Spice Mix

Abstract

The present invention relates to a method for preparing a monoester and / or a diester of mesaconic acid and use of the monoester and / or the diester of mesaconic acid as a perfume material.

Description

[0001] This application is a divisional application of a patent application with an application date of September 27, 2017, an invention name of “Spice Mixture” and an application number of 201780079996.1 (PCT / EP2017 / 074461). Technical Field

[0002] The invention belongs to the field of spices and relates to a spice mixture with a fruity pear-like fragrance (aroma), a preparation containing a special spice or a spice mixture, a method for preparing a special spice with a pear-like fragrance, a scenting process, and the use of producing a special spice with a pear-like fragrance. Background Art

[0003] Despite the large number of existing fragrances, there is still a general demand for new fragrances in the perfume industry. In particular, there is a demand for fragrances that not only have completely new original notes, but also have other positive additional properties in addition to their olfactory properties, such as higher stability and diffusibility under specific conditions of use, better adhesion, greater radiation power, lower thresholds or better results in dermatopathology and toxicology tests, such as good biodegradability.

[0004] In particular, there is a need for fragrances that can provide the same or higher aroma value at a lower dose than similar substances, thereby intruding less into the environment (low-efficiency). Or fragrances that can significantly reduce costs while providing the same aroma. Among them, there is a need for fragrances with complex odor characteristics, such as a fruity pear-like aroma. However, amyl acetate, although well-known for its pear-like aroma, does not meet these conditions.

[0005] The object of the present invention is therefore to provide fragrances and fragrance compositions with and similar pear aromas based on renewable raw materials, preferably waste materials, which overcome the disadvantages of the prior art, namely provide higher aroma values, especially at low dosages, can be incorporated more easily and stably into various perfumes and end product formulations, and can be produced with little technical effort and low cost. Summary of the invention

[0006] A first object of the present invention relates to a fragrance mixture comprising an organoleptically effective amount of one, two or all three compounds selected from the group formed by oils of formula (i), (ii) and (iii):

[0007]

[0008] Among them, R1 represents a straight chain, branched or cyclic alkyl, araliphatic or aromatic group having 1 to 10 carbon atoms, preferably a methyl or ethyl group, and R2 represents a straight chain, branched or cyclic alkyl, araliphatic or aromatic group having 1 to 10 carbon atoms, preferably a methyl or ethyl group.

[0009] Surprisingly, it has been found that in particular the compounds of formula (i) are suitable as fragrances with a pear-like aroma and fully meet the above-mentioned complex requirements. The substances in formula (ii) and formula (iii) are present in the production process and also have a weakened pear-like aroma. It is particularly noteworthy that these substances are obtained from renewable raw materials, in particular waste materials from the sugar industry. Another surprising discovery is that these substances can be incorporated into a large number of different formulations in a durable and stable manner, in particular, they exceed the standards of ethyl decadienoate.

[0010] Preferably, R1 and R2 are each the same or different straight-chain, branched or cyclic alkyl radicals having 1 to 8 or 1 to 6 carbon atoms, preferably methyl or ethyl. In this case, straight-chain radicals are particularly valuable, especially for alkyl radicals having 1 to 4 carbon atoms. Alternatively, branched alkyl radicals having this number of carbon atoms are preferred.

[0011] In the compounds of formula (i), formula (ii) and / or formula (iii), the preferred linear alkyl groups of R1 and R2 having 1 to 10 carbon atoms are formed by the following groups: methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl and n-decyl. Preferred linear alkyl groups are methyl, ethyl, but also suitable are n-propyl, n-butyl, n-pentyl and n-hexyl. Particularly preferred linear alkyl groups are methyl, ethyl, n-propyl and n-butyl.

[0012] In the compounds of formula (i), formula (ii) and / or formula (iii), the group of the branched alkyl of R1 and R2 having 1 to 10 carbon atoms is formed by the following groups: isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, tert-pentyl, isohexyl, tert-hexyl, isoheptyl, isooctyl, tert-octyl, isononyl, tert-nonyl, tert-decyl and isodecyl. Preferred branched alkyl groups are isopropyl, isobutyl, sec-butyl and tert-butyl. Particularly preferred branched alkyl groups are isopropyl and isobutyl.

[0013] In the compounds of formula (i), (ii) and / or (iii), the cyclic alkyl groups of R1 and R2 having 1 to 10 carbon atoms are formed by cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane and cyclooctane. Preferred cyclic alkyl groups are cyclopentane and cyclohexane.

[0014] In the compounds of formula (i), (ii) and / or (iii), the aromatic aliphatic groups of R1 and R2 refer to alkyl groups in which one or more hydrogen atoms are replaced by an aromatic group. In the compounds of formula (i), (ii) and / or (iii), the aromatic aliphatic groups are formed by the following substances: toluene, 2-methylfuran, 3-methylfuran, methylpyridine, cresol, xylene, 1-methylnaphthalene, 2-methylnaphthalene and ethylbenzene. Preferred aromatic aliphatic groups are toluene and ethylbenzene.

[0015] In the compounds of formula (i), (ii) and / or (iii), the aromatic groups R1 and R2 are formed from the following: pyrimidine, furan, thirane, benzene, naphthalene, phenol, pyridine and benzodiazepine. Preferred aromatic groups are furan and benzene.

[0016] The organoleptically effective dose refers to the proportion of the substances of formula (i), formula (ii) and / or formula (iii) in the mixture that is sufficient to produce a pear-like fruity aroma effect. To produce such a pear-like fruity aroma effect, it is usually necessary that one, two or all three compounds of formula (i), formula (ii) and formula (iii) are present in an amount of at least 0.001 wt.% in the fragrance mixture.

[0017] In a preferred embodiment of the present invention, the groups R1 and / or R2 of the compounds represented by formula (i), formula (ii) and / or formula (iii) in the above-mentioned fragrance mixture are independently C1 to C4 groups, in particular methyl, ethyl, propyl and butyl. These compounds are particularly easy to prepare and have the most impressive odor characteristics.

[0018] In an alternative preferred embodiment of the present invention, the groups R1 of the compounds represented by formula (i), formula (ii) and / or formula (iii) in the above-mentioned fragrance mixture are each independently methyl, ethyl, propyl and / or butyl, and the groups R2 of the compounds represented by formula (i), formula (ii) and / or formula (iii) in the above-mentioned fragrance mixture are each independently methyl or ethyl.

[0019] In another preferred embodiment of the present invention, the groups R2 of the compounds represented by formula (i), formula (ii) and / or formula (iii) in the above-mentioned fragrance mixture are each independently methyl, ethyl, propyl and butyl, and the groups R1 of the compounds represented by formula (i), formula (ii) and / or formula (iii) in the above-mentioned fragrance mixture are each independently methyl or ethyl.

[0020] In a second embodiment of the present invention, the radicals R1 and R2 of the compounds of formula (i), (ii) and / or (iii) in the above-mentioned fragrance mixture are each the same radical. This simplifies the preparation.

[0021] In a third embodiment of the present invention, the radicals R1 and R2 of the compounds of formula (i), (ii) and / or (iii) in the above-mentioned perfume mixture are independently selected from the group consisting of the following radicals: linear or branched methyl, ethyl, propyl and butyl alkyl radicals. In particular, linear alkyl radicals and shorter branched alkyl radicals are suitable for selection as odor-binding materials.

[0022] In a preferred embodiment of the present invention, the groups R1 and R2 of the compounds represented by formula (i), formula (ii) and / or formula (iii) in the above-mentioned fragrance mixture are independently methyl, ethyl, propyl and butyl.

[0023] In another preferred embodiment of the present invention, the groups R1 and R2 of the compounds represented by formula (i), formula (ii) and / or formula (iii) in the above-mentioned fragrance mixture are each independently a methyl group and a propyl group.

[0024] In a fourth embodiment of the present invention, there is provided a fragrance mixture comprising one, two or all three compounds selected from the group consisting of:

[0025] (i) (E)-Diethyl 2-methyl-but-2-enedicarboxylate,

[0026] (ii) (Z)-2-methyl-but-2-enedicarboxylic acid diethyl ester, and

[0027] (iii) Diethyl 2-methylenebutanedicarboxylate.

[0028] The three compounds (i), (ii) and (iii) represent particularly preferred embodiments of the formula of the fragrance mixture according to the invention, but the methyl or propyl esters are also advantageous. Combinations of ethyl, methyl and / or propyl esters are also possible.

[0029] Perfume: In the perfume of the present invention, the substance (E)-2-methyl-but-2-enedicarboxylic acid diethyl ester of formula (I) is

[0030]

[0031] Mesacon acid diethyl ester, also known as mesacon acid diethyl ester, is of particular importance to the present invention and has been documented. Relevant reference citations are as follows: Advanced Synthesis&Catalysis, 2012, 354(14-15), 2859-2864; Organic Letters, 2008; 10(21), 4815-4818; Organic & Biomolecular Chemistry, 2010, 8(19), 4444-4450; Journal of American Chemical Society, 2005, 127 (15), 5518-5527; Tetrahedron Letters, 1996, 37 (5), 629-632; Tetrahedron Letters, 1983, 39 (9), 1475-1485; Journal of American ChemicalSociety,2015,137(26),8556-8563; Organic Letters,2011;13(7),1884-1887;Australian Journal of Chemistry,1984,37(2),417-424;Tetrahedron Letters,1981,22(5),381-384;Synthetic Communications,1977,7(6),375-382;Helvetica ChimicaActa,1974,57(3),856-863.

[0032] In the following, the two names (E)-2-methyl-but-2-enedicarboxylate and diethyl mesaconic acid ester are used interchangeably. What is not known so far is the organoleptic properties of this compound, in particular its suitability as a fragrance with a special strong pear aroma. Therefore, the use of this compound as a fragrance is also the subject of the present invention.

[0033] The two compounds of formula (ii) and formula (iii) are diethyl citrate and diethyl itaconate, which are usually used together with diethyl mesaconic acid to prepare an isomeric mixture. Particularly preferably, compound (ii) is (Z)-2-methyl-but-2-ene dicarboxylic acid diethyl ester and compound (iii) is 2-methylene butane dicarboxylic acid diethyl ester, which together with diethyl mesaconic acid (E)-2-methyl-but-2-ene dicarboxylic acid diethyl ester give a preferred compound mixture. According to the present invention, the use of these compounds alone or in combination with diethyl mesaconic acid as a fragrance or a fragrance mixture is also provided.

[0034] Preferably, the compound of formula (i) is preferably an isomeric mixture of (E)-2-methyl-but-2-enedicarboxylate, wherein the content of the compound of formula (i) is at least 50 wt.% to 100 wt.%, particularly preferably about 70 wt.% to 90 wt.%, and more preferably 75 wt.% to 85 wt.%.

[0035] In a fifth preferred embodiment of the invention, the content of the compound of formula (i) in the perfume mixture is 50 wt.% to 100 wt.%, based on the sum of the compounds of formula (i), formula (ii) and formula (iii). This also applies to the particularly preferred compounds of the various diethyl esters. According to the invention, diethyl mesaconic acid esters with a purity of at least 98% are also preferred, preferably 100% purity. Such perfume mixtures containing pure or almost pure diethyl mesaconic acid esters have a particularly strong pear aroma.

[0036] In a preferred embodiment of the present invention, in the fragrance mixture, the ratio of the compound of formula (i) to the sum of the two compounds of formula (ii) and formula (iii) is at least 8 (compound of formula (i)) to 1 (the sum of the two compounds of formula (ii) and formula (iii)), and the particularly preferred ratio is 9:1 or contains a higher proportion of the compound of formula (i). This ratio also applies to the compound mixture of diethyl mesaconic acid, diethyl citraconic acid and diethyl itaconate. A higher proportion of diethyl mesaconic acid will produce a stronger pear aroma.

[0037] In particular, it has been found that the isomeric mixtures of (i), (ii) and (iii), as well as the mesaconic acid esters represented by compound (i), in particular diethyl mesaconic acid, are particularly suitable for imparting, modifying and / or enhancing a pear-like aroma. The fact that the compound has such a strong aroma is surprising, since it differs from known substances with similar structures in terms of the above-mentioned odor properties. Thus, for example, diethyl fumarate (II) also has a butenedicarboxylic acid structure, but is considered to have almost no odor: (Source: Diethyl Fumarate Safety Data Sheet, from Merck):

[0038]

[0039] In contrast, compounds with similar odors, such as 2,4-ethyldecadienoate (III), have a completely different structure (see: H. Surburg, J. Panten, Common Fragrance and Flavor Materials, 6th edition, Wiley-VCH, Weinheim, 2016, p. 25):

[0040]

[0041] Furthermore, these substances were also shown to be much weaker in terms of odor intensity and adhesion.

[0042] In addition to the special odor advantages, they also have excellent material properties, such as solubility in conventional cosmetic solvents, compatibility with other components of these products, and toxicological safety of the compounds, which highlight the special suitability of the compounds of the present invention for the applications described. Another advantage compared to traditional fragrances with similar odor characteristics (e.g., formula III) is their very favorable availability and preparation conditions.

[0043] In a sixth preferred embodiment of the present invention, the total content of the compounds of formula (i), formula (ii) and / or formula (iii) is 0.001 wt.% to 99.999 wt.%, based on the fragrance mixture.

[0044] More preferably, the total content of compounds of formula (i), formula (ii) and / or formula (iii) is 0.05 wt.% to 50 wt.%, based on the fragrance mixture. This also applies to the particularly preferred diethyl esters of the compounds.

[0045] In another preferred embodiment of the present invention, the total content of the compounds of formula (i), formula (ii) and / or formula (iii) is 1 wt.% to 30 wt.% based on the fragrance mixture.

[0046] In a particularly preferred embodiment of the present invention, the fragrance mixture generally comprises compounds of formula (i), formula (ii) and / or formula (iii), or only comprises diethyl (E)-2-methyl-but-2-enedicarboxylate, in particular a mixture of diethyl mesaconic acid with diethyl citraconic acid and diethyl itaconate, and the sensory effective content of diethyl mesaconic acid may be 0.001 wt.% to 99.999 wt.%, preferably about 0.01 wt.% to 90 wt.%, further preferably about 0.05 wt.% to 50 wt.%, and more preferably about 0.5 wt.% to about 25%. In the fragrance mixture, the sum of 100 wt.% is usually formed by other fragrances, and if appropriate, can also be formed by solvents and / or preservatives. Other additives can also be added depending on the application.

[0047] Flavors: The flavor mixtures according to the invention must contain another flavor, i.e. at least two flavor components, or consist of an isomeric mixture of compounds of formula (i), (ii) and / or (iii), in particular a combination of an organoleptically effective dose of diethyl (E)-2-methyl-but-2-enedicarboxylate and at least one other flavor. Generally speaking, flavors are not used in binary or ternary mixtures, but as components of sophisticated and complex mixtures, which may include 10, 20, 50, 100 or more flavors, sometimes in very small amounts, to provide a particularly full odor profile. In this sense, the mixtures of the invention should be regarded as mixtures of compounds of formula (i), (ii) and / or (iii) with one, two, three, four, five, ten, preferably a greater number of flavors.

[0048] In a seventh embodiment of the present invention, the fragrance mixture contains any amount of other fragrances selected from the group consisting of: (1) hydrocarbons; (2) aliphatic alcohols; (3) aliphatic aldehydes and their acetals; (4) aliphatic ketones and their oximes; (5) aliphatic sulfur compounds; (6) aliphatic nitriles; (7) aliphatic carboxylic acid esters; (8) acyclic terpene alcohols; (9) acyclic terpene aldehydes and ketones; (10) cyclic terpene alcohols; (11) cyclic terpene aldehydes and ketones; (12) cyclic alcohols; (13) alicyclic alcohols; (14) cyclic and alicyclic ethers; (15) cyclic and Macrocyclic ketones; (16) alicyclic aldehydes; (17) alicyclic ketones; (18) esters of cyclic alcohols; (19) esters of alicyclic alcohols; (20) esters of alicyclic carboxylates; (21) aromatic aliphatic alcohols; (22) esters of aromatic aliphatic alcohols and aliphatic carboxylic acids; (23) aromatic aliphatic ethers; (24) aromatics and aromatic aldehydes; (25) aromatic and aromatic aliphatic ketones; (26) aromatic and aromatic aliphatic carboxylic acids and their esters; (27) nitrogen-containing aromatic compounds; (28) phenols, phenyl ethers and phenyl esters; (29) heterocyclic compounds; (30) lactones; and mixtures thereof.

[0049] The choice of fragrances is very broad; corresponding substances which can be advantageously combined with diethyl conate can be found, for example, in: "S. Arctander, Perfume and Flavor Chemicals, Vol. I und II, Montclair, NJ, 1969, Selbstverlag" or "H. Surburg und J. Panten, Common Fragrance and Flavor Materials, 6th edition., Wiley-VCH, Weinheim, 2016". The detailed information is stated below:

[0050] Extracts from natural raw materials: This group of substances includes: essential oils, concretes, absolutes, resins, balsams, tinctures, for example, ambergris tincture; amyris oil; angelicae oil; angelica root oil; anise oil; valerian oil; basil oil; tree moss absolute; bay oil; mugwort oil; benzoin resin; bergamot oil; beeswax absolute; birch tar oil; bitter almond oil; savory oil; bucco leaf oil; cabreuva oil oil; cade oil; calmus oil; camphor oil; cananga oil; cardamom oil; cascarilla oil; cassia oil; cassie absolute; castoreum absolute; cedar leaf oil; cedar wood oil; cistus essential oil; citronella oil; lemon oil; copaiba balsam; copaiba essential oil; coriander oil; costus root oil; cumin oil; cypress essential oil; davana essential oil; dill herb oil; dill seed oil; eau de parfum absolute debrouts-absolute; oakmoss absolute; elemi oil; tarragon oil; eucalyptus citriodora oil; eucalyptus oil; fennel oil; spruce needle oil; galbanum oil; galbanum resin; geranium oil; grapefruit oil; guaiac wood oil; gurjun balsam; gurjun balsam oil; helichrysum absolute; helichrysum oil; ginger oil; iris root absolute; iris root oil; jasmine absolute; calamus oil; blue chamomile oil;Roman chamomile oil; carrot seed oil; quinoa oil; pine needle oil; crisp mint oil; caraway oil; labdanum oil; labdanum absolute; labdanum resin; lavandin absolute; lavender oil; lavender absolute; lavender oil; lemongrass oil; lovage oil; lime oil distilled; pressed lime oil; agarwood oil; litsea cubeba oil; bay leaf oil; mace oil; marjoram oil; mandarin oil; massoia bark oil; mimosa absolute; musk seed oil; musk tincture; sage sage oil; nutmeg oil; myrrh absolute; myrrh oil; myrtle oil; clove leaf oil; clove flower oil; neroli oil; frankincense absolute; frankincense oil; red myrrh oil; neroli absolute; orange oil; oregano oil; palmarosa oil; patchouli oil; basil oil; Peru balsam oil; coriander leaf oil; coriander seed oil; orange leaf oil; peppermint oil; pepper oil; pimento oil; pine oil; poley oil; rose absolute; sandalwood oil; rose oil; rosemary essential oil; Dalmatian sage oil; Spanish sage oil; sandalwood oil; celery seed oil; spike lavender oil; star anise oil. anise oil; styrax essential oil; marigold oil; fir needle oil; tea tree oil; turpentine oil; thyme oil; tolu balsam; tonka absolute; tuberose absolute; vanilla extract; violet leaf absolute; verbena oil; vetiver oil; juniperberry oil; wine yeast oil; wormwood oil; wintergreen oil; ylang-ylang oil; ysop oil; civet absolute; cinnamon leaf oil; cinnamon bark oil and fractions thereof, or components isolated therefrom.

[0051] Single spices: Single spices can be divided into several categories, namely:

[0052] Hydrocarbons, such as 3-carene; α-pinene; β-pinene; α-terpinene (pinolene); γ-terpinene; p-cymene; bisabolene; camphene; caryophyllene; cedrene; afarnesene; limonene; longifolene; myrcene; ocimene; valencene; (E,Z)-1,3,5-undecatriene; styrene; diphenylmethane;

[0053] Aliphatic alcohols, for example hexanol; octanol; 3-octanol; 2,6-dimethylheptanol; 2-methyl-2-heptanol; 2-methyl-2-octanol; (E)-2-hexenol; (E)- and (Z)-3-hexenols; 1-octen-3-ol; a mixture of 3,4,5,6,6-pentamethyl-3 / 4-hepten-2-ol and 3,5,6,6-tetramethyl-4-methyleneheptan-2-ol; (E,Z)-2,6-nonadienol; 3,7-dimethyl-7-methoxyoctan-2-ol; 9-decenol; 10-undecanol; 4-methyl-3-decen-5-ol;

[0054] Aliphatic aldehydes and acetals thereof, for example hexanal; heptanal; octanal; nonanal; decanal; undecanal; dodecanal; tridecanal; 2-methyloctanal; 2-methylnonanal; (E)-2-hexenal; (Z)-4-heptenal; 2,6-dimethyl-5-heptenal; 10-undecenal; (E)-4-decenal; 2-dodecenal; 2,6,10-trimethyl-9-undecenal; 2,6,10-trimethyl-5,9-undecadienal; heptaldehyde diethyl acetal; 1,1-dimethoxy-2,2,5-trimethyl-4-hexene; citronellyloxyacetaldehyde; 1-(1-methoxy-propoxy)-(E / Z)-3-hexene;

[0055] Aliphatic ketones and their oximes, for example, 2-heptanone; 2-octanone; 3-octanone; 2-nonanone; 5-methyl-3-heptanone; 5-methyl-3-heptanone oxime; 2,4,4,7-tetramethyl-6-octen-3-one; 6-methyl-5-hepten-2-one;

[0056] Aliphatic sulfur compounds, for example, 3-methylmercaptohexanol; 3-methylmercaptohexanol acetate; 3-mercaptohexanol; 3-mercaptohexyl acetate; 3-mercaptohexyl butyrate; 3-acetylthiohexyl acetate; 1-menthene-8-thiol;

[0057] Aliphatic nitriles, for example, 2-nonenoic acid nitrile; 2-undecenoic acid nitrile; 2-tridecenoic acid nitrile; 3,12-tridecadienoic acid nitrile; 3,7-dimethyl-2,6-octadienoic acid nitrile; 3,7-dimethyl-6-octenoic acid nitrile;

[0058] Aliphatic carboxylic acid esters, for example, (E) and (Z)-3-hexenol formate; ethyl acetoacetate; isoamyl acetate; hexyl acetate; 3,5,5-trimethylhexyl acetate; 3-methyl-2-butenyl acetate; (E)-2-hexenyl acetate; (E)- and (Z)-3-hexenol acetate; octyl acetate; 3-octyl acetate; 1-octen-3-ol acetate; ethyl butyrate; butyl butyrate; isoamyl butyrate; hexyl butyrate; (E)- and (Z)-3-hexenol isobutyrate; butyl butyrate Hexyl beanate; ethyl isovalerate (ethyl isovalerate); ethyl 2-methylvalerate; ethyl hexanoate; allyl hexanoate; ethyl heptanoate; allyl heptanoate; ethyl octanoate; ethyl (E, Z)-2,4-decadienoate; methyl 2-octinate; methyl 2-noninate; propenyl 2-isopentyloxyacetate; methyl 3,7-dimethyl-2,6-octadienoate; 4-methyl-2-pentyl-crotonate;

[0059] Acyclic terpene alcohols, for example, citronellol; geraniol; nerol; linalool; lavadulol; nerolidol; farnesol; tetrahydrolinalool; tetrahydrogeraniol; 2,6-dimethyl-7-octen-2-ol; 2,6-dimethyloctan-2-ol; 2-methyl-6-methylene-7-octen-2-ol; 2,6-dimethyl-5,7-octadien-2-ol; 2,6-dimethyl-3,5- Octadien-2-ol; 3,7-dimethyl-4,6-octadien-3-ol; 3,7-dimethyl-1,5,7-octatrien-3-ol; 2,6-dimethyl-2,5,7-octatrien-1-ol; and their formates, acetates, propionates, isobutyrates, butyrates, isovalerates, valerates, hexanoates, crotonates, tiglinates, 3-methyl-2-butenoates;

[0060] Acyclic terpene aldehydes and ketones, for example, geranial; neral; citronellal; 7-hydroxy-3,7-dimethyloctanal; 7-methoxy-3,7-dimethyloctanal; 2,6,10-trimethyl-9-undecenal; geranylacetone; and the dimethyl and diethyl acetals of geranial, neral, and 7-hydroxy-3,7-dimethyloctanal;

[0061] Cyclic terpene alcohols, for example, menthol, isopulegol; α-terpineol (terpineol); terpineol-4; menth-8-ol (menth-8-ol); menth-1-ol; menth-7-ol; bornyl alcohol (borneol); isobornyl alcohol; linalool oxide; nopol; cedrol; ambroxanol; vetivol; guaiacol; and their formates, acetates, propionates, isobutyrates, butyrates, isovalerates, valerates, hexanoates, crotonates, tiglic acid esters, 3-methyl-2-butenoates;

[0062] Cyclic terpene aldehydes and ketones, for example, menthone; isomenthone; 8-mercaptomenthone-3-one (8-mercaptomenthone-3-one); carvone; camphor (camphor); fenchone; α-ionone; β-ionone; α-n-methylionone; β-n-methylionone; α-isomethylionone; β-isomethylionone; α-irone; α-damascenone; β-damascenone; β-damascenone; δ-damascenone; γ-damascenone; 1-(2,4,4-trimethyl-2-cyclohexen-1-yl)-2-butene-1-one; 1,3,4,6,7,8a-hexahydro-1,1, 5,5-Tetramethyl-2H-2,4a-methanonaphthalen-8(5H)-one (1,3,4,6,7,8a-hexahydro-1,1,5,5-tetramethyl-2H-2,4a-methanonaphthalen-8(5H)-one); 2-Methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal; Nootkatone; Dihydronootkatone; 4,6,8-Meganotriene-3-one; α-Auricularial; β-Auricularial; Acetylated cedarwood oil (methyl cedarone);

[0063] Cyclic alcohols, for example, 4-tert-butylcyclohexanol; 3,3,5-trimethyl-cyclohexanol; 3-isobornylcyclohexanol; 2,6,9-trimethyl-Z2,Z5,E9-cyclododecatrien-1-ol; 2-isobutyl-4-methyltetrahydro-2H-pyran-4-ol;

[0064] Cycloaliphatic alcohols, for example, α-3,3-trimethylcyclohexylmethanol; 1-(4-isopropylcyclohexyl)ethanol; 2-methyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)butanol; 2-methyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)-2-buten-1-ol; 2-ethyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)-2-buten-1-ol; 3-methyl-5- (2,2,3-trimethyl-3-cyclopent-1-yl)-penten-2-ol; 3-methyl-5-(2,2,3-trimethyl-3-cyclopent-1-yl)-4-penten-2-ol; 3,3-dimethyl-5-(2,2,3-trimethyl-3-cyclopent-1-yl)-4-penten-2-ol; 1-(2,2,6-trimethylcyclohexyl)penten-3-ol; 1-(2,2,6-trimethylcyclohexyl)hexan-3-ol;

[0065] Cyclic and alicyclic ethers, for example: eucalyptol; methyl cedar ether; cyclododecyl methyl ether; 1,1-dimethoxycyclododecane; (ethoxymethoxy)cyclododecane; α-cedar oxide; 3a,6,6,9a-Tetramethyldodecahydronaphtho[2,1-b]furan; 3a-Ethyl-6,6,9a-trimethyldodecahydronaphtho[2,1-b]furan; 1,5,9-Trimethyl-13-oxabicyclo[10.1.0]-tridecyl-4,8-diene; rose oxide; 2-(2,4-dimethyl-3-cyclohexen-1-yl)-5-methyl-5-(1-methylpropyl)-1,3-dioxane;

[0066] Cyclic and macrocyclic ketones, for example: 4-tert-butylcyclohexanone; 2,2,5-trimethyl-5-pentylcyclopentanone; 2-heptylcyclopentanone; 2-pentylcyclopentanone; 2-hydroxy-3-methyl-2-cyclopenten-1-one; 3-methyl-cis-2-penten-1-yl-2-cyclopenten-1-one; 3-methyl-2-pentyl-2-cyclopenten-1-one; 3-methyl-4-cyclopentadecenone ; 3-methyl-5-cyclopentadecenone; 3-methylcyclopentadecanone; 4-(1-ethoxyvinyl)-3,3,5,5-tetramethylcyclohexanone; 4-tert-pentylcyclohexanone; 5-cyclohexadecene-1-one; 6,7-dihydro-1,1,2,3,3-pentamethyl-4(5H)-indanone; 8-cyclohexadecene-1-one; 9-cycloheptadecene-1-one; cyclopentadecanone; cyclododecanone;

[0067] Cycloaliphatic aldehydes, for example: 2,4-dimethyl-3-cyclohexenecarboxaldehyde; 2-methyl-4-(2,2,6-trimethyl-cyclohexen-1-yl)-2-butenal; 4-(4-hydroxy-4-methylpentyl)-3-cyclohexenecarboxaldehyde; 4-(4-methyl-3-penten-1-yl)-3-cyclohexenecarboxaldehyde;

[0068] Cycloaliphatic ketones, for example: 1-(3,3-dimethylcyclohexyl)-4-penten-1-one; 2,2-dimethyl-1-(2,4-dimethyl-3-cyclohexen-1-yl)-1-propanone; 1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one; 2,3,8,8-tetramethyl-1,2,3,4,5,6,7,8-octahydro-2-naphthylmethyl ketone; methyl-2,6,10-trimethyl-2,5,9-cyclododecantrienone; tert-butyl-(2,4-dimethyl-3-cyclohexen-1-yl) ketone;

[0069] Esters of cyclic alcohols, for example: 2-tert-butyl cyclohexyl acetate; 4-tert-butyl cyclohexyl acetate; 2-tert-pentyl cyclohexyl acetate; 4-tert-pentyl cyclohexyl acetate; 3,3,5-trimethylcyclohexyl acetate; decahydro-2-naphthyl acetate; acetate); 2-cyclopentylcyclopentyl crotonate; 3-pentyltetrahydro-2H-pyran-4-yl acetate; decahydro-2,5,5,8a-tetramethyl-2-naphthylacetate; 4,7-methano-3a,4,5,6,7,7a-hexahydro-5- or -6-indenyl acetate; 4,7-methano-3a,4,5,6,7,7a-hexahydro-5- or -6-indenyl propionate; 4,7-methano-3a,4,5,6,7,7a-hexahydro-5- or -6-indenyl isobutyrate; 4,7-methanooctahydro-5- or -6-indenyl acetate;

[0070] Esters of cycloaliphatic alcohols, for example, 1-cyclohexylethyl crotonate;

[0071] Cycloaliphatic carboxylic acid esters, for example, allyl 3-cyclohexylpropionate; allyl cyclohexyloxyacetate; methyl cis- and trans-dihydrojasmonate; methyl cis- and trans-jasmonate; methyl-2-hexyl-3-oxocyclopentanecarboxylate; ethyl 2-ethyl-6,6-dimethyl-2-cyclohexenecarboxylate; ethyl 2,3,6,6-tetramethyl-2-cyclohexenecarboxylate; ethyl-2-methyl-1,3-dioxolan-2-acetate;

[0072] Aromatic aliphatic alcohols, for example: benzyl alcohol, 1-phenylethanol; 2-phenylethanol; 3-phenylpropanol; 2-phenylpropanol; 2-phenoxyethanol; 2,2-dimethyl-3-phenylpropanol; 2,2-dimethyl-3-(3-methylphenyl)propanol; 1,1-dimethyl-2-phenylethanol; 1,1-dimethyl-3-phenylpropanol; 1-ethyl-1-methyl-3-phenylpropanol; 2-methyl-5-phenylpentanol; 3-methyl-5-phenylpentanol; 3-phenyl-2-propen-1-ol; 4-methoxybenzyl alcohol; 1-(4-isopropylphenyl)ethanol;

[0073] Esters of aromatic aliphatic alcohols and aliphatic carboxylic acids, for example: benzyl acetate; benzyl propionate; benzyl isobutyrate; benzyl isovalerate; 2-phenethyl acetate (2-phenethyl acetate); 2-phenethyl propionate (2-phenethyl propionate); 2-phenethyl isobutyrate (2-phenethyl isobutyrate); 2-phenethyl isovalerate (2-phenethyl isovalerate); 1-phenethyl acetate (1-phenethyl acetate); α-trichloromethylbenzyl acetate (α-trichloromethylbenzyl acetate); α,α-dimethylphenethyl acetate (α,α-dimethylphenethyl acetate); α,α-dimethylphenethyl butyrate (α,α-dimethylphenethyl butyrate); cinnamyl acetate; 2-phenoxyethyl isobutyrate (2-phenoxyethyl isobutyrate); 4-methoxybenzyl acetate (4-methoxybenzyl acetate);

[0074] Aromatic aliphatic ethers, 2-phenylethyl methyl ether; 2-phenylethyl isopentyl ether; 2-phenylethyl 1-ethoxyethyl ether; phenylacetaldehyde dimethylacetal; phenylacetaldehyde diethylacetal; hydratropaldehyde dimethylacetal; phenylacetaldehyde glycerol acetal; 2,4,6-trimethyl-4-phenyl-1,3-dioxane; 4,4a,5,9b-tetrahydroindene-[1,2-d]-m-dioxin; 4,4a,5,9b-tetrahydro-2,4-dimethylindene[1,2-d]-m-dioxin;

[0075] Aromatic and aromatic aliphatic aldehydes, for example, benzaldehyde; phenylacetaldehyde; 3-phenylpropanal; solanum nigrum aldehyde; 4-methylbenzaldehyde; 4-methylphenylacetaldehyde; 3-(4-ethylphenyl)-2,2-dimethylpropanal; 2-methyl-3-(4-isopropylphenyl)propanal; 2-methyl-3-(4-tert-butylphenyl)propanal; 2-methyl-3-(4-isobutylphenyl)propanal; 3-(4-tert-butylphenyl)propanal; cinnamon Aldehyde; α-butylcinnamaldehyde; α-amylcinnamaldehyde; α-hexylcinnamaldehyde; 3-methyl-5-phenylpentanal; 4-methoxybenzaldehyde; 4-hydroxy-3-methoxybenzaldehyde; 4-hydroxy-3-ethoxybenzaldehyde; 3,4-methylenedioxybenzaldehyde; 3,4-dimethoxybenzaldehyde; 2-methyl-3-(4-methoxyphenyl)propanal; 2-methyl-3-(4-methylenedioxyphenyl)propanal;

[0076] Aromatic and aromatic aliphatic ketones, for example, acetophenone; 4-methylacetophenone; 4-methoxyacetophenone; 4-tert-butyl-2,6-dimethylacetophenone; 4-phenyl-2-butanone; 4-(4-hydroxyphenyl)-2-butanone; 1-(2-naphthalenyl)ethanone; 2-benzofuranylethanone; (3-methyl-2-benzofuranyl)ethanone; 1,1,2,3,3,6-hexamethyl-5-indanyl methyl ketone; 6-tert-butyl-1,1-dimethyl-4-indanyl methyl ketone; 1-[2,3-dihydro-1,1,2,6-tetramethyl-3-(1-methylethyl)-1H-5-indanyl]ethanone; 5',6',7',8'-tetrahydro-3',5',5',6',8',8'-hexamethyl-2-naphthyl acetonide;

[0077] Aromatic and araliphatic carboxylic acids and their esters, for example: benzoic acid; phenylacetic acid; methyl benzoate; ethyl benzoate; hexyl benzoate; benzyl benzoate; methyl phenylacetate; ethyl phenylacetate; geranyl phenylacetate; phenylethyl phenylacetate; methyl cinnamate; ethyl cinnamate; benzyl cinnamate; phenylethyl cinnamate; cinnamyl cinnamate; allyl phenoxyacetate; methyl salicylate; isoamyl salicylate; hexyl salicylate; cyclohexyl salicylate; cis-3-hexenyl salicylate; benzyl salicylate; phenylethyl salicylate; methyl 2,4-dihydroxy-3,6-dimethylbenzoate; ethyl-3-phenyl glycidate; ethyl-3-methyl-3-phenylglycidate;

[0078] Aromatic nitrogen compounds, for example: 2,4,6-trinitro-1,3-dimethyl-5-tert-butylbenzene; 3,5-dinitro-2,6-dimethyl-4-tert-butylacetophenone; cinnamic acid nitrile; 3-methyl-5-phenyl-2-pentenenitrile; 3-methyl-5-phenylvaleronitrile; methyl anthranilate; methyl N-methyl anthranilate; Schiff base of methyl anthranilate and 7-hydroxy-3,7-dimethyloctanal; 2-methyl-3-(4-tert-butylphenyl)propanal; 2,4-dimethyl-3-cyclohexenecarboxaldehyde; 6-isopropylquinoline; 6-isobutylquinoline; 6-sec-butylquinoline; 2-(3-phenylpropyl)pyridine; indole; skatole; 2-methoxy-3-isopropylpyrazine; 2-isobutyl-3-methoxypyrazine;

[0079] Phenols, phenyl ethers and phenyl esters, for example, estragole; anethole; eugenol; eugenol methyl ether; isoeugenol; isoeugenol methyl ether; thymol; carvacrol; diphenyl ether; β-naphthyl methyl ether; β-naphthyl ethyl ether; β-naphthyl isobutyl ether; 1,4-dimethoxybenzene; eugenyl acetate; 2-methoxy-4-methylphenol; 2-ethoxy-5-(1-propenyl)phenol; p-cresyl phenylacetate;

[0080] Heterocyclic compounds, for example: 2,5-dimethyl-4-hydroxy-2H-furan-3-one; 2-ethyl-4-hydroxy-5-methyl-2H-furan-3-one; 3-hydroxy-2-methyl-4H-pyran-4-one; 2-ethyl-3-hydroxy-4H-pyran-4-one;

[0081] Lactones, for example: 1,4-octanolactone; 3-methyl-1,4-octanolactone; 1,4-nonalactone; 1,4-decanolide; 8-decene-1,4-lactone; 1,4-undecanolide; 1,4-dodecanolide; 1,5-decanolide; 1,5-dodecanolide; 4-methyl-1,4-decanolide; 1,15-pentadecanolactone; cis- and trans-11-pentadecanolactone; cis- and trans-12-pentadecanolactone; 1,16-decanolide Hexalactone; 9-hexadecene-1,16-lactone; 10-Oxa-1,16-hexadecanolid; 11-Oxa-1,16-hexadecanolid; 12-Oxa-1,16-hexadecanolid; Ethylen-1,12-dodecandioate; Ethylen-1,13-tridecandioate; Coumarin; 2,3-dihydrocoumarin; Octahydrocoumarin;

[0082] and any mixtures thereof.

[0083] Application form

[0084] The eighth aspect of the present invention relates to a perfume oil, a cosmetic, an ointment or a washing and cleaning agent containing the perfume mixture of the present invention.

[0085] Creams are to be understood here as meaning all preparations mentioned here which do not belong to perfume oils, cosmetics or washing and cleaning agents.

[0086] For these preparations according to the ninth embodiment of the present invention, these preparations contain the fragrance mixture of the present invention, and its content is 0.05wt.% to 5wt.% of the amount of the preparation. Therefore, the present invention relates to both perfume oils, cosmetics, lotions, and washing and cleaning agents, and also includes fragrance or fragrance products, which generally include compounds of formula (i), formula (ii) and / or formula (iii), or (E)-2-methyl-but-2-enedicarboxylic acid diethyl ester alone, especially a mixture of diethyl mesaconic acid ester with diethyl citraconic acid and diethyl itaconate, or the corresponding fragrance mixture described above, based on the preparation, its content is about 0.05wt.% to 5wt.%, preferably about 0.1wt.% to 3wt.%, and particularly preferably about 0.5wt.% to 2wt.%.

[0087] The perfume mixture and the perfume oil containing the compound of formula (i), formula (ii) and / or formula (iii), or preferably (E)-2-methylbut-2-enedicarboxylate, or the mixture of diethyl mesaconic acid with diethyl citraconic acid and diethyl itaconate, can be used for perfume in liquid, undiluted or diluted with solvent. Suitable solvents can be ethanol, isopropanol, diethylene glycol monoethyl ether, glycerol, propylene glycol, 1,2-butylene glycol, dipropylene glycol, diethyl phthalate, triethyl citrate, isopropyl myristate, etc.

[0088] These fragrance mixtures may contain up to 90 wt.%, preferably about 5 to 70 wt.%, particularly preferably about 10 to 50 wt.%, more preferably about 15 to 25 wt.% of said solvent.

[0089] For specific applications, it may also be advantageous to use a perfume oil (fragrance mixture) comprising a compound of formula (i), (ii) and / or (iii), or preferably (E)-diethyl 2-methylbut-2-enedicarboxylate, or a mixture of diethyl mesaconic acid with diethyl citrate and diethyl itaconate absorbed on a carrier that ensures both a fine distribution of the fragrance in the product and a controlled release thereof in use. Such a carrier may be a porous inorganic material, for example light sulphates, silica gel, zeolite, gypsum, clay, clay particles, aerated concrete, etc., or an organic material, for example wood, cellulose-based substances, sugars or plastics, for example PVC, polyvinyl acetate or polyurethane.

[0090] For other applications, it is advantageous to use the fragrance oil or fragrance mixture according to the invention in microencapsulated, spray-dried form as inclusion complex or extrusion product and in this form to add to perfumed (pre)products.

[0091] The properties of such modified fragrance oils or fragrance mixtures can in certain cases be further optimized by so-called "coating" with suitable materials for a more targeted release of the fragrance, for which purpose waxy plastics such as polyvinyl alcohol are preferably used.

[0092] Microencapsulation of the aromatic oil or spice mixture of the present invention can be obtained by so-called coagulation method with capsule materials such as polyurethanes or soft gelatin. Spray-dried aromatic oils can be prepared, for example, by spray-drying an emulsion or dispersant containing aromatic oils using modified starch, protein, dextrin and vegetable gum as carriers. Inclusion complexes can be prepared, for example, by adding aromatic oils and dispersants of cyclodextrin or urea derivatives to a suitable solvent (e.g., water). Extruded products can be obtained by melting aromatic oils with a suitable waxy substance and by extrusion and subsequent solidification (in a suitable solvent, such as isopropanol, if necessary).

[0093] Cosmetics and body care products

[0094] The cosmetic and body care products according to the invention may contain, in addition to compounds of the formula (i), (ii) and / or (iii), or preferably diethyl (E)-2-methylbut-2-enedicarboxylate, or a mixture of diethyl mesaconic acid with diethyl citraconic acid and diethyl itaconate, or a fragrance mixture containing these compounds or mixtures, further typical auxiliaries and additives, for example mild surfactants, oil bodies, emulsifiers, pearlescent waxes, consistency enhancers, thickeners, superfatting agents, stabilizers, polymers, silicone compounds, fats, waxes, lecithins, phospholipids, UV light protection factors, wetting agents, biologically active ingredients, antioxidants, deodorants, antiperspirants, antidandruff agents, film formers, swelling agents, insect repellents, self-tanning agents, tyrosine inhibitors (depigmenting agents), hydrotropes, solubilizers, preservatives, fragrance oils, colorants, etc., as described below. The terms "cosmetic product", "body care product" and "perfuming product" are used interchangeably, provided that the agents have an organoleptically effective dose of a compound of formula (i), (ii) and / or (iii), or preferably (E)-diethyl 2-methylbut-2-enedicarboxylate, or a mixture of diethyl mesaconic acid with diethyl citraconic acid and diethyl itaconate, or a perfume mixture containing these diesters. Preferred additives are described below.

[0095] Surfactants:

[0096] Useful surfactants are anionic, nonionic, cationic and / or amphoteric or zwitterionic surfactants, and their proportion in the agent (preparation) is usually about 1-70 wt.%, preferably 5-50 wt.%, particularly preferably 10-30 wt.%. Typical examples of anionic surfactants are soaps, alkylbenzenesulfonates, paraffinsulfonates, olefinsulfonates, alkylethersulfonates, glycerylethersulfonates, alphamethylestersulfonates, sulfofatty acids, alkyl sulfates, alkylethersulfates, glycerylethersulfates, fatty acid ethersulfates, hydroxy mixed ethersulfates, monoglyceride (ether)sulfates, fatty acid amide (ether)sulfates, mono- and dialkylsulfosuccinates, mono- and dialkylsulfosuccinates, sulfotriglycerides, amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurine, N-acylamino acids, such as acyl lactylates, acyl tartrates, acylglutamates and acylaspartates, alkyl oligoglucoside sulfates, protein fatty acid condensates (especially wheat-based vegetable products) and alkyl (ether)phosphates. As long as the anionic surfactants contain polyethylene glycol ether chains, they can have a conventional, but preferably narrow, homolog distribution. Typical examples of nonionic surfactants are aliphatic alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amides, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers and mixed formals, or partially oxidized alkyl (en) oligoglycosides or glucuronic acid derivatives, fatty acid-N-alkyl glucamides, protein hydrolysates (especially wheat-based plant products), polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and amine oxides. As long as the nonionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably narrow homolog distribution. Typical examples of cationic surfactants are quaternary ammonium compounds, for example, dimethyl distearyl chloride, ester quaternary ammonium salts, especially quaternized fatty acid trialkanolamine ester salts. Typical examples of amphoteric or zwitterionic surfactants are alkyl betaines, alkyl amido betaines, aminopropionates, aminoglycine, imidazolinium betaines and sulfobetaines. The above-mentioned surfactants are all known compounds. Typical examples of particularly suitable mild (i.e. particularly skin-compatible) surfactants are fatty alcohol polyglycol ether sulfates, monoglyceride sulfates, mono- and / or dialkyl sulfosuccinates, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurine, fatty acid glutamic acid, alpha-olefin sulfonates, ether carboxylic acids, alkyl oligoglucosides, fatty acid glucamides, alkylamidobetaines, amphoacetates and / or protein fatty acid condensates, the latter preferably being based on wheat protein.

[0097] Oil body:

[0098] Suitable oil bodies may be Guerbet alcohols based on aliphatic alcohols having 6 to 18, preferably 8 to 10, carbon atoms, linear C6-C 22 Fatty acids with straight or branched C6-C 22 Aliphatic alcohol esters, or branched C6-C 13 Carboxylic acid with straight or branched C6-C 22 Esters of aliphatic alcohols, for example myristyl myristate, myristyl palmitate, myristyl stearate, myristyl isostearate, myristyl oleate, myristyl behenate, myristyl erucate, cetyl myristate, cetyl palmitate, cetyl stearate, cetyl isostearate, cetyl oleate, cetyl behenate, cetyl erucate, stearyl myristate, stearyl palmitate, stearyl stearate, stearyl isostearate, stearyl oleate, stearyl behenate, stearyl erucate, isostearyl myristate, isostearyl palmitate Suitable alcohols include esters of isostearyl stearate, isostearyl isostearate, isostearyl oleate, isostearyl behenate, isostearyl oleate, oleyl myristate, oleyl palmitate, oleyl stearate, oleyl isostearate, oleyl oleate, oleyl behenate, oleyl erucate, behenyl myristate, behenyl palmitate, behenyl stearate, behenyl isostearate, behenyl oleate, behenyl behenate, behenyl erucate, erucyl myristate, erucyl palmitate, erucyl stearate, erucyl isostearate, erucyl oleate, erucyl behenate and erucyl erucate. Also suitable are straight-chain C6-C8 alcohols with branched alcohols, especially 2-ethylhexanol. 22 Fatty acid esters, with straight or branched C6-C 22 Aliphatic alcohol C 18 -C 38 Alkylhydroxycarboxylates (especially dioctyl malate), linear and / or branched fatty acid esters with polyols (such as propylene glycol, dimer diol or trimer triol) and / or Guerbet alcohols, C6-C 10 Triglycerides of fatty acids, liquid mono / di / triglyceride mixtures based on C6-C18 fatty acids, 22 Esters of aliphatic alcohols and / or Guerbet alcohols with aromatic carboxylic acids, especially benzoic acid, C2-C4 esters of linear or branched alcohols having 1 to 22 carbon atoms or polyols having 2 to 10 carbon atoms and 2 to 6 hydroxyl groups 12 Dicarboxylates, vegetable oils, branched primary alcohols, substituted cyclohexanes, straight and branched C6-C 22 Aliphatic alcohol carbonates, such as dicaprylyl carbonate ( CC), Guerbet carbonates based on aliphatic alcohols having 6 to 18, preferably 8 to 10, carbon atoms, with linear and / or branched C6-C 22 Benzoic acid esters of alcohols (e.g. TN), a straight chain or branched, symmetrical or asymmetrical dialkyl ether having 6 to 22 carbon atoms in each alkyl group, such as dioctyl ether ( OE), ring-opening products of epoxidized fatty acid esters and polyols, silicone oils (cyclomethylsiloxane, silicone-methicone type, etc.) and / or aliphatic or cycloalkane, such as squalane, squalene or dialkylcyclohexanes.

[0099] Emulsifier: Suitable emulsifiers include at least one nonionic surfactant selected from the group consisting of:

[0100] addition products of 2 to 30 mol of ethylene oxide and / or 0 to 5 mol of propylene oxide with linear aliphatic alcohols having 8 to 22 carbon atoms, with fatty acids having 12 to 22 carbon atoms, with alkylphenols having 8 to 15 carbon atoms in the alkyl radical and with alkylamines having 8 to 22 carbon atoms in the alkyl radical;

[0101] - alkyl and / or alkenyl oligoglycosides having 8 to 22 carbon atoms in the alkyl (alkenyl) group and their ethoxylated analogs;

[0102] Addition products of 1 to 15 mol of ethylene oxide onto castor oil and / or hydrogenated castor oil;

[0103] Addition products of 15 to 60 mol of ethylene oxide onto castor oil and / or hydrogenated castor oil;

[0104] Partial esters of glycerol and / or sorbitan of unsaturated linear or saturated branched fatty acids having 12 to 22 carbon atoms and / or hydroxycarboxylic acids having 3 to 18 carbon atoms, and adducts thereof with 1 to 30 mol of ethylene oxide;

[0105] polyglycerols (average degree of self-condensation of 2-8) of saturated and / or unsaturated linear or branched fatty acids having 12 to 22 carbon atoms and / or hydroxycarboxylic acids having 3 to 18 carbon atoms, polyethylene glycols (molecular weight 400-5000), trimethylolpropane, pentaerythritol, partial esters of sugar alcohols (e.g. sorbitol), alkyl glucosides (e.g. methyl glucoside, butyl glucoside, lauryl glucoside) and polyglucosides (e.g. cellulose), and adducts thereof with 1 to 30 mol of ethylene oxide;

[0106] Pentaerythritol, fatty acids, mixed esters of citric acid and aliphatic alcohols, mixed esters of fatty acids having 6 to 22 carbon atoms, methyl glucose and polyols, preferably glycerol or polyglycerol.

[0107] Mono-, di- and tri-alkyl phosphates and mono-, di- and / or tri-PEG-alkyl phosphates and their salts;

[0108] ·Wool wax alcohol;

[0109] Polysiloxane-polyalkyl-polyether copolymers or corresponding derivatives;

[0110] Block copolymers, such as polyethylene glycol-30 dihydroxystearate;

[0111] Polymeric emulsifiers, such as Goodrich's Pemulen types (TR-1, TR-2) or Cognis' SP;

[0112] Polyalkylene glycols and

[0113] Glycerol carbonate.

[0114] Particularly suitable emulsifiers are described in more detail below:

[0115] Alkoxylation: Addition products of ethylene oxide and / or propylene oxide with aliphatic alcohols, fatty acids, alkylphenols or castor oil are known commercial products. They are homologous mixtures whose average degree of alkoxylation corresponds to the molar ratio of ethylene oxide and / or propylene oxide to the substrate subjected to the addition reaction. 12 / 18 Fatty acid mono- and diesters are useful as re-fattening agents in cosmetic formulations.

[0116] Alkyl and / or alkenyl oligoglycosides: Alkyl and / or alkenyl oligoglycosides, the processes for their preparation and their use are known in the prior art. They can be prepared in particular by reacting glucose or oligosaccharides with primary alcohols having 8 to 18 carbon atoms. With regard to the glycosidic group, both monoglycosides (in which a cyclic sugar group is glycosidically bonded to an aliphatic alcohol) and oligoglycosides having a degree of oligomerization preferably not exceeding 8 are suitable. The degree of oligomerization is a statistical average value, which is based on the typical homologue distribution of these technical products.

[0117] Partial glycerides: Typical examples of suitable partial glycerides are hydroxystearic acid monoglyceride, hydroxystearic acid diglyceride, isostearic acid monoglyceride, isostearic acid diglyceride, oleic acid monoglyceride, oleic acid diglyceride, ricinoleic acid monoglyceride, ricinoleic acid diglyceride, linoleic acid monoglyceride, linoleic acid diglyceride, linoleic acid monoglyceride, linoleic acid diglyceride, erucic acid monoglyceride, erucic acid diglyceride, tartaric acid monoglyceride, tartaric acid diglyceride, citric acid monoglyceride, citric acid diglyceride, malic acid monoglyceride, malic acid diglyceride and technical mixtures thereof, which may contain small amounts of triglycerides from the manufacturing process. Also suitable are addition products of 1 to 30, preferably 5 to 10 mol of ethylene oxide to the partial glycerides.

[0118] Sorbitan esters: Sorbitan esters include sorbitan monoisostearate, sorbitan sesquiisostearate, sorbitan diisostearate, sorbitan triisostearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan dioleate, sorbitan trioleate, sorbitan monoerucic acid, sorbitan sesquierucic acid, sorbitan dierucic acid, sorbitan trierucic acid, sorbitan monoricinoleate, sorbitan sesquiricinoleate, sorbitan diricinoleate, sorbitan triricinoleate, dehydrated sorbitan esters. Sorbitan monohydroxystearate, sorbitan sesquihydroxystearate, sorbitan dihydroxystearate, sorbitan trihydroxystearate, sorbitan monotartrate, sorbitan sesquitartrate, sorbitan ditartrate, sorbitan tritartrate, sorbitan monocitrate, sorbitan sesquicitrate, sorbitan dicitrate, sorbitan tricitrate, sorbitan monomaleate, sorbitan sesquimaleate, sorbitan dimaleate, sorbitan trimalate, and technical mixtures thereof. Also suitable are addition products of 1 to 30, preferably 5 to 10, mol of ethylene oxide to the sorbitan esters.

[0119] Polyglycerol esters: A typical example of a suitable polyglycerol ester is polyglyceryl-2 dipolyhydroxystearate ( PGPH), polyglyceryl-3-diisostearate ( TGI), polyglyceryl-4-isostearate ( GI 34), polyglyceryl-3 oleate, diisostearyl polyglyceryl-3-diisostearate ( PDI), polyglyceryl-3 methyl glucose distearate (Tego 450), Polyglyceryl-3-Beeswax (Cera )、Polyglycerol Caprate T2010 / 90)、Polyglycerol-3 hexadecene ( NL), Polyglyceryl-3 Distearate ( GS 32) and polyglycerol ricinoleic acid polyester ( WOL 1403) polyglyceryl dimethyl isostearate and mixtures thereof. Other examples of suitable polyol esters are trimethylolpropane or pentaerythritol esters with lauric acid, coconut fatty acid, tallow fatty acid, palmitic acid, stearic acid, oleic acid, behenic acid, etc., optionally reacted with 1 to 30 moles of ethylene oxide.

[0120] Anionic emulsifiers: Typical anionic emulsifiers are aliphatic fatty acids having 12 to 22 carbon atoms, such as palmitic acid, stearic acid or behenic acid, and dicarboxylic acids having 12 to 22 carbon atoms, such as azelaic acid or sebacic acid.

[0121] Amphoteric and Cationic Emulsifiers: In addition, zwitterionic surfactants can be used as emulsifiers. Zwitterionic surfactants are surface-active compounds that carry at least one quaternary ammonium group and at least one carboxylate group and sulfonate group in the molecule. Particularly suitable zwitterionic surfactants are so-called betaine-type surfactants, such as N-alkyl-N,N-dimethylammonium glycinates, for example cocoalkyldimethylammonium glycinates, N-acylaminopropyl-N,N-dimethylammonium glycinates, for example cocoacylaminopropyldimethylammonium glycinates, and 2-alkyl-3-carboxymethyl-3-hydroxyethylimidazolines containing 8 to 18 carbon atoms in the alkyl or acyl group and cocoacylaminoethylhydroxyethylcarboxymethylglycinate. Particularly preferred zwitterionic surfactants are fatty acid amide derivatives known by the CTFA name Cocamidopropyl Betaine. Suitable emulsifiers are also amphoteric surfactants. Amphoteric surfactants are surfactants that contain at least one quaternary ammonium group and at least one carboxylate group and sulfonate group in the molecule. 8 / 18 A surface-active compound that contains at least one free amino group and at least one -COOH or -SO3H group in addition to the alkyl or acyl group and can form an inner salt. Examples of suitable amphoteric surfactants are N-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N-alkyliminodipropionic acid, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyltaurine, N-alkylsarcosine, 2-alkylaminopropionic acid and alkylaminoacetic acid, each containing about 8 to 18 carbon atoms in the alkyl group. Particularly preferred amphoteric surfactants are N-coconut alkylaminopropionate, cocoacylaminoethylaminopropionate and C 12 / 18 Acylsarcosine. Finally, cationic surfactants are also suitable as emulsifiers, particularly preferably of the esterquat type, more preferably methyl-quaternized difatty acid triethanolamine ester salts.

[0122] Fats and waxes: Typical examples of fats are glycerides, i.e. solid or liquid vegetable or animal products which consist essentially of mixed glycerides of higher fatty acids. Natural waxes such as candelilla wax, carnauba wax, Japan wax, Spanish grass wax, cork wax, guaruma wax, rice germ oil wax, sugar cane wax, carnauba wax, montan wax, beeswax, shellac wax, spermaceti, lanolin (wool wax), tail fat, ceresin, ozokerite (mineral wax), vaseline, hard paraffin, microcrystalline wax; chemically modified waxes (hardened waxes), such as montan ester wax, Sasol wax and hydrogenated jojoba wax; and synthetic waxes such as polyalkylene waxes and polyethylene glycol waxes. In addition to fats, lipid substances such as lecithins and phospholipids are also suitable as additives. By the term "lecithin", the person skilled in the art understands it as a glycerophospholipid formed by esterification of fatty acids, glycerol, phosphoric acid and choline. Therefore, lecithin is often referred to as phosphatidylcholine (PC) in the professional field. Examples of natural lecithin include cephalin, also known as phosphatidic acid, and derivatives of 1,2-diacyl-sn-glycero-3-phosphate. In contrast, phospholipids are usually understood as monoesters and preferably diesters of phosphoric acid and glycerol (glycerophosphate), which are usually considered fats. In addition, sphingoids or sphingolipids are also suitable.

[0123] Pearlescent waxes: Pearlescent waxes that can be used are: alkylene glycol esters, especially ethylene glycol distearate; fatty acid alkanolamides, especially coconut fatty acid diethanolamide; partial glycerides, especially stearic acid monoglyceride; esters of polybasic, optionally hydroxy-substituted carboxylic acids with fatty alcohols having 6 to 22 carbon atoms, especially long-chain esters of tartaric acid; fatty substances having a total of at least 24 carbon atoms, such as fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates, especially laurone and distearyl ether; fatty acids such as stearic acid, hydroxystearic acid or behenic acid, ring-opening products of olefin epoxides having 12 to 22 carbon atoms with fatty alcohols having 12 to 22 carbon atoms and / or polyols having 2 to 15 carbon atoms and 2 to 10 hydroxyl groups, and mixtures thereof.

[0124] Cooling Agents: Cooling agents are chemical compounds that produce a cooling sensation on the skin. Typically, they are menthol compounds which, in addition to the menthol base, can be selected from menthol methyl ether, menthone glycerol acetal (FEMA GRAS 3807), menthone glycerol ketal (FEMA GRAS 3808), menthyl lactate (FEMA GRAS 3748), menthol ethylene glycol carbonate (FEMA GRAS 3805), menthol propylene glycol carbonate (FEMA GRAS 3806), menthyl-N-ethyl oxamate, monomethyl succinate (FEMA GRAS 3810), monomenthyl glutamate (FEMA GRAS 4006), menthyl-1,2-propanediol (FEMA GRAS 3784), menthyl-2-methyl-1,2-propanediol (FEMA GRAS 3849) and menthane carboxylic acid esters and amides WS-3, WS-4, WS-5, WS-12, WS-14 and WS-30 and mixtures thereof. FEMA stands for "Flavor and Extract Manufacturers Association" and GRAS is defined as "Generally Regarded as Safe." The FEMA GRAS designation means that the substances so named have been tested according to standard methods and are regarded as toxicologically safe.

[0125] The first important representative of these substances is monomenthyl succinate (FEMA GRAS 3810). Both the succinate ester and the further analog monomenthyl glutarate (FEMA GRAS 4006) are important representatives of the class of monomenthyl esters based on dicarboxylic acids and polycarboxylic acids:

[0126]

[0127] Examples of the use of these substances can be found in publications such as WO 2003 043431 (Unilever) or EP 1332772 Al (IFF).

[0128] Another important group of preferred menthol compounds within the meaning of the present invention comprises menthol carbonates and polyols, for example glycols, glycerol or carbohydrates, for example menthol glycol carbonate (FEMA GRAS 3805 = MGC), menthol propylene glycol carbonate (FEMA GRAS MPC), menthol 2-methyl-1,2-propylene carbonate (FEMA GRAS 3849) or the corresponding sugar derivatives. Also preferred is the menthol compound menthyl lactate (FEMA GRAS ML), especially menthone glycerol acetal (FEMA GRAS 3807), or Menthone glycerol acetal / ketal and menthyl lactate and menthol ethylene glycol carbonate or menthol propylene glycol carbonate, which are respectively marketed by the applicant under the trade names Menthone glycerol acetal / ketal and menthyl lactate and menthol ethylene glycol carbonate or menthol propylene glycol carbonate, respectively. MGA, ML, MGC or MPC Sales.

[0129] Menthol compounds with a C-C bond in the 3-position were first developed in the 1970s. And among them are many available representative substances. These substances are generally referred to as WS types. The base material is a menthol derivative in which the hydroxyl group is replaced by a carboxyl group (WS-1). All other WS types are derived from this structure, such as the preferred species WS-3, WS-4, WS-5, WS-12, WS-14 and WS-30.

[0130] Consistency enhancers and thickeners: Consistency enhancers mainly used are fatty alcohols or hydroxy fatty alcohols containing 12 to 22 and preferably 16 to 18 carbon atoms and also partial glycerides, fatty acids or hydroxy fatty acids. Preference is given to using combinations of these substances with alkyl oligoglucosides and / or fatty acid N-methylglucamides of the same chain length and / or polyglycerol poly-12-hydroxystearate. Suitable thickeners are, for example, Aerosil types (hydrophilic silicates), polysaccharides, more particularly xanthan gum, guar gum, agar, alginates and methylcellulose, carboxymethylcellulose and hydroxyethyl and hydroxypropylcellulose, and also relatively high molecular weight polyethylene glycol monoesters and diesters of fatty acids, polyacrylates (for example Goodrich's and Pemulen type; Sigma's Synthalene type Kelco's Keltrol type; Seppic's Sepigel type; Allied Colloids' Salcare type), polyacrylamides, polymers, polyvinyl alcohol and polyvinyl pyrrolidone. Other consistency enhancers that have proven particularly effective are bentonites, such as Gel VS-5PC (Rheox), which is a mixture of cyclopentasiloxane, disteardimonium hectorite and propylene carbonate. Other suitable consistency enhancer surfactants are, for example, ethoxylated fatty acid glycerides, esters of fatty acids with polyols such as pentaerythritol or trimethylolpropane, fatty alcohol ethoxylates or alkyl oligoglucosides with narrow homolog distribution and electrolytes such as sodium chloride and ammonium chloride.

[0131] Superfatting Agents and Stabilizers: Superfatting agents may be used, for example lanolin and lecithin and polyethoxylated or polyacylated lanolin and lecithin derivatives, polyol fatty acid esters, monoglycerides and fatty acid alkanolamides, the latter also acting as foam stabilizers.

[0132] Metal salts of fatty acids, for example magnesium, aluminum and / or zinc stearate or magnesium, aluminum and / or zinc ricinoleate, can be used as stabilizers.

[0133] Polymer: Suitable cationic polymers are, for example, cationic cellulose derivatives, such as those available under the name Polymer JR Quaternized hydroxyethylcellulose, cationic starch, copolymers of diallyl ammonium salts and acrylamides, quaternized vinylpyrrolidone / vinylimidazole polymers, such as those available from Amerchol (BASF), condensation products of polyethylene glycols and amines, quaternized collagen polypeptides such as lauryl dimethyl ammonium hydroxypropyl hydrolyzed collagen ( L / Grünau), quaternized wheat polypeptides, polyethyleneimine, cationic silicone polymers such as amodimethicone, copolymers of adipic acid and dimethylaminohydroxypropyldiethylenetriamine ( / Sandoz), copolymer of acrylic acid and dimethyldiallylammonium chloride ( 550 / Chemviron), polyaminopolyamides and crosslinked water-soluble polymers thereof, cationic chitin derivatives such as quaternized chitosan optionally distributed in microcrystalline form, condensation products of dihaloalkyls such as dibromobutane with bis-dialkylamines such as bis-dimethylamino-1,3-propane, cationic guar gum such as Celanese's CBS, C-17, C-16, quaternized ammonium salt polymers, such as Miranol A-15, AD-1, AZ-1.

[0134] Suitable anionic, zwitterionic, amphoteric and nonionic polymers are, for example, vinyl acetate / crotonic acid copolymers, vinyl pyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and their esters, non-crosslinked and polyol-crosslinked polyacrylic acids, acrylamidopropyltrimethylammonium chloride / acrylate copolymers, octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers, polyvinylpyrrolidone, vinylpyrrolidone / vinyl acetate copolymers, vinylpyrrolidone / dimethylaminoethyl methacrylate / vinylcaprolactam terpolymers and optionally derivatized cellulose ethers and silicones.

[0135] Silicone compounds: Suitable silicone compounds are, for example, dimethylpolysiloxanes, methylphenylpolysiloxanes, cyclosiloxanes and amino-, fatty acid-, alcohol-, polyether-, epoxy-, fluorine-, glycoside- and / or alkyl-modified silicone compounds, which can be liquid or resin-like at room temperature. Other suitable silicone compounds are dimethicone oils, which are mixtures of dimethicone oils with an average chain length of 200 to 300 dimethylsiloxane units and hydrogenated silicates.

[0136] UV light protection factor: UV light protection factor is an organic substance (filter) which is liquid or crystalline at room temperature and is capable of absorbing ultraviolet radiation and releasing the absorbed energy (e.g. heat) in the form of long-wave radiation. UV light protection factor is usually added in an amount of 0.1 wt.% to 5 wt.%, preferably 0.2 wt.% to 1 wt.%. UVB filters can be oil-soluble or water-soluble. The following are examples of oil-soluble substances:

[0137] 3-Benzylidenecamphor or 3-benzylidenenorcamphor and derivatives thereof, for example 3-(4-methylbenzylidene)-camphor;

[0138] 4-aminobenzoic acid derivatives, preferably 4-(dimethylamino)-benzoic acid 2-ethylhexyl ester, 4-(dimethylamino)-benzoic acid 2-octyl ester and 4-(dimethylamino)-benzoic acid pentyl ester;

[0139] Cinnamic acid esters, preferably 2-ethylhexyl 4-methoxycinnamate, propyl 4-methoxycinnamate, isopentyl 4-methoxycinnamate, 2-ethylhexyl 2-cyano-3,3-phenylcinnamate (octyl cyanoacrylate);

[0140] Salicylate esters, preferably 2-ethylhexyl salicylate, 4-isopropylbenzyl salicylate, homomenthol salicylate;

[0141] Benzophenone derivatives, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone;

[0142] Benzalmalonic acid esters, preferably di-2-ethylhexyl 4-methoxybenzalmalonate;

[0143] Triazine derivatives, such as 2,4,6-triphenylamino-(p-carbo-2'-ethyl-1'-hexyloxy)-1,3,5-triazine and octyl triazone or dioctyl butyrylamino triazone ( HEB);

[0144] Propane-1,3-dione, for example 1-(4-tert-butylphenyl)-3-(4'-methoxyphenyl)-propane-1,3-dione;

[0145] Ketotricyclo(5.2.1.0)decane derivatives.

[0146] Suitable water-soluble substances are:

[0147] 2-Phenylbenzimidazole-5-sulfonic acid and its alkali metal, alkaline earth metal, ammonium, alkylammonium, alkanolammonium and gluconammonium salts;

[0148] ·1H-benzimidazole-4,6-disulfonic acid, 2,2'-(1,4-phenylene)bis-, disodium salt (Neo AP)

[0149] Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts;

[0150] Sulfonic acid derivatives of 3-benzylidenecamphor, for example 4-(2-oxo-3-bornylidenemethyl)-benzenesulfonic acid and 2-methyl-5-(2-oxo-3-bornylidene)-sulfonic acid and their salts.

[0151] Typical UV-A filters are, in particular, derivatives of benzoylmethane, such as 1-(4'-tert-butylphenyl)-3-(4'-methoxyphenyl)-propane-1,3-dione, 4-tert-butyl-4'-methoxydibenzoylmethane ( 1789), 2-(4-diethylamino-2-hydroxybenzoyl)-benzoic acid hexyl ester ( A Plus), 1-phenyl-3-(4'-isopropylphenyl)-propane-1,3-dione and enamine compounds. UV-A and UV-B filters can of course also be used in the form of mixtures. Particularly advantageous combinations are those of benzoylmethane derivatives, such as 4-tert-butyl-4'-methoxydibenzoylmethane ( 1789) and 2-cyano-3,3-phenylcinnamic acid-2-ethylhexyl ester (octocrylene) with cinnamic acid esters, preferably 4-methoxycinnamic acid-2-ethylhexyl ester and / or 4-methoxycinnamic acid propyl ester and / or 4-methoxycinnamic acid isopentyl ester. Advantageously, these combinations can be combined with water-soluble filters, such as 2-phenylbenzimidazole-5-sulfonic acid and its alkali metal, alkaline earth metal, ammonium, alkylammonium, alkanolammonium and gluconammonium salts.

[0152] In addition to the soluble substances mentioned, insoluble light-shielding pigments, i.e. finely dispersed metal oxides or salts, can also be used for this purpose. Examples of suitable metal oxides are in particular zinc oxide and titanium dioxide, as well as oxides of iron, zirconium, silicon, manganese, aluminum and cerium and mixtures thereof. Silicates (talc), barium sulfate and zinc stearate can be used as salts. Oxides and salts are used in the form of skin care pigments and skin care emulsions and decorative cosmetics. The particles should have an average diameter of less than 100 nm, preferably 5-50 nm, more preferably 15-30 nm. They can have a spherical shape, however, elliptical particles or other non-spherical particles can also be used. The pigment can also be surface treated, i.e. hydrophilized or hydrophobized. Typical examples are coated titanium dioxide, such as Ti tandioxid T 805 (Degussa) or T2000, T. T-ECO, TS, T-Aqua, T-45D (both Merck), Uvinul TiO2 (BASF). Suitable hydrophobic coating materials are primarily silicones and the like, especially trialkoxyoctylsilane or dimethicone. In sunscreens, so-called micronized or nano pigments are preferably used. Micronized zinc oxide, for example or

[0153] Humectants: Humectants are used to further optimize the sensory properties of the composition and regulate the moisture of the skin. At the same time, they improve the low temperature stability of the composition of the present invention, especially in emulsions. The humectant is typically present in an amount of 0.1-15 wt.%, preferably 1-10 wt.%, more preferably 5-10 wt.%.

[0154] Suitable humectants for the present invention are amino acids, pyrrolidone carbonate, lactic acid and its salts, lactitol, urea and urea derivatives, uric acid, glucosamine, creatinine, hydrolyzates of collagen, chitosan or chitosan salts / derivatives, etc., in particular polyols and polyol derivatives (for example, glycerol, diglycerol, triglycerol, ethylene glycol, propylene glycol, butylene glycol, erythritol, 1,2,6-hexanetriol, polyethylene glycol such as PEG-4, PEG-6, PEG-7, PEG-8, PEG-9, PEG-10, PEG-12, PEG PEG-14, PEG-16, PEG-18, PEG-20), sugars and sugar derivatives (especially fructose, glucose, maltose, maltitol, mannitol, inositol, sorbitol, sorbitol silanediol, sucrose, trehalose, xylose, xylitol, glucuronic acid and its salts, etc.), ethoxylated sorbitol (Sorbeth-6, Sorbeth-20, Sorbeth-30, Sorbeth-40), honey and hydrogenated honey, hydrogenated starch hydrolyzate and mixtures of hydrogenated wheat protein and PEG-20 acetate copolymer. Particularly preferred moisturizers of the present invention are glycerol, diglycerol (diglycerol), triglycerine and butylene glycol.

[0155] Bioactive ingredients and antioxidants: Examples of bioactive ingredients include tocopherol, tocopheryl acetate, tocopheryl palmitate, ascorbic acid, (deoxy)ribonucleic acid and its fragmentation products, β-glucans, retinol, bisabolol, allantoin, phytotriol, panthenol, AHA acid, amino acids, ceramides, pseudoceramides, essential oils, plant extracts such as Prunus extract, Bambara nut extract, and multivitamins.

[0156] Antioxidants interrupt the photo-chemical reaction chain that is initiated as soon as UV rays enter the skin. Typical examples are amino acids (e.g. glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles (e.g. urocanic acid) and their derivatives, peptides such as D,L-carnosine, D-carnosine, L-carnosine and their derivatives (e.g. anserine), carotenoids, carotenes (e.g. α-carotene, β-carotene, lycopene) and their derivatives, chlorogenic acid and its derivatives, liponic acid and its derivatives (e.g. dihydroliponic acid), aurothioglucose, propylthiouracil and other thiols (e.g. thioredoxin, glutathione, cysteine, cystine, cystamine and their sugar groups, N-acetyl , methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleoyl, gamma-linoleoyl, cholesteryl and their glycerides) and their salts, dilaurylthiodipropionate, distearylthiodipropionate, thiodipropionic acid and its derivatives (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) and thiosulfoximine compounds (e.g. buthionine thiosulfoximines, homocysteine ​​thiosulfoximine, buthionine sulfones, pentyl-, hexyl- and heptyl-thionine thiosulfoximine) in very small compatible doses (e.g. pmol-μmol / kg), and (metal) chelates (e.g. α-hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin), alpha-hydroxy acids (e.g. citric acid, lactic acid, malic acid), humic acid, bile acid, bile extracts, bilirubin, biliverdin, EDTA, EGTA and its derivatives, unsaturated fatty acids and their derivatives (e.g. gamma linolenic acid, linoleic acid, oleic acid), folic acid and its derivatives, ubiquinone and ubiquinol and their derivatives, vitamin C and its derivatives (e.g. ascorbyl palmitate, magnesium ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (e.g. vitamin E acetate), vitamin A and derivatives (vitamin A palmitate) and benzoic acid of benzoin resin Rosin, rutinic acid and its derivatives, α-glycosylrutin, ferulic acid, furfurylidene glucitol, carnosine, butylated hydroxytoluene, butylated hydroxyanisole, nordihydroguaiaretic acid, nordihydroguaiaretic acid, trihydroxybutyrophenone, uric acid and its derivatives, mannose and its derivatives, superoxide dismutase, zinc and its derivatives (e.g. ZnO, ZnSO4), selenium and its derivatives (e.g. methionine selenium), stilbenes and their derivatives (e.g. stilbene oxide, trans-stilbene oxide) and derivatives of these active substances suitable for the purpose of the present invention (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids).

[0157] Deodorants and Bacteriostatics: Cosmetic deodorants combat, mask or eliminate body odor. Body odor is formed by the action of skin bacteria during perspiration via apical secretion, which produces degradation products that form unpleasant odors. Deodorants therefore contain active ingredients that act as bacteriostatics, enzyme inhibitors, odor absorbers or odor masking agents.

[0158] Bacteriostatic agents: Suitable bacteriostatic agents are primarily all substances that are effective against Gram-positive bacteria, for example 4-hydroxybenzoic acid and its salts and esters, N-(4-chlorophenyl)-N'-(3,4-dichlorophenyl)urea, 2,4,4'-trichloro-2'-hydroxy-diphenyl ether (triclosan), 4-chloro-3,5-dimethyl-phenol, 2,2'-methylenebis(6-bromo-4-chlorophenol), 3-methyl-4-(1-methylethyl)phenol, 2-benzyl-4-chlorophenol, 3- (4-Chlorophenoxy)-1,2-propanediol, 3-iodo-2-propynyl butylcarbamate, chlorhexidine, 3,4,4'-trichlorocarbanilide (TTC), antibacterial fragrances, thymol, thyme oil, eugenol, clove oil, menthol, peppermint oil, farnesol, phenoxyethanol, glyceryl monocaprate, glyceryl monocaprylate, glyceryl monolaurate (GML), diglyceryl monocaprate (DMC), salicylic acid N-alkylamides such as n-octyl salicylamide or n-decyl salicylamide.

[0159] Enzyme inhibitors: For example, esterase inhibitors are suitable as enzyme inhibitors. They are preferably trialkyl citrates, such as trimethyl citrate, tripropyl citrate, triisopropyl citrate, tributyl citrate, and in particular triethyl citrate ( CAT). These substances inhibit the enzyme activity, thereby reducing the odor formation. Other substances suitable as esterase inhibitors are sterol sulfates or phosphates, for example lanosterol, cholesterol, campesterol, stigmasterol and sitosterol sulfates or phosphates, dicarboxylic acids and their esters, for example glutaric acid, monoethyl glutarate, diethyl glutarate, adipic acid, monoethyl adipate, diethyl adipate, malonic acid and diethyl malonate, hydroxycarboxylic acids and their esters, such as citric acid, malic acid, tartaric acid or diethyl tartrate and zinc glycinate.

[0160] Odor absorber: Suitable odor absorber refers to a substance that can absorb and retain a large amount of compounds that form odor. They can reduce the partial pressure of each component, thereby also reducing its dispersion rate. It is important that the spices must remain intact during this process. Odor absorbers are ineffective against bacteria. They contain complex zinc salts of ricinoleic acid as a main component or specific significant odor neutralizing spices known to those skilled in the art as "fixatives", such as extracts of labdanum or styrax or some styric acid derivatives. Odor masking agents are spices or aromatic oils, which, in addition to their function as odor masking agents, give deodorants corresponding aromatic characteristics. The aromatic oils that can be cited are, for example, mixtures of natural and synthetic spices. Natural spices are extracts from flowers, stems and leaves, fruits, peels, roots, wood, herbs and grasses, needle-shaped leaves and branches and resins and balsams. Also suitable are animals, such as civet and castoreum products. Typical synthetic fragrance compounds are products of ester, ether, aldehyde, ketone, alcohol and hydrocarbon types. The example of the perfume compound of ester type is benzyl acetate, acetate p-tert-butyl cyclohexyl, linalyl acetate, phenylethyl acetate, benzoic acid linalyl, benzyl formate, cyclohexyl propionate allyl, propionic acid styraxyl and benzyl salicylate.Ethers include for example benzyl ethyl ether, and aldehydes include for example straight chain alkanals, citral, citronellal, citronellyloxy acetaldehyde, saxyl aldehyde, hydroxycitronellal, lily aldehyde and borgeron aldehyde comprising 8-18 carbon atoms, ketones include for example ionone and methyl cedryl ketone, alcohols include anethole, citronellol, eugenol, isoeugenol, geraniol, linalool, phenylethyl alcohol and terpineol, and hydrocarbons mainly include terpenes and balsams.However, it is preferred to use a mixture of different perfume compounds, which produce pleasant fragrance characteristics together. Also suitable as fragrance oils are relatively low-volatility essential oils used primarily as aroma components, such as sage oil, chamomile oil, clove oil, melissa oil, peppermint oil, cinnamon leaf oil, linden flower oil, juniper berry oil, rockweed oil, frankincense oil, cuprum balsam oil, labdanum oil, and lavender oil. Preference is given to using bergamot oil, dihydroxymyrcenol, lilyral, lyral, citronellol, phenylethyl alcohol, α-hexylcinnamaldehyde, geraniol, benzyl acetone, cyclamen aldehyde, linalool, boisambrene Forte, ambroxan, indole, methyl dihydrojasmonate, sandelice, lemon oil, tangerine peel oil, orange oil, allyl amyl glycolate, 3,6-dimethyl-3-cyclohexene-carboxaldehyde (cyclovertal), lavender oil, clary sage oil, β-damascenone, bourbon geranium oil, cyclohexyl salicylate, Vertofix Coeur, iso-E-Super, Fixolide NP, evernyl, iraldein gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, romilat, irotyl and floramat, alone or in mixtures.

[0161] Antiperspirants: Antiperspirants reduce sweat formation by affecting the activity of the eccrine sweat glands, thereby preventing underarm wetness and body odor. Aqueous or anhydrous preparations of antiperspirants usually contain the following ingredients:

[0162] Astringent active ingredients;

[0163] Oil composition;

[0164] Nonionic emulsifier;

[0165] · Auxiliary emulsifier;

[0166] ·Consistency factor;

[0167] · Additives, such as thickeners or compounding agents; and / or

[0168] • Non-aqueous solvents, such as ethanol, propylene glycol and / or glycerol.

[0169] Aluminum, zirconium or zinc salts are particularly suitable as astringent antiperspirant active ingredients. Such suitable antiperspirant active ingredients include, for example, aluminum chloride, aluminum chlorohydrate, aluminum dichlorohydrate, aluminum sesquichlorohydrate and its complexes, for example, with propylene glycol-1,2, hydroxyaluminum allantoin, aluminum chlorotartrate, aluminum zirconium trichlorohydrate, aluminum zirconium tetrachlorohydrate, aluminum zirconium pentahydrate and its complexes with amino acids (e.g., glycine). In addition, the antiperspirant may contain relatively small amounts of conventional oil-soluble and water-soluble adjuvants. Such oil-soluble adjuvants may be, for example:

[0170] Essential oils that reduce inflammation, protect the skin, or have a pleasant smell;

[0171] Synthetic skin care products; and / or

[0172] Oil-soluble aromatic oils.

[0173] Commonly used water-soluble additives include, for example, preservatives, water-soluble flavors, pH adjusters such as buffer mixtures, water-soluble thickeners such as water-soluble natural or synthetic polymers such as xanthan gum, hydroxyethylcellulose, polyvinyl pyrrolidone or high molecular weight polyethylene oxide.

[0174] Film formers: Typical film formers include, for example, chitosan, microcrystalline chitosan, quaternized chitosan, polyvinyl pyrrolidone, vinyl pyrrolidone / vinyl acetate copolymers, polymers of the acrylic acid series, quaternary ammonium cellulose derivatives, collagen, hyaluronic acid and its salts and similar compounds.

[0175] Anti-dandruff agents: Suitable anti-dandruff agents include piroctone olamine (1-hydroxy-4-methyl-6-(2,4,4-trimethylpentyl)-2-(1H)-pyridinone monoethanolamine salt), (climbazole), ketoconazole, (4-acetyl-1-{-4-[2-(2,4-dichlorophenyl) r-2-(lH-imidazol-1-ylmethyl)-1,3-di-p-benzylphenylcarboxamide (dioxylan)-c-4-methoxyphenyl}piperazine, ketoconazole, neoconazole, selenium disulfide, colloidal sulfur, sulfur polyethylene glycol dehydrated sorbitan monooleate, ricinole polyethoxylated sulfur, sulfur tar fraction, salicylic acid (or a combination with hexachlorophene), undecylenic acid, monoethanolamide sulfosuccinic acid sodium salt, UD (protein undecylenic acid condensate), zinc pyrithione, aluminum pyrithione, and magnesium pyrithione / magnesium dipyrithione sulfate.

[0176] Swelling agents: Suitable swelling agents for the aqueous phase include montmorillonite, clay minerals, pemulen and alkyl-modified carbomer types (Goodrich). Other suitable polymers or swelling agents can be found in Cosm. Toil by R. Lochhead. 108 ,95(1993)Review.

[0177] Insect repellents: Suitable insect repellents include N,N-diethyl-m-toluamide, 1,2-pentanediol or ethyl butyrylaminopropionate. Dihydroxyacetone is suitable as a self-tanning agent. Suitable tyrosine inhibitors that prevent melanin formation and are used in depigmenting agents include, for example, arbutin, ferulic acid, kojic acid, coumaric acid and ascorbic acid (vitamin C).

[0178] Ingredients for oral and dental care products: Toothpastes and tooth creams are generally understood to be gel or paste compositions of water, thickeners, humectants, abrasives or cleaning agents, surfactants, sweeteners, flavoring agents, deodorants, and active agents against oral and dental disorders. The toothpastes of the present invention may contain any commonly used cleaning agents, such as chalk, dicalcium phosphate, insoluble sodium metaphosphate, aluminum silicate, calcium pyrophosphate, microparticulate synthetic resins, silicic acid, aluminum oxide, and aluminum oxide trihydrate.

[0179] Preferably, particularly suitable preferred cleaning agents for use in the toothpaste of the present invention include microparticulate silicic acid xerogel, silicic acid hydrogel, precipitated silicic acid, trihydrated aluminum oxide and microparticulate α-alumina or mixtures of said cleaning agents, in an amount of 15-40 wt.% of the toothpaste. Suitable preferred humectants preferably include low molecular weight polyethylene glycols, glycerol, sorbitol or mixtures of these products, in an amount of up to 50 wt.%. Suitable known thickeners are thickening microparticulate gel silicic acid and hydrocolloids, such as carboxymethylcellulose, hydroxyethylcellulose, hydroxypropyl guar gum, hydroxyethyl starch, polyvinyl pyrrolidone, high molecular weight polyethylene glycol, plant gums, such as tragacanth, agar, chondrus bryophyte, gum arabic, xanthan gum and carboxyvinyl polymers (e.g. In addition to the menthofuran and menthol compound mixture, the oral and dental care products may also contain, in particular, surface-active substances, preferably anionic and nonionic foaming surfactants such as those mentioned above, in particular alkyl ether sulfates, alkyl polyglycosides and mixtures thereof.

[0180] Other commonly used toothpaste additives include:

[0181] Preservatives and antimicrobial agents, such as methyl / ethyl or propyl p-hydroxybenzoate, sodium sorbate, sodium benzoate, bromochlorophenol, phenyl salicylate, thymol, etc.;

[0182] Anti-tartar agents, such as organic phosphates, such as 1-hydroxyethyl-1,1-diphosphonic acid, 1-phosphonopropane-1,2,3-tricarboxylic acid, etc., which are from patent documents such as US 3,488,419, DE 2224430 A1 and DE 2343196 A1;

[0183] Other anti-caries substances such as sodium fluoride, sodium fluorophosphate, stannous fluoride;

[0184] Sweeteners, such as sodium saccharin, sodium cyclamate, sucrose, lactose, maltose, fructose or (L-aspartyl-L-phenylalanine-methyl ester), stevia extracts and their sweet compounds, especially rebaudioside;

[0185] Additional aroma substances, such as eucalyptus oil, anise oil, cumin oil, caraway oil, methyl acetate, cinnamaldehyde, anethole, vanillin, thymol and mixtures thereof and other natural and synthetic aroma substances;

[0186] Pigments, such as titanium dioxide;

[0187] ·dye;

[0188] Buffer substances, such as primary, secondary or tertiary alkali phosphates or citric acid / sodium citrate;

[0189] Wound-healing and anti-inflammatory substances, such as allantoin, urea, azulene, chamomile active ingredients, and acetylsalicylic acid derivatives.

[0190] A preferred embodiment of the cosmetic preparation is a toothpaste in the form of an aqueous paste dispersion comprising a polishing agent, a moisturizing agent, a viscosity regulator, and, if necessary, customary ingredients and 0.5-2 wt. % of a mixture of menthofuran and menthol compounds.

[0191] As for mouthwashes, combinations with different levels of essential oils, emulsifiers, astringent and toning drug extracts, stone inhibitors, antibacterial additives and flavoring agents can be easily achieved. Another preferred embodiment of the present invention is a mouthwash in the form of water or a hydroalcoholic solution, which contains 0.5-2 wt.% of a mixture of menthofuran and menthol compounds. In the mouthwash diluted before application, depending on the desired dilution ratio, sufficient effects can be obtained at higher concentrations.

[0192] Hydrotropes: In addition, hydrotropes such as ethanol, isopropanol or polyols can be used to improve fluidity. These substances are mostly equivalent to the above-mentioned carriers. Suitable polyols preferably contain 2-15 carbon atoms and at least 2 hydroxyl groups. Polyols can contain other functional groups, in particular amino groups, or be modified with nitrogen. Typical examples include:

[0193] ·glycerin;

[0194] Alkylene glycols, for example ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, hexylene glycol and polyethylene glycols having an average molecular weight of 100 to 1000 daltons;

[0195] Technical oligoglycerol mixtures having a degree of self-condensation of 1.5 to 10, for example technical diglycerol mixtures having a diglycerol content of 40 to 50 wt.%;

[0196] methylol compounds, such as, in particular, trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol and dipentaerythritol;

[0197] - lower alkyl glycosides, especially those containing 1 to 8 carbon atoms in the alkyl group, such as methyl and butyl glycosides;

[0198] Sugar alcohols containing 5-12 carbon atoms, such as sorbitol or mannitol;

[0199] Sugars containing 5-12 carbon atoms, such as glucose or sucrose;

[0200] Amino sugars, such as glucosamine;

[0201] Diolamines, for example diethanolamine or 2-amino-1,3-propanediol.

[0202] Preservatives: Suitable preservatives include, for example, phenoxyethanol, formaldehyde solution, parabens, pentylene glycol or sorbic acid and the known preservatives. Silver complexes of chlorinated compounds and other types of compounds listed in Parts A and B of Annex 6 to the Cosmetics Regulation.

[0203] Dye: Suitable dye is any substance suitable for and approved for use in cosmetic purposes, see the compilation document "Cosmetic Dyes" of the Dye Research Committee of the German Research Foundation (published by Weinheim Chemical Publishing House, 1984, pages 81-106). Examples include Carmine A (CI16255), Patent Blue V (CI42051), Indigo (CI73015), Water-soluble Chlorophyll (CI75810), Quinoline Yellow (CI47005), Titanium Dioxide (CI77891), Indanthrene Blue RS (CI69800) and Orchid Lake (CI58000). Luminol can also be present as a luminescent dye. Based on the total mixture, these dyes are usually used in a concentration of 0.001-0.1wt.%.

[0204] The total amount of auxiliaries and additives, based on these agents, can be 1-50, preferably 5-40 wt. %-. The agents can be produced by conventional cold or hot processes; preferably the phase transfer temperature method is used.

[0205] Detergents and Cleaners

[0206] Detergents and cleaning agents (abbreviated as WSR agents) containing compounds of formula (i), formula (ii) and / or formula (iii), or preferably (E)-2-methylbut-2-ene diethyl carboxylate, or a mixture of diethyl mesaconic acid with diethyl citraconic acid and diethyl itaconate, or the corresponding fragrance mixture of the present invention can be present in solid form such as powder, granules, tablets, etc., but can also be present in liquid, gel or paste form. These detergents are preferably suitable for manual or machine washing, especially textiles. They can also be detergents or cleaning agents for industrial or household use. Cleaning agents can also be used, for example, to clean hard surfaces. They can be, for example, dishwashing detergents for manual or automatic dishwashing. They can also be ordinary industrial or household cleaning agents for cleaning hard surfaces, such as furniture surfaces, tiles, walls and floors, etc. In addition to tableware, hard surfaces also include all other hard surfaces in the home and industrial fields, especially glass, ceramics, plastics or metals.

[0207] WSR preparations may contain other commercially available ingredients such as surfactants, builders, bleaching agents, bleach activators, thickeners, enzymes, electrolytes, pH adjusters, dyes and fragrances, foam inhibitors, anti-redeposition agents, fluorescent brighteners, graying inhibitors, anti-wrinkle agents, antibacterial agents, preservatives, antioxidants, antistatic agents, UV adsorbents, heavy metal complexing agents, etc. These auxiliaries are described in more detail as follows:

[0208] Surfactant: As a surfactant for preparing a detergent or a cleaning agent, in addition to a nonionic surfactant, an anionic, cationic, amphoteric and / or nonionic surfactant and a branched alkyl sulfate may be used.

[0209] The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 mol of ethylene oxide (EO) per mole of alcohol, wherein the alcohol radical may be straight-chain or, preferably, branched with methyl at position 2, or a mixture of straight-chain and methyl branched radicals, as they are usually present in oxo alcohol radicals. However, particular preference is given to alcohol ethoxylates having straight-chain radicals of alcohols of natural origin having 12 to 18 carbon atoms, such as coconut oil, palm oil, tallow or oleyl alcohol, and preferably an average of 2 to 8 ethylene oxide (EO) per mole of alcohol. Preferred ethoxylated alcohols include, for example, C12-14 alcohols containing 3EO, 4EO or 7EO, C9-11 alcohols containing 7EO, C13-5 alcohols containing 3EO, 5EO, 7EO or 8EO, C12-18 alcohols containing 3EO, 5EO or 7EO, and mixtures thereof, for example mixtures of C12-4 alcohols containing 3EO and C12-8 alcohols containing 7EO. The given degrees of ethoxylation represent statistical averages and may be integers or fractions for specific products. Preferred alcohol ethoxylates have a narrow homologue distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, aliphatic alcohols with more than 12EO may also be used. Examples include tallow fatty alcohols with 14EO, 25EO, 30EO or 40EO. According to the present invention, nonionic surfactants containing EO and PO groups together in the molecule may also be used. Here, block copolymers with EO-PO block units or PO-EO block units can be used, but also EO-PO-EO copolymers or PO-EO-PO copolymers can be used. Of course, it is also possible to use mixed alkoxylated nonionic surfactants in which the EO and PO units are not distributed in blocks but randomly. These products are obtainable by the simultaneous action of ethylene and propylene oxide on aliphatic alcohols.

[0210] Another class of nonionic surfactants that can be used in the production of detergents or cleaning agents is alkyl polyglycosides (APG). Available alkyl polyglycosides satisfy the formula RO(G)Z, where R represents a linear or branched, in particular a 2-methyl branched, saturated or unsaturated aliphatic group having 8 to 22, preferably 12 to 18 carbon atoms, and G represents the symbol of a glucose unit having 5 or 6 C atoms, preferably glucose. The degree of glycosidation z is 1.0 to 4.0, preferably 1.0 to 2.0, particularly preferably 1.1 to 1.4.

[0211] Amine oxide type nonionic surfactants, such as N-coconut alkyl-N,N-dimethylamine oxide and N-tallow alkyl-N,N-diethyl dihydroxyethyl oxide, and fatty acid alkanolamides are suitable for the preparation of detergents or cleaners. The amount of these nonionic surfactants is preferably not more than the amount of ethoxylated aliphatic alcohol, in particular not more than half thereof.

[0212] Other suitable surfactants are polyhydroxy fatty acid amides of the formula R-CO-N(R1)-[Z], wherein RCO represents an aliphatic acyl group having 6 to 22 carbon atoms, R1 represents hydrogen, an alkyl group or a hydroxyalkyl group having 1 to 4 carbon atoms, and [Z] represents a linear or branched polyhydroxyalkyl group having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. Polyhydroxy fatty acid amides are known substances which are usually obtained by reductive amination of reducing sugars with ammonia, alkylamines or alkanolamines and subsequent acylation with fatty acids, fatty acid alkyl esters or fatty acid chlorides. The group of polyhydroxy fatty acid amides also includes compounds of the formula R-CO-N(R1-O-R2)-[Z], wherein R represents a straight-chain or branched alkyl or alkenyl group having 7-12 carbon atoms, R1 represents a straight-chain, branched or cyclic alkyl or aryl group having 2-8 carbon atoms, R2 represents a straight-chain, branched or cyclic alkyl or aryl group or an oxyalkyl group having 1-8 carbon atoms, wherein preferably a C1-4 alkyl or phenyl group, and [Z] represents a straight-chain polyhydroxyalkyl group, wherein the alkyl chain is substituted by at least two hydroxy groups, or an alkoxylated, preferably ethoxylated or propoxylated derivative of this group. [Z] is preferably obtained by reductive amination of sugars, such as glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of alkoxides as catalysts.

[0213] The content of nonionic surfactants in liquid detergents and cleaners is preferably 5 to 30%, preferably 7 to 20%, particularly preferably 9 to 15%, based in each case on the total preparation.

[0214] As anionic surfactants, for example, sulfonates and sulfates can be used. As surfactants of the sulfonate type, preference is given to C9-3-alkylbenzenesulfonates, olefinsulfonates, i.e. mixtures of olefin and hydroxyalkylsulfonates and disulfonates, obtained, for example, from C12-8 monoolefins with terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation product. Also suitable are alkylsulfonates, which are obtained from C12-8 alkanes, for example by sulfochlorination or sulfoxidation, and subsequent hydrolysis or neutralization. Also suitable are α-sulfonated fatty acid esters (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

[0215] Also suitable are small amounts of sulfonated unsaturated fatty acids, such as oleic acid, preferably not more than about 2 to 3 wt.%. Particularly preferred are α-sulfofatty acid alkyl esters, which have an alkyl chain of not more than 4 carbon atoms in the ester group, such as methyl, ethyl, propyl and butyl esters. It is particularly advantageous to use the methyl esters of α-sulfofatty acids (MES), and their saponified disalts.

[0216] Suitable further anionic surfactants are fatty acid derivatives of amino acids, for example N-methyltaurine (Tauride) and / or N-methylglycine (sarcosides). Particularly preferred are sarcosides or sarcosinates, here especially sarcosinates with higher levels and optionally monounsaturated / or polyunsaturated fatty acids (such as oleoylsarcosinate).

[0217] Other suitable anionic surfactants are sulfurized fatty acid glycerides. Fatty acid glycerides are understood to mean mono-, di- and triesters and mixtures thereof, such as those obtained in the preparation by esterification of monoglycerol with 1 to 3 mol of fatty acids or transesterification of triglycerides with 0.3 to 2 mol of glycerol. Preferred sulfurized fatty acid glycerides are sulfurization products of saturated fatty acids having 6 to 22 carbon atoms, such as caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

[0218] Alkyl / alkenyl sulfates include alkali metal salts, in particular sodium salts of sulfuric acid half esters of C12-C18 aliphatic alcohols, such as coconut aliphatic alcohol, tallow alcohol, dodecyl, myristyl, hexadecyl or stearyl alcohol or C10-C20 oxo alcohols and half esters of secondary alcohols of these chain lengths. In addition, preferred are alk(en)yl sulfates of the chain lengths described, which contain petrochemical-based linear alkyl syntheses, which have a degradation behavior similar to that of the corresponding compounds based on oleochemical raw materials. In order to optimize the washing effect, C12-C16 alkyl sulfates and C12-C15 alkyl sulfates and C14-C15 alkyl sulfates are preferred. 2,3-Alkyl sulfates are also suitable anionic surfactants, which can be purchased from Shell Oil Company under the name DAN(R).

[0219] In addition, sulfuric acid monoesters of linear or branched C7-21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide, for example 2-methyl branched C9-11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C12-18 aliphatic alcohols with 1 to 4 EO are also suitable. Due to their high foaming properties, they are used in detergents only in relatively small amounts, for example in an amount of 1 to 5 wt.%.

[0220] Other suitable anionic surfactants include salts of alkyl sulfosuccinic acids, which are also referred to as sulfosuccinates or sulfosuccinic acid esters, and monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably aliphatic alcohols, particularly ethoxylated aliphatic alcohols. Preferred sulfosuccinates contain C8-18 aliphatic alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain aliphatic alcohol residues derived from ethoxylated aliphatic alcohols, which themselves constitute nonionic surfactants (see description below). Sulfosuccinates whose aliphatic alcohol residues are derived from ethoxylated aliphatic alcohols with narrow homologue distribution are also particularly preferred. Similarly, alk(en)yl succinic acids containing 8-18 carbon atoms in the preferred alk(en)yl chains or their salts may also be used.

[0221] Particularly preferred anionic surfactants are soaps. Soaps made from saturated and unsaturated fatty acids, such as salts of lauric acid, myristic acid, palmitic acid, stearic acid, (hydrogenated) erucic acid and behenic acid, especially soap mixtures of naturally derived fatty acids, such as coconut oil, palm kernel, olive oil or tallow fatty acids.

[0222] Anionic surfactants including soaps may be present in the form of their sodium, potassium or ammonium salts and soluble salts of organic bases such as mono-, di- or triethanolamine. Anionic surfactants are preferably present in the form of their sodium or potassium salts, especially in the form of their sodium salts.

[0223] The content of anionic surfactants in preferred liquid detergents and cleaners is 1-30 wt.%, preferably 4-25 wt.%, in particular 5-22 wt.%, each based on the total formulation amount. Particularly preferably, the amount of fatty acid soap is at least 2 wt.%, more preferably at least 3 wt.%, particularly preferably at least 4 wt.%.

[0224] Other surfactants that can be used to prepare the detergents or cleaning agents of the present invention are so-called gemini surfactants. They generally refer to those compounds that have two hydrophilic groups and two hydrophobic groups per molecule. These groups are usually separated by a so-called "spacer group". The spacer group is usually a carbon chain, which should be long enough to separate the hydrophilic groups long enough so that they can act independently of each other. Such surfactants are generally characterized by an abnormally low critical micelle concentration and are able to greatly reduce the surface tension of water. However, in special cases, the term "gemini surfactant" is understood to mean not only dimeric surfactants but also trimerizable surfactants.

[0225] Gemini surfactants for producing detergents or cleaning agents are, for example, the hydroxysulfate mixed ethers according to German patent application DE-A-4321 022 or dimer alcohol di- and trimer trisulfates and ether sulfates according to German patent application DE-A-195 03 061. The blocked dimer and trimer mixed ethers according to German patent application DE-A-195 13 391 are characterized by their bifunctional and multifunctional properties. The blocked surfactants mentioned therefore have good wetting properties and low foaming, so that they are particularly suitable for automatic rinsing and cleaning processes.

[0226] From the application point of view, a mixture of anionic and nonionic surfactants is preferred. The total surfactant content of the liquid detergent and cleaning agent is preferably less than 40 wt.%, particularly preferably less than 35 wt.%, based on the total amount of the liquid detergent and cleaning agent.

[0227] Builders: Suitable builders which may be present in liquid detergents and cleaners are, in particular, silicates, aluminum silicates (in particular zeolites), carbonates, organic cobuilders, phosphates, salts of organic di- and polycarboxylic acids, and mixtures of these substances.

[0228] Suitable crystalline layered sodium silicates have the general formula NaMSi x O 2x+1 *H2O, wherein M represents sodium or hydrogen, x represents a number from 1.9 to 4, y represents a number from 0 to 20, and the preferred value of x is 2, 3 or 4. In the preferred crystalline layered silicates of the formula given below, M represents sodium and x represents a value of 2 or 3. In particular, beta and delta sodium disilicate Na2Si2O5*yH2O are preferred.

[0229] Amorphous sodium silicate can also be used, and its Na2O:SiO2 modulus (modulus) is 1:2 to 1:3.3, preferably 1:2 to 1:2.8, more preferably 1:2 to 1:2.6, they are delayed in dissolution, and have secondary washing performance. Compared with conventional amorphous sodium silicate, dissolution delay can be caused in various ways, for example, by surface treatment, compounding, compaction / compression or adopting over-drying mode. In the present invention, the term "amorphous" can also be understood as "X-ray amorphous". This means that silicate does not produce the sharp X-ray reflection of typical crystalline materials in X-ray diffraction experiments, but has at most one or more maxima of scattered X-rays with a diffraction angle width of several degrees. However, if the silicate particles provide vague or even sharp diffraction maxima in electron diffraction experiments, it can even produce particularly good builder performance. This should be interpreted as that the product has a microcrystalline region with a size of 10 to several hundred nm, preferably a value of at most 50nm, particularly a value of at most 20nm. Compared to conventional water glass, this so-called X-ray amorphous silicate also has a delayed dissolution. Particularly preferred are compressed / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.

[0230] Useful finely crystallized, synthetic and bound hydrous zeolites are preferably zeolite A and / or P. Zeolite P is particularly preferably zeolite MAP TM (a commercial product of Crosfield). However, zeolite X and mixtures of A, X and / or P are also suitable. Commercially available products that can be used preferably in the present invention are, for example, cocrystals of zeolite X and zeolite A (about 80 wt. % zeolite X), which are sold by SASOL under the trade name VEGOBOND AX (R), which is represented by:

[0231] nNa2O*(1-n)K2O*Al2O3.(2-2,5)*SiO2.(3,5-5,5)*H2O

[0232] The zeolite can be used as a spray-dried powder or as an undried, still moist, stable suspension prepared therefrom. If the zeolite is used as a suspension, it may contain a small amount of a nonionic surfactant as a stabilizer, for example an ethoxylated C 60-60 having 2 to 5 ethylene oxide groups, equivalent to 1-3 wt. % of the zeolite. 12 -C 18 Aliphatic alcohols, C with 4 to 5 ethylene oxide groups or ethoxylated isotridecanol 12 -C 14 Aliphatic alcohols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22 wt. %, particularly preferably 20 to 22 wt. % of bound water.

[0233] Of course, the well-known phosphates can also be used as builders, unless such phosphates are to be avoided for environmental reasons. Particularly suitable are the sodium salts of orthophosphates, pyrophosphates and especially tripolyphosphates.

[0234] Suitable builders are organic cobuilders, in particular polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins and phosphonates.

[0235] Polymeric polycarboxylates are, for example, alkali metal salts of polyacrylic acid or polymethacrylic acid, for example relative molecular weights are those of 500-70,000 g / mol. According to this document, the molecular weight specified by polymeric polycarboxylates is the weight-average molecular weight Mw of a specific acid form, which is measured in principle by gel permeation chromatography (GPC), wherein a UV detector is used. Measurement is based on an external polyacrylic acid standard, which provides a true molecular weight value due to its structural relationship with the polymer under study. These data are significantly different from molecular weight data, wherein polystyrene sulfonic acid is used as standard. The molar mass measured relative to polystyrene sulfonic acid is usually significantly higher than the molecular weight specified in this document.

[0236] Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of 2,000 to 20,000 g / mol. Due to their excellent solubility, short-chain polyacrylates with a molecular weight of 2000 to 10,000 g / mol, particularly preferably 3000 to 5000 g / mol, are preferred.

[0237] Likewise suitable are copolymeric polycarboxylates, in particular copolymers of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid containing 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 the free acid, is generally from 2,000 to 70,000 g / mol, preferably from 20,000 to 50,000 g / mol, particularly preferably from 30,000 to 40,000 g / mol.

[0238] Furthermore, particularly preferred are biodegradable polymers having two or more different monomer units, such as polymers containing monomer salts of acrylic acid and maleic acid and vinyl alcohol or a vinyl alcohol derivative, or monomer salts of acrylic acid and 2-alkylallylsulfonic acid and a sugar derivative.

[0239] Further preferred copolymers are those which preferably have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.

[0240] Other preferred builders are polymeric aminodicarboxylic acids, their salts or their precursors. Particularly preferred are polyaspartic acid or its salts and derivatives which, in addition to their co-binder properties, also have a bleach-stabilizing effect.

[0241] Other suitable builder materials are polyacetals which can be obtained by reacting dialdehydes with polyol carboxylic acids having 5 to 7 carbon atoms and at least 3 hydroxyl groups. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

[0242] Other suitable organic builder materials are dextrins, such as oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starch. Hydrolysis can be carried out by conventional methods, such as acid or enzyme catalysis methods. Preferably, the hydrolyzate of the mean molecular weight is 400-500,000 g / mol. In this case, preferably the polysaccharide of dextrose equivalent (DE) is between 0.5 and 40, particularly between 2 and 30, wherein DE is the common measure of polysaccharide reduction compared with glucose with DE of 100. Available is maltodextrin with DE of 3 to 20 and dry glucose syrup with DE of 20 to 37 and so-called yellow dextrin and white dextrin with higher molecular weight of 2000 to 30,000 g / mol.

[0243] Oxidized derivatives of such dextrins are the products of their reaction with an oxidizing agent capable of oxidizing at least one alcohol function of the sugar ring to a carboxylic acid function. Products oxidized at C6 of the sugar ring may be particularly advantageous.

[0244] Preferred dextrins are described in British patent application GB 9,419,091 B1. Oxidized derivatives of such dextrins are the reaction products of these with an oxidizing agent capable of oxidizing at least one alcohol functional group of the sugar ring to a carboxylic acid functional group. Such oxidized dextrins and methods for their preparation can be found in European patent applications EP 032202A, EP 0427349 A, EP 0472042 A and EP 0542496 A and international patent applications WO 1992 / 018542 A, WO 1993 / 008251A, WO 1994 / 028030 A, WO 1995 / 007303 A, WO 1995 / 012619 A and WO 1995 / 020608 A. Products oxidized at C6 of the sugar ring may be particularly advantageous.

[0245] Other derivatives of oxydisuccinates and disuccinates, preferably ethylenediamine disuccinates, are other suitable co-builders. Among them, ethylenediamine-N,N'-disuccinate (EDDS) is preferably used in the form of its sodium salt or magnesium salt. In addition, glyceryl disuccinate and glyceryl trisuccinate are also preferred, such as described in U.S. Patent Application Nos. 4,524,009, 4,639,325, EP Patent Application No. 0150930 A and Japanese Patent Application No. JP 1993 / 339896 A.

[0246] Other organic co-builders that can be used are, for example, acetylated hydroxycarboxylic acids or their salts, which can also optionally be present in lactone form and contain at least 4 carbon atoms and at least one hydroxyl group and at most two acid groups. Such co-builders are described in the International Patent Application WO 1995 / 020029 A.

[0247] Another class of substances with co-builder properties is phosphonates. Especially hydroxyalkanes or aminoalkylphosphonates. Among the hydroxyalkanephosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is a particularly important builder. It is preferably used as a sodium salt, wherein the disodium salt reacts neutrally and the tetrasodium salt reacts alkaline (pH 9). Preferred aminoalkylphosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues. They are preferably used in the form of neutral sodium salts, for example, as hexasodium salts of EDTMP or as hepta- and octasodium salts of DTPMP. The builder used here is preferably HEDP from the phosphonate class. Aminoalkanephosphonates also have a significant heavy metal binding capacity. Therefore, especially when detergents and cleaning agents also contain bleaching agents, it is preferred to use aminoalkanephosphonates, especially DTPMP, or use a mixture of the phosphonates to prepare the preparation.

[0248] Furthermore, all compounds which are able to form complexes with alkaline earth ions can be used as cobuilders.

[0249] Other organic builders that can be used are also polycarboxylic acids used in the form of their sodium salts, where polycarboxylic acids are those carboxylic acids with more than one acid function. They are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), unless their use is not permitted for ecological reasons, and mixtures thereof. Preferred salts are salts of polycarboxylic acids, for example citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.

[0250] Acids themselves can also be used. In addition to their builder action, acids generally also have the properties of acidifying components and are therefore also used to adjust the pH value of lower and milder detergents and / or cleaners. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof.

[0251] Bleaching agents and bleaching catalysts: Among the compounds used as bleaching agents in water H2O2, sodium perborate tetrahydrate and sodium perborate monohydrate are particularly important. Other useful bleaching agents include, for example, sodium percarbonate, peroxyphosphates, citrate perhydrates and peroxyacids or peracids that generate H2O2, such as perbenzoates, peroxyphthalates, diazelaic acid, phthalic acid omenoic acid or docosanoic acid. In order to obtain a better bleaching effect when washing at temperatures of 60°C and below, bleach activators can be incorporated into detergents and cleaning agents. As bleach activators, compounds can be used which, under perhydrolysis conditions, generate aliphatic peroxycarboxylic acids and / or optionally substituted perbenzoic acids having preferably 1 to 10 carbon atoms, particularly preferably 2 to 4 carbon atoms. Suitable substances are substances with O- and / or N-acyl groups and / or optionally substituted benzoyl groups with the stated number of carbon atoms. Preferred are polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetyl glycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular nonanoyl or isononanoyloxybenzenesulfonates (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran. In addition to or as an alternative to the conventional bleach activators, so-called bleach catalysts can also be incorporated into the textile treatment agents. These substances are bleach-enhancing transition metal salts or transition metal complexes, such as manganese, iron, cobalt, ruthenium or molybdenum salt complexes or carbonyl complexes. Furthermore, manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripodal ligands and cobalt, iron, copper and ruthenium ammines can also be used as bleach catalysts.

[0252] Thickeners: Liquid detergents and cleansers may contain thickeners. Thickeners may include, for example, polyacrylate thickeners, xanthan gum, gellan gum, guar gum, alginates, carrageenan, carboxymethyl cellulose, bentonite, welan gum, locust bean gum, agar, tragacanth gum, gum arabic, pectin, polysaccharides, starch, dextrin, gelatin, and casein. Modified natural substances such as modified starches and celluloses, for example carboxymethyl cellulose and other cellulose ethers, hydroxyethyl and hydroxypropyl cellulose, and gum ethers may also be used as thickeners.

[0253] Polyacrylic acid and polymethyl thickeners include, for example, high molecular weight crosslinked homopolymers of acrylic acid (INCI name according to the International Cosmetic Ingredient Dictionary of the Cosmetic, Toiletries and Fragrance Association (CTFA): Carbomer), also known as carboxyvinyl polymers, and having polyalkenyl polyethers, in particular allyl ethers of sucrose, pentaerythritol or propylene. Such polyacrylic acids are known by the trade name Purchase from 3V Sigma, for example Polygel DA, or by brand name Available from BFGoodrich, for example, Carbopol 940 (molecular weight about 4 million), Carbopol 941 (molecular weight about 1.25 million) or Carbopol 934 (molecular weight about 3 million). In addition, the following acrylic copolymers are also included: (i) copolymers of two or more monomers selected from acrylic acid, methacrylic acid and their simple ester groups, preferably with C1-4 alkanols (INCI acrylate copolymers), including methacrylic acid, butyl acrylate and methyl methacrylate (CAS name according to Chemical Abstracts Service: 25035-69-2) or butyl acrylate and methyl methacrylate (CAS 25852-37-3), which can be obtained by the name and Purchased from Rohm andHaas, and by brand name Polymers available from Degussa (Goldschmidt), such as the anionic non-associative polymers Aculyn 22, Aculyn 28, Aculyn 33 (crosslinked), Acusol 810, Acusol 820, Acusol 823 and Acusol 830 (CAS 25852-37-3); (ii) crosslinked high molecular weight acrylic copolymers comprising copolymers of C10-30 alkyl acrylates crosslinked with propyl ethers of sucrose or pentaerythritol and having one or more monomers derived from acrylic acid, methacrylic acid and simple ester groups thereof, preferably with C1-4-alkanols (INCI Acrylates / C10-30 Alkyl Acrylate Crosspolymers), which are available under the trade name Available from BF Goodrich Company, for example, are hydrophobized Carbopol ETD 2623 and Carbopol 1382 (INCI Acrylates / C10-30 Alkyl Acrylate Crosspolymer) and Carbopol Aqua 30 (formerly Carbopol EX 473).

[0254] Another preferred polymeric thickener is xanthan gum, which is a microbial anionic heteropolysaccharide produced under aerobic conditions by Xanthomonas and some other species with a molecular weight of 2-15 million Daltons. Xanthan gum is formed by β-1,4-bonded glucose (cellulose) chains with side chains. The structure of the subgroups consists of glucose, mannose, glucuronic acid acetate and pyruvate, the number of pyruvate units determining the viscosity of the xanthan gum. In particular, aliphatic alcohols are also suitable as thickeners. The aliphatic alcohols can be of natural or petrochemical origin in branched or unbranched form. Preferred aliphatic alcohols have a carbon chain length of 10 to 20 carbon atoms, preferably 12 to 18. Preference is given to using mixtures of different carbon chain lengths, such as tallow aliphatic alcohol or coconut aliphatic alcohol. For example Spezial (C12-14-ROH) or industrial use (C12-18-ROH) (both from Cognis). Preferred liquid detergents and cleaners contain 0.01-3 wt.%, preferably 0.1-1 wt.%, of thickener, based on the total amount of reagents. The amount of thickener used depends on the type of thickener and the desired degree of thickening.

[0255] Enzymes: Detergents and cleaning agents may contain enzymes in the form of capsules and / or enzymes directly contained in the detergents and cleaning agents. Suitable enzymes include, in particular, hydrolases, such as proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases, hemicellulases, cutinases, beta-glucanases, oxidases, peroxidases, perhydrolases and / or laccases and mixtures of said enzymes. All of these hydrolases contribute to the removal of stains, such as protein, greasy or starch stains and graying, during the washing process. In addition, cellulases and other glycosyl hydrolases contribute to color retention and increase the softness of fabrics by removing pilling and microfibers. Oxidoreductases may also be used for bleaching or inhibiting fading. Particularly suitable are enzyme agents derived from bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens. Preferably, subtilisin-type proteases are used, in particular proteases from Bacillus lentus. The main enzyme mixture comprises for example protease and amylase or protease and lipase or lipolytic enzyme or protease and cellulase or cellulase and lipase or lipolytic enzyme or protease, amylase and lipase or lipolytic enzyme or protease, lipase or lipolytic enzyme and cellulase mixture, particularly containing protease and / or lipase mixture or lipolytic enzyme mixture.The example of such lipolytic enzyme is known cutinase.In some cases, peroxidase or oxidase also prove to be suitable.Suitable amylase especially comprises alpha-amylase, isoamylase, pullulanase and pectinase.The cellulase used is preferably cellobiohydrolase, endoglucanase and beta-glucosidase, also referred to as cellobiase, or their mixture.Because different cellulase types are different because of their CMCase and microcrystalline cellulose enzyme activity, therefore can adjust the required activity by suitable mixture of cellulase.

[0256] The enzyme may be adsorbed onto a carrier to prevent premature degradation. The proportion of enzymes, enzyme liquid preparations or enzyme granules directly into detergents and cleaners may be, for example, about 0.01 to 5 wt.%, preferably 0.12 to about 2.5 wt.%.

[0257] However, in special detergents and cleaners for allergic consumers, it is preferred that the detergents and cleaners do not contain enzymes.

[0258] Electrolyte: As the electrolyte from inorganic salts, many different kinds of salts can be used. Preferred cations are alkali metals and alkaline earth metals, and preferred anions are halides and sulfates. From the viewpoint of production conditions, it is preferred to use NaCl or MgCl2 in detergents and cleaners. The proportion of the electrolyte in the detergents and cleaners is generally 0.1 to 5 wt.%.

[0259] Solvents: Non-aqueous solvents that can be used in liquid detergents and cleaners, for example, from the group of mono- or polyhydric alcohols, alkanolamines or glycol ethers, as long as they are miscible with water within a specific concentration range. Preferably, the solvent is selected from ethanol, n- or isopropanol, butanol, ethylene glycol, propane or butanediol, glycerol, diethylene glycol, propyl or butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl-, ethyl or propyl ether, dipropylene glycol monomethyl ether or ethyl ether, diisopropylene glycol monomethyl or ethyl ether, methoxy, ethoxy or butoxy triglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol tert-butyl ether and mixtures of these solvents. Non-aqueous solvents can be used in liquid detergents and cleaners in an amount of 0.5-15 wt.%, but preferably less than 12 wt.%, particularly preferably less than 9 wt.%.

[0260] Viscosity modifier: The viscosity of detergents and cleaning agents in liquid form can be determined using general standard methods (e.g., Brookfield viscometer LVT-II, conditions: 20 U / min, 20° C., spindle 3), and the preferred range for liquid detergents is 500 to 5000 mPas. Preferred liquid detergents and cleaning agents have a viscosity of 700 to 4000 mPas, particularly preferably values ​​of 1000 to 3000 mPas. The viscosity of fabric softeners is preferably 20 to 4000 mPas, particularly preferably values ​​of 40 to 2000 mPas. The viscosity of fabric softeners is more preferably 40-1000 mPas.

[0261] pH regulator: In order to bring the pH value of liquid detergents and cleaning agents into the desired range, a pH regulator can be used. All known acids or bases can be used unless they are prohibited for use for technical reasons or environmental reasons or for consumer protection reasons. Usually, the amount of these regulators does not exceed 7 wt.% of the total formulation weight. The pH of liquid detergents and cleaning agents is preferably 4-10, more preferably 5.5-8.5. The pH of liquid fabric softeners is preferably 1 to 6, more preferably 1.5 to 3.5.

[0262] Dyes: To improve the aesthetic effect of textile treatments, they can be dyed with suitable dyes. Preferred dyes, the selection of which is very simple for a professional, should have high storage stability and be insensitive to other ingredients of detergents and cleaning agents and to light, and should not adhere significantly to textile fibers, thereby soiling them.

[0263] Anti-redeposition agents: Suitable soil release polymers, also referred to as "anti-redeposition agents", are, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose having a methoxy content of 15 to 30 wt.% and a hydroxypropyl content of 1 to 15 wt.% (relative to the nonionic cellulose ether, respectively), and polymers of phthalic acid and / or terephthalic acid or derivatives thereof, polymers of ethylene terephthalate and / or polyethylene and / or polytrimethylene terephthalate, or anionic and / or nonionic modified derivatives thereof as known in the art. Suitable derivatives include sulfonated derivatives of phthalic acid and terephthalic acid polymers.

[0264] Fluorescent whitening agents: Fluorescent whitening agents (so-called "brighteners") can be added to detergents and cleaning agents to eliminate the graying and yellowing of treated textile fabrics. These substances attach to fibers and cause a brightening and simulated bleaching effect by converting invisible ultraviolet radiation into visible long-wave light, wherein the ultraviolet light absorbed from sunlight is emitted as a weak blue fluorescence and forms a pure white color with the yellow tint of graying or yellowing clothing. Suitable compounds include, for example, 4,4'-diamino-2,2'-stilbene disulfonic acid (flavonoids), 4,4'-stilbene biphenyl, the material classes of methylumbelliferone, coumarin, dihydroquinolinone, 1,3-diarylpyrazoline, naphthalimide, benzoxazole, benzisoxazole and benzimidazole, and heterocyclic substituted pyrene derivatives. Fluorescent whitening agents are generally used in amounts of 0-0.3 wt.%, based on the finished detergent and cleaning agent.

[0265] Gray inhibitor: The task of the gray inhibitor is to keep the dirt separated from the fibers suspended in the liquid, thereby preventing the dirt from reattaching. For this purpose, water-soluble colloids of organic nature are generally suitable, such as salts of glue, gelatin, starch or cellulose ether sulfonic acid or salts of acidic sulfates of cellulose or starch. Moreover, water-soluble polyamides containing acidic groups are suitable for this purpose. Soluble starch preparations and other starch products other than those mentioned above, such as degraded starch, aldehyde starch, etc. can also be used. Polyvinylpyrrolidone is also available. However, it is preferred to use cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof in an amount of 0.1-5wt.% of the detergent and cleaning agent.

[0266] Anti-wrinkle agents: Since fabrics, in particular rayon, artificial wool, cotton and their mixtures, may be susceptible to wrinkling because the individual fibers are sensitive to bending, folding, pressing and squeezing transversely to the fiber direction, detergents and cleaning agents may contain synthetic anti-wrinkle agents. These include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, alkanol esters, alkanolamides or aliphatic alcohols, which are usually reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid esters.

[0267] Antimicrobial agents: To combat microorganisms, detergents and cleaning agents may contain antimicrobial agents. Based on the antimicrobial spectrum and the mechanism of action, a distinction can be made between bacteriostatics and bactericides, fungistatics and fungicides, etc. Important substances in these groups are, for example, benzalkonium chloride, alkylaryl sulfonates, halogenphenols and phenolic mercuric acetates, wherein the detergents and cleaning agents of the present invention may also not use these compounds at all.

[0268] Preservatives: The detergents and cleaners of the present invention may contain preservatives, and preferably preservatives that have no or only a slight potential for skin sensitization. For example, sorbic acid and its salts, benzoic acid and its salts, salicylic acid and its salts, phenoxyethanol, 3-iodo-2-propynyl butylcarbamate, N-sodium (hydroxymethyl) glycinate, biphenyl-2-ol, and mixtures thereof. Suitable preservatives include diazolidinyl urea, a solvent-free aqueous combination of sodium benzoate and potassium sorbate (available under the trade name K500ex Schülke and Mayr), which can be used in a pH range of up to 7. In particular, preservatives based on organic acids and / or their salts are suitable as preservatives for the skin-friendly washing and cleaning agents according to the invention.

[0269] Antioxidants: To prevent adverse changes in detergents and cleaning agents and / or treated fabrics caused by oxygen contact and other oxidative processes, detergents and cleaning agents may contain antioxidants. Such compounds include, for example, substituted phenols, hydroquinones, catechols and aromatic amines, as well as organic sulfides, polysulfides, dithiocarbamates, phosphites, phosphonates and vitamin E.

[0270] Antistatic agents: Wearing comfort can be increased by the additional use of antistatic agents, which can be additionally added to detergents and cleaning agents. Antistatic agents increase the surface conductivity and thus improve the discharge of the charges formed. Antistatic agents are generally substances which have at least one hydrophilic molecular ligand and produce a more or less hygroscopic film on the surface. These predominantly surface-active antistatic agents can be subdivided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphate esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents. Dodecyl (or stearyl) dimethylbenzyl ammonium chloride is suitable as an antistatic agent for textile fabrics or as an additive to detergents and cleaning agents and achieves an additional softening effect.

[0271] Foam inhibitors: In order to improve the rewetting of treated fabrics and to facilitate ironing of treated fabrics, for example, silicone derivatives can be used in fabric treatment agents. They additionally improve the rinsing properties of detergents and cleaning agents through their foam-inhibiting properties. Preferred silicone derivatives are, for example, polydialkyl or alkylaryl siloxanes, in which the alkyl group has 1 to 5 carbon atoms and is fully or partially fluorinated. Preferred silicones are polydimethylsiloxanes, which may be derivatized, then amino-functional or quaternized, or have Si-OH, Si-H and / or Si-Cl bonds. Preferred silicones have a viscosity at 25° C. in the range of 100 to 100.000 mPas, wherein the silicones may be used in an amount of 0.2 to 5 wt.%, based on the total amount of detergents and cleaning agents.

[0272] UV absorbers: Finally, detergents and cleaners may also contain UV absorbers, which adsorb onto the treated fabric and improve the light fastness of the fiber. Compounds having these desired properties include, for example, non-radiation inactivating compounds and benzophenone derivatives having substituents at the 2- and / or 4-positions. Also suitable are substituted benzotriazoles, acrylates substituted with a phenyl group at the 3-position (cinnamic acid derivatives), or having a cyano group at the 2-position, salicylates, organic Ni complexes, and natural substances such as umbelliferone and endogenous urocanic acid.

[0273] Heavy metal complexing agents: In order to avoid heavy metal-catalyzed decomposition of certain detergent ingredients, heavy metal complexing agents can be used. Suitable heavy metal complexing agents are, for example, alkali metal salts of ethylenediaminetetraacetic acid (EDTA) or nitrilotriacetic acid (NTA) and alkali metal salts of anionic polyelectrolytes, such as polymaleates and polysulfonates. A preferred class of complexing agents is phosphonates, which are present in preferred textile treatment agents in an amount of 0.01-2.5 wt.%, preferably 0.02-2 wt.%, particularly preferably 0.03-1.5 wt.%. These preferred compounds include in particular organic phosphonates, such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), aminotri(methylenephosphonic acid) (ATMP), diethylenetriaminepenta(methylenephosphonic acid) (DTPMP or DETPMP) and 2-phosphonobutane-1,2,4-tricarboxylic acid (PBS-AM), which are mainly used in the form of ammonium or alkali metal salts.

[0274] Preparation of formulations: The preparation of solid WSR agents can be carried out by conventional methods, such as tower spraying, fluidized bed drying, agglomeration, powder mixing, tableting, granulation, especially SKET granulation.

[0275] The preparation of liquid WSR agents can also be carried out by conventional processes and methods, for example, the ingredients are simply mixed in a stirred tank, water, non-aqueous solvents and surfactants are added as needed, and other ingredients are added in batches. Therefore, in order to prepare liquid detergents and cleaning agents, it is necessary to provide acidic components, such as linear alkyl sulfonates, citric acid, boric acid, phosphonic acid, aliphatic alcohol ether sulfates, etc., and to provide non-ionic surfactants. It is preferred to also add a solvent component at this time, but it can also be added at a later time. A thickener, such as a polyacrylate, can be added to these components. Subsequently, a base such as NaOH, KOH, triethanolamine or monoethanolamine is added, followed by a fatty acid (if available). Then, the remaining ingredients and the remaining solvent of the aqueous liquid detergent and cleaning agent are added to the mixture, and the pH value is adjusted to about 8.5. Finally, the particles to be dispersed can be added and evenly distributed in the aqueous liquid detergent and cleaning agent by mixing.

[0276] The invention relates to perfume oils or preparations which are perfumed or scented in this way. The invention therefore relates to perfume oils, cosmetics, lotions, detergents and cleaning agents, and also to perfumes or perfumed products which comprise the general compounds of the formula (i), (ii) and / or (iii), or diethyl (E)-2-methylbut-2-enedicarboxylate, in particular a mixture of diethyl mesaconic acid with diethyl citrate and diethyl itaconate, or the corresponding perfume mixtures described above, and these perfume oils or preparations include: perfume extracts, perfumes, eau de toilette, aftershaves, colognes, pre-shave products, dip-colognes and perfumed wet wipes, as well as perfumes for acidic, alkaline and neutral cleaning agents, such as floor cleaners, window glass cleaners, dishwashing detergents, bathroom and sanitary cleaners, cleaning creams, solid and liquid toilet bowl cleaners, powdered and foamed carpet cleaners, liquid detergents, powdered detergents, laundry pretreaters, such as bleaches, soaking agents and stain removers , fabric softeners, washing soaps, washing tablets, disinfectants, surface disinfectants, and air fresheners in liquid or gel or solid substrate form, sprays, waxes and polishes, such as furniture polishes, floor waxes, shoe polishes and body care products such as solid and liquid soaps, shower gels, shampoos, shaving soaps, shaving foams, bath oils, cosmetic emulsions of the oil-in-water, water-in-oil and water-in-oil-in-water type, for example, skin creams and lotions, face creams and lotions, sunscreens and lotions, After-sun skin creams and lotions, hand creams and-lotions, foot creams and lotions, hair removal creams and lotions, aftershave creams and lotions, sun tan creams and lotions, hair care products, for example, hair sprays, hair gels, shampoos, conditioners, permanent and semi-permanent hair dyes, hair styling agents, such as cold perms and hair straighteners, hair washes, hair creams and lotions, deodorants and antiperspirants, for example, underarm sprays, roll-ons, deodorant sticks, deodorant creams or products of decorative make-up.

[0277] In particular, the tenth aspect of the present invention includes the following preparations: solid and liquid soaps, shower gels, shampoos, shaving soaps, shaving foams, bath oils, cosmetic lotions, skin creams and lotions, face creams and face lotions, sunscreen creams and lotions, aftersun creams and lotions, hand creams and lotions, foot creams and lotions, depilatory creams and lotions, aftershave creams and lotions, tanning creams and lotions, hair sprays, hair gels, shampoos, conditioners, permanent and semi-permanent hair dyes, hair styling products, shampoos, hair creams and lotions, deodorants, underarm sprays, roll-ons, deodorant sticks, deodorant creams or decorative cosmetics and perfume extracts perfumes, eau de toilette, aftershaves, colognes, pre-shave products, touch-up colognes and scented wipes, as well as acidic, alkaline and neutral cleaning agents, floor cleaners, window glass cleaners, dishwashing detergents, bathroom and sanitary cleaners, cleaning creams, solid and liquid toilet bowl cleaners, powdered and foaming carpet cleaners, liquid detergents, powdered detergents, laundry pretreaters, bleaches, soaking and stain removers, fabric softeners, washing soaps, washing tablets, disinfectants, surface disinfectants, air fresheners in liquid, gel or solid substrate form, aerosol sprays, furniture polishes, floor wax, shoe polish.

[0278] Preparation Method I

[0279] The eleventh aspect of the present invention relates to a method for preparing a monoester and / or diester of mesaconic acid, which comprises the following steps:

[0280] (i) reacting itaconic acid with acetic anhydride to obtain itaconic anhydride;

[0281] (ii) isomerizing itaconic anhydride to citraconic anhydride;

[0282] (iii) esterifying citraconic anhydride with an aliphatic, araliphatic or aromatic alcohol having 1 to 10 carbon atoms or a diol having 1 to 5 hydroxyl groups to obtain mono- and / or diesters of citraconic acid;

[0283] (iv) rearranging the monoester and / or diester of citraconic acid into the monoester and / or diester of mesaconic acid.

[0284] To illustrate the process, the preferred preparation of diethyl (E)-2-methylbut-2-enedicarboxylate (diethyl mesaconic acid ester) or its mixture with diethyl citrate and diethyl itaconate is taken as an example, see Figure A below.

[0285] In the first reaction step, itaconic acid (preferably diethyl itaconate) is usually reacted with an approximately equimolar amount of acetic anhydride to form the cyclic anhydride and liberate acetic acid. The reaction is usually carried out at a temperature of 50 to 95° C., and the acetic acid is then distilled off in vacuo.

[0286] In the second step, the itaconic anhydride is isomerized to citraconic anhydride under thermodynamic control. The reaction is preferably carried out in a solvent and requires temperatures of 200 to 250° C. The solvent is then removed again.

[0287] In the third step, esterification is carried out with excess ethanol and acid catalysis under reflux. Subsequently, the unreacted alcohol is distilled off.

[0288] The final fourth step is to rearrange the citraconate (preferably diethyl citrate) to mesaconic acid (preferably diethyl mesaconic acid). The reaction is preferably carried out in a suitable solvent such as MtBE at a temperature of 170 to 200°C; iodine is added to the mixture as a catalyst. Subsequently, distillation is performed again to remove the solvent.

[0289] The description of the implementation of the process from step (i) to step (iv) can be found in the Examples section.

[0290] Plan A

[0291]

[0292] According to an embodiment of the present invention, particularly preferred is a method for preparing mesaconic acid monoesters and / or diesters, wherein a high boiling point solvent is used in step (ii), preferably a polyalkylene glycol (PAG) having the following structure: RO-[CH2-C(CH3)HO] n -[CH2CH2O] m -H.

[0293] The high boiling point solvent preferably comprises a solvent having a boiling point above 250° C., more preferably above 300° C. Suitable products here are based on polyalkylene glycols (PAG). Such products include, for example 50-B SYNALOX TM 50-xB (used as a lubricant), and an alcohol-containing material containing ethylene oxide and propylene oxide groups, which has a single terminal hydroxyl group and has the following structure:

[0294] RO-[CH2-C(CH3)HO] n -[CH2CH2O] m -H

[0295] What is known about 50-50B SYNALOX is: Molecular weight: 1300.

[0296] In a twelfth embodiment of the present invention, a solvent system is used in step (ii) which comprises a high boiling point solvent, preferably a polyalkylene glycol (PAG), having a boiling point above 150°C, and further comprises a co-solvent having a boiling point between 90°C and 120°C, preferably dioxane. This system significantly improves the yield, because without a protective solvent, the distilled product tends to polymerize on a larger scale over a longer distillation path with a larger reaction vessel. Thus, it can be demonstrated that even with larger batches, the yield can be increased or maintained at a very high level when the protective solvent has a boiling point, so that it can also be distilled with the product to prevent the product from polymerizing during distillation. Particularly preferably, the boiling point of the co-solvent or protective solvent is between 95°C and 110°C, more preferably between 100°C and 105°C. A suitable substance is dioxane.

[0297] After the distillation step, the co-solvent can be separated by conventional methods.

[0298] Other suitable co-solvents include:

[0299] aliphatic hydrocarbons, in particular paraffins, such as, in particular, octane, isooctane, nonane, decane, undecane, tetradecane; aromatic hydrocarbons, in particular toluene, xylene, ethylbenzene, diethylbenzene, p-, trimethylbenzene, isopropylbenzene, pseudocumene, petroleum fractions consisting of mixtures of alkylbenzenes, in particular Type of fraction,

[0300] Chlorinated aliphatic hydrocarbons, such as 1,1,2-trichloroethane, pentachloroethane, 1-iodo-2-methylpropane, 1-chlorohexane, 1-chloro-2-ethylhexane; chlorinated aromatic hydrocarbons and special chlorobenzenes, chlorotoluenes,

[0301] Ethers, especially aliphatic ethers, such as butyl ether, isobutyl ether, ethyl hexyl ether, 1-butoxy-2-methoxyethane, 1,1-diethoxybutane, amyl ether, isopentyl ether, dipropoxymethane, etc.; aromatic ethers, such as phenylpropyl ether, mesityl oxide,

[0302] Nitrated compounds, such as nitropropane, nitrobenzene,

[0303] Aliphatic, cycloaliphatic or aromatic ketones, preferably methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, methyl n-amyl ketone, methyl isoamyl ketone, cyclohexanone, methylcyclohexanone, diacetone alcohol.

[0304] Cosolvents may also be used as separate mixtures.

[0305] Preparation method II

[0306] The thirteenth aspect of the present invention relates to a method for preparing a monoester and / or diester of mesaconic acid, which comprises the following steps:

[0307] (i) providing a solution comprising at least one citraconic acid monoester and / or diester and optionally a solvent;

[0308] (ii) adding iodine to the solution;

[0309] (iii) heating the iodine-containing solution to about 170 to about 200° C.

[0310] (iv) Purifying the obtained product by distillation if necessary.

[0311] Furthermore, it is preferred that the production method II is used as step (iv) of the production method I. Therefore, the final rearrangement step is performed after the production method II, that is, immediately after steps (i) to (iii) in the production method I.

[0312] In the fourteenth embodiment of the present invention, in the above methods I and II, the monoester and / or diester of mesaconic acid is (E)-2-methyl-but-2-ene dicarboxylate, preferably (E)-2-methyl-but-2-ene dicarboxylic acid diethyl ester.

[0313] Therefore, in a preferred embodiment of the present invention, it relates to a method for preparing (E)-2-methyl-but-2-enedicarboxylic acid diethyl ester, which comprises the following steps:

[0314] (i) providing a solution containing at least diethyl citraconic acid and optionally a solvent;

[0315] (ii) adding iodine to the solution;

[0316] (iii) heating the iodine-containing solution to a temperature of about 170 to about 200° C.;

[0317] (iv) Purifying the obtained product by distillation if necessary.

[0318] Preferably, mono- and / or diesters of citraconic acid with aliphatic, araliphatic or aromatic alcohols having 1 to 10 carbon atoms or diols having 2 to 6 hydroxyl groups are used as starting materials. In particular, mono- and diesters of citraconic acid with methanol, isopropanol, isobutyl alcohols, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol or glycerol, especially ethanol, are used. With regard to the details of the process, reference is made to the description for the first preparation process, step (iv).

[0319] application

[0320] The fifteenth aspect of the present invention relates to a method for imparting, changing or enhancing a pear-like fragrance note in a perfume mixture, a perfume oil, a cosmetic, a lotion or a detergent and a cleanser, comprising the following steps:

[0321] (a1) providing at least one or more compounds of formula (i), formula (ii) and / or formula (iii) according to the present invention, or a fragrance mixture according to the present invention comprising these compounds,

[0322] (a2) mixing the substance(s) with a mixture of other flavoring agents in an organoleptically effective amount sufficient to induce a pear-like fruity aroma in the finished formulation,

[0323] or

[0324] (b1) providing at least one or more compounds of formula (i), formula (ii) and / or formula (iii) according to the present invention, or a fragrance mixture according to the present invention comprising these compounds,

[0325] (b2) mixing an organoleptically effective amount of the substance(s) with perfume oils, cosmetics, lotions or washing and cleaning agents, which is sufficient to induce a fruity, pear-like aroma note in the finished preparation.

[0326] Preferably, the compounds of formula (i), formula (ii) and / or formula (iii) that comply with the present invention are (E)-2-methyl-but-2-enedicarboxylate (diethyl mesaconic acid ester), diethyl citrate and diethyl itaconate, or a mixture of (E)-2-methyl-but-2-enedicarboxylate with diethyl citrate and diethyl itaconate.

[0327] The sixteenth and seventeenth items of the present invention relate to the general use of the compounds of formula (i), formula (ii) and / or formula (iii) or their mixtures, or (E)-2-methyl-but-2-enedicarboxylic acid diethyl ester itself, in particular a mixture of diethyl mesaconic acid ester with diethyl citraconic acid and diethyl itaconate, or a corresponding fragrance mixture according to the present invention, on the one hand:

[0328] As a spice, on the other hand

[0329] To impart, modify or intensify a pear-like fruity note in perfume mixtures, perfume oils, cosmetics, lotions or detergents and cleansers.

[0330] With regard to preferred starting materials and materials, reference is made to the above examples applicable here, so they are not repeated here. Compounds of formula (i), formula (ii) and / or formula (iii) or mixtures thereof are generally regarded as preferred compounds. In particular, it should be pointed out again that particularly preferred embodiments and modifications of any embodiment of the present invention are based on diethyl mesaconic acid, as compound (i), or isomer mixtures, in particular (E)-diethyl 2-methylbut-2-enedicarboxylate, with diethyl citraconic acid and diethyl itaconate, respectively, containing at least 50 wt.% of such compounds.

[0331] Example

[0332] Example of Preparation Method 1: Preparation of diethyl mesaconic acid ester = (E)-2-methyl-but-2-enedicarboxylate diethyl ester

[0333] Stage 1: Itaconic Anhydride

[0334]

[0335] In a 2-liter three-necked flask equipped with a KPG stirrer, a 15 Vigreux distillation column and a column head, 612 g (6.0 mol) of acetic anhydride are added and mixed with 780 g (6.0 mol) of solid itaconic acid under stirring. The mixture is then slowly heated to 80° C. until the solid dissolves and stirring is continued at this temperature for 30 minutes. Approximately 680 g of acetic acid are then distilled off under a vacuum between 150 and 10 mbar and a column bottom temperature of 80 to 82° C. Approximately 690 g of the column bottom product remain, and the crude product is 680 g. The crude product is used directly in the second stage.

[0336] A 5 g sample of the ester was purified by distillation in a bulb distillation furnace and analyzed by gas chromatography to obtain a composition of 11 wt.% citraconic anhydride and 89 wt.% itaconic anhydride.

[0337] Stage 2: Citraconic Anhydride

[0338]

[0339] In a 2-liter three-necked flask equipped with a KPG stirrer, a 15 Vigreux distillation column and a tower head, 100 g of a high boiling point solvent (Synalox 50-B) was added and heated to 230°C under stirring. Subsequently, 690 g of itaconic anhydride (crude product of the first stage) was dissolved in 100 g of Synalox within 4 hours under a vacuum of about 350 mbar. The isomerized product, citraconic anhydride, was continuously taken out at an R / D ratio of 1:1. After the batching was completed, the vacuum was raised to 10 mbar to obtain a total of 630 g of distillate, which was equivalent to a yield of 94% in two stages. The GC purity was 99%.

[0340] Stage 3: Diethyl Citraconic Acid

[0341]

[0342] In a 2-liter three-necked flask equipped with a KPG stirrer, a 15 Vigreux distillation tower and a tower head, 780 g of ethanol was added and mixed with 630 g (5.63 mol) of citraconic anhydride under stirring at room temperature. Subsequently, 30 g of concentrated sulfuric acid was added within 5 minutes and refluxed for 2 hours. Thereafter, 530 g of a mixture of ethanol / water (80 / 20 wt.%) (R / D 1:3, duration of about 80 minutes) was distilled out at atmospheric pressure and a tower head temperature of 86°C. The sample was purified by distillation in a bulb distillation furnace and analyzed by gas chromatography to obtain 10 wt.% of citraconic anhydride and 89 wt.% of diethyl citraconic acid.

[0343] Subsequently, 230 g of ethanol was added again and refluxed again at 84° C. tower head temperature for 1 hour. Thereafter, 170 g of a mixture of ethanol / water (90 / 10 wt.%) was distilled out (R / D 1:3, duration about 40 minutes). The sample was treated by distillation in a bulb distillation furnace and analyzed by gas chromatography to obtain 5 wt.% of citraconic anhydride and 95 wt.% of diethyl citraconic acid.

[0344] 140 g of ethanol was added again, refluxed for 1 hour, and 110 g of a mixture of ethanol / water (90 / 10 wt.%) was distilled out at 82° C. tower head temperature (R / D 1:3, duration of about 25 minutes). The sample was distilled in a bulb distillation furnace and analyzed by gas chromatography. In this way, 2 wt.% of citraconic anhydride and 96 wt.% of diethyl citraconic acid were obtained.

[0345] It was then cooled to room temperature and the reaction product was washed with 400 g of water after addition of 400 g of MTBE. The organic phase was then first washed three times with saturated sodium bicarbonate solution with vigorous carbon dioxide evolution and then with 400 g of 5 wt.% saline solution. After phase separation, a total of 1,970 g of aqueous phase (wastewater fraction I, pH 6) and 1,140 g of organic phase were present.

[0346] 10% of the organic phase was worked up by distillation and analyzed by gas chromatography: yield: 74 g (71% of theory); purity: 99% diethyl citraconic acid ester.

[0347] Stage 4: Diethyl Mesaconic Acid

[0348]

[0349] In a 2-liter three-necked flask equipped with a KPG stirrer, a 15 Vigreux distillation column and a column head, 1100 g of diethyl citraconic acid were added to MTBE (crude product of the third stage) and the solvent was distilled at a bottom temperature of no more than 150° C. and a vacuum of 50-80 mbar. In this way, about 320 g of MTBE that can be used again (see below) were obtained. It was then cooled to about 80° C., ventilated and mixed with 8 g (31 mmol) of iodine under stirring. It was heated to 190° C. for 1 hour. The sample was purified by distillation in a bulb distillation furnace and analyzed by gas chromatography to obtain 72.9 wt.% of diethyl mesaconic acid, 1.1 wt.% of diethyl itaconate and 25.9 wt.% of diethyl citraconic acid.

[0350] Since the content of mesaconic acid ester was still below 80 wt.%, heating to 190° C. was continued for another hour. The sample was purified by distillation in a bulb distillation furnace and analyzed by gas chromatography to obtain 84.6 wt.% of diethyl mesaconic acid ester, 1.4 wt.% of diethyl itaconate and 13.8 wt.% of diethyl citraconic acid ester.

[0351]

[0352] Diethyl mesaconic acid = (E)-2-methyl-but-2-enedicarboxylate diethyl ester

[0353]

[0354] Diethyl citraconic acid = (Z)-2-methyl-but-2-enedicarboxylate diethyl ester

[0355]

[0356] Diethyl itaconate = diethyl 2-methylene-butanedicarboxylate

[0357] After cooling to about 40 to 45° C., 320 g of recycled MTBE was added with stirring, and the mixture was washed four times with 300 g of a 40 wt.% sodium bisulfite solution, once with 300 g of a 5 wt.% sodium bicarbonate solution, and once with 300 g of a 10 wt.% saline solution, wherein phase separation occurred within 5 minutes. A total of about 1,800 g of an aqueous phase (wastewater fraction II, pH 4) and about 1,000 g of an organic phase were obtained. The product in an amount of about 1000 g was purified by a 10-cm-FKK distillation column, see Table 1.

[0358] Table 1: Distillation purification

[0359]

[0360] The product turns pink during the distillation or changes color when standing. For decolorization, 14 g of activated carbon are added with stirring, stirred at room temperature for 30 minutes, and then filtered. The yield is 705 g (95% of theory).

[0361] Rearrangement step (ii) via solvent system

[0362] An improved method using a solvent mixture is described below.

[0363]

[0364] In the preparation of citraconic anhydride from itaconic anhydride, the solvent mixture Synalox and 1,4-dioxane was used. It provides good yields even for larger batches. For this purpose, the following procedure was performed.

[0365] Itaconic anhydride is first added to dioxane or, recovered as a residue from step (i) (3 mol), mixed with 390 g of 1,4-dioxane and bottled via a dropping funnel.

[0366] Thereafter, step (ii) is performed according to the following rules.

[0367]

[0368] The product was then evaporated on a rotary column (60-70° C. / 100-20 mbar) to give 296 g (GC purity = 96.6%) of citraconic anhydride with a yield of 85%.

[0369] Preparation of other esters

[0370] Similar to the above-mentioned example of the preparation of diethyl (E)-2-methyl-but-2-enedicarboxylate, other esters were prepared. In particular, the methyl, propyl and n-butyl esters of mesaconic acid were synthesized and analyzed. A total of four compounds were produced:

[0371] (E)-2-Methyl-but-2-enedicarboxylic acid-dimethyl ester,

[0372] (E)-2-Methyl-but-2-enedicarboxylic acid-diethyl ester,

[0373] (E)-2-Methyl-but-2-enedicarboxylic acid-dipropyl ester,

[0374] (E)-2-Methyl-but-2-enedicarboxylic acid-dibutyl ester.

[0375] Spectral data:

[0376] (E)-2-Methyl-but-2-enedicarboxylic acid dimethyl ester

[0377] 1H-NMR (400MHz, CDCl3): δ = 2.31 (d, J = 1.6Hz, 3H), 3.78 (s, 3H), 3.28 (s, 3H), 6.80 (q, J = 1.6Hz, 1H).

[0378] 13 C NMR (CDCl3, 101MHz): δ=167.6(C=O), 166.3(C=O), 143.7(C), 126.5(CH), 52.6(CH3), 51.7(CH3), 14.3(CH3).

[0379] MS(70eV):158,143,127,113,99.

[0380] (E)-Diethyl 2-methylbut-2-enedicarboxylate

[0381] 1 H-NMR (400MHz, CDCl3): δ = 1.32ppm (t, J = 7.1Hz, 3H), 1.33ppm (t, J = 7.1Hz, 3H), 2.29 (d,J=1.6Hz,3H),4.23(q,J=7.1Hz,2H),4.26(q,J=7.1Hz,2H),6.78(q,1,6Hz,1H).

[0382] 13 C NMR (CDCl3, 101MHz): δ = 167.16 (C = O), 165.97 (C = O), 143.76 (C), 126.66 (CH), 61, 57 (CH2), 60, 62 (CH2), 14.27 (CH3), 14.20 (CH3), 14.13 (CH3).

[0383] MS(70eV):186,157,141,113,99.

[0384] (E)-2-Methylbut-2-enedicarboxylic acid dipropyl ester,

[0385] 1 H-NMR (400MHz, CDCl3): δ = 0.98 (t, J = 7.4Hz, 3H), 0.98 (t, J = 7.4Hz, 3H), 1.79-1.64 (m, 4H), 2.29(d,J=1.6Hz,3H), 4.13(t,J=6.5Hz,2H), 4.16(t,J=6.5Hz,2H), 6.79(q,J=1.6Hz,1H).

[0386] 13C NMR (CDCl3, 100MHz): δ=167.3(C), 166.1(C), 143.7(C), 126.7(CH), 67.2(CH2), 66.3(CH2), 21.9(CH2), 21.6(CH2), 14.3(CH3), 10.4(CH3), 10.4(CH3).

[0387] MS(70eV):214,199 185,155,131,96.

[0388] (E)-2-Methylbutane-2-dicarboxylic acid dibutyl ester

[0389] 1 H-NMR (400MHz, CDCl3): δ = 0.95 (t, J = 7.3Hz, 3H), 0.96 (t, J = 7.3Hz, 3H), 1.47-1.36 (m, 4H), 1.72-1.6 1(m,4H),2.29(d,J=1.6Hz,3H),4.18(t,J=6.7Hz,2H),4.20(t,J=6.6Hz,2H),6.77(q,J=1.6Hz,1H).

[0390] 13 C NMR (CDCl3, 100MHz): δ = 167.3 (C), 166.1 (C), 143.7 (C), 126.7 (CH), 65.5 (CH2), 64 .6(CH2),30.5(CH2),30.6(CH2),19.19(CH2),19.18(CH2),14.3(CH3),13.7(CH3).

[0391] MS(70eV):242,227,213,169,131,68.

[0392] The GC spectra and the results of the fragrance note test of the prepared esters are shown in Table 2. The abbreviations DD and TN stand for the professional terms "dry down" and "top note", respectively.

[0393] Table 2

[0394]

[0395] Application Examples

[0396] Example 1: Shower gel

[0397]

[0398] Fragrance ingredients in shower gel

[0399]

[0400]

[0401] Diethyl mesaconic acid can be easily and stably incorporated into any fragrance composition and brings a natural, fruity and radiant aroma.

[0402] Example 2: Body lotion

[0403]

[0404] This body lotion's fragrance oil

[0405]

[0406]

[0407] Adding mesaconic acid diethyl ester (MSDEE) to the fragrance composition creates a fresher fruity scent. In addition, the top notes are brighter and the base notes are more moisturizing.

[0408] Example 3: Fabric softener

[0409]

[0410] Fragrance Oil for This Fabric Softener

[0411]

[0412]

[0413] Mesaconic acid diethyl ester (MSDEE) is added to the flavor composition to produce a more natural, rounded, transparent fruity flavor.

[0414] Example 4: Soap

[0415]

[0416]

[0417] Fragrance Oils for This Soap

[0418]

[0419]

[0420] Adding diethyl mesaconic acid (MSDEE) results in a more natural, transparent, fruity aroma similar to the aroma of pears. In addition, diethyl mesaconic acid makes the composition more vibrant and richer.

[0421] Example 5: Pearlescent Brightening Shampoo

[0422]

[0423]

[0424] The fragrance oils in this Pearlescent Shine Shampoo:

[0425]

[0426]

[0427] When the dosage of fragrance oil in shampoo was 0.5%, the following results were obtained: The addition of mesaconic acid diethyl ester (MSDEE) to fragrance oil G2 enhanced the radiant fruity characteristics. In addition, the diffusion was increased.

[0428] Example 6: Transparent deodorant stick (formula A, B) or deodorant cream stick (formula C, D)

[0429]

[0430]

[0431] Fragrance oils in clear deodorant sticks or deodorant cream sticks

[0432]

[0433]

[0434] Example 7: UV protection conditioner

[0435]

[0436] Example 8: Sunscreen (W / O)

[0437]

[0438] Manufacturing process

[0439] Part A: Heat to about 85°C.

[0440] Part B: Heat to about 85°C. Add B to A. Allow to cool with stirring.

[0441] Part C: Add and homogenize.

[0442] Example 9: Blonde hair dye

[0443]

[0444] Mix parts A, B and C together except Covaquat 16 and heat at 80°C for 20 minutes. Once the product is homogenized, allow to cool. Add Covaquat 16 at 50°C. Stop stirring when the product starts to thicken. Add NH4OH at room temperature and stir the mixture until homogenized.

[0445] Example 10: Candle

[0446]

[0447] Melt the candle wax and stir. Add the fragrance oil and stir well. Mold into the desired shape.

[0448] Example 11: Fragrance oil of Eau De Toilette (10% concentration in ethanol)

[0449]

[0450]

[0451] The combination with diethyl mesaconic acid gives a natural and strong pear-like fragrance.

[0452] Example 12: Fragrance oil of Eau De Toilette (10% concentration in ethanol)

[0453]

[0454]

[0455]

[0456] The base note is diethyl mesaconic acid, which has a stronger pear-like aroma.

[0457] Example 13: Fragrance oil of Eau de Toilette (10% concentration in ethanol)

[0458]

[0459]

[0460]

[0461] Diethyl mesaconic acid brings a more intense fruity aroma similar to the aroma of pear.

[0462] Example 14: Sensory and physicochemical evaluation of diethyl mesaconic acid

[0463] test standard Diethyl mesaconic acid <![CDATA[Threshold in DEP 1) > 1-13 6.3 <![CDATA[Impact on blotting paper 1) > 1-9 5 <![CDATA[Residence time on blotting paper 1) > 1-9 2.7 <![CDATA[Threshold in the air 1) > 5-13 6.4 <![CDATA[Threshold in air 1) > ppm 0.047 <![CDATA[Intensity in air 1) > 1-9 4 Diffusion 1-9 7.2 <![CDATA[Flowering from water 1) > 1-9 6 <![CDATA[Olfactory disorder 2) > ％ 0 <![CDATA[Water-soluble 3) > 1-9 6.2 <![CDATA[Polarity 4) > 1-9 3.4 <![CDATA[Volatile 5) > 1-9 6.4 <![CDATA[Estimated alkali stability 6) > <![CDATA[Estimated acid stability 6) > <![CDATA[Estimated antioxidant stability 6) > <![CDATA[Reduce bathroom odor 8) > 0-7 4.1 <![CDATA[Odor intensity in the bathroom 9) > 1-9 5.4 <![CDATA[Reduce kitchen odors 8) > 0-7 4.5 <![CDATA[Odor intensity in the kitchen 9) > 1-9 4.9 <![CDATA[Reduce body odor 8) > 0-7 4.2 <![CDATA[Sweat odor intensity 9) > 1-9 5.1 <![CDATA[Reduce the smell of smoke 8) > 1-7 3.5 <![CDATA[Smoke odor intensity 9) > 1-9 4.5

[0464] in:

[0465] (1) The higher the value, the higher the olfactory performance

[0466] (2) Percentage of subjects who were unable to detect odor

[0467] (3) The higher the value, the higher the water solubility

[0468] (4) The higher the value, the lower the polarity

[0469] (5) The higher the value, the higher the volatility, and the lower the value, the higher the adhesion.

[0470] (6) Grading: High-Medium-Low

[0471] (7) Standard: Linalool (value = 5)

[0472] (8) Level 1 (strong unpleasant odor) to Level 7 (no unpleasant odor)

[0473] (9) Level 1 (no odor) to Level 9 (strong odor)

[0474] Example 15: Stability test

[0475] Mesconate diethyl ester (MSDEE) alone or as part of various formulations was stored at extreme conditions of 60°C and 5 bar for more than 24 or 72 hours. Then, the remaining amount of active ingredient was determined. The results are summarized in Table 3 below:

[0476] Table 3: Storage stability

[0477] product MSDEEE content [wt. %] After 24 hours [%] After 72 hours [%] MSDEE 100 98 98 Eau de Toilette 4.5 99 99 Deodorant 0.5 94 48 Shampoo 0.5 100 100 Fabric softener 0.5 92 89

Claims

1. A method for preparing a monoester and / or diester of mesaconic acid, comprising the following steps: (i) reacting itaconic acid with acetic anhydride to obtain itaconic anhydride; (ii) isomerizing itaconic anhydride to citraconic anhydride; (iii) esterifying citraconic anhydride with an aliphatic, araliphatic or aromatic alcohol having 1 to 10 carbon atoms or a diol having 1 to 5 hydroxyl groups to obtain a monoester and / or diester of citraconic acid; (iv) rearranging the monoester and / or diester of citraconic acid into the monoester and / or diester of mesaconic acid, wherein in step (ii), a solvent system is used which comprises a high boiling point solvent having a boiling point above 150°C and further comprises a co-solvent having a boiling point between 90°C and 120°C, The high boiling point solvent is polyalkylene glycol, and the co-solvent is dioxane.

2. The method for preparing monoesters and / or diesters of mesaconic acid according to claim 1, wherein the step (iv) comprises the following sub-steps: (i) providing a solution comprising at least one citraconic acid monoester and / or diester and optionally a solvent; (ii) adding iodine to the solution; (iii) heating the iodine-containing solution to a temperature between 170°C and 200°C; and (iv) Optionally, purifying the obtained product by distillation.

3. The method according to any one of claims 1 to 2, characterized in that: The monoester and / or diester of the mesaconic acid is ( E )-2-methyl-but-2-enedicarboxylate.

4. The method according to any one of claims 1 to 2, characterized in that: The monoester and / or diester of the mesaconic acid is ( E )-2-methyl-but-2-enedicarboxylic acid diethyl ester.

Images