EP3080238B1 - Automatic dishwasher detergents containing oxazolidine odoriferous substance precursors - Google Patents

Description

The present invention relates to the use of perfume precursors in the form of oxazolidines for preventing and / or controlling malodors in dishwashing machines, particularly in the form of automatic dishwashing detergents containing these oxazolidine fragrance precursors, the dishwashing compositions per se, and a machine dishwashing method using the same this dishwashing detergent.

It is known that automatic dishwashers display problems with odor development after use and longer periods of non-use or larger time intervals between the filling time and the next rinsing. These are perceived by the consumer as unpleasant and have their cause in food residues and / or their bacterial degradation products in the dishwasher, especially the water in the dishwasher sump.

Although currently commercially available dishwashing detergents usually contain fragrances, they are not suitable for satisfactorily controlling the bad odors which develop after prolonged non-use of the dishwasher in its interior.

The object of the present invention was to provide compounds for use in automatic dishwashing detergents which cover unpleasant odors which arise in the course of automatic dishwashing and, in particular, prolonged non-use of the dishwasher and / or storage of dirty dishes in the interior thereof reduce or even completely neutralize it.

It has now been found that perfume precursors in the form of oxazolidines are surprisingly able to cover such malodors effectively over a period of several days of non-use of the dishwasher.

A first aspect of the present invention therefore relates to means for use in an automatic dishwashing machine as defined in claim 1. Another aspect of the invention is directed to the use of such an agent for controlling or neutralizing bad odors in a machine dishwashing machine.

Yet another aspect relates to automatic dishwashing processes, characterized in that an agent, in particular a machine dishwashing detergent, according to the invention is used.

Finally, the invention also relates to the use of an oxazolidine precursor compound of a fragrance according to claim 9 for controlling or neutralizing malodors in a machine dishwashing machine.

All amounts stated in connection with the agents described herein, unless otherwise indicated, are by weight in each case based on the total weight of the composition. Furthermore, such amounts referring to at least one constituent always refer to the total amount of that type of constituent contained in the composition, unless explicitly stated otherwise. That is, such quantities, for example in connection with "at least one nonionic surfactant", refer to the total amount of nonionic surfactants contained in the middle.

"At least one" as used herein refers to 1 or more, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9 or more. In the context of ingredients of the compositions described herein, this indication does not refer to the absolute amount of molecules but to the nature of the ingredient. Thus, "at least one nonionic surfactant" means, for example, one or more different nonionic surfactants, i. one or more different types of nonionic surfactants. Together with quantities, the quantities refer to the total amount of the corresponding designated type of ingredient as defined above.

wobei

• R ausgewählt wird aus substituiertem oder unsubstituiertem, verzweigtem oder linearem C_6-24 Alk(en)yl, substituiertem oder unsubstituiertem C_6-24 Cycloalk(en)yl, substituiertem oder unsubstituiertem C_6-24 (Hetero-)Aryl und substituiertem oder unsubstituiertem C_6-24 Heterocyclyl;
• R¹ ausgewählt wird aus H, substituiertem oder unsubstituiertem, verzweigtem oder linearem C_1-10 Alkyl, substituiertem oder unsubstituiertem, verzweigtem oder linearem C_2-10 Alkenyl, substituiertem oder unsubstituiertem C_3-15 Cycloalk(en)yl, substituiertem oder unsubstituiertem C_6-15 (Hetero-)Aryl und substituiertem oder unsubstituiertem C_6-24 Heterocyclyl, oder
• R und R¹ zusammen mit dem Kohlenstoffatom an welches sie gebunden sind einen 3- bis 10-gliedrigen substituierten oder unsubstituierten Cycloalk(en)yl- oder Heterocyclyl-Ring oder einen 5-10-gliedrigen (Hetero-)Aryl-Ring bilden;
• R², R³, R⁴, R⁵ und R⁶ unabhängig voneinander ausgewählt werden aus H, substituiertem oder unsubstituiertem, verzweigtem oder linearem C_1-10 Alkyl, substituiertem oder unsubstituiertem, verzweigtem oder linearem C_2-10 Alkenyl, substituiertem oder unsubstituiertem C_3-15 Cycloalk(en)yl, substituiertem oder unsubstituiertem C_6-15 (Hetero-)Aryl, substituiertem oder unsubstituiertem C_6-24 Heterocyclyl, -OH, -(CH₂)_x-COR⁷, und -(CR¹⁰R¹¹)_y(CHR¹²CHR¹³O)_zR¹⁴, oder jeweils zwei von R², R³, R⁴, und R⁵ zusammen mit dem/den Kohlenstoffatom(en) an welche(s) sie gebunden sind einen 3- bis 10-gliedrigen substituierten oder unsubstituierten Cycloalk(en)yl- oder Heterocyclyl-Ring oder einen 5-10-gliedrigen (Hetero-)Aryl-Ring bilden, oder R² und R³ oder R⁴ und R⁵ zusammen eine Carbonylgruppe bilden;
• R⁷ ausgewählt wird aus -OH, -OR⁸, -N(R¹)₂, substituiertem oder unsubstituiertem, verzweigtem oder linearem C_1-22 Alkyl, substituiertem oder unsubstituiertem, verzweigtem oder linearem C_2-22 Alkenyl, substituiertem oder unsubstituiertem C_3-22 Cycloalk(en)yl, substituiertem oder unsubstituiertem C_6-24 (Hetero-)Aryl und substituiertem oder unsubstituiertem C_6-24 Heterocyclyl; R⁸ ausgewählt wird aus H, substituiertem oder unsubstituiertem, verzweigtem oder linearem C_1-15 Alkyl, substituiertem oder unsubstituiertem, verzweigtem oder linearem C_2-22 Alkenyl, und M, wobei M ein wasserlösliches Kation ist;
• R⁹ ausgewählt wird aus H und substituiertem oder unsubstituiertem, verzweigtem oder linearem C_1-6 Alkyl;
• R¹⁰, R¹¹ und R¹² unabhängig ausgewählt werden aus H, -OH und C_1-4 Alkyl; oder R¹⁰ und R¹¹ zusammen mit dem Kohlenstoffatom an welches sie gebunden sind einen 3- bis 10-gliedrigen substituierten oder unsubstituierten Cycloalk(en)yl- oder Heterocyclyl-Ring, einen 5-10-gliedrigen (Hetero-)Aryl-Ring oder eine Carbonylgruppe bilden;
• R¹³ und R¹⁴ unabhängig ausgewählt werden aus H und C_1-4 Alkyl;
• x eine ganze Zahl von 0 bis 22 ist;
• y eine ganze Zahl von 1 bis 10 ist; und
• z eine ganze Zahl von 1 bis 50 ist.

Oxazolidine precursors capable of liberating a fragrance aldehyde or fragrance ketone by hydrolysis include compounds of the formula

in which

• R is selected from substituted or unsubstituted, branched or linear C _6-24 alk (en) yl, substituted or unsubstituted C _6-24 cycloalk (en) yl, substituted or unsubstituted C _6-24 (hetero) aryl, and substituted or unsubstituted C _6-24 heterocyclyl;
• R ^{1 is} selected from H, substituted or unsubstituted, branched or linear C _1-10 alkyl, substituted or unsubstituted, branched or linear C _2-10 alkenyl, substituted or unsubstituted C _3-15 cycloalk (en) yl, substituted or unsubstituted C _6-15 (hetero) aryl, and substituted or unsubstituted C _6-24 heterocyclyl, or
• R and R ¹ together with the carbon atom to which they are attached form a 3- to 10-membered substituted or unsubstituted cycloalk (en) yl or heterocyclyl ring or a 5-10 membered (hetero) aryl ring;
• R ² , R ³ , R ⁴ , R ⁵ and R ^{6 are} independently selected from H, substituted or unsubstituted, branched or linear C _1-10 alkyl, substituted or unsubstituted, branched or linear C _2-10 alkenyl, substituted or unsubstituted C _3-15 cycloalk (en) yl, substituted or unsubstituted C _6-15 (hetero) aryl, substituted or unsubstituted C _6-24 heterocyclyl, -OH, - (CH ₂ ) _x -COR ⁷ , and - (CR ¹⁰ R ¹¹ ) _y (CHR ¹² CHR ¹³ O) _z R ¹⁴ , or any two of R ² , R ³ , R ⁴ , and R ⁵ together with the carbon atom (s) to which they are attached are a 3 - form a 10-membered substituted or unsubstituted cycloalk (en) yl or heterocyclyl ring or a 5-10 membered (hetero) aryl ring, or R ² and R ³ or R ⁴ and R ⁵ together form a carbonyl group ;
• R ^{7 is} selected from -OH, -OR ⁸ , -N (R ¹ ) ₂ , substituted or unsubstituted, branched or linear C _1-22 alkyl, substituted or unsubstituted, branched or linear C _2-22 alkenyl, substituted or unsubstituted C _3-22 cycloalk (en) yl, substituted or unsubstituted C _6-24 (hetero) aryl and substituted or unsubstituted C _6-24 heterocyclyl; R ^{8 is} selected from H, substituted or unsubstituted, branched or linear C _1-15 alkyl, substituted or unsubstituted, branched or linear C _2-22 alkenyl, and M, wherein M is a water-soluble cation;
• R ^{9 is} selected from H and substituted or unsubstituted, branched or linear C _1-6 alkyl;
• R ¹⁰ , R ¹¹ and R ^{12 are} independently selected from H, -OH and C _1-4 alkyl; or R ¹⁰ and R ¹¹ together with the carbon atom to which they are attached are a 3- to 10-membered substituted or unsubstituted cycloalk (en) yl or heterocyclyl ring, a 5-10 membered (hetero) aryl ring or form a carbonyl group;
• R ¹³ and R ^{14 are} independently selected from H and C _1-4 alkyl;
• x is an integer from 0 to 22;
• y is an integer from 1 to 10; and
• z is an integer from 1 to 50.

wobei

• R ausgewählt wird aus substituiertem oder unsubstituiertem, verzweigtem oder linearem C_6-24 Alk(en)yl, substituiertem oder unsubstituiertem C_6-24 Cycloalk(en)yl, substituiertem oder unsubstituiertem C_6-24 (Hetero-)Aryl und substituiertem oder unsubstituiertem C_6-24 Heterocyclyl;
• R¹ ausgewählt wird aus H, substituiertem oder unsubstituiertem, verzweigtem oder linearem C_3-10 Alkyl, substituiertem oder unsubstituiertem, verzweigtem oder linearem C_4-10 Alkenyl, substituiertem oder unsubstituiertem C_3-15 Cycloalk(en)yl, substituiertem oder unsubstituiertem C_6-15 (Hetero-)Aryl und substituiertem oder unsubstituiertem C_6-24 Heterocyclyl, oder
• R und R¹ zusammen mit dem Kohlenstoffatom an welches sie gebunden sind einen 3- bis 10-gliedrigen substituierten oder unsubstituierten Cycloalk(en)yl- oder Heterocyclyl-Ring oder einen 5-10-gliedrigen (Hetero-)Aryl-Ring bilden;
• R², R³, R⁴, R⁵ und R⁶ unabhängig voneinander ausgewählt werden aus H, substituiertem oder unsubstituiertem, verzweigtem oder linearem C_3-10 Alkyl, substituiertem oder unsubstituiertem, verzweigtem oder linearem C_4-10 Alkenyl, substituiertem oder unsubstituiertem C_3-15 Cycloalk(en)yl, substituiertem oder unsubstituiertem C_6-15 (Hetero-)Aryl, substituiertem oder unsubstituiertem C_6-24 Heterocyclyl, -OH, -(CH₂)_x-COR⁷, und -(CR¹⁰R¹¹)_y(CHR¹²CHR¹³O)_zR¹⁴, oder jeweils zwei von R², R³, R⁴, und R⁵ zusammen mit dem/den Kohlenstoffatom(en) an welche(s) sie gebunden sind einen 3- bis 10-gliedrigen substituierten oder unsubstituierten Cycloalk(en)yl- oder Heterocyclyl-Ring oder einen 5-10-gliedrigen (Hetero-)Aryl-Ring bilden, oder R² und R³ oder R⁴ und R⁵ zusammen eine Carbonylgruppe bilden;
• R⁷ ausgewählt wird aus -OH, -OR⁸, -N(R¹)₂, substituiertem oder unsubstituiertem, verzweigtem oder linearem C_3-22 Alkyl, substituiertem oder unsubstituiertem, verzweigtem oder linearem C_4-22 Alkenyl, substituiertem oder unsubstituiertem C_3-22 Cycloalk(en)yl, substituiertem oder unsubstituiertem C_6-24 (Hetero-)Aryl und substituiertem oder unsubstituiertem C_6-24 Heterocyclyl;
• R⁸ ausgewählt wird aus H, substituiertem oder unsubstituiertem, verzweigtem oder linearem C_3-15 Alkyl, substituiertem oder unsubstituiertem, verzweigtem oder linearem C_4-22 Alkenyl, und M, wobei M ein wasserlösliches Kation ist;
• R⁹ ausgewählt wird aus H und substituiertem oder unsubstituiertem, verzweigtem oder linearem C_3-6 Alkyl;
• R¹⁰, R¹¹ und R¹² unabhängig ausgewählt werden aus H, -OH und C_1-4 Alkyl; oder R¹⁰ und R¹¹ zusammen mit dem Kohlenstoffatom an welches sie gebunden sind einen 3- bis 10-gliedrigen substituierten oder unsubstituierten Cycloalk(en)yl- oder Heterocyclyl-Ring, einen 5-10-gliedrigen (Hetero-)Aryl-Ring oder eine Carbonylgruppe bilden;
• R¹³ und R¹⁴ unabhängig ausgewählt werden aus H und C_1-4 Alkyl;
• x eine ganze Zahl von 0 bis 22 ist;
• y eine ganze Zahl von 1 bis 10 ist; und
• z eine ganze Zahl von 1 bis 50 ist.

A preferred embodiment of the oxazolidine precursors capable of releasing a fragrance aldehyde or fragrance ketone by hydrolysis comprises compounds of the formula

in which

• R is selected from substituted or unsubstituted, branched or linear C _6-24 alk (en) yl, substituted or unsubstituted C _6-24 cycloalk (en) yl, substituted or unsubstituted C _6-24 (hetero) aryl, and substituted or unsubstituted C _6-24 heterocyclyl;
• R ^{1 is} selected from H, substituted or unsubstituted, branched or linear C _3-10 alkyl, substituted or unsubstituted, branched or linear C _4-10 alkenyl, substituted or unsubstituted C _3-15 cycloalk (en) yl, substituted or unsubstituted C _6-15 (hetero) aryl and substituted or unsubstituted C _6-24 heterocyclyl, or
• R and R ¹ together with the carbon atom to which they are attached form a 3- to 10-membered substituted or unsubstituted cycloalk (en) yl or heterocyclyl ring or a 5-10 membered (hetero) aryl ring;
• R ² , R ³ , R ⁴ , R ⁵ and R ^{6 are} independently selected from H, substituted or unsubstituted, branched or linear C _3-10 alkyl, substituted or unsubstituted, branched or linear C _4-10 alkenyl, substituted or unsubstituted C _3-15 cycloalk (en) yl, substituted or unsubstituted C _6-15 (hetero) aryl, substituted or unsubstituted C _6-24 heterocyclyl, -OH, - (CH ₂ ) _x -COR ⁷ , and - (CR ¹⁰ R ¹¹ ) _y (CHR ¹² CHR ¹³ O) _z R ¹⁴ , or any two of R ² , R ³ , R ⁴ , and R ⁵ together with the carbon atom (s) to which they are attached are a 3 - form a 10-membered substituted or unsubstituted cycloalk (en) yl or heterocyclyl ring or a 5-10 membered (hetero) aryl ring, or R ² and R ³ or R ⁴ and R ⁵ together form a carbonyl group ;
• R ^{7 is} selected from -OH, -OR ⁸ , -N (R ¹ ) ₂ , substituted or unsubstituted, branched or linear C _3-22 alkyl, substituted or unsubstituted, branched or linear C _4-22 alkenyl, substituted or unsubstituted C _3-22 cycloalk (en) yl, substituted or unsubstituted C _6-24 (hetero) aryl and substituted or unsubstituted C _6-24 heterocyclyl;
• R ^{8 is} selected from H, substituted or unsubstituted, branched or linear C _3-15 alkyl, substituted or unsubstituted, branched or linear C _4-22 alkenyl, and M, wherein M is a water-soluble cation;
• R ^{9 is} selected from H and substituted or unsubstituted, branched or linear C _3-6 alkyl;
• R ¹⁰ , R ¹¹ and R ^{12 are} independently selected from H, -OH and C _1-4 alkyl; or R ¹⁰ and R ¹¹ together with the carbon atom to which they are attached are a 3- to 10-membered substituted or unsubstituted cycloalk (en) yl or heterocyclyl ring, a 5-10 membered (hetero) aryl ring or form a carbonyl group;
• R ¹³ and R ^{14 are} independently selected from H and C _1-4 alkyl;
• x is an integer from 0 to 22;
• y is an integer from 1 to 10; and
• z is an integer from 1 to 50.

"Substituted" as used herein in connection with the definition of oxazolidine compounds means that one hydrogen atom is replaced by another group. Suitable groups include, but are not limited to, linear or branched C _1-22 hydrocarbon groups including alkyl, alkenyl, alkynyl (the latter including 2-22 carbon atoms), -OH, -CN, -NO ₂ -C (O). H, -C (O) OR ', -C (O) NR'R ", -NR'-C (O) -R", -NR'R ", where R' and R" are C _1-12 linear or branched alkyl.

"Heterocyclyl" refers to heteroalicyclic compounds which may contain one or more double bonds and one or more hetero ring atoms, especially O, N or S, but are not aromatic.

"(Hetero) aryl" refers to aryl and heteroaryl compounds, the latter containing one or more hetero ring atoms, especially selected from O, N and S.

1. (i) sind R² und/oder R³ und/oder R⁴ Wasserstoff oder C_1-6 Alkyl, vorzugsweise Wasserstoff; und/oder
2. (ii) ist R⁵ ein Alkylrest, insbesondere Methyl, Ethyl oder Hydroxymethyl; und/oder
3. (iii) ist R⁶ Wasserstoff oder bildet zusammen mit R⁵ einen Ring, insbesondere einen Oxazolidinring.

In preferred embodiments

1. (i) R ² and / or R ³ and / or R ^{4 are} hydrogen or C _1-6 alkyl, preferably hydrogen; and or
2. (ii) R ^{5 is} an alkyl radical, in particular methyl, ethyl or hydroxymethyl; and or
3. (iii) R ^{6 is} hydrogen or together with R ⁵ forms a ring, in particular an oxazolidine ring.

ein Riechstoff-Aldehyd ergibt.In preferred embodiments, R ^{1 is} H and R is a group represented by the formula

gives a fragrance aldehyde.

ein Riechstoff-Keton ergeben.In further preferred embodiments, R ¹ and R are not hydrogen, but radicals represented by the formula

result in a fragrance ketone.

wobei R und R¹ wie oben definiert sind und ferner mit der Maßgabe, dass in den Riechstoff-Aldehyden R¹ H ist und in den Riechstoff-Ketonen R¹ nicht H ist, mit einem β-Aminoalkohol der Formel:

wobei R³-R⁶ wie oben definiert sind.The oxazolidine precursors described herein are, in particular, reaction products of a fragrance aldehyde or ketone of the formula:

wherein R and R ^{1 are} as defined above and further provided that in the fragrance aldehydes R ^{1 is} H and in the fragrance ketones R ^{1 is} not H, with a β-aminoalcohol of the formula:

wherein R ³ -R ^{6 are} as defined above.

From these oxazolidine precursor compounds, the fragrance can be released again by hydrolysis. The conditions for the release are the typical environmental conditions encountered in a machine dishwasher. The release is preferably delayed such that the fragrances are released over a period of several days, in particular of up to 10 days, preferably over a period of 1-5 days.

Although it is preferred that the aldehyde or ketone component is the actual fragrance, in other embodiments it is also possible for the beta-aminoalcohol to be a fragrance. In certain embodiments, both the aldehyde / ketone and the aminoalcohol may be a fragrance.

In various embodiments of the invention, the fragrance aldehyde may be selected from adoxal (2,6,10-trimethyl-9-undecenal), anisaldehyde (4-methoxybenzaldehyde), cymal (3- (4-isopropylphenyl) -2-methylpropanal), Ethyl vanillin, florhydral (3- (3-isopropylphenyl) butanal]), helional (3- (3,4-methylenedioxyphenyl) -2-methylpropanal), heliotropin, hydroxycitronellal, lauraldehyde, lyral (3- and 4- (4-hydroxy) 4-methylpentyl) -3-cyclohexene-1-carboxaldehyde), methylnonylacetaldehyde, Lilial (3- (4-tert-butylphenyl) -2-methylpropanal), phenylacetaldehyde, undecylenealdehyde, vanillin, 2,6,10-trimethyl-9-undecenal , 3-Dodecene-1-al, alpha-n-amylcinnamaldehyde, melonal (2,6-dimethyl-5-heptenal), 2,4-dimethyl-3-cyclohexene-1-carboxaldehyde (Triplal), 4-methoxybenzaldehyde, benzaldehyde , 3- (4-tert-butylphenyl) -propanal, 2-methyl-3- (para-methoxyphenyl) propanal, 2-methyl-4- (2,6,6-t-ethyl-2 (1) -cyclohexene-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-isopropylbenzylaldehyde, 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, 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-trimethyl-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-trimethyl-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-methoxyhexahydro-4,7 methanindane-1 or 2-carboxaldehyde, 3,7-dimethyloctan-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-trimethyl-3-cyclohexene 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) benzene-acetaldehyde, 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-ene-2-carbaldehyde, 9-decenal, 3-methyl-5-phenyl-1-pentanal, methylnonylacetaldehyde, hexanal, trans-2-hexenal and mixtures thereof.

Preferred aldehydes include, without limitation, lilial, helional, anisaldehyde, cyclamen aldehyde, triplal, melonal, methyl undecanal, undecanal, nonanal and octanal.

Suitable ketones include, but are not limited to, methyl-beta-naphthyl ketone, muskedanone-1-one (1,2,3,5,6,7-hexahydro-1,1,2,3,3-pentamethyl-4H-indene-4 on), tartalide (6-acetyl-1,1,2,4,4,7-hexamethyltetralin), alpha-damascone, beta-damascone, delta-damascone, iso-damascone, damascenone, methyldihydrojasmonate, menthone, carvone, camphor, Koavon (3,4,5,6,6-pentamethylhept-3-en-2-one), fenchone, alpha-ionone, beta-ionone, gamma-methyl-ionone, fleuramon (2-heptylcyclopentanone), dihydrojasmon, cis- Jasmon, 1 - (1,2,3,4,5,6,7,8-octahydro-2,3,8,8-tetramethyl-2-naphthalenyl) -ethan-1-one and isomers thereof, methyl cydrenyl ketone, acetophenone , Methylacetophenone, para-methoxyacetophenone, methyl-beta-naphthyl ketone, benzylacetone, benzophenone, para-hydroxyphenylbutanone, celery ketone (3-methyl-5-propyl-2-cyclohexenone), 6-isopropyldeca-hydro-2-naphthone, dimethyloctenone, Frescomenthe (2-butan-2-ylcyclohexan-1-one), 4- (1-ethoxyvinyl) -3,3,5,5-tetramethylcyclohexanone, methylheptenone, 2- (2- (4-methyl-3-cyclohex en-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-pentamethyl-4 (5H) in-danone, 4-damascol, dulcinyl (4- (1,3-benzodioxol-5-yl ) butan-2-one), hexalone (1- (2,6,6-trimethyl-2-cyclohexene-1-yl) -1,6-heptadien-3-one), isocyclone E (2-acetonaphthone-1 , 2,3,4,5,6,7,8-octahydro-2,3,8,8-tetramethyl), methylnonyl ketone, methylcyclocitron, methyllavedelketone, orivone (4-tert-amylcyclohexanone), 4-tert-butylcyclohexanone, Delphon (2-pentyl cyclopentanone), Muscon (CAS 541-91-3), neobutenone (1- (5,5-dimethyl-1-cyclohexenyl) pent-4-en-1-one), Plicaton (CAS 41724-19 -0), Veloutone (2,2,5-trimethyl-5-pentylcyclopentan-1-one), 2,4,4,7-tetramethyl-oct-6-en-3-one, tetrameran (6,10-dimethylundecene -2-on) and mixtures thereof.

In addition, as fragrance aldehydes and / or fragrance ketones basically all the usual fragrance aldehydes and / or fragrance ketones can be used, which are used in particular to bring about a pleasant smell sensation in humans. Such perfume aldehydes and / or perfume ketones are known in the art and also in the patent literature, for example in US 2003/0158079 A1 , Paragraphs [0154] and [0155]. For other suitable fragrances be on Steffen Arctander, Aroma Chemicals Volume 1 and Volume 2 (published 1960 and 1969, reissue 2000; ISBN: 0-931710-37-5 and 0-931710-38-3 ).

wobei R³-R⁶ wie oben definiert sind, mit Aldehyden, Ketonen oder Mischungen von Ketonen und Aldehyden unter Ringschluss umgesetzt werden. Die Umsetzung wird dabei vorzugsweise in einem geeigneten Lösungsmittel oder in situ durchgeführt. Geeignete Lösungsmittel sind beispielsweise aromatenhaltige Kohlenwasserstoffe wie Toluol. Die Umsetzung wird dabei vorzugsweise bei einer Temperatur im Bereich von 80 bis 150 °C, besonders bevorzugt 100 bis 140 °C durchgeführt. Beispielsweise wird der Aminoalkohol mit der oben dargestellten allgemeinen Formel unter Stickstoffatmosphäre zusammen mit dem gewünschten Keton und/oder Aldehyd im Lösungsmittel vorgelegt. Sodann wird das Reaktionsgemisch erhitzt. Häufig wird sodann unter Rückfluss am Wasserabscheider erhitzt. Das erhaltene Umsetzungsprodukt wird nach üblichen Verfahren isoliert und gegebenenfalls gereinigt.For the preparation of the compounds to be used according to the invention, a compound of the general formula of the formula:

wherein R ³ -R ^{6 are} as defined above, be reacted with aldehydes, ketones or mixtures of ketones and aldehydes with ring closure. The reaction is preferably carried out in a suitable solvent or in situ. Suitable solvents are, for example, aromatic hydrocarbons such as toluene. The reaction is preferably carried out at a temperature in the range of 80 to 150 ° C, more preferably 100 to 140 ° C. For example, the aminoalcohol having the general formula shown above under a nitrogen atmosphere together with the desired ketone and / or aldehyde in the solvent. Then the reaction mixture is heated. Often, it is then heated under reflux at the water separator. The resulting reaction product is isolated by conventional methods and optionally purified.

Surprisingly, the oxazolidine compounds used have the property of at least partially masking malodors that develop in the interior of automatic dishwashers during prolonged non-use or the storage of soiled dishes and to mitigate or even neutralize the perceived by people as unpleasant odors.

The oxazolidine precursors described above are used in the compositions according to the invention as mixtures with at least one further perfume.
The other fragrances which may optionally be included in the compositions are not particularly limited. Thus, individual fragrance compounds of natural or synthetic origin, for example of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons can be used. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate (DMBCA), phenylethylacetate, benzylacetate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate, benzylsalicylate, cyclohexylsalicylate, floramate, melusate and jasmacyclate. The ethers include, for example, benzyl ethyl ether and ambroxane, to the aldehydes the above-mentioned, for example, the linear alkanals having 8 - 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde (3- (4-propan-2-ylphenyl) butanal), Lilial and bourgeonal, among the ketones, for example, the ionones, [alpha] -Isomethylionon and methylcedryl ketone to the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons include mainly terpenes such as limonene and pinene. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance.
The compositions according to the invention may also contain natural fragrance mixtures, such as those obtainable from plant sources, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are Muskateller sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil and orange blossom oil, neroli oil, orange peel oil and sandalwood oil. Further conventional fragrances which may be present in the compositions according to the invention in the context of the present invention are, for example, the essential oils such as angelica root oil, aniseed oil, arnica blossom oil, basil oil, Bay oil, Champacablütenöl, Edeltannöl, Edeltannenzapfen oil, Elemiöl, Eucalyptusöl, Fennelöl, Fichtennadelöl, Galbanumöl, Geranium oil, ginger grass oil, guaiac wood oil, gurdy balm oil, helichrysum oil, ho oil, ginger oil, iris oil, cajeput oil, calamus oil, chamomile oil, camphor oil, kanga oil, cardamom oil, cassia oil, pine oil, kopaivabalam oil, coriander oil, spearmint oil, caraway oil, cumin oil, lavender oil, lemongrass oil, Lime oil, Tangerine oil, Melissa oil, Musk grain oil, Myrrh oil, Clove oil, Neroli oil, Niaouli oil, Olibanum oil, Origanum oil, Palmarosa oil, Patchouli oil, Peru balsam oil, Petitgrain oil, Pepper oil, Peppermint oil, Pimento oil, Pine oil, Rose oil, Rosemary oil, Sandalwood oil, Celery oil, Spik oil, Star aniseed oil, turpentine, Thuja oil, thyme oil, verbena oil, vetiver oil, juniper berry oil, wormwood oil, green oil, ylang-ylang oil, hyssop oil, cinnamon oil, cinnamon oil, citronella oil, lemon oil and cypress oil and ambrettolide, ambroxane, α-amylcinnamaldehyde, anethole, anisaldehyde, anisalcohol, anisole, Methyl anthranilate, acetophenone, benzylacetone, benzaldehyde, ethyl benzoate, benzophenone, benzyl alcohol, Benzyl acetate, benzyl benzoate, benzyl formate, benzyl valerate, borneol, bornyl acetate, Boisambrene forte, α-bromostyrene, n-decyl aldehyde, n -dodecyl aldehyde, eugenol, eugenol methyl ether, eucalyptol, farnesol, fenchone, fenchyl acetate, geranyl acetate, geranyl formate, heliotropin, heptincarboxylic acid methyl ester, heptaldehyde , Hydroquinone dimethyl ether, hydroxycinnamaldehyde, hydroxycinnamyl alcohol, indole, Iran, isoeugenol, isoeugenolmethyl ether, isosafrole, jasmone, camphor, karvakrol, karvon, p-cresol methyl ether, coumarin, p-methoxy-acetophenone, methyl n-amyl ketone, methyl anthranilate, p-methylacetophenone , Methylchloravanol, p-methylquinoline, methyl-β-naphthylketone, methyl-n-nonylacetaldehyde, methyl-n-nonylketone, muscon, β-naphtholethyl ether, β-naphthol methyl ether, nerol, n-nonylaldehyde, nonyl alcohol, n-octyl-aldehyde , p-oxy-acetophenone, pentadecanolide, β-phenylethyl alcohol, phenylacetic acid, pulegone, safrole, salicylic acid isoamyl ester, salicylic acid methyl ester, salicylic acid hexyl ester, saline cyclohexyl ester, santalol, sandelice, skatole, terpineol, thymes, thymol, troenan, γ-undelactone, vanillin, veratrumaldehyde, cinnamaldehyde, cimat alcohol, cinnamic acid, cinnamic acid ethyl ester, cinnamic acid benzyl ester, diphenyloxide, limonene, linalool, linalyl acetate and propionate, melusate, menthol, menthone , Methyl-n-heptenone, pinene, phenylacetaldehyde, terpinyl acetate, citral, citronellal and mixtures thereof. The claimed agents use the oxazolidine fragrance precursors with the corresponding aldehydes and / or ketones. According to a preferred embodiment of the invention, such compositions are characterized in that the molar ratio of fragrance aldehyde and / or fragrance ketone to the corresponding oxazolidine fragrance precursor 20: 1 to 1:20 preferably 10: 1 to 1:10, advantageously 5 : 1 to 1: 5, more preferably 3: 1 to 1: 3, more preferably 2: 1 to 1: 2 and especially 1.2: 1 to 1: 1.2. It has been found that such mixtures of perfume aldehyde and / or perfume ketone and corresponding oxazolidine perfume precursors produce particularly good results in the sense of this invention, especially with regard to stability and fragrance of the agents, as well as with regard to the fragrance of it treated dishwashers.
The agent may in principle comprise further constituents, in particular further fragrances, as defined above, and / or solvents. Also typical perfume compositions may include adjuvants such as antioxidants (generic term for compounds of various chemical structure which inhibit or prevent undesirable changes due to oxygenation and other oxidative processes in the compositions to be protected), preservatives (collective term for compounds of various chemical types) Structure that inhibit or prevent undesirable changes in the compositions to be protected due to the action of microorganisms or microorganisms) or eg fixatives. Fixatives, which are optionally used as auxiliaries, are substances that can give fragrances increased resistance. As fixers are particularly suitable are the so-called self-fixatives which retain their odor for a long time without hindering other, more volatile components in their odor development, in particular the synthetic musk body, furthermore the so-called pseudofixates as low-odor substances, such as diethylene glycol methyl ether, and further by Adsorber fixing fixatives, such as in particular extracts of Labdanum, Styrax, Tolubalsam, Benzoin, Iris, Oakmoss or Opopanax etc ..
Suitable optional solvents are, in particular, those customary in perfumery, such as preferably dipropylene glycol, diethylene glycol, isopropyl myristate, ethanol, propylene glycol and / or castor oil. Other suitable optional auxiliaries are, for example, complexing agents.

The agents of the invention may be, for example, automatic dishwashing detergents, automatic dishwashing detergents, rinse aids or automatic dishwashing perfume compositions.

The agents of the invention, in particular the dishwashing perfume compositions ("dishwashing deodorant") may, in certain embodiments, consist essentially only of perfume aldehyde and / or perfume ketone and an oxazolidine corresponding to exactly this perfume aldehyde and / or perfume ketone -Riechstoffvorläufer, which can release the same fragrance aldehyde or the same fragrance ketone and which satisfies the above formula exist. "Substantially" here means that these agents to> 90 wt .-%, preferably> 95 wt .-% and in particular to> 99 wt .-% or even to 100 wt .-% consists of said components. Such agents may contain the at least one oxazolidine precursor compound of a fragrance based on the total weight of the agent in amounts up to 30% by weight, especially up to 25% by weight.

In general, the agents described herein may contain the at least one oxazolidine precursor compound of a fragrance based on the total weight of the agent in amounts of from 0.01 to 30% by weight, more preferably from 0.01 to 25% by weight, more preferably from 0.01 to 10 wt .-% included.

Some agents, for example dishwashing detergents, dishwashing detergents or rinse aids, contain the at least one oxazolidine precursor compound of a perfume, based on the total weight of the agent, usually in amounts of from 0.01 to 2% by weight, in particular from 0.05 to 1% by weight. more preferably from 0.1 to 0.5% by weight.

The compositions according to the invention, in particular automatic dishwasher detergents, can be solid or liquid in nature and can be present in particular as pulverulent solids, in densified particle form, as homogeneous solutions or suspensions. In a preferred Embodiment of the invention, the means, in particular the automatic dishwashing detergent, in a pre-portioned form. In a further preferred embodiment of the invention, such a composition has a plurality of spatially separate compositions, whereby it is possible to separate incompatible ingredients from one another, or to offer compositions in combination, which are used at different times in the dishwasher. This is particularly advantageous when the agents are in pre-portioned form. At least one of the compositions is solid and / or at least one of the compositions is liquid, and the oxazolidine fragrance precursors are present in at least one of the compositions, but may also be present in several compositions.

The agents according to the invention preferably comprise at least one further constituent, in particular at least two further constituents selected from the group consisting of builders, surfactants, polymers, bleaches, bleach activators, bleach catalysts, in particular catalysts based on manganese or cobalt, enzymes, corrosion inhibitors and glass corrosion inhibitors, Disintegration aids and perfume carriers.

The following describes possible ingredients which can advantageously be used in the compositions according to the invention, in particular the automatic dishwasher detergents. Even if reference is made below to dishwashing detergent in particular, it is clear to the person skilled in the art that similar ingredients can also be used in other of the abovementioned agents. For example, rinse aids typically typically contain surfactants, for example, those described below. The person skilled in the art therefore readily understands that the corresponding disclosure in connection with automatic dishwashing detergents can also readily be applied to other means.

For example, builders can be used. The builders include, in particular, the zeolites, silicates, carbonates, organic cobuilders and, where there are no ecological prejudices against their use, also the phosphates.

Preference is given to using crystalline layered silicates of the general formula NaMSi _x O _{2x + 1} .yH ₂ O, in which M represents sodium or hydrogen, x represents from 1.9 to 22, preferably from 1.9 to 4, with particularly preferred Values for x are 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20. The crystalline layer-form silicates of the formula NaMSi _x O _{2x + 1} .yH ₂ O are sold, for example, by the company Clariant GmbH (Germany) under the trade name Na-SKS. Examples of these silicates are Na-SKS-1 (Na ₂ Si ₂₂ O ₄₅ .xH ₂ O, Kenyaite), Na-SKS-2 (Na ₂ Si ₁₄ O ₂₉ .xH ₂ O, magadiite), Na-SKS -3 (Na ₂ Si ₈ O ₁₇ .xH ₂ O) or Na-SKS-4 (Na ₂ Si ₄ O ₉ .xH ₂ O, Makatite). For the purpose of crystalline phyllosilicates of the formula NaMSi _x O _{2x + 1} .yH ₂ O, in which x is 2, are particularly suitable. In particular, both .beta.- and δ-sodium Na ₂ Si ₂ O ₅ · y H ₂ O, and further in particular Na-SKS-5 (α-Na ₂ Si ₂ O _5), Na-SKS-7 (.beta.-Na ₂ Si ₂ O _5, natrosilite), Na-SKS-9 (NaHSi ₂ O ₅ · H ₂ O), Na-SKS-10 (NaHSi ₂ O ₅ · 3 H ₂ O, kanemite), Na-SKS-11 ( t-Na ₂ Si ₂ O ₅ ) and Na-SKS-13 (NaHSi ₂ O ₅ ), but especially Na-SKS-6 (δ-Na ₂ Si ₂ O ₅ ).

Machine dishwashing detergents preferably contain a weight fraction of the crystalline layered silicate of the formula NaMSi _x O _{2x + 1} .yH ₂ O of from 0.1 to 20% by weight, preferably from 0.2 to 15% by weight and in particular of 0, 4 to 10 wt .-%, each based on the total weight of these agents.

It is also possible to use amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which preferably delayed release and have secondary washing properties. The dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying. In the context of this invention, the term "amorphous" is understood to mean that the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle , cause.

In the context of the present invention, it is preferred that these silicate (s), preferably alkali metal silicates, particularly preferably crystalline or amorphous Alkalidisilikate, in the compositions in amounts of from 3 to 60 wt .-%, preferably from 8 to 50 wt. % and in particular from 20 to 40 wt .-%, each based on the weight of the automatic dishwashing detergent are included.

Of course, a use of the well-known phosphates as builders is possible, unless such use should not be avoided for environmental reasons. Of the large number of commercially available phosphates, the alkali metal phosphates, with particular preference of pentasodium or Pentakaliumtriphosphat (sodium or potassium tripolyphosphate) in the washing or cleaning industry have the greatest importance.

Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO ₃ ) _n and orthophosphoric H ₃ PO _{4 in} addition to higher molecular weight representatives. The phosphates combine several advantages: they act as Alkaline carriers, prevent limescale deposits on machine parts or Kalkinkrustationen in tissues and also contribute to the cleaning performance.

Technically particularly important phosphates are the pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate) and the corresponding potassium salt pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate). Preferably usable according to the invention are the sodium potassium tripolyphosphates.

If phosphates are used as washing or cleaning substances in machine dishwashing detergent in the present application, preferred agents comprise this phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate ), in amounts of 5 to 80 wt .-%, preferably from 15 to 75 wt .-% and in particular from 20 to 70 wt .-%, each based on the weight of the automatic dishwashing detergent.

Further builders are the alkali carriers. Suitable alkali carriers are, for example, alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal sesquicarbonates, the cited alkali metal silicates, alkali metal silicates, and mixtures of the abovementioned substances, it being possible to use the alkali metal carbonates, in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate, for the purposes of this invention. Particularly preferred is a builder system comprising a mixture of tripolyphosphate and sodium carbonate. Also particularly preferred is a builder system comprising a mixture of tripolyphosphate and sodium carbonate and sodium disilicate. Because of their low chemical compatibility with the other ingredients of dishwasher detergents in comparison with other builders, the optional alkali metal hydroxides are preferably only in small amounts, preferably in amounts below 10 wt .-%, preferably below 6 wt .-%, more preferably below 4 % By weight and in particular below 2% by weight, in each case based on the total weight of the automatic dishwashing detergent. Particularly preferred are agents which, based on their total weight, contain less than 0.5% by weight and in particular no alkali metal hydroxides.

Particularly preferred is the use of carbonate (s) and / or bicarbonate (s), preferably alkali metal carbonate (s), more preferably sodium carbonate, in amounts of 2 to 50 wt .-%, preferably from 5 to 40 wt .-% and in particular from 7.5 to 30 wt .-%, each based on the weight of the automatic dishwashing detergent. Particular preference is given to compositions which, based on the weight of the automatic dishwashing agent, are less than 20% by weight, preferably less than 17% by weight, preferably less than 13% by weight and in particular less than 9% by weight of carbonate (s) and / or hydrogencarbonate (s), preferably alkali metal carbonate (s), particularly preferably sodium carbonate.

Particularly suitable organic co-builders are polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, further organic cobuilders and phosphonates. These classes of substances are described below.

Useful organic builders are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures of these. In addition to their builder effect, the free acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of the automatic dishwashing detergents. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.

The use of citric acid and / or citrates in these compositions has proved to be particularly advantageous for the cleaning and rinsing performance of agents according to the invention. Therefore, automatic dishwashing detergents are preferred according to the invention in that the automatic dishwashing agent contains citric acid or a salt of citric acid and the weight fraction of citric acid or of the salt of citric acid is preferably more than 10% by weight, preferably more than 15% by weight in particular between 20 and 40 wt .-% is.

Another important class of phosphate-free builders are aminocarboxylic acid and / or its salts. Particularly preferred members of this class are methylglycinediacetic acid (MGDA) or its salts, and glutamic diacetic acid (GLDA) or its salts or ethylenediaminediacetic acid or its salts (EDDS). The content of these aminocarboxylic acids or their salts may for example be between 0.1 and 15% by weight, preferably between 0.5 and 10% by weight and in particular between 0.5 and 6% by weight. Aminocarboxylic acids and their salts can be used together with the abovementioned builders, in particular also with the phosphate-free builders.

Further suitable builders are polymeric polycarboxylates, for example the alkali metal salts of polyacrylic acid or of polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g / mol.

Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.

The (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution. The content of the automatic dishwashing agents in (co) polymeric polycarboxylates is preferably from 0.5 to 20% by weight and in particular from 3 to 10% by weight.

To improve the water solubility, the polymers may also contain allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer.

Further preferred copolymers are those which have as their monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

In addition, all compounds capable of forming complexes with alkaline earth ions can be used as builders.

The compositions of the invention may contain surfactants, wherein the nonionic, the anionic, the cationic and the amphoteric surfactants are counted among the group of surfactants.

As nonionic surfactants, it is possible to use all nonionic surfactants known to the person skilled in the art. Suitable nonionic surfactants are, for example, alkyl glycosides of the general formula RO (G) _x in which R is a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol that is for a glycose unit with 5 or 6 C atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.

Another class of preferred nonionic surfactants which can be used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain.

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.

Further suitable surfactants are the polyhydroxy fatty acid amides known as PHFA.

Low-foaming nonionic surfactants can be used as preferred surfactants. With particular preference, the automatic dishwashing detergents contain nonionic surfactants from the group of the alkoxylated alcohols. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 moles of EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohols with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C _12-14 -alcohol with 3 EO and C _12-18 -alcohol with 5 EO. The stated degrees of ethoxylation represent statistical averages, which may correspond to a particular product of an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

Particular preference is given to nonionic surfactants which have a melting point above room temperature. Nonionic surfactant (s) having a melting point above 20 ° C, preferably above 25 ° C, more preferably between 25 and 60 ° C and in particular between 26.6 and 43.3 ° C, is / are particularly preferred.

Preferably used surfactants come from the groups of alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols.

Anionic surfactants can also be used as a component of automatic dishwashing detergents. These include in particular alkylbenzenesulfonates, (fatty) alkyl sulfates, (fatty) alkyl ether sulfates and alkanesulfonates. The content of the anionic surfactant is usually 0 to 10% by weight.

worin jede Gruppe R¹ unabhängig voneinander ausgewählt ist aus C_1-6-Alkyl-, -Alkenyl- oder -Hydroxyalkylgruppen; jede Gruppe R² unabhängig voneinander ausgewählt ist aus C_8-28-Alkyl- oder -Alkenylgruppen; R³ = R¹ oder (CH₂)_n-T-R²; R⁴ = R¹ oder R² oder (CH₂)_n-T-R²; T = - CH₂-, -O-CO- oder -CO-O- und n eine ganze Zahl von 0 bis 5 ist.Instead of the surfactants mentioned or in conjunction with them, it is also possible to use cationic and / or amphoteric surfactants. As cationic active substances, for example, cationic compounds of the following formulas can be used:

wherein each R ^{1 group is} independently selected from C _1-6 alkyl, alkenyl or hydroxyalkyl groups; each R ^{2 group is} independently selected from C _8-28 alkyl or alkenyl groups; R ³ = R ¹ or (CH ₂ ) _n -TR ² ; R ⁴ = R ¹ or R ² or (CH ₂ ) _n -TR ² ; T = - CH ₂ -, -O-CO- or -CO-O- and n is an integer from 0 to 5.

In automatic dishwashing detergents, the content of cationic and / or amphoteric surfactants is preferably less than 6% by weight, preferably less than 4% by weight, very particularly preferably less than 2% by weight and in particular less than 1% by weight. %. Automatic dishwashing detergents containing no cationic or amphoteric surfactants are particularly preferred.

The group of polymers includes, in particular, the washing or cleaning-active polymers, for example the rinse aid polymers and / or polymers which act as softeners. In general, cationic, anionic and amphoteric polymers can be used in machine dishwashing detergents in addition to nonionic polymers.

"Cationic polymers" in the context of the present invention are polymers which carry a positive charge in the polymer molecule. This can be realized, for example, by (alkyl) ammonium groups or other positively charged groups present in the polymer chain. Particularly preferred cationic polymers come from the groups of quaternized cellulose derivatives, the polysiloxanes with quaternary groups, the cationic guar derivatives, the polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid, the copolymers of vinylpyrrolidone with quaternized derivatives of dialkylamino and methacrylates, the vinylpyrrolidone-methoimidazolinium chloride copolymers, the quaternized polyvinyl alcohols or the polymers specified under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27.

For the purposes of the present invention, "amphoteric polymers" furthermore have, in addition to a positively charged group in the polymer chain, also negatively charged groups or monomer units. These groups may be e.g. to act carboxylic acids, sulfonic acids or phosphonic acids.

Preferred employable amphoteric polymers are from the group of the alkylacrylamide / acrylic acid copolymers, the alkylacrylamide / methacrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid copolymers, the alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / methacrylic acid / alkylaminoalkyl (meth ) -acrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / alkymethacrylate / alkylaminoethylmethacrylate / alkylmethacrylate copolymers and the copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally further ionic or nonionic monomers.

Preferably usable zwitterionic polymers are selected from the group of acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their alkali metal and ammonium salts, the acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali metal and ammonium salts and the methacroylethylbetaine / methacrylate copolymers.

• die Verkapselung der Polymere mittels wasserlöslicher oder wasserdispergierbarer Beschichtungsmittel, vorzugsweise mittels wasserlöslicher oder wasserdispergierbarer natürlicher oder synthetischer Polymere;
• die Verkapselung der Polymere mittels wasserunlöslicher, schmelzbarer Beschichtungsmittel, vorzugsweise mittels wasserunlöslicher Beschichtungsmittel aus der Gruppe der Wachse oder Paraffine mit einem Schmelzpunkt oberhalb 30 °C;
• die Cogranulation der Polymere mit inerten Trägermaterialien, vorzugsweise mit Trägermaterialien aus der Gruppe der wasch- oder reinigungsaktiven Substanzen, besonders bevorzugt aus der Gruppe der Builder (Gerüststoffe) oder Cobuilder.

In a particularly preferred embodiment of the present invention, the polymers are present in prefabricated form. For the preparation of the polymers is suitable inter alia

• the encapsulation of the polymers by means of water-soluble or water-dispersible coating compositions, preferably by means of water-soluble or water-dispersible natural or synthetic polymers;
• the encapsulation of the polymers by means of water-insoluble, meltable coating compositions, preferably by means of water-insoluble coating agents from the group of waxes or paraffins having a melting point above 30 ° C;
• the co-granulation of the polymers with inert carrier materials, preferably with carrier materials from the group of washing- or cleaning-active substances, more preferably from the group of builders or cobuilders.

Machine dishwashing detergents preferably contain the abovementioned cationic and / or amphoteric polymers in amounts of from 0.01 to 10% by weight, based in each case on the total weight of the automatic dishwashing detergent. In the context of the present application, however, preference is given to those automatic dishwasher detergents in which the weight fraction of the cationic and / or amphoteric polymers is between 0.01 and 8% by weight, preferably between 0.01 and 6% by weight, preferably between 0, 01 and 4 wt .-%, particularly preferably between 0.01 and 2 wt .-% and in particular between 0.01 and 1 wt .-%, each based on the total weight of the automatic dishwashing detergent is.

The bleaching agents are a substance which can be used with particular preference for washing or cleaning. Among the compounds serving as bleaches in water H ₂ O ₂ , sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -forming peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. It is also possible to use all other inorganic or organic peroxy bleaches known to the person skilled in the art.

As a bleaching agent and chlorine or bromine releasing substances can be used. Among the suitable chlorine or bromine releasing materials are, for example, heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or salts thereof with cations such as potassium and sodium. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.

According to the invention, automatic dishwashing agents are preferred which contain from 1 to 35% by weight, preferably from 2.5 to 30% by weight, particularly preferably from 3.5 to 20% by weight and in particular from 5 to 15% by weight of bleaching agent, preferably sodium percarbonate , contain.

As bleach activators, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Of all the bleach activators known to the person skilled in the art, polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), are acylated Glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS) are particularly preferably used. Combinations of conventional bleach activators can also be used. These bleach activators are preferably used in amounts of up to 10% by weight, in particular from 0.1% by weight to 8% by weight, especially from 2 to 8% by weight and more preferably from 2 to 6% by weight, based in each case on the total weight of bleach activator-containing agents.

Enzymes can also be used to increase the washing or cleaning performance of automatic dishwasher detergents. These include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in automatic dishwasher detergents, which can be used correspondingly preferred. Machine dishwashing detergents preferably contain enzymes in total amounts of from 1 × 10 ^-6 to 5% by weight, based on active protein. The protein concentration can be determined by known methods, for example the BCA method or the biuret method. However, it is also possible to use enzymatic systems comprising a peroxidase and hydrogen peroxide or a substance which produces hydrogen peroxide in water. The addition of a mediator compound for the peroxidase, for example an acetosyringone, a phenol derivative or a phenotiazine or phenoxazine, is preferred in this case, with the above-mentioned conventional polymeric color transfer inhibiting agents can additionally be used.

The enzymes can be used in any form known in the art. These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, sparing in water and / or added with stabilizers.

Alternatively, the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer. Preferably, a plurality of enzymes and / or enzyme preparations, preferably protease preparations and amylase preparations, in amounts of 0.1 to 5 wt .-%, preferably from 0.2 to 4.5 wt .-% and in particular from 0.4 to 4 wt .-%, each based on the total enzyme-containing agent used.

Glass corrosion inhibitors prevent the occurrence of haze, streaks and scratches, but also iridescence of the glass surface of machine-cleaned glasses. Preferred glass corrosion inhibitors come from the group of magnesium and zinc salts and magnesium and zinc complexes. In the context of the present invention, the content of zinc salt in dishwasher detergents is preferably between 0.1 and 5 wt.%, Preferably between 0.2 and 4 wt.% And in particular between 0.4 and 3 wt the content of zinc in oxidized form (calculated as Zn ²⁺ ) is between 0.01 and 1% by weight, preferably between 0.02 and 0.5% by weight and in particular between 0.04 and 0.2% by weight .-%, each based on the total weight of the glass corrosion inhibitor-containing agent.

In order to facilitate the disintegration of preformed moldings, it is possible to incorporate disintegration aids, so-called tablet disintegrants, into these compositions in order to shorten the disintegration times. By tablet disintegrants or disintegrants are meant excipients which ensure the rapid disintegration of tablets in water or other media and for the rapid release of the active ingredients. Desintegration aids may preferably be used in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, based in each case on the total weight of the disintegration assistant-containing agent.

In various embodiments of the invention, the detergents are, for example, sodium carbonate as builder and / or the washing or cleaning-active polymers described above, preferably acrylate (co) polymers, which are commercially available, for example, under the trade name Acusol ™ included.

The preparation of automatic dishwashing agents according to the invention can take place in different ways. The agents may be in solid or liquid form as well as in a combination of solid and liquid forms. In particular, powder, Granules, extrudates, compacts, in particular tablets. The liquid supply forms based on water and / or organic solvents may be thickened, in the form of gels. Inventive agents can be formulated in the form of single-phase or multi-phase products. In particular, automatic dishwashing detergents with one, two, three or four phases are preferred. Machine dishwashing detergent, characterized in that it is in the form of a prefabricated dosing unit with two or more phases, are particularly preferred. The individual phases of multiphase agents may have the same or different states of matter. Machine dishwashing detergents which have at least two different solid phases and / or at least two liquid phases and / or at least one solid and at least one solid phase are preferred.

Automatic dishwasher detergents according to the invention are preferably prefabricated to form metering units. These metering units preferably comprise the necessary for a cleaning cycle amount of washing or cleaning-active substances. Preferred metering units have a weight between 12 and 30 g, preferably between 14 and 26 g and in particular between 16 and 22 g. In order to achieve an optimum cleaning and rinse-aid result, preference is given to those automatic dishwashing agents which are present in the form of a prefabricated dosing unit and between 0.001 and 1 g, preferably between 0.01 and 0.1 g, particularly preferably between 0.01 and 0, 07 g and in particular between 0.01 and 0.05 g of the polymer a) or between 0.1 and 2.5 g, preferably between 0.2 and 2.2 g, particularly preferably between 0.3 and 1.9 g and in particular between 0.4 and 1.5 g of nonionic (s) surfactant (s) b). The volume of the aforementioned metering units and their spatial form are selected with particular preference so that a metering of the prefabricated units is ensured via the metering chamber of a dishwasher. The volume of the dosing unit is therefore preferably between 10 and 35 ml, preferably between 12 and 30 ml.

The automatic dishwasher detergents according to the invention, in particular the prefabricated metering units, have a water-soluble coating, with particular preference.

The present application furthermore relates to a process in which an agent of the invention, in particular a machine dishwashing detergent of the invention, is used. The method may be a method for cleaning dishes in a dishwashing machine, in which the agent according to the invention is metered into the interior of a dishwasher during the passage of a dishwashing program before the start of the main wash cycle or during the main wash cycle. The metering or the entry of the agent according to the invention into the interior of the dishwasher can be done manually, but preferably the agent is metered by means of the metering chamber into the interior of the dishwasher.

A typical framework formulation for a machine dishwashing detergent preferably used, for example in tablet form, comprises the following substances: Na tripolyphosphate 20-50% by weight sodium 10-30% by weight sodium 5-18% by weight bleach 0.5-5% by weight bleach catalyst 0.01-1% by weight sulfopolymer 2.5-15% by weight polycarboxylate 0.1-10% by weight nonionic surfactant 0.5-10% by weight phosphonate 0.5-5% by weight protease 0.1-5% by weight amylase 0.1-5% by weight, the data in% by weight are based on the total agent. Instead of the or a part of the tripolyphosphate, it is also possible in particular to use 10-50% by weight of citrate or MGDA or GLDA or EDDS or mixtures of two or three of these substances in the formulation.

The invention also relates to the use of the agents described herein for controlling or neutralizing bad odors in a machine dishwashing machine. These bad odors can be caused for example by non-use or storage of dirty dishes in the dishwasher. The agents may be used in the context of such use according to their nature. For example, automatic dishwashing detergents and rinse aids are used in normal rinsing operation. Conditioners are also used in normal spills or idle, i. Spüläufen used without (dirty) dishes. Dishwasher perfume compositions may also be used with the means mentioned in the normal rinse cycles. The compounds described herein are preferably characterized by the fact that over a relatively long period of time, usually over a period of days or weeks, the fragrances are released and, as a result, the malodor is / are continuously counteracted / neutralized.

The invention also relates to the use of an oxazolidine precursor compound of a fragrance, in particular a fragrance aldehyde or ketone, described herein for controlling or neutralizing malodors in a machine dishwashing machine.

In principle, all embodiments disclosed in connection with the means of the invention are also applicable to the described methods and uses and vice versa. For example, it is understood that all of the specific oxazolidine fragrance precursors described herein in connection with the agents of the present invention are applicable to said processes and may find use in controlling malodors in the interior of dishwashers.

reference example Example 1:

• 50 Gew.-% flüssigen Ballastschmutz;
• 6,67 Gew.-% Zwiebeln (frisch);
• 3,33 Gew.-% Knoblauch (frisch)
• 23,33 Gew.-% Sardellenpaste (Dittmann); und
• 16,67 Gew.-% Harzer Käse (Loose).

On the basis of a standardized real substance mixture, which simulates the dirt in a dishwasher, tests were carried out with different application forms. The real substance mixture for the bad odor test contained:

• 50% by weight of liquid ballast soil;
• 6.67% by weight onions (fresh);
• 3.33% by weight garlic (fresh)
• 23.33% by weight anchovy paste (Dittmann); and
• 16.67% by weight of Harzer cheese (Loose).

• 71,14 Gew.-% Leitungswasser
• 5,08 Gew.-% H-Milch 1,5% Fett (Muh)
• 2,54 Gew.-% Tomatenketchup (Kühne)
• 2,54 Gew.-% Senf (Löwensenf extra)
• 2,54 Gew.-% Bratensoße (Knorr)
• 0,51 Gew.-% Kartoffelstärke (Emsland)
• 0,41 Gew.-% Benzoesäure
• 10,16 Gew.-% Margarine (Risso)
• 5,08 Gew.-% Eigelb (Wiesenhof Eifix)

The ballast dirt contained:

• 71.14 wt .-% tap water
• 5.08% by weight H-milk 1.5% fat (Muh)
• 2.54% by weight of tomato ketchup (Kühne)
• 2.54% by weight mustard (lion mustard extra)
• 2.54% by weight gravy (Knorr)
• 0.51% by weight potato starch (Emsland)
• 0.41% by weight of benzoic acid
• 10.16% by weight of margarine (Risso)
• 5.08% by weight egg yolk (Wiesenhof Eifix)

The interior of a dishwasher was evaluated after completion of the cleaning program using the above Realstoffmischung with respect to the intensities of fragrance and bad smell by 8 subjects on a scale of 1-10, where 1 very weak and 10 very strong means after 24, 48 and 72 h after Termination of the cleaning program.
The results are shown in Table 1. Table 1: Odor tests product Dosage (% by weight) intensity fragrance bad smell 24 hours 48h 72h 24 hours 48h 72h Somat Multi Gel - 4.3 2.3 2.0 5.0 5.8 3.0 + Oxazolidine scent precursor 1 0.2 6.8 4.8 2.5 1.0 3.5 2.5 + Oxazolidine scent precursor 2 0.2 6.6 4.8 1.5 3.0 3.0 1.5 + Oxazole id in scent precursor 3 0.2 3.6 2.5 2.5 1.0 5.5 2.5 1st attempt Second attempt 1st attempt Second attempt Somat 10 - 5.0 6.0 7.0 5.0 + Oxazole id in perfume precursor 1 0.15 6.0 6.0 3.0 2.0 + Oxazole id in perfume precursor 2 0.15 7.0 5.0 3.0 4.0 + Oxazole id in scent precursor 3 0.15 6.0 5.0 4.0 2.0 Somat Deo Perls - 4.5 4.0 7.0 6.5 + Oxazole id in perfume precursor 1 30 7.0 7.0 5.0 5.5 + Oxazole id in perfume precursor 2 26 5.0 5.5 6.0 6.0 + Oxazole id in scent precursor 3 30 7.5 8.0 3.0 3.0

It can be seen that the test compositions according to the invention mediated a longer-lasting fragrance and reduced the bad odors more than the compositions without the invention

Claims (11)

1. An agent for use in an automatic dishwasher, characterized in that the agent contains at least one oxazolidine precursor compound of an odorant which can release an odorant aldehyde or odorant ketone, and at least one odorant, wherein the at least one oxazolidine precursor compound of an odorant which can release an odorant aldehyde or odorant ketone being a compound of formula

   

   wherein R being selected from substituted or unsubstituted, branched or linear C_6-24 alk(en)yl, substituted or unsubstituted C_6-24 cycloalk(en)yl, substituted or unsubstituted C_6-24 (hetero)aryl and substituted or unsubstituted C_6-24 heterocyclyl;

   R¹ being selected from H, substituted or unsubstituted, branched or linear C_1-10 alkyl, substituted or unsubstituted, branched or linear C_2-10 alkenyl, substituted or unsubstituted C_3-15 cycloalk(en)yl, substituted or unsubstituted C_6-15 (hetero)aryl and substituted or unsubstituted C_6-24 heterocyclyl, or

   R and R¹, together with the carbon atom to which they are bonded, forming a 3 to 10 membered, substituted or unsubstituted cycloalk(en)yl or heterocyclyl ring, or a 5 to 10 membered (hetero)aryl ring;

   R², R³, R⁴, R⁵ and R⁶ being selected independently of one another from H, substituted or unsubstituted, branched or linear C_1-10 alkyl, substituted or unsubstituted, branched or linear C_2-10 alkenyl, substituted or unsubstituted C_3-15 cycloalk(en)yl, substituted or unsubstituted C_6-15 (hetero)aryl, substituted or unsubstituted C_6-24 heterocyclyl, -OH, -(CH₂)_x-COR⁷, and - (CR¹⁰R¹¹)_y(CHR¹²CHR¹³O)_zR¹⁴, or

   in each case two of R², R³, R⁴ and R⁵, together with the carbon atom(s) to which they are bonded, forming a 3 to 10 membered, substituted or unsubstituted cycloalk(en)yl or heterocyclyl ring, or a 5 to 10 membered (hetero)aryl ring, or R² and R³ or R⁴ and R⁵ together forming a carbonyl group;

   R⁷ being selected from -OH, -OR⁸, -N(R⁹)₂, substituted or unsubstituted, branched or linear C_1-22 alkyl, substituted or unsubstituted, branched or linear C_2-22 alkenyl, substituted or unsubstituted C_3-22 cycloalk(en)yl, substituted or unsubstituted C_6-24 (hetero)aryl and substituted or unsubstituted C_6-24 heterocyclyl;

   R⁸ being selected from H, substituted or unsubstituted, branched or linear C_1-15 alkyl, substituted or unsubstituted, branched or linear C_2-22alkenyl, and M, wherein M being a watersoluble cation;

   R⁹ being selected from H and substituted or unsubstituted, branched or linear C_1-6 alkyl;

   R¹⁰, R¹¹ and R¹² being independently selected from H, -OH and C_1-4 alkyl; or R¹⁰ and R¹¹, together with the carbon atom to which they are bonded, forming a 3 to 10 membered, substituted or unsubstituted cycloalk(en)yl or heterocyclyl ring, a 5 to 10 membered (hetero)aryl ring or a carbonyl group;

   R¹³ and R¹⁴ being independently selected from H and C_1-4 alkyl;

   x being an integer from 0 to 22;

   y being an integer from 1 to 10; and

   z being an integer from 1 to 50; and

   wherein the at least one odorant being an odorant aldehyde or odorant ketone which corresponds to the odorant aldehyde or odorant ketone released by the at least one oxazolidine precursor compound of an odorant.
2. The agent according to claim 1, characterized in that the oxazolidine precursor compound of an odorant, which can release an odorant aldehyde or odorant ketone by means of hydrolysis, comprises compounds of formula

   

   wherein R being selected from substituted or unsubstituted, branched or linear C_6-24 alk(en)yl, substituted or unsubstituted C_6-24 cycloalk(en)yl, substituted or unsubstituted C_6-24 (hetero)aryl and substituted or unsubstituted C_6-24 heterocyclyl;

   R¹ being selected from H, substituted or unsubstituted, branched or linear C_3-10 alkyl, substituted or unsubstituted, branched or linear C_4-10 alkenyl, substituted or unsubstituted C_3-15 cycloalk(en)yl, substituted or unsubstituted C_6-15 (hetero)aryl and substituted or unsubstituted C_6-24 heterocyclyl, or

   R and R¹, together with the carbon atom to which they are bonded, forming a 3 to 10 membered, substituted or unsubstituted cycloalk(en)yl or heterocyclyl ring, or a 5 to 10 membered (hetero)aryl ring;

   R², R³, R⁴, R⁵ and R⁶ being selected independently of one another from H, substituted or unsubstituted, branched or linear C_3-10 alkyl, substituted or unsubstituted, branched or linear C_4-10 alkenyl, substituted or unsubstituted C_3-15 cycloalk(en)yl substituted or unsubstituted C_6-15 (hetero)aryl, substituted or unsubstituted C_6-24 heterocyclyl, -OH, -(CH₂)_x-COR⁷, and - (CR¹⁰R¹¹)_y(CHR¹²CHR¹³O)_zR¹⁴, or

   in each case two of R², R³, R⁴ and R⁵, together with the carbon atom(s) to which they are bonded, forming a 3 to 10 membered, substituted or unsubstituted cycloalk(en)yl or heterocyclyl ring, or a 5 to 10 membered (hetero)aryl ring, or R² and R³ or R⁴ and R⁵ together forming a carbonyl group;

   R⁷ being selected from -OH, -OR⁸, -N(R⁹)₂, substituted or unsubstituted, branched or linear C_3-22 alkyl, substituted or unsubstituted, branched or linear C_4-22 alkenyl, substituted or unsubstituted C_3-22 cycloalk(en)yl, substituted or unsubstituted C_6-24 (hetero)aryl and substituted or unsubstituted C_6-24 heterocyclyl;

   R⁸ being selected from H, substituted or unsubstituted, branched or linear C_3-15 alkyl, substituted or unsubstituted, branched or linear C_4-22 alkenyl, and M, wherein M being a watersoluble cation;

   R⁹ being selected from H and substituted or unsubstituted, branched or linear C_3-6 alkyl;

   R¹⁰, R¹¹ and R¹² being independently selected from H, -OH and C_1-4 alkyl; or R¹⁰ and R¹¹, together with the carbon atom to which they are bonded, forming a 3 to 10 membered, substituted or unsubstituted cycloalk(en)yl or heterocyclyl ring, a 5 to 10 membered (hetero)aryl ring or a carbonyl group;

   R¹³ and R¹⁴ being independently selected from H and C_1-4 alkyl;

   x being an integer from 0 to 22;

   y being an integer from 1 to 10; and

   z being an integer from 1 to 50.
3. The agent according to one of claims 1 or 2, characterized in that the molar ratio of odorant aldehyde and/or odorant ketone to the corresponding oxazolidine odorant precursor is from 20:1 to 1:20, preferably from 10:1 to 1:10, more preferably from 5:1 to 1:5, even more preferably from 3:1 to 1:3, still more preferably from 2:1 to 1:2 and in particular from 1.2:1 to 1:1.2.
4. The agent according to one of claims 1-3, characterized in that the odorant aldehyde or odorant ketone is selected from adoxal (2,6,10-trimethyl-9-undecenal), anisaldehyde (4-methoxybenzaldehyde), cymene (3-(4-isopropylphenyl)-2-methylpropanal), ethyl vanillin, Florhydral (3-(3-isopropylphenyl)butanal]), helional (3-(3,4-methylendioxyphenyl)-2-methylpropanal), heliotropin, hydroxycitronellal, lauraldehyde, Lyral (3- and 4-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carboxaldehyde), methyl nonyl acetaldehyde, Lilial (3-(4-tert-butylphenyl)-2-methylpropanal), phenylacetaldehyde, undecylene aldehyde, vanillin, 2,6,10-trimethyl-9-undecenal, 3-dodecen-1-al, alpha-n-amylcinnamaldehyde, melonal (2,6-dimethyl-5-heptenal), 2,4-dimethyl-3-cyclohexene-1-carboxaldehyde (Triplal), 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-octadien-1-al, 3,7-dimethyl-6-octen-1-al, [(3,7-dimethyl-6-octenyl)oxy]acetaldehyde, 4-isopropylbenzylaldehyde, 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, 2,6-dimethyl-5-heptenal, 4-(tricyclo[5.2.1.0(2,6)]-decyliden-8)-butanal, octahydro-4,7-methan-1H-indencarboxaldehyde, 3-ethoxy-4-hydroxybenzaldehyde, para-ethyl-alpha, alpha-dimethyl hydrocinnamaldehyde, alpha-methyl-3,4-(methylenedioxy)-hydrocinnamaldehyde, 3,4-methylenedioxybenzaldehyde, alpha-n-hexylcinnamaldehyde, m-cymen-7-carboxaldehyde, alpha-methyl-phenyl-acetaldehyde, 7-hydroxy-3,7-dimethyloctanal, undecenal, 2,4,6-trimethyl-3-cyclohexene-1-carboxaldehyde, 4-(3)(4-methyl-3-pentenyl)-3-cyclohexenecarboxaldehyde, 1-dodecanal, 2,4-dimethylcyclohexene-3-carboxaldehyde, 4-(4-hydroxy-4-methylpentyl)-3-cylohexene-1-carboxaldehyde, 7-methoxy-3,7-dimethyloctane-1-al, 2-methylundecanal, 2-methyldecanal, 1-nonanal, 1-octanal, 2,6,10-trimethyl-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-methoxyhexahydro-4,7-methanoindane-1-or-2-carboxaldehyde, 3,7-dimethyloctan-1-al, 1-undecanal, 10-undecen-1-al, 4-hydroxy-3-methoxybenzaldehyde, 1-methyl-3-(4-methylpentyl)-3-cyclohexenecarboxaldehyde, 7-hydroxy-3,7-dimethyl-octanal, trans-4-decenal, 2,6-nonadienal, para-tolylacetaldehyde, 4-methylphenylacetaldehyde, 2-methyl-4-(2,6,6-trimethyl-1-cyclohexene-1-yl)-2-butenal, ortho-methoxycinnamaldehyde, 3,5,6-trimethyl-3-cyclohexene carboxaldehyde, 3,7-dimethyl-2-methylene-6-octenal, phenoxyacetaldehyde, 5,9-dimethyl-4,8-decadienal, peony aldehyde (6,10-dimethyl-3-oxa-5,9-undecadien-1-al), hexahydro-4,7-methanoindan-1-carboxaldehyde, 2-methyloctanal, alpha-methyl-4-(1-methylethyl)benzolacetaldehyde, 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, methyl-beta-naphthylketone, musk indanone (1,2,3,5,6,7-hexahydro-1,1,2,3,3-pentamethyl-4H-inden-4-one), tonalide (6-acetyl-1,1,2,4,4,7-hexamethyltetraline), alpha-damascone, beta-damascone, delta-damascone, iso-damascone, damascenone, methyl dihydrojasmonate, menthone, carvone, camphor, Koavone (3,4,5,6,6-pentamethylhept-3-en-2-one), fenchone, alpha-ionone, beta-ionone, gamma-methyl-ionone, Fleuramone (2-heptyl cyclopentanone), dihydrojasmone, cis-jasmone, 1-(1,2,3,4,5,6,7,8-octahydro-2,3,8,8-tetramethyl-2-naphthalenyl)-ethan-1-one and isomers thereof, methyl cedrenyl ketone, acetophenone, methylacetophenone, para-methoxyacetophenone, methyl beta-naphtylketone, benzylacetone, benzophenone, para-hydroxyphenylbutanone, celery ketone (3-methyl-5-propyl-2-cyclohexenone), 6-isopropyldeca-hydro-2-naphtone, dimethyloctenone, Freskomenthe (2-butan-2-ylcyclohexan-1-one), 4-(1-ethoxyvinyl)-3,3,5,5-tetramethylcyclohexanone, methylheptenone, 2-(2-(4-methyl-3-cyclohexene-1-yl)propyl)cyclopentanone, 1-(p-menthen-6(2)yl)-1-propanone, 4-(4-hydroxy-3-methoxyphenyl)-2-butanone, 2-acetyl-3,3-dimethyl norbornane, 6,7-dihydro-1,1,2,3,3-pentamethyl-4(5H)in-danone, 4-damascol, dulcinyl (4-(1,3-benzodioxol-5-yl)butan-2-one), Hexalon (1-(2,6,6-trimethyl-2-cyclohexene-1-yl)-1,6-heptadien-3-one), isocyclemone E (2-acetonaphthon-1,2,3,4,5,6,7,8-octahydro-2,3,8,8-tetramethyl), methyl nonyl ketone, methyl cyclocitrone, methyl lavendel ketone, Orivone (4-tert-amylcyciohexanone), 4-tert-butyl cyclohexanone, delphone (2-pentyl cyclopentanone), muscone (CAS 541 -91 -3), neobutenone (1-(5,5-dimethyl-1-cyclo-hexenyl)pent-4-en-1-one), plicatone (CAS 41724-19-0), veloutone (2,2,5-trimethyl-5-pentylcyclopentan-1-one), 2,4,4,7-tetramethyl-oct-6-en-3-one, tetrameran (6,10-dimethyl undecen-2-one) and mixtures thereof, in particular of Lilial, helional, anisaldehyde, cyclamen aldehyde, Triplal, melonal, methyl undecanal, undecanal, nonanal and octanal.
5. The agent according to one of claims 1 to 4, characterized in that the agent contains the at least one oxazolidine precursor compound of an odorant in amounts of from 0.01 to 30 wt.%, in particular from 0.01 to 25 wt.% and even more preferably from 0.01 to 10 wt.%, based on the total weight of the agent.
6. The agent according to one of claims 1 to 5, characterized in that the agent is selected from automatic dishwasher detergents, care agents for automatic dishwashers, clear rinsers and perfume compositions for automatic dishwashers.
7. The agent according to one of claims 1 to 6, characterized in that

   (1) the agent is present in solid form or in liquid form; and/or

   (2) the agent is present in pre-portioned form; and/or

   (3) the agent has compositions which are spatially separate from one another, at least one of which compositions is solid and/or one is liquid, wherein the at least one oxazolidine precursor compound being contained in at least one of the compositions; and/or

   (4) the agent contains at least one further component, preferably at least two further components, selected from the group consisting of builders, surfactants, polymers, bleaching agents, bleach activators, bleach catalysts, enzymes, corrosion inhibitors, glass corrosion inhibitors, disintegration aids and perfume carriers, in particular sodium carbonate and/or acrylate polymers or copolymers.
8. An automatic dishwashing method, characterized in that an agent, in particular an automatic dishwasher detergent, according to one of claims 1 to 7 is used.
9. The use of an oxazolidine precursor compound of an odorant which can release an odorant aldehyde or odorant ketone, or the use of an agent containing said oxazolidine precursor compound of an odorant, wherein the at least one oxazolidine precursor compound of an odorant which can release an odorant aldehyde or odorant ketone is a compound of formula

   

   wherein

   R is selected from substituted or unsubstituted, branched or linear C_6-24 alk(en)yl, substituted or unsubstituted C_6-24 cycloalk(en)yl, substituted or unsubstituted C_6-24 (hetero)aryl and substituted or unsubstituted C_6-24 heterocyclyl;

   R¹ is selected from H, substituted or unsubstituted, branched or linear C_1-10 alkyl, substituted or unsubstituted, branched or linear C_2-10 alkenyl, substituted or unsubstituted C_3-15 cycloalk(en)yl, substituted or unsubstituted C_6-15 (hetero)aryl and substituted or unsubstituted C_6-24 heterocyclyl, or

   R and R¹, together with the carbon atom to which they are bonded, form a 3 to 10 membered, substituted or unsubstituted cycloalk(en)yl or heterocyclyl ring, or a 5 to 10 membered (hetero)aryl ring;

   R², R³, R⁴, R⁵ and R⁶ are selected independently of one another from H, substituted or unsubstituted, branched or linear C_1-10 alkyl, substituted or unsubstituted, branched or linear C_2-10 alkenyl, substituted or unsubstituted C_3-15 cycloalk(en)yl, substituted or unsubstituted C_6-15 (hetero)aryl, substituted or unsubstituted C_6-24 heterocyclyl, -OH, -(CH₂)_x-COR⁷, and - (CR¹⁰R¹¹)_y(CHR¹²CHR¹³O)_zR¹⁴, or

   in each case two of R², R³, R⁴ and R⁵, together with the carbon atom(s) to which they are bonded, form a 3 to 10 membered, substituted or unsubstituted cycloalk(en)yl or heterocyclyl ring, or a 5 to 10 membered (hetero)aryl ring, or R² and R³ or R⁴ and R⁵ together form a carbonyl group;

   R⁷ is selected from -OH, -OR⁸, -N(R⁹)₂, substituted or unsubstituted, branched or linear C_1-22 alkyl, substituted or unsubstituted, branched or linear C_2-22 alkenyl, substituted or unsubstituted C_3-22 cycloalk(en)yl, substituted or unsubstituted C_6-24 (hetero)aryl and substituted or unsubstituted C_6-24 heterocyclyl;

   R⁸ is selected from H, substituted or unsubstituted, branched or linear C_1-15 alkyl, substituted or unsubstituted, branched or linear C_2-22 alkenyl, and M, wherein M is a watersoluble cation;

   R⁹ is selected from H and substituted or unsubstituted, branched or linear C_1-6 alkyl;

   R¹⁰, R¹¹ and R¹² are independently selected from H, -OH and C_1-4 alkyl; or R¹⁰ and R¹¹, together with the carbon atom to which they are bonded, form a 3 to 10 membered, substituted or unsubstituted cycloalk(en)yl or heterocyclyl ring, a 5 to 10 membered (hetero)aryl ring or a carbonyl group;

   R¹³ and R¹⁴ are independently selected from H and C_1-4 alkyl;

   x is an integer from 0 to 22;

   y is an integer from 1 to 10; and

   z is an integer from 1 to 50

   for combatting or neutralizing unpleasant smells in an automatic dishwasher.
10. The use according to claim 9, characterized in that the agent contains at least one odorant.
11. The use according to claim 10, characterized in that the agent is an agent according to one of claims 1 to 7.