EP2134770A2

EP2134770A2 - Reactive polyorganosiloxanes modified with aromatic substances

Info

Publication number: EP2134770A2
Application number: EP08749505A
Authority: EP
Inventors: Horst Lange; Christopher Roos; Roland Wagner; Martin Kropfgans
Original assignee: Momentive Performance Materials GmbH; Momentive Performance Materials Inc
Current assignee: Momentive Performance Materials GmbH; Momentive Performance Materials Inc
Priority date: 2007-03-19
Filing date: 2008-03-19
Publication date: 2009-12-23
Also published as: WO2008113820A3; WO2008113820A2; DE102007012909A1; US20100120657A1

Abstract

The invention relates to polyorganosiloxanes modified with aromatic substances and comprising reactive groups, to a method for coating a substrate using the polyorganosiloxanes according to the invention, to the use of the polyorganosiloxanes according to the invention for releasing the aromatic substance, to a method for producing the polyorganosiloxanes according to the invention, and to the use thereof for example in cleaning agents or detergents, in care products, in products for finishing surfaces, and in cosmetics.

Description

MODIFIED, REACTIVE POLYORGANOSILOXANE

DESCRIPTION:

The invention relates to fragrance-modified polyorganosiloxanes having reactive groups, to a process for coating a substrate using the polyorganosiloxanes of the invention, to the use of the polyorganosiloxanes according to the invention for releasing the fragrance, to processes for preparing the polyorganosiloxanes according to the invention and to their use, for example, in detergents or detergents. in care products, in finishing agents and cosmetics.

In many applications of cosmetic products and everyday products for textile and household cleaning or care, one wants to achieve in the application of a long-lasting specific fragrance, which is perceived by the user as pleasant.

For this purpose, it has been proposed to use reaction products of linear aminoalkylpolysiloxanes with ketone or aldehyde groups (EP 1062265 A1). The proposed products, upon contact with moisture at low pH, undergo hydrolytic cleavage to reform the fragrance molecule containing keto groups or aldehyde groups, as well as the aminoalkyl polysiloxane. However, in the application by the reformation of Aminoalkylpolysiloxanen to disturbing secondary olfactory impressions come, which become stronger in particular to the extent that the liberated fragrance flies and the smell of the aminoalkylpolysiloxane comes to fruition. A further problem with these compounds is that they are easily rinsed off the substrates, in particular in liquid systems, and that this also entails a loss of fragrance capacity. It is therefore the object of the present invention to provide perfume-modified polyorganosiloxanes which, on the one hand, have high substantivity (ie durability of adherence to a substrate) and, on the other hand, the lowest possible odor after release of the perfume therefrom. This is absolutely necessary, in particular because of the desired high substantivity. In addition, the improved substantivity allows for the residual polyorganosiloxane to continue to exert its beneficial other properties, such as its surface-modifying properties, such as softening properties, even after release of the fragrance. Furthermore, increasing the substantivity of the polyorganosiloxanes of the invention not only allows for the prolongation of the fragrance release time, but also allows for a higher application rate, which results in a more concentent release of perfume, and hence a stronger fragrance. This also makes it possible to use those fragrances whose fragrance is perceivable only at higher concentrations. The low substantivity of the known perfume-modified polyorganosiloxanes furthermore leads, in particular in liquid applications, such as washing processes, to a relatively high release of the polyorganosiloxanes, which leads to undesirable side effects in use, for example by reducing the desired foaming in detergent formulations or by undesired formation of a silicone phase the substrate to disturbing acting greasy-looking, can lead to very difficult to remove silicone stains. A further advantage of the fragrance-modified polyorganosiloxanes having reactive groups according to the invention is that further active molecules, for example other fragrances in the sense of a fragrance bouquet, optionally also the fragrances with different release kinetics, can be introduced into the polyorganosiloxane via the reactive groups. In this way, in particular, the introduction of different fragrances, so as to achieve a characteristic fragrance and to control the perceived fragrance character after application over time and change. These possibilities exist after the State of the art not. Also, there are described only polyorganosiloxanes having a linear structure without reactive groups, so that they do not have a particularly pronounced affinity for the surfaces to be treated due to their structure and have neither a favorable deposition efficiency on a treated substrate surface nor a good persistence on the treated surface. Due to its high substantivity, the fragrance-free organopoplysiloxane obtained after the removal of the fragrance from the polyorganosiloxane according to the invention unfolds its nourishing or conditioning action on the substrates without appearing through an unpleasant odor.

Accordingly, the problem arose to find a suitable, technically and economically equally attractive alternative to the prior art and to find a simple method for producing these compounds, which avoids the disadvantages of the prior art described.

This problem has been solved by the provision of fragrance-modified reactive groups containing polyorganosiloxanes.

The reactive groups mentioned are, in particular, those which are capable of reacting with a substrate and / or of condensation.

Substrates which can react with the polyorganosiloxanes of the invention include, for example, the following: fibers, textiles, plasters, paper, wallpapers, moldings, ceramics, lacquer coatings, films, hair, skin, wood, glass, plastics, etc.

The reactive group in the polyorganosiloxanes according to the invention in particular include those of the formula (I):

-SiR ² _n X ₃ -n (I) wherein n = 0 to 2,

R ^{2 is} selected from optionally substituted alkyl and phenyl,

X is halogen, -OR ³ , -OC (O) R ³ , -N = CR ³ ₂ , -NR ³ ₂ , -NC (O) R ³ , -R ⁴ -Y,

wherein R ^{3 is} selected from the group consisting of hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted cycloalkyl and aryl,

R ^{4 is} a divalent optionally substituted, optionally one or more heteroatoms having organic radical, and

Y is selected from the group consisting of -NCO, -OH, -NR ³ _2, -C (O) CI, -SO ₂ CI, -SO ₂ -vinyl (vinylsulfone), Thazinyl, Halogenthazinyl, pyrimidinyl.

Functional groups on the substrate which can react with the above reactive groups of the polyorganosiloxanes of the invention sit, in particular, on the surface of the substrates and are selected, for example, from the group consisting of: hydroxy, amino, carboxy, carbonyloxy (ester), disulfide , Mercapto, etc.

The polyorganosiloxanes according to the invention are obtainable, in particular, by the reaction of functionalized polyorganosiloxanes containing reactive groups with fragrances or by condensation of perfume-modified polyorganosiloxanes or organosilanes. Fragrances contained in the polyorganosiloxanes according to the invention preferably have at least one functional group selected from the group consisting of keto, aldehyde and / or hydroxy groups which react with suitable functional groups of the polyorganosiloxanes or organosilanes used as starting material. Accordingly, the functionalized polyorganosiloxanes or organosilanes used as starting compounds have at least one functional group capable of reacting with keto, aldehyde and / or hydroxy-functionalized perfumes, wherein after the reaction with the perfume according to the invention at least one reactive group in the polyorganosiloxane obtained must remain. Said functional groups on the polyorganosiloxanes or organosilanes which react with the fragrance are preferably selected from the group consisting of aminoalkyl groups, hydroxyalkyl groups and alkoxy groups each attached to a silicon atom. In this context, it should be noted that the said functional groups may also be the reactive groups remaining on the polyorganosiloxane. For example, the functional group may be an alkoxysilyl group which only partially reacts with a perfume alcohol such that alkoxysilyl groups remain in the resulting polyorganosiloxane of the invention and are thus available for reaction with a substrate or condensation of the polyorganosiloxanes (after water access). In a preferred embodiment of the invention, the functionalized polyorganosiloxanes or organosilanes used as starting compounds have at least one primary or secondary amine radical.

The perfume-modified polyorganosiloxanes according to the invention have in particular the following silicon structural units: o _1/2 R ¹ R 'R ¹

-0 ^ Si-O ₁ - -0 ^ Si-O ₁ - - o 1/2 -Si-O ₁ - O ₁ IIsi-R '

1/2 1/2 R ¹

wherein

R ^{1 is} selected from the group consisting of:

optionally substituted, straight-chain, branched or cyclic saturated or unsaturated, optionally interrupted by one or more heteroatoms alkyl, optionally substituted aryl, in particular methyl, ethyl, vinyl, allyl, propyl, octyl, dodecyl, capryl, stearyl, phenyl, phenylethyl, phenylpropyl, Limonenyl, cyclohexylethyl, norbornenyl,

Fragrance-emitting groups capable of cleaving one or more fragrance molecules,

Reactive groups capable of reacting with substrates,

wherein the fragrance-modified polyorganosiloxanes contain on average per molecule at least one fragrance-emitting group.

The polyorganosiloxanes according to the invention suitably comprise at least one structural element of the formula:

Du-A-Si-O-Si -

in which the group ^' Du ^{' represents} a structural unit derived from the fragrance, from which the fragrance is released again by splitting off,

A represents a silicon-free spacer unit, and

the free valences on the silicon atoms are saturated by radicals selected from organic radicals and siloxane radicals, with the proviso that at least one of the free valencies is saturated by a siloxane radical.

The polyorganosiloxanes according to the invention expediently contain on average at least two, preferably at least 5, more preferably at least 8, preferably at most 1000, more preferably at most 200, even more preferably at most 50 siloxy groups per molecule.

Fragrance-comprising structural units are in particular derived from keto, aldehyde and / or hydroxy groups-containing fragrances.

Suitable ketones, aldehydes or alcohols which are traditionally used in perfumery are, for example, those described in Perfume and Flavor Chemicals, Volumes I and II, S. Arctander, Allured Publishing, 1994, ISBN 0-931 71 0-35-. 5, mentioned.

Fragrance ketones include, for example: buccoxime; iso-jasmone; Methyl naphthyl ketone; musk indanone; Tona-Iid / Musk plus; alpha Damascon, beta damascone, delta damascone, iso-damascone, damascenone, damarose, methyl dihydrojasmonate, menthone, carvone, camphor, fenchone, alpha-ionone, beta-ionone, gamma-methyl called ionone, fleuramon, dihydrojasmon, cis-Jasmon, iso-E-Super®, methyl cedryl ketone or methyl cedrone, acetophenone, methyl acetophenone, para-methoxy acetophenone, methyl beta-naphthyl ketone, benzyl acetone, benzophenone, para-hydroxyphenyl butanone, celery ketone or live scone, 6-isopropyl decahydro-2 -naphtone, dimethyloctenone, frescomenthe, 4- (1-ethoxy- vinyl) -3,3,5,5-tetrannethylcyclohexanone, methylheptenone, 2- (2- (4-methyl-3-cyclohexen-1-yl) -propyl) -cyclopentanone, 1- (p-menthene-6 (2) yl) 1-Propanone, 4- (4-hydroxy-3-methoxyphenyl) -2-butanone, 2-acetyl-3,3-dimethylnorbornane, 6,7-dihydro-1,1,2,3,3-pentan-ethyl-4 (5H) indanone, 4-damascol, dulcinyl or cassione, gelson, hexalon, isocyclone E, methylcyclo- citron, methyllavedel- ketone, orivone, para-tert-butylcyclohexanone, Verdon, Delphon, Muscon, neobutenonone, Plicaton, Velouton, 2 , 4,4,7-Tetramethyl-oct-6-en-3-one, tetramer.

Preferably, the perfume ketones are selected from alpha-damascone, delta-damascone, iso-damascone, carvone, gamma-methylionone, iso-E-Super® (7-acetyl-1,2,3,4,5,6,7,8 octahydro-1, 1, 6,7-tetramethylnaphthalene), 2,4,4,7-

Tetramethyl-oct-6-en-3-one, benzylacetone, beta-damascone, damascenone, methyldihydrojasmonate, methylatedrylon and mixtures thereof.

Particularly preferred is alpha Damascone.

Fragrance aldehydes include, for example: Adoxal; anisaldehyde; cymal; ethyl vanillin; florhydral; helional; heliotropin; Hydroxycitronellal; koavone; lauraldehyde; lyral; methylnonylacetaldehyde; pt-Bucinal, phenylacetaldehyde, undecylenealdehyde, vanillin, 2,6,10-trimethyl-9-undecenal, 3-dodecene-1-al, alpha-n-amylcinnamaldehyde, 4-methoxybenzaldehyde, benzaldehyde, 3- (4-tert-butylphenyl ) -propanal, 2-methyl-3- (para-methoxyphenyl) propanal, 2-methyl-4- (2,6,6-timethyl-2 (1) -cyclohexen-1-yl) butanal, 3-phenyl-2 -propenal, cis- / trans-3,7-dimethyl-2,6-octadiene-1-al, 3,7-dimethyl-6-octene-1-al, [(3,7-dimethyl-6-octenyl) oxy] acetaldehyde, 4-isopropylbenzyaldehyde, 1,2,3,4,5,6,7,8-octahydro-8,8-dimethyl-2-naphthaldehyde, 2,4-dimethyl-3-cyclohexene-1-carboxaldehyde , 2-methyl-3- (isopropylphenyl) propanal, 1-decanal; Decyl aldehyde, 2,6-dimethyl-5-heptenal, 4- (tricyclo [5.2.1.0 (2,6)] decylidene-8) butanal, octahydro-4,7-methane-1H-indenecarboxaldehyde, 3-ethoxy 4-hydroxybenzaldehyde, para-ethyl-alpha, alpha-dimethylhydrocinnamaldehyde, alpha-methyl-3,4- (methylenedioxy) -hydrocinnamaldehyde, 3,4-methylenedioxybenzaldehyde, alpha-n-hexylcinnamaldehyde, m-cymene-7 carboxaldehyde, alpha-methylphenylacetaldehyde, 7-hydroxy-3,7-dimethyloctanal, undecenal, 2,4,6-trin-ethyl-3-cyclohexene-1-carboxaldehyde, 4- (3) (4-methyl-3-pentenyl) -3 cyclohexene carboxaldehyde, 1-dodecanal, 2,4-dimethylcyclohexene-3-carboxaldehyde, 4- (4-hydroxy-4-methylpentyl) -3-cyclohexene-1-carboxaldehyde, 7-methoxy-3,7-dimethyloctan-1-al , 2-methylundecanal, 2-methyldecanal, 1-nonanal, 1-octanal, 2,6,10-thmethyl-5,9-undecadienal, 2-methyl-3- (4-tert-butyl) -propanal, dihydrocinnamaldehyde, 1 Methyl 4- (4-methyl-3-pentenyl) -3-cyclohexene-1-carboxaldehyde, 5- or 6-methoxy-hexahydro-4,7-methanindan-1 or 2-carboxaldehyde, 3,7-dimethyloctane 1-al, 1-undecanal, 10-undecene-1-al, 4-hydroxy-3-methoxybenzaldehyde, 1-methyl-3- (4-methylpentyl) -3-cyclohexene-carboxaldehyde, 7-hydroxy-3,7- dimethyl-octanal, trans-4-decenal, 2,6-nonadienal, para-tolylacetaldehyde, 4-methylphenylacetaldehyde, 2-methyl-4- (2,6,6-trimethyl-1-cyclohexen-1-yl) - 2-butenal, ortho-methoxycinnamaldehyde, 3,5,6-thymethyl-3-cycl ohexene carboxaldehyde, 3,7-dimethyl-2-methylene-6-octenal,

Phenoxyacetaldehyde, 5,9-dimethyl-4,8-decadienal, peonyaldehyde (6,10-dimethyl-3-oxa-5,9-undecadiene-1-al), hexahydro-4,7-methanindane-1-carboxaldehyde, 2 Methyloctanal, alpha-methyl-4- (1-methylethyl) benzeneacetaldehyde, 6,6-dimethyl-2-norpinen-2-propionaldehyde, para-methylphenoxyacetaldehyde, 2-methyl-3-phenyl-2-propene-1-al 3 , 5,5-trimethylhexanal, hexahydro-8,8-dimethyl-2-naphthaldehyde, 3-propylbicyclo [2.2.1] -hept-5-en-2-carbaldehyde, 9-decenal, 3-methyl-5-phenyl- 1-pentanal, methylnonylacetaldehyde, hexanal, trans-2-hexenal, 1-p-menthene-q-carboxaldehyde, and mixtures thereof.

Preferred aldehydes are selected from: 1-decanal, benzaldehyde, Florhydral, 2,4-dimethyl-3-cyclohexene-1-carboxaldehyde, cis- / trans-3,7-dimethyl-2,6-octadiene-1-al, heliotropin 2,4,6-thymethyl-3-cyclohexene-1-carboxaldehyde, 2,6-nonadienal; alpha-n-amylcinnamaldehyde, alpha-n-hexylcinnamic aldehyde, pt-buccinal, lyral, cymal, methylnonylacetaldehyde, hexanal, trans-2-hexenal, and mixtures thereof. Preferred perfume alcohols are selected, for example, from 2-methylbutanol, 3-pentanol, n-pentanol, 2-pentanol, n-nexanol, 2-methylpentanol, 1-decanol, sandela, nonadol, dimetol, thymol, 1-heptanol, menthol, Eugenol, vanillin, o-vanillin, 4- (p-hydroxyphenyl) -2-butanone, syhnealdehyde, prenol, cis-3-hexanol, trans-3-hexanol, cis4-heptenol, trans-2-octenol, trans-2- cis-6-nonanediazole, geraniol, nerol, ebanol, citronellol, crotyl alcohol, oleyl alcohol, linalool, α-terpineol, β-phenethyl alcohol, cinnamyl alcohol, benzyl alcohol, α-methylbenzyl alcohol, nonyl alcohol, 1-octanol, 3-octanol , Phenethyl salicylate, hydrocinnamyl alcohol, cis-6-nonene-1-ol, trans-2-nonene-1-ol, methyl salicylate, cis-3-octene-ol anisyl alcohol, carvacrol, dihydrocarveol, benzyl salicylate, tetra hydrogeraniol, ethyl salicylate, ethyl vanillin, Isoeugenol, isopuegol, lauryl alcohol, tetrahydrolinalool, 2-phenoxyethanol, citronellol, eugenol, farnesol, thymol and geraniol. Compounds of this type are described, for example, in EP 0 799 885, EP 0 771 785, WO 96/38528, US 5 958 870.

Silicon-free spacer units are in particular selected from divalent, saturated, one or more heteroatoms having hydrocarbon radicals having up to 30 carbon atoms.

In a preferred embodiment of the invention, in the methylsiloxane compounds preferably used, one or more methyl groups are replaced by phenyl groups in order to obtain resinous compounds melting, for example, at 40 to 120 ^° C., in order to be able to store the compound on the one hand in solid form, and on the other hand For example, during a washing process, a liquefaction of the compound, thus achieving better distribution availability.

In a preferred embodiment of the invention the solids are gel-like and have branched fragrance-modified poly organosiloxanes according to the invention a penetrometer value (DIN ISO 2137 2. Output - 1985- 11 -01) at 25 ⁰ C of less than 50 mm / sec with 6 the cone C2 (62.5 g) in beaker B2. The term also includes solid elastomeric solids that have at least a Shore A hardness of more than 10 ° to DIN 53505 when one misses a shaped plate, a melt body or a compact having 6 mm thickness at 25 ⁰ C.

Dhdie fragrance-modified polyorganosiloxanes according to the invention are solid at room temperature (25 ⁰ C) in a preferred embodiment, viscous to non-flowable solid, in particular solid compositions. An advantage of this embodiment, in addition to the low odor intensity of the remaining after the separation of the fragrance functionalized branched polysiloxane due to its low vapor pressure, in the possibility, the non-flowable, in particular solid masses, optionally after their comminution, in solid formulations, such as pasty or in particular to incorporate powdered formulations, such as detergent powder. In this way, in particular, eliminates the need to raise the polyorganosiloxanes on solid support and obtained so by weight or volume relatively high perfume concentrations, so that the polyorganosiloxanes provide a high fragrance capacity.

By using Phenylsiloxygruppen, especially the use of the structural unit PhSiO _3/2 in the inventive polyorganosiloxanes fusible links are preferably obtained at 40 to 120 ⁰ C, with the aforementioned advantages. In a preferred embodiment of the invention, the polyorganosiloxanes therefore preferably have at least one phenylsiloxy group, preferably at least one PhSiO3 / 2 unit. Melting point or range means that in a differential thermal calorimeter (DSC), the melting temperature is determined by measuring a melting enthalpy of> 0 joules at this temperature, when the sample is moved from an underlying temperature at a rate of 0 , 5-5 ⁰ K / min heats up.

In a preferred embodiment, reactive siloxane structures are selected which are in contact with the substrate, preferably with the fiber of textiles connect that the reaction products of Siloxanduftstoff and fiber below 180 ⁰ C, more preferably below 250 ⁰ C lead to no discoloration on the substrate. Discoloration means that white tissue pieces after the temperature load of up to 180 ⁰ C, more preferably up to 250 ⁰ C for 5 min have no discoloration, which is above an untreated tissue after this treatment and thus extreme heating under an iron over 5 min survive without adverse discoloration. The polyorganosiloxanes used as starting compounds, preferably polydimethylsiloxanes, preferably have at least one functional group which is capable of reacting with the keto, aldehyde and / or hydroxy-functionalized fragrances. In particular, this functional group includes groups selected from aminoalkyl groups each attached to a silicon atom, sec-aminoalkyl groups such as alkylaminoalkyl groups, cycloalkyl groups such as cyclohexylaminoalkyl groups, or arylaminoalkyl groups, hydroxyalkyl groups and alkoxy groups. According to the invention, these groups also include polyaminoalkyl and polyhydroxyalkyl groups which are suitable for delivering more than one perfume molecule per residue R ¹ .

Preferred Si-bonded aminoalkyl groups are, in particular, the aminopropyl and the aminomethyl groups. Preferred hydroxyalkyl groups are analogous to the hydroxypropyl and the hydroxymethyl group.

The starting compounds having such functional groups may be, for example, the following compounds:

wherein FG is the functional group capable of reacting with a fragrance,

R ^{1 is} as defined above

R ⁵ is a Ci to C-io-alkyl, C ₆ -C ₀ is cycloalkyl or aryl radical, m = 1 to 8, and z = 0, 1, 2 or 3;

wherein R ⁵ , FG n and m are as defined above, in particular compounds of the formula:

wherein R, m and n are as defined above,

WJE ZB H ₂ NCH ₂ CH ₂ CH ₂ -Si (OEt) ₂ - [SiMe ₂ O] I ₀ OSi (OEt) ₂ -CH ₂ CH ₂ CH ₂ NH _2.

By reacting the above-mentioned functional group capable of reacting with the fragrance, for example, the following fragrance-emitting groups -A-Du are formed:

For example, forming from an aminoalkyl radical on the silicon of a siloxane radical and a keto and / or aldehyde-containing perfume, the following group -A-Du forms with ^' D ^' = perfume molecule without a binding group, ie in each case substituents or structural units to complete the Molecular structure of a fragrance are:

wherein

R ^{6 is} a Ci to C ₈ alkylene radical, and

is a residue that results formally from the elimination of oxygen from an O = C group of a fragrance.

In the case of α, β-unsaturated carbonyl fragrances, a competing addition may occur: e.g. the aminoalkyl radical in the siloxane can add to an α, β-unsaturated carbonyl fragrance, with the following -A-Du corresponding radical being formed:

wherein R is defined above, and the rest

from the α, β-unsaturated carbonyl fragrance

by addition of the aminoalkyl radical to the C = C double bond of the α, β-unsaturated carbonyl fragrance, wherein D are each substituents to complete the molecular structure of a fragrance. Furthermore, for example, from a hydroxyalkyl radical on the siloxane and a keto and / or aldehyde-containing perfume, a hemiacetal or hemi-ketal may form as group -A-D:

wherein R ^{6 is} as defined above, and

a radical which is formally derived from the elimination of oxygen from an O = C group of a perfume, is de facto naturally from the reaction of a hydroxyalkyl group with the keto group of the perfume

arises.

Analogously, two hydroxyalkyl radicals on the siloxane and a keto and / or aldehyde-containing perfume can form an acetal or ketal:

-A-Du then formally corresponds to a radical - (A) ₂ -Du of the formula:

in which R is as defined above and the rest

is a residue that is formally from the elimination of oxygen from an O = C group of a perfume

shows, and de facto from the implementation of two hydroxyalkyl groups on the silicon with a keto or aldehyde group of the fragrance is formed.

Furthermore, the alkoxy groups which are bonded to the silicon and hydroxy-containing perfumes can be formed into the following perfume-generating groups:

in which

Formally from the elimination of the hydroxy group from a hydroxy-containing perfume, de facto from the implementation

Si-OR HO-H-OR evident. This reaction also includes the possibility of reacting a keto and / or aldehyde-containing perfume in its enol form.

Examples of keto and / or aldehyde containing perfumes also include mixtures thereof.

The concentration of the fragrance-emitting groups in the polyorganosiloxanes according to the invention is preferably at least about 1 mol% to 200 mol%, based on the number of siloxy units. A concentration of over 100 mol% is made possible by appropriate use of multiple -A-Du-substituted siloxy groups. Preferred concentrations are about 10 to 100 mol%. Particularly preferably, the corresponding concentration is 12 to 80 mol%.

The fragrance-modified polyorganosiloxanes of the invention have, in addition to the fragrance-donating groups -A-Du, groups capable of reacting with substrates. As already mentioned, this entails numerous advantages. On the one hand, it leads to an immobilization of the polyorganosiloxane on a substrate, whereupon the polyorganosiloxane exhibits its advantageous effects, which in addition to the delivery of the fragrance, in particular the softening, hydrophobing or hydrophilizing effects, in particular on the surface of the substrate. Furthermore, the perfume-modified polyorganosiloxane can delay the perfume from its immobilization on the substrate from there, ie in particular release long-lasting. Furthermore, immobilization by means of the abovementioned groups which are reactive toward the substrate results in the polyorganosiloxane, after the release of the fragrance, virtually no longer producing an odor due to its immobilization. Preferred substrates on which the polyorganosiloxanes provided with such groups can react are, in particular, fibers, plasters, wallpapers, plastic moldings, ceramics, lacquer layers, films, hair, skin and wood. Preferred for reaction with substrates competent groups in the polyorganosiloxane include reactive functional groups of the formula (I):

-SiR ² _n X ₃ -n (I) wherein

n = 0 to 2,

R ^{2 is} selected from optionally substituted alkyl and phenyl,

Y is selected from the group consisting of -NCO, -OH, -NR ³ _2, -C (O) CI, -SO ₂ CI, -SO ₂ -vinyl (vinylsulfone), triazinyl, halogenotriazinyl, pyrimidinyl.

The preferred reactive group capable of reacting with a substrate is the alkoxy group.

The concentration of the reactive groups in the polyorganosiloxanes according to the invention is preferably based on the number of siloxy units at least about 1 mole% to 200 mole%. A concentration of over 100 mol% is made possible by appropriate use of multiply substituted siloxy groups. Preferred concentrations are about 10 to 100 mol%. Particularly preferably, the corresponding concentration is 20 to 80 mol%.

The invention also includes the case in which the groups which are capable of reacting with a substrate can also serve to condense the polyorganosiloxanes with one another. This includes, in particular, the case in which part of the reactive groups reacts in the condensation of the polyorganosiloxane and another part of the reactive groups reacts with the substrate. A reactive functional which can perform the said dual function is, in particular, the alkoxy-silyl group.

The substrates to which the polyorganosiloxanes according to the invention are preferably bonded have on their surface preferably functional groups selected for example from the group consisting of: hydroxy, amino, carboxy, carbonyloxy (ester), disulfide, mercapto. The substrates particularly preferably have hydroxyl groups.

The starting compounds which are preferably used for the preparation of the polyorganosiloxanes are polyorganosiloxanes which preferably have at least one primary or secondary amine radical.

In a further embodiment of the invention, the polyorganosiloxanes can be immobilized on a support. Suitable carriers include, for example, silicas, zeolites, cyclodextrins, kaolins, bentonites, polyalkylene oxide waxes, polyacrylates, etc. The polyorganosiloxanes are attached in particular in the same way as in the case of the abovementioned substrates. That is, reactive groups of the polyorganosiloxanes such as alkoxysilyl compounds can react with the carriers having, for example, hydroxy groups on the surface of the carrier. The polyorganosiloxanes according to the invention are naturally used in particular as fragrances, more precisely as fragrance-releasing so-called "profragances", that is to say for the release of the fragrance.

In one embodiment of the invention, this relates in particular to a process for producing a fragrance, which comprises treating the above-mentioned substrate with at least one polyorganosiloxane according to the invention and also releasing the fragrance therefrom.

The invention furthermore relates to a process for preparing the polyorganosiloxanes according to the invention, which comprises the reaction of functionalized polyorganosiloxanes with the fragrances, as already outlined above. Alternatively, the polyorganosiloxanes according to the invention can also be prepared by optionally catalyzed condensation with the addition of water, in particular alkoxysilyl groups of perfume-modified polyorganosiloxanes or organosilanes. Suitable perfume-modified organosilanes are described, for example, in WO 2005/041908. The perfume-modified organosilanes of WO 2005/041908 are in particular those of the DU-A-Si (OR) _{3 type,} which in this form are completely unsuitable for the solution of the problem of the invention because they have too high a vapor pressure and thus after elimination of the fragrance can lead to odor impairment.

In one embodiment of the invention, the polyorganosiloxane obtained is applied in particular to a carrier material by spray-drying or fluidized-bed granulation. The resulting supported material may contain the polyorganosiloxane bound to the support material by adsorption and / or by a chemical reaction. In the preparation variant which comprises the reaction of functionalized polyorganosiloxanes or organosilanes which have condensable groups capable of forming Si-O-Si bonds with perfumes and subsequent condensation to form branched polyorganosiloxanes, it is surprisingly found that these reactions are conducted can that the actually hydrolysis-sensitive alkoxypolysiloxane in spite of, for example, the elimination of dehydration condensation of, for example, aminoalkyl groups with, for example, the ketonic or aldehydic fragrances completely or partially and thus the condensation to form branched polyorganosiloxanes or the reaction with a suitable substrate still accessible are.

The polyorganosiloxanes of the invention can be advantageously prepared by both batch and continuous reaction of corresponding alkoxyaminoalkylpolysiloxanes with ketonic and aldehydic odors. Preferably, to mixtures of the alkoxy aminoalkylpolysiloxanes particular with the ketonic or aldehydic perfumes are used, which at temperatures above 40 ⁰ C, preferably heated above 100 ⁰ C. The reaction can be carried out by adding to the reaction mixture a solvent which forms a distillatively separable azeotrope with the water formed from the condensation reaction. When using the alkoxyaminopolysiloxanes, the use of azeotrope-forming entrainers for separating off water can be dispensed with. It is a particular advantage of this procedure that it is possible to carry out both the attachment of the fragrance and the condensation in a reaction stage, the water released causing the condensation of the alkoxysilyl groups. Another advantage of this process variant is that higher temperatures are avoided by the fact that the water does not need to be removed, which allows the economic production of very pure products and costly separation steps to remove unwanted entrained residual contaminants or decomposition products unnecessary power. By controlling the ratio of alkoxysilyl groups to the amount of water released in the reaction system and / or the amount of water added to the reaction system, the amount of alkoxy groups remaining in the final product can be controlled, and thus the reactivity to certain substrates can be controlled.

The alkoxy groups of the polyorganosiloxanes or organosilanes can also after the reaction with the perfume after addition of water by using suitable condensation catalysts, in particular organometallic compounds, such as. organotin compounds such as dibutyltin dilaurate, organotin oxides, organometallic compounds such as carboxylates, alcoholates or chelates, titanium, calcium, aluminum, zirconium or zinc are brought to condensation. In a further preferred embodiment, the reaction mixture of alkoxyaminoalkyl polysiloxane and the ketonic or aldehydic perfume before, during or after the amine ketone resp. Amine-aldehyde reaction in addition fragrance alcohols are added, which are capable of transesterification reactions with the alkoxysilyl groups.

In a further embodiment of the invention, for example, different fragrances with, for example, different chemical attachment to the polysiloxane polymer backbone will be included. From such substances, the chemically bound odors are released at different reaction rates on contact with moisture. Accordingly, this embodiment opens up the possibility of changing the odor characteristic during the release period by chemically different binding and / or chemically different fragrances.

In particular, the polyorganosiloxanes of the present invention also have good separation efficiency from an application solution such as an emulsion or microemulsion, and their high surface affinity can be exploited to: surface-conditioning or conditioning effects, such as softening, fiber-elastic effects or color-preserving, color-enhancing or gloss effects to achieve.

The perfume-modified polyorganosiloxanes according to the invention are used, for example, in the following functions or applications in which they function as perfume dispensers or for imparting further properties, such as softening properties:

In cleaning agents, such as detergents, dishwashing agents, in care products, such as means for fabric care, fragrance strips based on paper or textile materials, fragrance dispensers in soaps or soap formulations, toilet fragrance dispensers, in wallpaper, in paper, as impregnating agents in the sanitary area, in fragrance inlets, in Clothing treatment preparations, in panty liners, as textile treatment preparations before and after washing, in particular in rinse-off applications, in finishes for finishing surfaces, such as in floor care products, in cosmetics, such as deodorants, make-up, such as mascara , Skin care products, hair cosmetics, such as shampoos, hair care products, hair gels, styling gels.

The polyorganosiloxanes according to the invention are particularly preferably used in compositions, in particular detergents, such as detergents, dishwashing detergents, as described in European patents 1095128, 1123376, 1161515, 1062265, 1144578, 1144579, 1360269, 1661978, 1280882, 1383858, WO 2005- 105970 as well as in WO 2006-029188. Such cleaning agents generally have nonionic, anionic and / or cationic surfactants.

To this end, perfume-modified polyorganosiloxanes having reactive groups are previously supported or dispersed or encapsulated in a solid or liquid immiscible carrier, especially when used in aqueous compositions. In the event that they are used in a non-aqueous composition, For example, the perfume modified polyorganosiloxanes may be blended directly into a perfume oil composition or blended in the nonaqueous carrier or solvent.

The invention further provides a composition of perfume-modified polyorganosiloxanes of the invention containing at least one inorganic or organic acid. It has been found that in such compositions the fragrance-modified branched polyorganosiloxanes according to the invention can be stabilized, and such compositions are therefore particularly suitable for the preparation of stabilized concentrates, so-called perfume oils. Naturally, these forms are particularly suitable as a form of sale of the perfume-modified branched polyorganosiloxanes according to the invention.

Examples of suitable acids include, for example, carboxylic acids, preferably hydroxycarboxylic acids, and citric acid is very preferred. Examples of inorganic acids include hydrochloric acid, phosphoric acid, sulfuric acid, nitric acid.

In addition to the fragrance-modified branched polyorganosiloxanes according to the invention, the perfume oils may contain further perfumes, solvents such as

Alcohols, esters, ketones.

Fragrance-modified branched polyorganosiloxane according to the invention:

100 parts by weight perfume-modified polyorganosiloxane

0 to 100 parts by weight of solvent, preferably C 1 -C 8 -alkyl alcohol, more preferably without solvent, with heat input,

0.5-1 mole of acid per basic equivalent of nitrogen, with citric acid,

Formic acid or HCl are preferred.

The amine content is determined by titration as a color change of tetrabromophenolphthalide in isopropanol / xylene: 1: 1 by acid-base titration. Due to their special properties, the perfume-modified, branched polyorganosiloxanes according to the invention can be permanently applied to the substrates treated with them, thereby beneficially modifying the surface properties of the substrates while at the same time fixing the fragrance to the surface, from which it is released for a long time.

Accordingly, the invention further relates to detergents, conditioners, surface finishing agents, and cosmetic agents containing at least one fragrance-modified polyorganosiloxane of the invention.

The fragrance-modified branched polyorganosiloxanes of this invention may be preferably used in compositions such as detergent compositions, cleaning compositions, especially hard surfaces, and personal care compositions, wherein the fragrance-modified branched polyorganosiloxanes may be used together with one or more Detergent or detergent ingredients are mixed.

Incorporation of the fragrance-modified, branched polyorganosiloxanes of this invention may be conveniently accomplished by incorporation, for example, by spraying or by dry addition. In the present invention, the fragrance-modified branched polyorganosiloxanes may be incorporated, for example, in detergent compositions, including those in liquid and solid form, such as powders and tablets, as well as softening compositions, including before or after washing. Purification process of rinse-added softener compositions and dryer-added softener compositions. With regard to customary plasticizer compositions into which the fragrance-modified, branched polyorganosiloxanes of the invention may be incorporated, reference may be made, for example, to EP-A-971 025, the disclosure of which is fully incorporated herein is involved. The fragrance-modified, branched polyorganosiloxanes according to the invention are preferably added to a detergent composition, preferably in solid form. Finished compositions typically contain the fragrance-modified branched polyorganosiloxanes of this invention in an amount of from 0.1% to 25%, more preferably from 0.2% to 10%, and most preferably from 0.5% to 5% by weight. , Detergent compositions containing the fragrance-modified branched polyorganosiloxanes of the invention preferably comprise a bleach precursor, a source of alkaline hydrogen peroxide necessary for the formation of a peroxyacid bleach in the wash solution, and preferably also include others for laundry detergents - Compositions usual ingredients. These include, for example, one or more surfactants, organic and inorganic builders, soil-carrying and anti-redeposition agents, suds suppressors (antifoam), enzymes, fluorescent whiteners, photoactivated bleaches, perfumes, colors, clay softeners, effervescent agents, and mixtures thereof. Typical ingredients can be found in EP-A-0 659 876 and EP-A-971 024, the disclosures of which are fully incorporated in the present application. The detergent compositions containing the fragrance-modified branched polyorganosiloxanes according to the invention may preferably contain clay, for example in a concentration of 0.05% to 40% by weight, more preferably 0.5% by weight. to 30% by weight, most preferably from 2% to 20% by weight of the composition. A preferred clay may be a bentonite clay. Very preferred are smectite clays such as disclosed in U.S. Patent Nos. 3,862,058, 3,948,790, 3,954,632 and 4,062,647 and European Patent Nos. EP-A-299,575 and EP-A-313,146. Specific examples of suitable smectite clays include those selected from the classes of montmorillonites, hectorites, volkonskoite, nontronites, saponites and sauconites, especially those having an alkali or alkaline earth metal ion within the crystalline lattice structure. Sodium or calcium montmorillonite particularly preferred. For example, clays have an average particle size of from 10 nm to 800 nm, more preferably from 20 nm to 500 mm, most preferably from 50 nm to 200 mm. The smectite clay materials suitable here typically have a cation exchange capacity of at least 50 meq / 100 g. The crystalline lattice structure of the clay mineral compounds may, in a preferred embodiment, contain a substituted cationic fabric softener. Such substituted clays are called "hydrophobically activated" clays The cationic fabric softeners are typically present in a weight ratio of cationic fabric softener to clay of from 1: 200 to 1:10, preferably from 1: 100 to 1: 20. Suitable cationic fabric softeners include water-insoluble tertiary amines or di-long-chain amide materials as disclosed in GB-A-1 514 276 and EP-B-011 340. A preferred commercially available "hydrophobically activated" clay is a bentonite clay containing about 40% by weight dimethylditaline quaternary ammonium salt (Claytone EM). The clay may be in an intimate mixture or in a particle with a humectant and a hydrophobic compound, preferably a wax or oil, such as paraffin oil. Preferred humectants are organic compounds including propylene glycol, ethylene glycol, dimers or trimers of glycol, most preferably glycerol. The particle is preferably an agglomerate. Alternatively, the particle may be such that the wax or oil and optionally the humectant form an envelope of the clay or, alternatively, the clay may be an envelope for the wax or oil and humectant. It may be preferred that the particle comprises an organic salt or silica or silicate. However, the clay is preferably mixed with one or more surfactants and optionally builders and optionally water, the mixture preferably being subsequently dried. Preferably, such a mixture is further processed in a spray-drying process to obtain a spray-dried particle comprising the clay. It may be preferred that the flocculant also be incorporated into the particle or granule comprising the clay, is included. It may also be preferred that the intimate mixture comprises a sequestering agent. The compositions of the invention may contain a clay flocculating agent, preferably at a level of from 0.005% to 10%, more preferably from 0.05% to 5%, most preferably 0, 1 wt .-% to 2 wt .-% of the composition is present. The clay flocculating agent has the function of bringing together the clay compound particles in the washing solution to aid their attachment to the surface of the fabrics during washing. Preferred clay-flocculating agents herein are organic polymeric materials having an average weight of from 100,000 to 10,000,000, preferably from 150,000 to 5,000,000, more preferably from 200,000 to 2,000,000. Suitable organic polymer materials include homopolymers or copolymers containing monomer units selected from alkylene oxide, especially ethylene oxide, acrylamide, acrylic acid, vinyl alcohol, vinylpyrrolidone and ethyleneimine. Homopolymers, in particular of ethylene oxide, but also of acrylamide and acrylic acid, are preferred. European Patent Nos. EP-A-299 575 and EP-A-313 146 describe preferred organic polymeric clay flocculating agents for use herein. The weight ratio of clay to the flocculant polymer is preferably from 1000: 1 to 1: 1. Inorganic clay flocculating agents are also suitable herein, typical examples of which include lime and alum. The flocculant is preferably present in a detergent base grain such as a detergent agglomerate, extrudate or spray dried particle, which generally comprises one or more surfactants and builders. Effervescent agents may also optionally be used in the compositions of the invention. Examples of acid and carbonate sources and other effervescent systems can be found in: Pharmaceutical Dosage Forms: Tablets, Vol. 1, pages 287 to 291. Suitable inorganic alkali and / or alkaline earth carbonate salts herein include carbonate and bicarbonate of potassium, lithium, sodium, etc., below which sodium and potassium carbonate are preferred. Suitable bicarbonates for use herein include all alkali metal salts of bicarbonate, such as Lithium, sodium, potassium, etc., among which sodium and potassium bicarbonate are preferred. However, the choice between carbonate or bicarbonate or mixtures thereof may be made depending on the desired pH in the aqueous medium in which the granules are dissolved. Other preferred optional ingredients include enzyme stabilizers, polymeric soil release agents, fabrics that inhibit the transfer of dyes from one fabric to another during the cleaning process (ie, dye transfer inhibiting agents), polymeric dispersants, suds suppressors, optical brighteners or other whiteners or whiteners, antistatic agents, other effective Ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations and solid fillers for bar compositions.

The fragrance-modified branched polyorganosiloxanes according to the invention may preferably be present in fabric softener formulations. In addition to the fragrance-modified branched polyorganosiloxanes according to the invention, which likewise have a softening effect, these can comprise further fabric conditioning components which impart softness and antistatic properties to the treated fabrics. The fabric softening components can be selected from cationic, nonionic, amphoteric or anionic fabric softening components become. Typical of the cationic softening components are the quaternary ammonium compounds or their amine precursors. Examples of fabric softening agents include; N, N-di (tallowoyloxy-ethyl) -N, N-dimethyl ammonium chloride; N ₁ N

Di (canoloyloxyethyl) -N, N-dimethyl ammonium chloride; N, N-di (tallowoyloxyethyl) -N-methyl, N- (2-hydroxyethyl) ammonium chloride; N, N-di (canoloyloxyethyl) -N-methyl, N- (2-hydroxyethyl) ammonium chloride; N, N-di (2-tallowoyloxy-2-oxoethyl) -N, N-dimethyl-ammonium chloride; N, N-di (2-canoloyloxy-2-oxoethyl) -N, N-dimethylammonium chloride N, N-di (2-tallowoyloxyethylcarbonyloxyethyl) -N, N-dimethylammonium chloride; N, N-di (2-canoloyloxyethylcarbonyloxyethyl) -N, N- dimethylammonium chloride; N- (2-tallowoyloxy-2-ethyl) -N- (2-tallowoyloxy-2-oxoethyl) -N, N-dimethyl-ammonium chloride; N- (2-canoloyloxy-2-ethyl) -N- (2-canoloyloxy-2-oxo-ethyl) -N, N-dimethylammonium chloride; N ₁ N ₁ N-

Tri (tallowoyloxy-ethyl) -N-methyl ammonium chloride; N, N, N-tricanoloyloxyethyl) -N-methylammonium chloride; N- (2-tallowoyl-oxy-2-oxoethyl) -N- (tallowoyl) -N, N-dimethylammonium chloride; N- (2-canoloyloxy-2-oxoethyl) -N- (canoyl) -N, N-dimethylammonium chloride; 1,2-ditallowoyloxy-3-N, N, N-trimethylammoniopropane chloride; and 1, 2-dicanoloyloxy-3-N, N, N-trimethyl-ammoniopropane chloride; and mixtures of the above active ingredients. Other examples of quaternary ammonium plasticizer compounds are methyl bis (tallowamidoethyl) (2-hydroxyethyl) ammonium methylsulfate and

Methyl bis (hydrogenated tallowamidoethyl) (2-hydroxyethyl) ammonium methylsulfate; These materials are available from Momentive Performance Materials under the trade names Varisoft 222 and Varisoft 110. Particularly preferred is N, N-di (tallowoyloxyethyl) -N, N-dimethylammonium chloride, where the Taq chains are at least partially unsaturated. Other suitable examples of fabric softener actives are derived from fatty acyl groups in which the names "tallowoyl" and "canoloyl" in the above examples are replaced by the names "cocoyl, palmoyl, lauroyl, oleoyl, ricinoleoyl, stearoyl, palmitoyl" These alternative fatty acyl sources may comprise either fully saturated or preferably at least partially unsaturated chains For ester fabric softeners, the pH of the compositions is important, the pH preferably being in the range of 2, 0 to 5, preferably in the range of 2.5 to 4.5, preferably 2.5 to 3.5 The pH of these compositions herein can be regulated by the addition of a Bronsted acid Examples of suitable acids include inorganic mineral acids, carboxylic acids , in particular the low molecular weight (Cr to CsJ carboxylic acids, and alkyl sulfonic acids acids include HCl, H ₂ SO ₄ , HNO ₃ and H ₃ PO ₄ . Suitable organic acids include formic, acetic, citric, methylsulfonic and ethylsulfonic acids. Preferred acids are Citric, hydrochloric, phosphorous, formic, methylsulfonic and benzoic acids. Other suitable quaternary ammonium compounds are cationic nitrogen Wäscheweichmacher- salts having two or more long chain acyclic aliphatic Cs to C ₂₂ hydrocarbon groups or one of these groups and an arylalkyl group which can be used either alone or as part of a mixture, and the selected from the group consisting of: (i) acyclic quaternary ammonium salts, (ii) diaminoalkoxylated quaternary ammonium salts and mixtures thereof. Examples are dialkyl dimethyl ammonium salts, such as ditallow dimethyl ammonium chloride, ditallow dimethyl ammonium methyl sulfate, di (hydrogenated tallow) dimethyl ammonium chloride, distearyl dimethyl ammonium chloride, dibehenyldimethyl ammonium chloride. Di (hydrogenated tallow) dimethyl ammonium chloride and ditallow dimethyl ammonium chloride.

Suitable amine fabric softening compounds are selected from: (i) reaction of higher fatty acid products with a polyamine selected from hydroxyalkylalkylenediamines and dialkylenetriamines and mixtures thereof. (For further examples, see "Cationic Surface Active Agents as Fabric Softeners," R.R. Egan, Journal of the American Oil Chemicals' Society, January 1978, pages 118-121).

Additional fabric softening materials may be used in addition or alternatively to the cationic fabric softener. These may be selected from nonionic, amphoteric or anionic fabric softening materials. A disclosure of such materials can be found in US 4,327,133; US 4,421,792; US 4,426,299; US 4,460,485; US 3,644,203; U.S. 4,661,269; US 4,439,335; U.S. 3,861,870; US 4,308,151; US 3,886,075; US 4,233,164; US 4,401,578; US 3,974,076; US 4,237,016 and EP 472,178. Preferred nonionic softening agents are fatty acid partial esters of polyhydric alcohols or their anhydrides. Preferred nonionic softening agents are the sorbitan esters and the glycerol esters. Other fabric softening components suitable for use herein are plasticizer clays, such as those having low ion exchange capability, described in EP-A-0,150,531.

The fabric softening compounds are present in amounts of from 1% to 80% of the softening compositions or detergent composition.

Further, the softener compositions and / or detergent composition may include, for example, whiteners in amounts of from 0.005% to 5%, by weight, e.g. 4,4'-bis [(4-anilino-6- (N-2-bis-hydroxyethyl) -s-triazin-2-yl) amino] -2,2'-stilbene disulfonic acid and disodium salt thereof.

Further, the softener compositions and / or detergent composition may include dispersing aids, such as (1) long chain alkyl long-chain alkyl surfactants; (2) nonionic surfactants; (3) amine oxides; (4) fatty acids and (5) mixtures thereof in amounts of, for example, from 2% to 25% by weight of the composition. Examples of (1) are quaternary cationic monoalkylammonium compounds, such as quaternary ammonium salts of the general formula: [RiangN ⁺ (Rkurz) 3] X ^~ wherein Rι _{ang is} a Cs to C22 alkyl or alkenyl group and Rn is a C1 to C6 Alkyl or substituted alkyl group (eg hydroxyalkyl), a benzyl group, hydrogen, a polyethoxylated chain having from 2 to 20 oxyethylene units and X ^"is an anion, for example monauryltrimethylammonium chloride and monotallowtrimethylammonium chloride, monooleyl or monocanolatrimethylammonium chloride, monococonut oil trimethylammonium chloride, monosojatrimethylammonium chloride.

Examples of (2) are nonionic surfactants which serve as viscosity / dispersibility improvers, include addition products of ethylene oxide and optionally propylene oxide, with fatty alcohols, fatty acids, fatty amines, etc. The nonionic surfactants herein are characterized by an HLB value (a hydrophile-lipophile balance) of 7 to 20, preferably 8 to 15. Examples of (3) include amine oxides having an alkyl or hydroxyalkyl moiety of 8 to 22 carbon atoms, such as dimethyloctylamine oxide, diethyldecylamine oxide, bis (2-hydroxyethyl) dodecylamine oxide, dimethyldodecylamine oxide, dipropyltetradecylamine oxide, methylethylhexadecylamine oxide, dimethyl 2-hydroxy-octadecylamine oxide and Coconut fatty alkyldimethylamine oxide.

Fragrance-modified, branched polyorganosiloxanes-containing detergents. Plasticizer formulations may further contain stabilizers, such as antioxidants and reducing agents in a concentration of 0 to 2% by weight, such as a mixture of ascorbic acid, ascorbic palmitate, propyl gallate, a mixture of BHT (butylated hydroxytoluene), BHA (butylated hydroxyanisole) , Propyl gallate and citric acid.

Fragrance-modified, branched polyorganosiloxanes-containing detergents. Plasticizer formulations may further contain soil release or soil detergency agents at levels of from 0% to 10% by weight.

Fragrance-modified, branched polyorganosiloxanes-containing detergents. Plasticizer formulations may further contain antifoaming or sludge dispersing agents in amounts of, for example, more than 2%, preferably at least 4%, of the formulation.

Fragrance-modified, branched polyorganosiloxanes-containing detergents. Plasticizer formulations may further contain bactericides, such as glutaraldehyde, formaldehyde, 2-bromo-2-nitropropane-1,3-diol, in amounts of, for example, from 1 to 1,000 ppm by weight of active ingredient.

Fragrance-modified, branched polyorganosiloxanes-containing detergents. Plasticizer formulations may further contain additional unbound perfumes. These may also be those used to produce the Fragrance-modified, branched polyorganosiloxanes used according to the invention act as fragrances. They can be added, for example, in a concentration of 0 to 10 wt .-%.

Fragrance-modified, branched polyorganosiloxanes-containing detergents. Plasticizer formulations may further contain sequestering agents, for example in an amount of from 0.1 to 15% by weight.

Fragrance-modified, branched polyorganosiloxanes-containing detergents. Plasticizer formulations may further contain crystal growth inhibiting components (including limestone inhibition) at, for example, a concentration of from 0.01% to 5% by weight, such as organophosphonic acids. Fragrance-modified, branched polyorganosiloxanes-containing detergents. Plasticizer formulations may further contain enzymes such as lipases, proteases, cellulases, amylases and peroxidases, for example, in amounts of from 0.001 to 5% by weight.

Fragrance-modified, branched polyorganosiloxanes-containing detergents. Plasticizer formulations may further include liquid carriers such as water in amounts greater than, for example, more than 50% by weight of the composition, or organic solvents such as lower monoalcohols such as ethanol, propanol, isopropanol or butanol, dihydric alcohols (glycol, etc.), trihydric Alcohols (glycerol, etc.) and higher polyhydric (polyol) alcohols.

Fragrance-modified, branched polyorganosiloxanes-containing detergents. Plasticizer formulations may further conventionally contain textile treatment agents, such as: colorants, preservatives; surfactants; Anti-wrinkle agent; fabric crisping agents; spotting agents; germicides; fungicides; Antioxidants, anti-corrosion agents; Enzyme stabilizing agents; Materials that are effective to prevent dye transfer from one substance to another during the cleaning process (e.g. Dye transfer inhibitors), hydrotropes, processing aids, dyes or pigments, and the like.

The fragrance-modified, branched polyorganosiloxanes of the invention may further be used in surface-treating agents in the broadest sense, where they raise on the surface due to high substantivity and exude long-lasting fragrance. Typical examples of materials with surfaces to be treated are, for example, dishes, floors, bathrooms, toilets, carpets, kitchens, leather, car seats, litter or animal litter.

Due to their special properties, the polyorganosiloxanes according to the invention are able to be permanently applied to the substrates treated with them, thereby beneficially modifying the surface properties of the substrates while at the same time fixing the fragrance to the surface, from which it is released for a prolonged period.

Furthermore, the invention relates to a method for coating a substrate, which comprises applying at least one polyorganosiloxane according to the invention to the surface of the substrate.

The invention further relates to the use of perfume-modified organosilanes for the preparation of linear or branched perfume-modified polyorganosiloxanes of the invention.

The invention is illustrated by the following example. example 1

Preparation of a condensation product of alpha-Damascon with an alkoxyaminopolysiloxane

0.5 mol of the alkoxyaminoalkylpolysiloxane NH ₂ CH ₂ CH ₂ CH ₂ -Si (OEt) ₂ - [Si (OMe) ₂ ] I ₀ -OSi (OEt) ₂ -CH ₂ CH ₂ CH ₂ NH ₂ are reacted with 1 mol of alpha Damascone and heated at 125 ⁰ C with stirring for 12 h. Volatile products are removed by a distillation bridge. Subsequently, any remaining volatile components are removed by distillation in a water jet vacuum (18 mbar, 3h, 100-140 ⁰ C). A dark amber oily liquid is obtained.

Example 2

Preparation of a condensation product of alpha-Damascon with an alkoxyaminopolysiloxane with further addition of phenylethanol.

0.5 mol of the alkoxyaminopolysiloxane from Example 1 are combined with 1 mol of alpha-damascone and 0.1 mol of phenylethanol and heated with stirring to 140 ⁰ C for 12 h. Volatile products such as ethanol are removed via a distillation bridge. Then remaining volatile components are removed by distillation in a water-jet vacuum at 140 ⁰ C and18 mbar, over 2 hours. It is obtained a reddish-brown oily liquid.

Example 3

Preparation of a cross-linked condensation product from the reaction of alpha-Damascone with an alkoxyaminosiloxane

To show that the product of Example 1 has reactive (in this case condensable) groups, it was mixed with vigorous stirring Dibutyltin dilaurate in the air 50% air humidity at 25 ⁰ C added. After 6 hours obtains a dark amber-colored, viscous mass with gel-like consistency.

Claims

CLAIMS:

1. fragrance-modified reactive groups containing polyorganosiloxanes.

2. polyorganosiloxanes according to claim 1, characterized in that they contain at least one reactive group which is capable of reacting with a substrate and / or for condensation.

3. Polyorganosiloxanes according to claim 2, wherein the substrate is selected from the group consisting of: fibers, textiles, plasters, paper, wallpapers, moldings, ceramics, lacquer layers, foils, hair, skin, wood, glass, plastics.

4. Polyorganosiloxanes according to claim 2 or 3, characterized in that the reactive group is at least one group of the formula (I):

-SiR ² _n X ₃ -n (I) wherein

n = 0 to 2,

R ^{2 is} selected from optionally substituted alkyl and phenyl,

wherein R ^{3 is} selected from the group consisting of hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted cycloalkyl and aryl, R ^{4 is} a divalent optionally substituted, optionally one or more heteroatoms having organic radical, and

Y is selected from the group consisting of -NCO, -OH, -NR ³ _2, -C (O) CI, -SO ₂ CI, -SO ₂ -vinyl, triazinyl, pyrimidinyl.

5. Polyorganosiloxanes according to one of claims 2 to 4, characterized in that the substrate has functional groups on the surface, which are selected from the group consisting of: hydroxy, amino, carboxy, carbonyloxy (ester), disulfide, mercapto.

6. polyorganosiloxanes according to any one of claims 1 to 5, obtainable by the reaction of functionalized polyorganosiloxanes with fragrances or by condensation of perfume-modified polyorganosiloxanes or organosilanes.

7. Polyorganosiloxanes according to claim 6, wherein the fragrances have at least one functional group selected from the group consisting of keto, aldehyde and / or hydroxy groups.

8. polyorganosiloxanes according to any one of claims 6 or 7, wherein the functionalized polyorganosiloxanes used as starting compounds have at least one functional group which are capable of reacting with keto, aldehyde and / or hydroxy-functionalized perfumes.

9. Polyorganosiloxanes according to any one of claims 6 to 8, wherein the functionalized polyorganosiloxanes or organosilanes used as starting compounds at least one functional group which is selected from the group consisting of aminoalkyl groups, hydroxyalkyl groups and alkoxy groups each attached to a silicon atom.

10. polyorganosiloxanes according to claim 9, characterized in that the functionalized polyorganosiloxanes or organosilanes used as starting compounds have at least one primary or secondary amine radical.

1 1. A method for coating a substrate, which comprises applying at least one polyorganosiloxane according to any one of claims 1 and 10 to the surface of the substrate.

12. Use of the polyorganosiloxanes according to any one of claims 1 and 10, which comprises the release of the fragrance.

13. A process for producing a fragrance, which comprises treating a substrate with at least one polyorganosiloxane according to any one of claims 1 and 10 and the release of the fragrance from the fragrance-modified substrate.

14. A process for the preparation of the polyorganosiloxanes according to one of claims 1 to 10, which comprises the reaction of functionalized polyorganosiloxanes with fragrances

15. A process for the preparation of the polyorganosiloxanes according to any one of claims 1 to 10, which comprises the condensation of fragrance-modified polyorganosiloxanes or organosilanes.

16. The method of claim 14, wherein the polyorganosiloxane obtained is applied to a support material.

17. The method of claim 20, wherein the polyorganosiloxane obtained is brought by spray drying or fluidized bed granulation on a support material.

18. Use of perfume-modified organosilanes for the preparation of linear or branched perfume-modified polyorganosiloxanes.

19. Use of polyorganosiloxanes according to any one of claims 1 to 10 in cleaning agents, in care products, in agents for finishing surfaces, in cosmetics.

20. Cleaning agent, care agent, surface finishing agent and cosmetic agent containing at least one polyorganosiloxane according to any one of claims 1 to 11.

21. A composition comprising at least one perfume-modified polyorganosiloxane according to any one of claims 1 to 1 1 and at least one surface-active compound selected from anionic, cationic or nonionic surfactants.

22. A non-aqueous composition containing at least one perfume-modified polyorganosiloxane according to any one of claims 1 to 1 1 and at least one organic medium.