonyl ketone, beta-naphthol methyl ether, nerol, para-anisic aldehyde, para-hydroxyphenyl-bu- tanone, phenylacetaldehyde, gamma-undecalactone and un- decylenic aldehyde. Suitable are also fragrant naturally occurring plant and animal oils and exudates and extracts obtained from plant and animal material .

The weight ratio of fragrance to carrier particles may be varied in a wide range and is preferably selected to be from 0.01 to 5 and most preferably 0.2 to 3. The weight ratio is selected, depending on the surface area and on the pore volume of the carrier particles, in such a manner that essentially all of the fragrance is adsorbed to or absorbed into the carrier particles to obtain a perfume delivery system which is a dry, free flowing powder.

IV) Process for making a perfume delivery system

The invention also provides a process for making a perfume delivery system of the present invention. This process comprises the steps

a) reacting water insoluble carrier particles having sur- face silanol groups with an organosilane having at least one organic residue comprising at least one amino group to obtain carrier particles, wherein at least part of said silanol groups are substituted with organic residues carrying said amino groups,

b) adding at least one polymer carrying positively charged functional groups to said carrier particles, and

c) contacting the particles obtained in step b) with a fra- grance to adsorb said fragrance onto said particles or absorb said fragrance into said particles.

The organosilane reacted with the carrier particles in step a) preferably has the formula

(R¹G)₃-HR²I₁Si (CH₂)₃Z

wherein R¹ and R² are independently methyl, ethyl, n-propyl or n-butyl,

n is 0 or 1,

Z is NR³R⁴,

R³ and R⁴ are independently hydrogen, methyl, ethyl,

C₃-₂₀ alkyl, C₇_₂6 aralkyl, (CH₂CH₂O)_1nR⁵ or (CH₂CH₂NH)_1nR⁵,

m is from 1 to 4, and

R⁵ is hydrogen, methyl, ethyl, C₃-₂₀ alkyl or C₇-₂6 aralkyl.

The most preferred organosilanes are:

(MeO)₃Si (CH₂) 3NH₂, (EtO)₃Si (CH₂) 3NH₂,

(EtO)₂MeSi (CH₂)₃NH₂,

(MeO) ₃Si (CH₂) ₃NH (CH₂) 3CH3, ,

(EtO) ₃Si (CH₂) ₃NH (CH₂) ₃CH₃, (MeO)₂MeSi (CH₂) ₃NH(CH₂J₃CH₃,

(EtO) ₂MeSi (CH₂) ₃NH (CH₂) ₃CH₃,

(MeO) ₃Si (CH₂) ₃NH (CH₂) ₂NH₂,

(EtO) ₃Si (CH₂) ₃NH (CH₂) ₂NH₂,

(MeO) ₂MeSi (CH₂) ₃NH (CH₂) ₂NH₂, (EtO)₂MeSi (CH₂) 3NH(CH₂J₂NH₂,

(MeO) ₃Si (CH₂) ₃NH (CH₂) ₂NHCH₂Ph,

(EtO) ₃Si (CH₂) ₃NH (CH₂) ₂NHCH₂Ph,

(MeO) ₂MeSi (CH₂) ₃NH (CH₂) ₂NHCH₂Ph,

(EtO) ₂MeSi (CH₂) ₃NH (CH₂) ₂NHCH₂Ph, (MeO) ₃Si (CH₂) ₃NH (CH₂) ₂NH (CH₂) ₂NH₂, (EtO) ₃Si (CH₂) ₃NH (CH₂) ₂NH (CH₂) ₂NH₂, (MeO) ₂MeSi (CH₂) ₃NH (CH₂) ₂NH (CH₂) ₂NH₂, (EtO) ₂MeSi (CH₂) ₃NH (CH₂) ₂NH (CH₂) ₂NH₂,

wherein

Me is methyl,

Et is ethyl, and

Ph is phenyl .

In step a) of the process, the organosilane is preferably reacted with the carrier particles in a weight ratio of from 1 : 1 to 1 : 100. More preferably, the weight ratio of organosilane to carrier particles is from 1 : 5 to 1 : 50.

The organosilane can be reacted with the carrier particles in a suitable solvent in the absence of water. The reaction is carried out for a suitable time to achieve grafting of the silane onto the carrier particle. The reaction temperature is selected according to the nature of the reactive groups on the silicon atom of the silane and is preferably in the range of 20 to 100 ⁰C.

The organosilane can also be reacted with the carrier particles in the presence • of water. In this case, the organosilane or a solution of the organosilane is sprayed onto the carrier particles and the resulting mixture is dried to complete the grafting reaction, preferably at a temperature of from 100 to 200 ⁰C, in particular from 100 to 150 ⁰C.

In step b) , at least one polymer carrying positively charged functional groups is added to the carrier particles obtained in step a) . Preferably, the addition of the polymer is performed in a manner to obtain an intimate mixture of the carrier particles and the polymer. If the polymer is a solid, the polymer can be dry mixed with the carrier par- tides.

In an alternative embodiment, a solution of the polymer in a solvent or a mixture of solvents is added to the carrier particles. In this case water is preferably used as a sol- vent. The one or more solvents are preferably removed from the resulting suspension by evaporation. Alternatively, the one or more solvents may be also be separated from the carrier particles by suitable mechanical means, such as filtration or centrifugation, after a sufficient amount of the polymer has adsorbed to the carrier particles.

In step c) , the contacting of the particles obtained in step b) with a fragrance is preferably carried out by spraying the fragrance or a solution of the fragrance in one or more suitable solvents onto the carrier particles while maintaining the carrier particles in a free flowing state. The spraying can be performed in a mixer, where the particles are moved by mechanical means, or in a fluidized bed, where the particles are moved by a fluidizing gas. If a solvent is used, the solvent may be conveniently removed during the spraying step, although this is not necessary.

V) Cleaning compositions

The invention further provides cleaning compositions comprising the perfume delivery system of the present invention and one or more surfactants. The cleaning compositions of the invention may be liquid or gel compositions with the perfume delivery system of the present invention dispersed in the liquid or gel phase. Apart from the perfume delivery system, further solid com- ponents of the detergent may be dispersed in the liquid or gel phase. The rheologic properties of the liquid or gel composition are preferably selected to maintain all solid components dispersed in the liquid or gel phase during storage with no settling of solids. Preferably, the liquid or gel composition shows thixotropic or pseudoplastic flow. Such flow properties may be achieved by additives, such as dispersable clays, in particular montmorillonites; precipitated or pyrogenic silicas; vegetable gums, in particular xanthanes; and synthetic polymeric thickeners, such as vi- nyl polymers comprising carboxyl groups.

The cleaning compositions of the present invention comprise one or more surfactants, preferably anionic, nonionic or cationic surfactants or combinations thereof.

Suitable anionic surfactants are for example surfactants with sulfonate groups, preferably alkylbenzenesulfonates, alkanesulfonates, alpha-olefinsulfonates, alpha-sulfofatty acid esters or sulfosuccinates . Preferred alkylbenzenesul- fonates comprise a linear or branched chain alkyl group with 8 to 20 carbon atoms, in particular 10 to 16 carbon atoms. Preferred alkanesulfonates comprise a linear chain alkyl group with 12 to 18 carbon atoms. Preferred alpha- olefinsulfonates are the products of sulfonating alpha-ole- fins having 12 to 18 carbon atoms. Preferred alpha-sulfofatty acid esters are the products of sulfonating fatty acid esters of fatty acids having 12 to 18 carbon atoms and short chain alcohols selected from methanol, etha- nol, 1-propanol and 2-propanol. A further class of suitable anionic surfactants are surfactants comprising sulfate groups, preferably alkylsulfates and ethersulfates. Preferred alkylsulfates comprise linear chain alkyl group with 12 to 18 carbon atoms. Suitable are also beta-branched alkylsulfates and alkylsulfates comprising one or more branchings at the center of the alkyl group. Preferred ethersulfates are the products of eth- oxylating linear chain alcohols having 12 to 18 carbon at- oms with 2 to 6 ethylene oxide units and subsequent sulfa- tation .

Another class of suitable anionic surfactants are soaps, such as for example alkali metal salts of lauric acid, my- ristic acid, palmitic acid, stearic acid or mixtures thereof and example alkali metal salts of natural fatty acid mixtures, such as for example coconut fatty acid, palm kernel fatty acid or tallow fatty acid.

Suitable non-ionic surfactants are for example alkoxylated compounds, in particular ethoxylated and propoxylated compounds. Preferred are condensation products of alkylphenols or fatty alcohols with 1 to 50 equivalents ethylene oxide, propylene oxide or mixtures thereof and in particular con- densation products with 1 to 10 equivalents. Another class of suitable non-ionic surfactants are polyhydroxyfatty acid amides with the amide nitrogen substituted by an organic residue carrying one or more hydroxyl groups which may additionally be alkoxylated. A further class of suitable non- ionic surfactants are alkyl glycosides comprising a linear or branched chain alkyl group with 8 to 22 carbon atoms, in particular 12 to 18 carbon atoms, and a mono- or diglyco- side unit which is preferably derived from glucose. Suitable cationic surfactants are for example monoalkoxyl- ated or dialkoxylated quaternary ammonium compounds comprising one or two hydroxyalkyl groups and an alkyl group with 6 to 18 carbon atoms bonded to nitrogen.

Suitable amphoteric surfactants are aminoxides, betaines and amphoglycinates .

The cleaner compositions of the present invention may com- prise further components, such as for example builders, alkaline components, bleaching agents, bleach activators, enzymes, chelating agents, graying inhibitors, foam inhibitors, brighteners or colorants.

Cleaner compositions of the present invention in the form of liquids or gels may further comprise up to 30 wt.-% of an organic solvent, preferably methanol, ethanol, n-propanol, iso-propanol, n-butanol, ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1,4-butylene glycol, glycerin, diethylene glycol, ethylene glycol methyl ether, ethanolamine, diethanolamine or triethanolamine or mixtures thereof.

Examples

The following examples are provided to illustrate the present invention without intending to limit the scope of the invention.

Example 1:

Grafting of silica with an aminosilane

2 g of 3-aminopropyltriethoxysilane (Dynasilane AMEO) were dissolved in 10 ml deionized water at room temperature. The resulting solution was added in small portions to 20 g precipitated silica Sipernat 22 made by Degussa AG at room temperature while constantly mixing the silica. The result- ing product was heated for 12 h at 110⁰C in a forced air oven to remove water and complete the grafting reaction.

Example 2 :

Addition of cationic polymer to grafted silica

5 g of the dry product obtained in example 1 was dry mixed with 0.5 g polyquaternium-10 (Celquat SC-240C made by National Starch & Chemical) and the mixture was heated to 5O⁰C for 2 h.

Example 3 :

Preparation of perfume delivery system

1 g of the dry product obtained in example 2 was placed in a mixer and 2 g of liquid fragrance composition 5862-HBH-LFS made by International Flavors & Fragrances Inc. was added slowly while mixing the grafted silica. A perfume carrier system comprising 67 wt . -% fragrance on carrier was obtained as a free flowing powder.

Example 4 (comparative example) : Addition of cationic polymer to silica

Example 2 was repeated, but untreated precipitated silica Sipernat 22 was used in place of the dry product obtained in example 1.

Example 5 (comparative example) : Preparation of perfume delivery system

Example 3 was repeated, but the dry product obtained in example 4 was used in place of the dry product obtained in example 2.

Example 6 :

Preparation of a carpet care product

A ready to use carpet care blend REWOPOL TS 40 PA com- prising lauryl sulfosuccinate, sodium laurylsulfate and a polyacrylate-polystyrene copolymer (30 % active matter) is diluted with water 1:3 and 1 % of perfume delivery system according to example 3 was added.

Example 7 :

Preparation of a carpet care product

A ready to use carpet care blend REWOPOL TS 40 PA comprising lauryl sulfosuccinate, sodium laurylsulfate and a polyacrylate-polystyrene copolymer (30 % active matter) is diluted with water 1:3 and 1 % of perfume delivery system according to example 5 was added.

Example 8 : Preparation of a carpet care product

A ready to use carpet care blend REWOPOL TS 40 PA comprising lauryl sulfosuccinate, sodium laurylsulfate and a polyacrylate-polystyrene copolymer (30 % active matter) is diluted with water 1:3 and 1 % of perfume was added.

All test materials were tested on carpet swatches 20 cm by 20 cm in size. The remaining fragrance smell was determined by panelists after the times mentioned in the table 1.

Table 1

++ easy to realize smell + fair smell

Example 9 :

Preparation of a toilet bowl cleaner

5 g Rewoteric ® AM TEG (tallow dihydroxyethyl betaine) are blended with 8 g citric acid and 4 g sodium chloride. 1 g of perfume delivery system according to example 3 was added and water to 100 g.

Example 10 :

Preparation of a toilet bowl cleaner

5 g Rewoteric ® AM TEG (tallow dihydroxyethyl betaine) are blended with 8 g citric acid and 4 g sodium chloride. 1 g of perfume delivery system according to example 5 was added and water to 100 g.

Example 11: Preparation of a toilet bowl cleaner

5 g Rewoteric ® AM TEG (tallow dihydroxyethyl betaine) are blended with 8 g citric acid and 4 g sodium chloride. 1 g of perfume was added and water to 100 g.

All test materials were tested on tiles 30 cm by 30 cm in size. The remaining fragrance smell was determined by panelists after the times mentioned in the table 2.

Table 2

++ easy to realize smell + fair smell

Claims

Claims :

1. A perfume delivery system comprising

a) water insoluble carrier particles having surface silanol groups, wherein at least part of said si- lanol groups are substituted with organic residues by grafting with at least one organosilane and wherein at least part of said organic resi- dues carry amino groups,

b) at least one polymer which carries positively charged functional groups and

c) a fragrance adsorbed to or absorbed into said carrier particles.

2. The perfume delivery system of claim 1, wherein the carrier particles comprise silica, a silicate, an alu- minosilicate or a mixture thereof.

3. The perfume delivery system of claim 2, wherein the silica is selected from the group comprising of precipitated silicas, fumed silicas and silica gels.

4. The perfume delivery system of claim 2, wherein the aluminosilicate is a zeolite.

5. The perfume delivery system of claim 4, wherein the zeolite is selected from the group comprising of zeolite X, zeolite Y and dealuminated zeolite Y.

6. The perfume delivery system of claim 1, wherein essentially all of the organic residues carry at least one amino group.

7. The perfume delivery system of claim 1, wherein at least part of the amino groups are primary amino groups .

8. The perfume delivery system of claim 1, wherein the positively charged functional groups of said polymer are quaternary ammonium groups .

9. The perfume delivery system of claim 1, wherein the polymer comprises of carbohydrate monomer units.

10. The perfume delivery system of claim 9, wherein the polymer is a modified starch or a modified cellulose.

11. The perfume delivery system of claim 1, wherein the weight ratio of fragrance to carrier particles is from

0.01 to 5.

12. A process for preparing a perfume delivery system according to claim 1, comprising the steps

a) reacting water insoluble carrier particles having surface silanol groups with an organosilane having at least one organic residue comprising at least one amino group to obtain carrier particles, wherein at least part of said silanol groups are substituted with organic residues carrying said amino groups, b) adding at least" one polymer carrying positively charged functional groups to said carrier particles, and

c) contacting the particles obtained in step b) with a fragrance to adsorb said fragrance onto said particles or absorb said fragrance into said particles.

13. The process of claim 12, wherein the organosilane has the formula

(R¹O) 3-_nR²nSi (CH₂) ₃Z wherein

R¹ and R² are independently methyl, ethyl, n-propyl or n-butyl,

n is 0 ^■ or 1,

is NR³R⁴,

R³ and R⁴ are independently hydrogen, methyl, ethyl, C₃-₂₀ alkyl, C₇_₂6 aralkyl, (CH₂CH₂O) _mR⁵ or (CH₂CH₂NH) _mR⁵,

m is from 1 to 4, and

R^α is hydrogen, methyl, ethyl, C3-20 alkyl or C₇-26 aralkyl.

14. Cleaner compositions comprising the system 1 for household applications, especially for carpet care, floor care, dish wash, car care, bathroom and toilet care and for applications in industrial and institutional areas .