Silicone-free hair care shampoo

Abstract

Silicone-free shampoos which contain, in addition to surfactants, at least one specific diesterquat and at least one lipophilic active hair-care ingredient of vegetable origin in a cosmetic carrier are suitable for improving the care properties of hair, in particular for improving the combability and softness of hair as well as for reducing hair breakage.

Description

[0001] “Silicone-free hair care shampoo”

[0002] The invention relates to silicone-free shampoos which, in addition to surfactants, contain at least one specific diesterquat and a lipophilic hair conditioning active ingredient of plant origin. The invention further relates to the use of the shampoo to improve the conditioning properties of hair.

[0003] Cosmetic cleaning agents, such as hair shampoos, can be used to clean human hair and scalp, removing sebum, styling product residue, and other impurities.

[0004] Due to the (mostly anionic) surfactants typically contained in cosmetic hair cleansing products, hair cleansing always involves the removal of lipids and / or proteins from the hair or scalp, which can lead to damage to the hair structure and / or drying of the scalp, especially with frequent cleansing.

[0005] Damage to the hair structure or hair fibers, especially split ends and / or breakage, can also be promoted by environmental influences (such as intense sun exposure), mechanical stresses (such as combing under heat from a hairdryer) as well as by chemical influences (such as dyeing, shaping or straightening the hair).

[0006] To prevent and / or reduce hair damage, oil-based conditioning agents, mostly silicones, were often added to hair shampoos in the past.

[0007] However, the use of silicones in hair cleaning products is now controversial and has disadvantages, because silicones reduce the penetration of active ingredients and additives into the hair fibers by coating the hair surface and make styling hair more difficult.

[0008] Furthermore, the regular use of shampoos containing silicones can sometimes lead to over-conditioning of the hair and a so-called buildup effect, which is caused by the deposition and adhesion of excessive amounts of silicone to the hair fibers.

[0009] Finally, for sustainability reasons, efforts are made to use as large a proportion as possible of biodegradable active ingredients and / or active ingredients of natural origin in cosmetic products.

[0010] The provision of nourishing cosmetic hair washes that are 'low in' or 'free from' silicones and / or ingredients declared as 'poly...' (which are not derived from natural sources) is therefore a relevant task in the field of (hair) cosmetics.

[0011] Low-silicone cosmetic hair washes – especially silicone-free shampoos – often exhibit inferior product performance in terms of their hair care properties compared to conventional formulations. In DE102019204975, a similar problem was solved by providing silicone-free shampoos based on a combination of two specific cationic polymers derived from natural sources.

[0012] The present application was based on the task of providing hair washes with the highest possible proportion of conditioning agents of natural origin, which achieve the product performance of conventional, silicone-containing hair washes.

[0013] The use of hair washes is intended not only to gently and thoroughly cleanse the (scalp) skin and hair, but also to improve hair care-relevant parameters such as combability, smoothness, shine, and to reduce or prevent hair damage such as breakage.

[0014] Another task was to increase consumer acceptance of conventional silicone-containing products by providing such cosmetic cleaning agents.

[0015] By combining specific diesterquats and lipophilic hair care ingredients of plant origin in a surfactant base, shampoos with high hair care potential have been developed. These offer comparable product performance to conventional (silicone-based) formulations and do not cause any buildup effect, even with regular use.

[0016] Hair cleaned with hair washing products according to the invention is easy to comb, it is also supple and silky shiny and prevents or reduces hair damage such as breakage.

[0017] The problems underlying the invention were solved by providing a silicone-free hair wash containing in a cosmetic carrier a) at least one anionic, amphoteric and / or zwitterionic surfactant, b) at least one diesterquat of the following formula (II) wherein

[0018] Ri, R2 are the same or different and represent a Ci-C4 alkyl group,

[0019] R3, R4 are the same or different and represent the grouping -CH2-CH(R5)-ORe, in which

[0020] R5 stands for H or for a Ci-Ce alkyl group,

[0021] Re represents an acyl group of a monounsaturated carboxylic acid with a C-chain length of 18 to 24 carbon atoms, and X represents a halide, methyl sulfate, ethyl sulfate, maleate, fumarate, citrate, lactate, oxalate, tartrate or acetate ion, and c) contains at least one lipophilic hair care active ingredient of plant origin.

[0022] The hair washing products according to the invention contain the active ingredients a) to c) preferably in a cosmetic carrier. Within the scope of the invention, this is preferably understood to be an aqueous or aqueous-alcoholic carrier.

[0023] The cosmetic carrier preferably contains at least 50 wt.%, more preferably at least 55 wt.%, particularly preferably at least 60 wt.% and especially preferably at least 65 wt.% water.

[0024] The hair washing products according to the invention contain as a first essential ingredient at least one surfactant a), selected from anionic, amphoteric, and / or zwitterionic surfactants.

[0025] The mildness and good foaming properties of the hair washes according to the invention can be controlled to a significant degree by the careful selection of the amounts and / or types of surfactants. Thus, the hair washes according to the invention preferably contain at least one anionic surfactant, which is essential for generating satisfactory amounts and properties of foam. A mixture of at least one anionic surfactant and at least one mild co-surfactant, which may preferably be selected from amphoteric and / or zwitterionic surfactants, has proven effective in achieving an optimal balance between mildness and foaming properties in the hair washes according to the invention.

[0026] The combination of at least one surfactant a) with components b) and c) in turn enables an increase in the relevant hair care parameters.

[0027] The at least one surfactant a) can preferably be used in the hair washing products according to the invention in a weight fraction of 1–35 wt.% of the total weight of the hair washing products. More preferred are amounts of 2–30 wt.%, particularly preferred 2.5–25 wt.% and especially preferred 5–20 wt.%.

[0028] In a preferred embodiment, the hair washing agents according to the invention contain (based on the weight of the entire agent) ai) 1 - 20 wt.% of at least one anionic surfactant and aii) 0.5 - 10 wt.% of at least one amphoteric and / or zwitterionic surfactant aiii) or mixtures of surfactants ai) and aii).

[0029] Suitable anionic surfactant types (ai) that can be used in the hair washing products according to the invention include, for example: linear and branched fatty acids with 8 to 30 carbon atoms (soaps), ether carboxylic acids of the formula RO-(CH2-CH2O) X -CH2-COOH, in which R is a linear or branched, saturated or unsaturated alkyl group with 8 to 30 C atoms and x = 0 or 1 to 16,

[0030] Acyl sarcosides with 8 to 24 carbon atoms in the acyl group (sarcosinate surfactants), acyl taurides with 8 to 24 carbon atoms in the acyl group (taurate surfactants), acylisethionates with 8 to 24 carbon atoms in the acyl group (isethionate surfactants), sulfosuccinic acid mono- and / or dialkyl esters with 8 to 24 carbon atoms in the alkyl group and sulfosuccinic acid monoalkyl polyoxyethyl esters with 8 to 24 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups (sulfosuccinate surfactants), alpha-olefin sulfonates with 8 to 24 carbon atoms (alpha-olefin sulfonate surfactants),

[0031] Alkyl sulfates and / or alkyl ether sulfate salts of the formula R-(OCH2-CH2)nO-SO3X, in which R preferably represents a straight-chain or branched, saturated or unsaturated alkyl group with 8 to 30 C atoms, x is the number 0 or 1 to 12 and X is an alkali, alkaline earth, ammonium or alkanolamine ion,

[0032] Sulfonates of unsaturated fatty acids with 8 to 24 carbon atoms and 1 to 6 double bonds, esters of tartaric acid and citric acid with alcohols, which are addition products of approximately 2-15 molecules of ethylene oxide and / or propylene oxide to fatty alcohols with 8 to 22 carbon atoms, and / or

[0033] Alkyl and / or alkenyl ether phosphates of the formula in the R 1 preferably for an aliphatic hydrocarbon residue with 8 to 30 carbon atoms, R 2 for hydrogen, a residue (CH2CH2O) n R 1 or X, n for numbers from 0 to 10 and X for hydrogen, an alkali or alkaline earth metal or the group -NR 3 R4 R 5 R 6 stands, with R 3 to R 6 independently representing a Ci to C4 hydrocarbon residue.

[0034] Particularly preferred are physiologically compatible alkyl sulfate, alkyl ether sulfate, ether carboxylic acid, sarcosinate, isethionate, taurate, sulfosuccinate and / or alpha olefin sulfonate salts; alkyl sulfate and / or alkyl ether sulfate salts are particularly preferred due to their excellent foaming properties.

[0035] The amount of anionic surfactants ai) used in the hair washing products according to the invention is preferably 1–20 wt.% (based on the weight of the entire product). More preferred are amounts of 2–20 wt.%, particularly preferred 2.5–18 wt.%, and especially 3–15 wt.%.

[0036] In a preferred embodiment, at least one physiologically compatible alkyl sulfate, alkyl ether sulfate, ether carboxylic acid, sarcosinate, isethionate, taurate, sulfosuccinate and / or alpha-olefin sulfonate salt; in particular preferably an alkyl sulfate and / or alkyl ether sulfate salt in the aforementioned amounts is used as the anionic surfactant ai) in the hair washing products.

[0037] Suitable amphoteric and / or zwitterionic surfactant types (aii) that can be used in the hair washes according to the invention include, for example, one or more compounds of the following formulas (i) to (vii). In these formulas, the R group preferably represents a straight-chain or branched, saturated or mono- or polyunsaturated alkyl or alkenyl group with 7 to 23 carbon atoms (formulas (i) and (ii)) or a straight-chain or branched, saturated or mono- or polyunsaturated alkyl or alkenyl group with 8 to 24 carbon atoms (formulas (iii) to (vii)).

[0038] Preferred amphoteric surfactants of the aforementioned formulas (i) to (vii) contain as residue R predominantly a straight-chain or branched, saturated, mono- or polyunsaturated alkyl residue with 8 to 20, more preferably 8 to 18 and in particular with 8 to 16 C atoms.

[0039] Amphoteric surfactants (b) are particularly preferred, where the R group is derived from coconut oil. Amphoteric surfactants known under the INCI names Sodium Cocoamphoacetate, Disodium Cocoamphodiacetate, Sodium Lauroamphoacetate, Sodium Lauroamphodiacetate, Sodium Cocoamphopropionate, Disodium Cocoamphodipropionate, Coco Betaine, Lauryl Betaine, Cocamidopropyl Betaine and / or Lauramidopropyl Betaine, and available commercially from several suppliers, are especially preferred.

[0040] Surfactants with the INCI names cocamidopropyl betaine, lauramidopropyl betaine, cocaampho(di)acetate, and / or lauroapho(di)acetate are particularly preferred. The amount of amphoteric and / or zwitterionic surfactants aii) used in the hair washes according to the invention is preferably 0.5–10% by weight (based on the weight of the entire product). Amounts of 0.5–8% by weight are more preferred, 0.5–6% by weight is particularly preferred, and 0.5–4% by weight is especially preferred.

[0041] Particularly preferred anionic surfactants according to the present invention are alkyl(ether) sulfates (ai) due to their excellent foaming properties. These are preferably combined with cocamidopropyl betaine and / or cocoampho(di)acetates as co-surfactant (aii) to increase mildness.

[0042] For some applications – for example, for cleaning and caring for severely damaged hair and / or particularly fine hair and / or baby or toddler hair – it may be advantageous to avoid the use of sulfate surfactants.

[0043] Avoiding sulfate surfactants often leads to a dramatic deterioration in foaming properties (both quantity and quality), making the selection of suitable surfactants very difficult. Furthermore, the incorporation of oil-based conditioning agents into hair cleansing products can negatively affect their stability, viscosity, and foaming properties.

[0044] It has been found that nourishing hair washes with good lathering properties and excellent conditioning potential can still be provided if at least one surfactant from the group of anionic taurate surfactants and / or isethionate surfactants and / or alpha-olefin sulfonate surfactants is selected as the anionic, sulfate-free surfactant base. Preferably, at least one of these surfactants is combined with cocamidopropyl betaine and / or cocoampho(di)acetate as a co-surfactant.

[0045] For some embodiments, it may still be preferred to add at least one non-ionic surfactant to the hair washing products according to the invention.

[0046] Suitable non-ionic surfactants include, for example,

[0047] Amine oxides, which may be selected from compounds of general formulas (I) or (II) in which R represents a straight-chain or branched, saturated or mono- or polyunsaturated alkyl or alkenyl group with 6 to 24 carbon atoms, preferably with 8 to 18 carbon atoms.

[0048] Particularly preferred are the surfactants known under the INCI names Cocamine Oxide, Lauramine Oxide and / or Cocamidopropylamine Oxide and commercially available from various suppliers, of the aforementioned formula (I) or (II). Fatty acid alkanolamides of the following general formula, in which R preferably represents a linear or branched, saturated or unsaturated alkyl or alkenyl group with 8 to 24 carbon atoms and the R' groups represent hydrogen or the group -(CH2)nOH, in which n represents the numbers 2 or 3, provided that at least one of the R' groups represents the aforementioned group -(CH2)nOH,

[0049] Mixtures of alkyl (oligo)glucosides and fatty alcohols, for example, the commercially available product Montanov®68, alkoxylated—preferably ethoxylated—linear or branched, saturated or unsaturated C10-C24 alcohols with a degree of ethoxylation of 1 to 25, preferably 1 to 10, and sterols. Sterols are a group of steroids that bear a hydroxyl group at carbon atom 3 of the steroid skeleton and are isolated from both animal tissue (zoosterols) and plant fats (phytosterols). Examples of zoosterols are cholesterol and lanosterol. Examples of suitable phytosterols are ergosterol, stigmasterol, and sitosterol. Sterols, the so-called mycosterols, are also isolated from fungi and yeasts.

[0050] Phospholipids. These include primarily glucose phospholipids, which are obtained, for example, as lecithins or phosphatidylcholines from egg yolks or plant seeds (e.g., soybeans).

[0051] Alkyl(oligo)glycosides. Suitable alkyl(oligo)glycosides may be selected from compounds of the general formula RO-[G] X , in which [G] is preferably derived from aldoses and / or ketoses with 5-6 carbon atoms, preferably from glucose.

[0052] The index number x represents the degree of oligomerization (DP), i.e., the distribution of mono- and oligoglycosides. The index number x preferably has a value in the range of 1 to 10, particularly preferably in the range of 1 to 3, and may not be a whole number but a fraction that can be determined analytically. Particularly preferred alkyl(oligo)glycosides have a degree of oligomerization between 1.2 and 1.5. The substituent R preferably represents at least one alkyl and / or alkenyl group with 4 to 24 carbon atoms.

[0053] Particularly preferred alkyl(oligo)glycosides are the compounds known under the INCI names Caprylyl / Capryl Glucoside, Decyl Glucoside, Lauryl Glucoside and Coco Glucoside.

[0054] Alkyl(oligo)glucosides are particularly preferred.

[0055] The amount of nonionic surfactants used in the hair washing products according to the invention can preferably be 0.05–10 wt.% (based on the weight of the entire product). More preferred are amounts of 0.1–7.5 wt.%, particularly preferred 0.25–6 wt.%, and especially 0.5–5 wt.%.

[0056] A second essential component in the hair washing products according to the invention is a diesterquat b) according to the aforementioned general formula (II).

[0057] Preferred diesterquats b) according to formula (II) within the meaning of the present invention are selected from compounds according to formula (II), wherein

[0058] - Ri and R2 each represent methyl groups,

[0059] - Rs, R4 each stand for the grouping -CH2-CH2-OR6, in which

[0060] - Re stands for an acyl group of at least a singly unsaturated carboxylic acid with a carbon chain length of 18 to 20 carbon atoms, in particular for the acyl group of oleic acid, and

[0061] - X- stands for a halide, methyl sulfate, ethyl sulfate, maleate, fumarate, oxalate, tartrate, citrate, lactate or acetate ion, in particular for a chloride or a methyl sulfate ion.

[0062] Particularly preferred are diesterquats b) according to formula (II), which are known as Dimethylbis[2-[(1-oxohexadecyl)oxy]ethyl]ammonium chloride salt) (INCI name: Dioleoylethyl Dimonium Chloride) and are commercially available, for example, under the name Microcare Quat® LDG from the company Thor.

[0063] Dioleoylethyl Dimonium Chloride is an environmentally friendly and biodegradable cationic surfactant derived from olive oil. In combination with lipophilic hair care ingredients of plant origin, it particularly improves the combability and feel of wet and dry hair and protects hair fibers from heat styling and damage such as breakage.

[0064] The at least one diesterquat b) according to formula (II) is used in the hair washing products according to the invention (based on the total weight of the product) preferably in an amount of 0.01 - 2 wt.%, more preferably 0.05 - 1.75 wt.%, particularly preferably 0.1 - 1.5 wt.% and particularly 0.1 - 1 wt.%.

[0065] In a particularly preferred embodiment, dioleoylethyl dimonium chloride is used in the aforementioned amounts in the hair washing products according to the invention.

[0066] A third essential component in the hair washing products according to the invention is at least one lipophilic hair care active ingredient of plant origin c).

[0067] This preferably includes compounds selected from the group consisting of c1) vegetable oils, c2) optionally hydrogenated mono- and / or diesters of saturated or unsaturated, linear or branched C8-C24 fatty acids with saturated or unsaturated, linear or branched C3-C24 alcohols, c3) terpene homopolymers and / or derivatives of terpene homopolymers, c4) any mixtures of c1) - c3).

[0068] The at least one lipophilic hair care substance of plant origin c) is preferably used in the hair washing products according to the invention in a weight fraction of 0.1–1.5 wt.% of the total weight of the hair washing product. More preferred are amounts of 0.2–1.5 wt.%, particularly preferred 0.2–1 wt.%, and especially 0.3–1 wt.%.

[0069] Suitable vegetable oils (c1) or vegetable oils within the meaning of the present invention are understood to be plant-based oils that preferably have a melting point of less than 50°C, more preferably less than 47°C, most preferably less than 44°C, and most preferably less than 40°C. Vegetable oils that are free-flowing at a temperature of less than 40°C are most preferred.

[0070] Plant oils (and / or butters and / or waxes) can enhance the hair-conditioning properties of the specific esterquats b) and impart additional conditioning power to the hair care products according to the invention. The addition of plant oils c) can particularly improve the shine and feel of the treated hair while maintaining hair volume. A build-up effect does not occur, even after regular use.

[0071] Examples of suitable vegetable oils according to the invention (c1) are, for example, amaranth seed oil, apricot kernel oil, argan oil, avocado oil, babassu oil, cottonseed oil, borage seed oil, camelina oil, canola oil, cranberry oil, safflower oil, peanut oil, pomegranate seed oil, grapefruit seed oil, hemp oil, rosehip seed oil, hazelnut oil, elderberry seed oil, blackcurrant seed oil, jojoba oil, cocoa butter, coconut oil, pumpkin seed oil, linseed oil, macadamia nut oil, corn germ oil, mallow oil, almond oil, mango kernel oil, marula oil, poppy seed oil, evening primrose oil, olive oil, palm oil, palm kernel oil, peach kernel oil, rambutan oil, rapeseed oil, rice bran oil, castor oil, sacha inchi oil, safflower oil, sea buckthorn pulp oil, sea buckthorn kernel oil, sasanqua oil, sesame oil, shea butter, soybean oil, sunflower oil, tea tree oil, Grape seed oil, tsubaki oil, walnut oil, wheat germ oil, meadowfoam oil and / or rosehip oil.

[0072] Preferred oils include amaranth seed oil, apricot kernel oil, argan oil, avocado oil, coconut oil, almond oil, macadamia nut oil, rosehip seed oil, sunflower oil, olive oil, peach kernel oil, jojoba oil and / or the plant butters shea butter and / or cocoa butter.

[0073] Apricot kernel oil, sunflower oil, jojoba oil, or mixtures thereof are particularly preferred. The invention also includes the possibility of mixing at least two vegetable oils together. Vegetable oils (c1) can be used in the hair washing products according to the invention (based on the weight of the entire product) preferably in an amount of 0.05–1.5 wt.%, more preferably 0.05–1 wt.%, particularly preferably 0.1–1 wt.%, and especially 0.1–0.75 wt.%.

[0074] Examples of suitable components c2) according to the invention are mono- and / or diesters of saturated or unsaturated, linear or branched Cs-C24 fatty acids with saturated or unsaturated, linear or branched C3-C24 alcohols.

[0075] Preferably, glycerol is esterified as a C3-C24 alcohol component with one or two branched or unbranched, saturated or unsaturated Cs-C24 fatty acids, particularly preferably C12-C22 fatty acids, and most preferably Ci2-C2o fatty acids.

[0076] In a preferred embodiment, the remaining hydroxyl groups of the glycerol ester, which are not esterified with any fatty acid, are free. Preferred fatty acids are selected from lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid, and erucic acid, as well as mixtures thereof, particularly preferably from lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, and oleic acid, and even more preferably from oleic acid.

[0077] Particularly preferred components c2) are the esters known under the INCI names Glyceryl Laurate, Glyceryl Myristate, Glyceryl Palmitate, Glyceryl Stearate, Glyceryl Isostearate, Glyceryl Oleate, in particular those having a monoglyceride content in the range of 50 to 95, preferably 60 to 90 wt.%.

[0078] Glyceryl oleate is particularly preferred.

[0079] In a preferred embodiment, the remaining hydroxyl groups of the glycerol ester, which are not esterified with any fatty acid, are free. Preferably, the ester bond is formed with a terminal hydroxyl group of the glycerol.

[0080] The glycerol esters described above can be used in the hair washes according to the invention in free form or as a mixture with at least one nonionic surfactant, preferably with an alkyl(oligo)glucoside. Such mixtures are commercially available, for example under the trade name Lamesoft® PO 65.

[0081] Further examples of suitable components according to the invention (c2) are esters based on natural raw materials, in which the fatty acid component has 12 to 22 carbon atoms and the alcohol component has 4 to 12 carbon atoms. An ester of olive oil is particularly preferred. The main fatty acid components of olive oil are oleic acid, linoleic acid, and palmitic acid. The alcohol is preferably a linear or branched, preferably a branched, alkyl alcohol with 4 to 10 carbon atoms.

[0082] Esters (C2) from olive oil and branched C4 cyanoalcohols are particularly suitable. Such esters are well-known and commercially available, for example under the INCI name Hydrogenated Ethylhexyl Olivate.

[0083] In accordance with the present invention, it is also possible that the ester c2), preferably hydrogenated ethylhexyl olivate, comprises, in addition to the esters described above, further components of olive oil. A particularly preferred mixture contains hydrogenated ethylhexyl olivate and hydrogenated olive oil unsaponifiables (the INCI names are given in each case). Such products are commercially available, for example, from Berg + Schmidt GmbH & Co. KG under the name BergaCare® FG Olive, from Alexmo Cosmetics under the name Natura Plantasil®, or from Natura-Tech under the trade names Plantsil® XCITE 100 or Plantsil® XCITE 350.

[0084] The component(s) c2) can be used in the hair washing products according to the invention (based on the weight of the total product) preferably in an amount of 0.05 - 1.5 wt.%, more preferably 0.05 - 1 wt.%, particularly preferably 0.1 - 1 wt.% and especially 0.1 - 0.75 wt.%.

[0085] Compounds or mixtures thereof known under the INCI names Glyceryl Oleate, Hydrogenated Ethylhexyl Olivate are particularly preferred as component(s) c2) in the quantities mentioned above.

[0086] Suitable components according to the invention (c3) are preferably terpene polymers or derivatives of terpene polymers, such as their salts or esters.

[0087] The term “terpene polymers” preferably refers to homopolymers of terpenes, such as polylinalool, polycitrollenol, polygeraniol, polynerol, and / or poly-trans-nerolidiol.

[0088] Citronellol homopolymers of the following formula are particularly preferred in the hair washing agents according to the invention. where n represents numbers >1 to 100, preferably >1 to 50 and especially >1 to 20.

[0089] Suitable derivatives include esters, ethers, salts, oxidation and reduction products, and quaternized and alkoxylated derivatives of terpene homopolymers, particularly citrrollenol homopolymers. Citrollenol homopolymers, or the aforementioned citrrollenol homopolymer derivatives, are ideally suited as silicone and / or mineral oil substitutes in cosmetic preparations. They are based on natural raw materials and can be easily incorporated into standard cosmetic bases. A range of blends is available that can be easily integrated into conventional cosmetic products without any loss of energy or stability.

[0090] Suitable products are commercially available, for example from P2 Science under the names Citropol®1A (INCI name: Polycitronellol Acetate), Citropol®HA (INCI name: Polycitronellol Acetate), Citropol®H (INCI name: Polycitronellol), Citropol®V5 (INCI name: Polycitronellol Acetate and Undecane and Tridecane), Citropol®F (INCI name: Polycitronellol), Citrolatum®B (INCI name: Polycitronellol and Beeswax), Citrolatum®C (INCI name: Polycitronellol and Candelilla Wax), CitroVisk®1000, CitroVisk®5000, CitroVisk®10K (INCI name: Polycitronellol and Hydrogenated Vegetable Oil), CitroButter® (INCI name: Polycitronellol and Helianthus). Annuus (Sunflower) Seed Wax and Butyrospermum Parkii (Shea) Butter).

[0091] Polycitronellol, polycitronellol acetate, and mixtures thereof are particularly preferred.

[0092] The component(s) c3) can be used in the hair washing products according to the invention (based on the weight of the entire product) preferably in an amount of 0.05 - 1.5 wt.%, more preferably 0.05 - 1 wt.%, particularly preferably 0.1 - 1 wt.% and especially 0.1 - 0.75 wt.%.

[0093] Compounds or mixtures thereof known under the INCI names polycitronellol, polycitronellol acetate in the aforementioned quantities are particularly preferred as component(s) c3).

[0094] To further enhance the care properties of the hair washing products according to the invention, it may be advantageous if they contain additional active ingredients and auxiliary substances that give them beneficial properties.

[0095] In a further preferred embodiment, the hair washing products according to the invention therefore contain at least one further conditioning active ingredient in a weight fraction of 0.1 - 10 wt.% of the total weight of the hair washing product, selected from

[0096] (i) C2-Ce polyols,

[0097] (ii) Trimethylglycin

[0098] (iii) cationic polymers of natural origin

[0099] (iv) or mixtures thereof.

[0100] Suitable C2-Ce polyols (i) within the meaning of the present invention are understood to be glycol, ethyl diglycol, 1,2-propylene glycol, glycerin, diglycerin, 1,2-butanediol, 1,3-butanediol, 1,2-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, sorbitol, sorbitan, erythritol, or mixtures of these C2-C6 polyols. Preferred are 1,2-propylene glycol, glycerin, diglycerin, or mixtures thereof. A particularly preferred C2-Ce polyol is glycerin.

[0101] C2-Ce polyols support the conditioning effect of the active ingredient combination b) and c) in the hair washing products according to the invention. At the same time, they can promote better solubilization of oils.

[0102] C2-Ce polyols (i) can preferably be used in the hair washing products according to the invention in a weight fraction of 0.1–10 wt.% of the total weight of the hair washing products. Preferred amounts are 0.25–7.5 wt.%, more preferably 0.5–7.5 wt.%, and particularly 1–5 wt.%.

[0103] In a preferred embodiment, the hair washing products according to the invention contain glycerin in a weight fraction of 1 - 10 wt.% of the total weight of the hair washing product.

[0104] Trimethylglycine (ii) is a well-known amino acid derivative used in cosmetics and is available from natural sources such as sugar beet molasses. It is commercially available, for example, from Evonik under the name Tego® Natural Betaine and is used as a humectant in skin treatments and as a firming agent in hair care products.

[0105] It has been observed that the hair-conditioning properties of a combination of specific diesterquats (b) and lipophilic hair-conditioning agents of plant origin (c) can be further enhanced by adding trimethylglycine. In particular, the detangling and combability of dry hair, as well as the soft feel of the hair right down to the ends, can be improved by combining these active ingredients.

[0106] Trimethylglycine can be used in the hair washing agents according to the invention (based on the total weight of the agent) preferably in an amount of 0.1 to 2.0 wt.%, more preferably from 0.2 to 1.75 wt.%, most preferably from 0.25 to 1.5 wt.% and particularly from 0.3 to 1.25 wt.%.

[0107] Suitable cationic polymers (iii) of natural origin within the meaning of the present invention include, for example: quaternized cellulose derivatives, such as those commercially available under the names Celquat® and Polymer JR®; cationic starch derivatives, such as those commercially available under the name Mirustyle®; hydrophobically modified cellulose derivatives, such as the cationic polymers marketed under the trade name SoftCat®; cationic alkyl polyglycosides; cationized honey, such as the commercial product Honeyquat® 50; cationic guar derivatives, such as, in particular, the products marketed under the trade names Cosmedia®Guar N-Hance® and Jaguar®; cationic cassia and / or inulin derivatives, such as the cationic polymers known under the INCI names Cassia Hydroxypropyltrimonium Chloride and Hydroxypropyltrimonium Inulin.Cationic glucan derivatives such as the cationic polymer available from IFF under the INCI name alpha-glucan hydroxypropyltrimonium chloride and the trade name Aurist® AGC.

[0108] Quaternized cellulose polymers, hydrophobically modified cationic cellulose derivatives and / or cationic guard derivatives are preferred.

[0109] Particularly preferred are the cationic polymers known under the INCI names Hydroxypropyl Guar Hydroxypropyltrinonium Chloride, Guar Hydroxypropyltrimonium Chloride, Polyquaternium-10, Polyquaternium-67 and / or Hydroxypropyltrimonium Hydrolyzed Corn Starch; Hydroxypropyl Guar Hydroxypropyltrinonium Chloride and Guar Hydroxypropyltrimonium Chloride are particularly preferred.

[0110] The cosmetic compositions according to the invention contain cationic polymers - preferably hydroxypropyl guar hydroxypropyltrimonium chloride and / or guar hydroxypropyltrimonium chloride - preferably in a weight fraction of 0 to 2 wt.%, more preferably 0.01 to 1.5 wt.% and in particular 0.05 to 1 wt.% of the total weight of the cosmetic compositions.

[0111] In a preferred embodiment, the hair washing product according to the invention contains at least two further hair conditioning active ingredients from one or more groups (i) to (iii).

[0112] Within this embodiment, it is particularly preferred if the hair washing products according to the invention contain at least two further conditioning active ingredients, selected from among the INCI names.

[0113] (i) Glycerines,

[0114] (ii) Trimethylglycine

[0115] (iii) Hydroxypropyl Guar Hydroxypropyltrinonium Chloride and / or Guar Hydroxypropyltrimonium chloride known compounds.

[0116] To further optimize the consistency and / or the optical appearance of the cosmetic cleaning agents according to the invention, it may be advantageous to add further components, in particular waxes, opacifying agents, and / or pearlescent agents. Suitable waxes within the meaning of the present invention are preferably crystalline glycerides containing hydroxyl groups, such as trihydroxystearin, hydrogenated oils, and / or modifications thereof. The waxes may be of natural, mineral, and / or synthetic origin.

[0117] Suitable waxes form a network in the hair washing products according to the invention, which prevents the coalescence and / or phase separation of immiscible components in the composition.

[0118] Examples of particularly suitable crystalline, hydroxyl-group-containing structuring agents, as used in the present invention, are primarily hydrogenated plant-based waxes such as hydrogenated (hydrogenated) jojoba oil and / or hydrogenated (hydrogenated) castor oil. Compounds commercially available from several suppliers under trade names such as Cutina® HR, Thixin®, or Castorwax® are especially preferred.

[0119] Waxes can be used in the hair washing products according to the invention (based on their total weight) preferably in an amount of 0.01 - 10 wt.%, more preferably 0.02 - 5 wt.%, particularly preferably 0.025 - 3 wt.% and especially 0.05 - 2 wt.%.

[0120] In a further preferred embodiment, the cleaning agents according to the invention contain at least one natural, mineral and / or synthetic ingredient in a weight fraction of 0.01 - 2 wt.% of the total weight of the cosmetic cleaning agent.

[0121] Within this embodiment, it is particularly preferred if the wax is selected from compounds known under the INCI name Hydrogenated Castor Oil.

[0122] In a further preferred embodiment, the hair washing agents according to the invention can additionally contain at least one hydroxycarboxylic acid in a preferred amount (based on the weight of the entire agent) of 0.1 to 5.0 wt.%, more preferably of 0.15 to 4.0 wt.%, particularly preferably of 0.2 to 3.0 wt.% and especially of 0.25 to 2.0 wt.% to adjust the pH value, but also to support the hair conditioning properties.

[0123] Suitable hydroxycarboxylic acids are preferably alpha-hydroxycarboxylic acids and, in particular, naturally occurring alpha-hydroxycarboxylic acids, for example in fruit acids.

[0124] Examples include malic acid, citric acid, glycolic acid, isocitric acid, mandelic acid, lactic acid, tartronic acid and / or tartaric acid.

[0125] Suitable hydroxycarboxylic acids also include the dicarboxylic acids glutamic acid and / or succinic acid.

[0126] Citric acid, lactic acid, glutamic acid and / or succinic acid are particularly preferred.

[0127] In addition to the aforementioned essential and optional components, the hair washing agents according to the invention may contain further ingredients that confer additional advantageous properties or that support or enhance their advantageous properties. Suitable additional components include, for example, emollients (plasticizers), protein hydrolysates, vitamins, anti-dandruff agents, or mixtures thereof.

[0128] For the purposes of the present invention, suitable emollients are preferably understood to be hydrophilic emollients.

[0129] Preferred hydrophilic emollients are ethoxylated glycerol esters, preferably calcium-carbonate fatty acid mono- and diesters of addition products of 1 to 30 moles of ethylene oxide to glycerol. A hydrophilic refatting agent known by the INCI name PEG-7 Glyceryl Cocoate is particularly preferred.

[0130] PEG-7 Glyceryl Cocoate is water-soluble and does not require additional stabilization in an aqueous base. Furthermore, it makes skin and hair more supple and can enhance the conditioning effect of the hair washes according to the invention.

[0131] PEG-7 Glyceryl Cocoate is also particularly suitable for use in the hair washing products according to the invention, as it improves the foam quality of the products and contributes to the emulsification of oils or perfume oils.

[0132] Hydrophilic plasticizers can preferably be used in the hair washing products according to the invention in a weight fraction of 0.01–1.5 wt.% of the total weight of the hair washing product. Preferred amounts are 0.02–1.4 wt.%, more preferably 0.025–1.25 wt.%, and particularly 0.03–1.1 wt.%.

[0133] In a particularly preferred embodiment, PEG-7 Glyceryl Cocoate is used in the aforementioned amounts in the hair washing products according to the invention.

[0134] Suitable protein hydrolysates are understood to be product mixtures that can be obtained by acid-, basic- or enzymatically catalyzed degradation of proteins.

[0135] Protein hydrolysates of plant, animal and / or marine origin can be used.

[0136] Animal protein hydrolysates include, for example, elastin, collagen, keratin, silk, and milk protein hydrolysates, which can also be present in salt form. Such products are marketed under brand names such as Dehylan® (Cognis), Promois® (Interorgana), Collapuron® (Cognis), Nutrilan® (Cognis), Gelita-Sol® (Deutsche Gelatine Fabriken Stoess & Co), Lexein® (Inolex), and Kerasol® (Croda). Protein hydrolysates of plant origin are preferred, such as soy, almond, rice, pea, potato, and wheat protein hydrolysates. These products are available under brand names such as Gluadin® (Cognis), DiaMin® (Diamalt), Lexein® (Inolex), and Crotein® (Croda).

[0137] Cationic protein hydrolysates can also be used, whereby the underlying protein hydrolysate can originate from animals, for example from collagen, milk, or keratin; from plants, for example from wheat, corn, rice, potatoes, soy, or almonds; from marine life forms, for example from fish collagen or algae; or from biotechnologically produced protein hydrolysates. The protein hydrolysates underlying the cationic derivatives can be obtained from the corresponding proteins by chemical hydrolysis, in particular alkaline or acidic hydrolysis, by enzymatic hydrolysis, and / or a combination of both hydrolysis methods. The hydrolysis of proteins generally yields a protein hydrolysate with a molecular weight distribution of approximately 100 Daltons to several thousand Daltons. Cationic protein hydrolysates whose underlying protein fraction has a molecular weight of 100 to 25,000 Daltons are preferred.preferably exhibits a hydrolysate hardness of 250 to 5000 Daltons. Furthermore, cationic protein hydrolysates include quaternized amino acids and mixtures thereof. The quaternization of the protein hydrolysates or the amino acids is frequently carried out using quaternary ammonium salts such as N,N-dimethyl-N-(n-alkyl)-N-(2-hydroxy-3-chloro-n-propyl)-ammonium halides. The cationic protein hydrolysates may also be further derivatized. Typical examples of cationic protein hydrolysates and derivatives include the following products known under INCI names and available commercially: Cocodimonium Hydroxypropyl Hydrolyzed Collagen, Cocodimonium Hydroxypropyl Hydrolyzed Casein, Cocodimonium Hydroxypropyl Hydrolyzed Collagen, Cocodimonium Hydroxypropyl Hydrolyzed Hair Keratin, Cocodimonium Hydroxypropyl Hydrolyzed Keratin, Cocodimonium Hydroxypropyl Hydrolyzed Rice Protein, Cocodimonium Hydroxypropyl Hydrolyzed Silk.Cocodimonium Hydroxypropyl Hydrolyzed Soy Protein, Cocodimonium Hydroxypropyl Hydrolyzed Wheat Protein, Cocodimonium Hydroxypropyl Silk Amino Acids, Hydroxypropyl Arginine Lauryl / Myristyl Ether HCl, Hydroxypropyltrimonium Gelatin, Hydroxypropyltrimonium Hydrolyzed Casein, Hydroxypropyltrimonium Hydrolyzed Collagen, Hydroxypropyltrimonium Hydrolyzed Conchiolin Protein, Hydroxypropyltrimonium Hydrolyzed Keratin, Hydroxypropyltrimonium Hydrolyzed Rice Bran Protein, Hydroxyproypltrimonium Hydrolyzed Silk, Hydroxypropyltrimonium Hydrolyzed Soy Protein, Hydroxypropyl Hydrolyzed Vegetable Protein, Hydroxypropyltrimonium Hydrolyzed Wheat Protein, Hydroxypropyltrimonium Hydrolyzed Wheat Protein / Siloxysilicate, Laurdimonium Hydroxypropyl Hydrolyzed Soy Protein, Laurdimonium Hydroxypropyl Hydrolyzed Wheat Protein, Laurdimonium Hydroxypropyl Hydrolyzed Wheat Protein / Siloxysilicate, Lauryldimonium Hydroxypropyl Hydrolyzed Casein, Lauryldimonium Hydroxypropyl Hydrolyzed Collagen,Lauryldimonium Hydroxypropyl Hydrolyzed Keratin, Lauryldimonium Hydroxypropyl Hydrolyzed Silk, Lauryldimonium Hydroxypropyl Hydrolyzed Soy Protein, Steardimonium Hydroxypropyl Hydrolyzed Casein, Steardimonium Hydroxypropyl Hydrolyzed Collagen, Steardimonium Hydroxypropyl Hydrolyzed Keratin, Steardimonium Hydroxypropyl Hydrolyzed Rice Protein, Steardimonium Hydroxypropyl Hydrolyzed Silk, Steardimonium Hydroxypropyl Hydrolyzed Soy Protein, Steardimonium Hydroxypropyl Hydrolyzed Vegetable Protein, Steardimonium Hydroxypropyl Hydrolyzed Wheat Protein, Steartrimonium Hydroxyethyl Hydrolyzed Collagen, Quaternium-76 Hydrolyzed Collagen, Quaternium-79 Hydrolyzed Collagen, Quaternium-79 Hydrolyzed Keratin, Quaternium-79 Hydrolyzed Milk Protein, Quaternium-79 Hydrolyzed Silk, Quaternium-79 Hydrolyzed Soy Protein, Quaternium-79 Hydrolyzed Wheat Protein.,

[0138] The weight fraction of the protein hydrolysate(s) in the total weight of the hair washing product is preferably 0.001 to 1 wt.%, more preferably 0.005 to 1 wt.% and in particular 0.01 to 1 wt.%.

[0139] Suitable vitamins preferably include the following vitamins, provitamins and vitamin precursors, as well as their derivatives:

[0140] • Vitamin A: The group of substances referred to as vitamin A includes retinol (vitamin A1) and 3,4-didehydroretinol (vitamin A2). Beta-carotene is the provitamin of retinol. Examples of vitamin A components include retinoic acid and its esters, vitamin A aldehyde, and vitamin A alcohol, as well as its esters such as vitamin A and acetate.

[0141] • Vitamin B: The vitamin B group or vitamin B complex includes, among others, vitamin B1 (thiamine), vitamin B2 (riboflavin), and vitamin B3. The compounds nicotinic acid and nicotinamide (niacinamide) are often referred to under this name. Vitamin B5 (pantothenic acid and panthenol). Panthenol is the preferred form of this group. Usable derivatives of panthenol include, in particular, its esters and ethers, pantolactone, and cationically derivatized panthenols. Examples include panthenol triacetate, panthenol monoethyl ether and its monoacetate, as well as cationic panthenol derivatives. Vitamin B1 (pyridoxine, pyridoxamine, and pyridoxal).

[0142] • Vitamin C (ascorbic acid): the use of the palmitic acid ester, glucosides, or phosphates may be preferred. Use in combination with tocopherols may also be preferred.

[0143] • Vitamin E (tocopherols, especially α-tocopherol).

[0144] • Vitamin F: The term “Vitamin F” usually refers to essential fatty acids, especially linoleic acid, linolenic acid, and arachidonic acid. • Vitamin H: Vitamin H refers to the compound (3aS,4S,6aR)-2-oxohexahydrothienol[3,4-d]-imidazole-4-valeric acid, for which the common name biotin has become more widely accepted.

[0145] Vitamins, provitamins and vitamin precursors from groups A, B, E and H are particularly preferred. Nicotinamide, biotin, pantolactone and / or panthenol are especially preferred.

[0146] The weight fraction of the vitamin(s), vitamin derivative(s), and / or vitamin precursor(s) in the total weight of the hair wash is preferably 0.001 to 1 wt.%, particularly preferably 0.005 to 1 wt.%, and especially 0.01 to 0.5 wt.%.

[0147] It was found that the hair washing products according to the invention are also suitable for use as an anti-dandruff preparation.

[0148] The weight fraction of anti-dandruff agents in the total weight of the hair cleansing agents can preferably be 0.01 to 1 wt.%, more preferably 0.025 to 1 wt.%, particularly preferably 0.05 to 1 wt.% and especially 0.075 to 1 wt.%.

[0149] Suitable anti-dandruff agents may be selected from piroctone olamine, climbazole, zinc pyrithione, ketoconazole, salicylic acid, sulfur, selenium sulfide, tar preparations, undecenic acid derivatives, burdock root extracts, poplar extracts, nettle extracts, walnut shell extracts, birch extracts, willow bark extracts, rosemary extracts, arnica extracts, propanediol (di)caprylate (for example, the product known under the trade name Crinipan® Green) and / or caproyl / lauroyl lactylate (for example, the product known under the trade name Dermosoft® decalact).

[0150] Climbazole, piroctone olamines, propanediol (di)caprylate, caproyl / lauroyl lactylate or mixtures thereof are preferred.

[0151] Other active ingredients, excipients and additives that may preferably be included in the cosmetic cleaning agents according to the invention are, for example:

[0152] Solubilizing agents such as PEG-40 Hydrogenated Castor Oil, PEG-60 Hydrogenated Castor Oil, and mixtures thereof,

[0153] Thickening agents such as PEG-120 methylglucose dioleate, alkali metal salts or mixtures thereof, perfumes,

[0154] - UV filter,

[0155] Structuralants such as maleic acid,

[0156] Dimethyl isosorbide

[0157] Cyclodextrins, fiber-improving agents, in particular mono-, di- and oligosaccharides such as glucose, galactose, fructose, fruit sugar and lactose, colorants for coloring the product, active ingredients such as bisabolol and / or allantoin,

[0158] Complexing agents such as EDTA, NTA, β-alanine diacetic acid and phosphonic acids,

[0159] Ceramides. Ceramides are understood to be N-acylsphingosine (fatty acid amides of sphingosine) or synthetic analogs of such lipids (so-called pseudo-ceramides), propellants such as propane-butane mixtures, N2O, dimethyl ether, CO2 and air, antioxidants,

[0160] Preservatives, such as sodium benzoate or salicylic acid.

[0161] Preferably, the hair washing agent according to the invention has a viscosity in the range of 3,500 mPas to 20,000 mPas, preferably from 4,500 mPas to 17,500 mPas, particularly preferably from 5,000 mPas to 15,000 mPas and especially preferably from 6,000 mPas to 12,500 mPas (Brookfield rotational viscometer RVDV2T; 20°C; spindle RV S5; 20 rpm).

[0162] Preferably, the hair washing product according to the invention has a pH value in the range of 3.0 - 6.0, preferably of 4.0 - 5.0.

[0163] A second object of the invention is the use of the silicone-free hair wash to improve the care properties of hair, in particular to improve combability and smoothness of hair and to reduce hair breakage.

[0164] Regarding further preferred embodiments of the use according to the invention, what has been said about the compositions according to the invention applies.

[0165] The following examples are intended to illustrate the subject matter of the present invention without limiting it.

[0166] Examples:

[0167] The following hair washing products according to the invention were produced (the quantities given refer to [wt.%]):

[0168] * Microcare® Quat LDG (INCI: Dioleylethyl Dimonium Chloride, Glyceryl Oleate, Oleic Alcohol); AS Diesterquat approx. 25% (Thor)

[0169] ** Plantsil® XCITE 350 (INCI: Hydrogenated Ethlyhexyl Olivate and Hydrogenated Olive Oil Unsaponifiables) (Natura-Tech)

[0170] *** Citropol®H (INCI name: Polycitronellol); P2 Science

[0171] Shampoo No. 6 was compared with a shampoo which contained a corresponding amount of silicone (Dimethicone) instead of the conditioning agents b) and c) (Dioleylethyl Dimonium Chloride and Polycitronellol).

[0172] The shampoos were used in a half-head test and evaluated by experienced hairdressers. 5.5 g of each shampoo was applied to one side of wet hair, massaged in as usual, and rinsed out in the same way with the same amount of water. The hairdressers then assessed various hair care parameters, assigning grades from 1 (poor) to 6 (very good). The results are shown in the table below, where an arithmetic mean (Wilcoxon signed-rank test) was calculated from the individual evaluation results:

Claims

Patent claims:

1. Silicone-free shampoo containing in a cosmetic carrier a) at least one anionic, amphoteric and / or zwitterionic surfactant, b) at least one diesterquat of the following formula (II) wherein Ri, R2 are the same or different and represent a Ci-C4 alkyl group, R3, R4 are the same or different and represent the grouping -CH2-CH(R5)-ORe, in which R5 stands for H or for an O-Ce alkyl group, Re represents an acyl group of a saturated or at least monounsaturated carboxylic acid with a carbon chain length of 18 to 24 carbon atoms, and X- represents a halide, methyl sulfate, ethyl sulfate, maleate, fumarate, citrate, lactate, oxalate, tartrate or acetate ion, and c) at least one lipophilic hair care active ingredient of plant origin.

2. Silicone-free hair wash according to claim 1, comprising (based on the total weight of the hair wash) ai) 1 - 20 wt.% of at least one anionic surfactant aii) 0.5 - 10 wt.% of at least one amphoteric and / or zwitterionic surfactant aiii) or mixtures of surfactants (i) and (ii).

3. Silicone-free hair wash according to one of the preceding claims, comprising as diesterquat b) according to general formula (II) at least one compound known under the INCI name Dioleylethyl Dimonium Chloride.

4. Silicone-free hair wash according to any of the preceding claims, comprising at least one diesterquat b) according to the general formula (II) in a weight fraction of 0.01 - 2 wt.% of the total weight of the hair care product.

5. Silicone-free hair wash according to one of the preceding claims, comprising as a lipophilic active ingredient of plant origin c) at least one compound selected from c1) plant oils c2) optionally hydrogenated mono- and / or diesters of saturated or unsaturated, linear or branched C8-C24 fatty acids with saturated or unsaturated, linear or branched C3-C24 alcohols c3) terpene homopolymers and / or derivatives of terpene homopolymers c4) any mixtures of c1) - c3).

6. Silicone-free hair wash according to one of the preceding claims, containing at least one oil and / or oil derivative of vegetable origin in a weight fraction of 0.1 - 1.5 wt.% of the total weight of the hair wash.

7. Silicone-free shampoo according to any one of the preceding claims, comprising as c1) optionally hydrogenated amaranth seed oil, apricot kernel oil, argan oil, avocado oil, babassu oil, cottonseed oil, borage seed oil, camelina oil, canola oil, cranberry oil, safflower oil, peanut oil, pomegranate seed oil, grapefruit seed oil, hemp oil, rosehip seed oil, hazelnut oil, elderberry seed oil, blackcurrant seed oil, jojoba oil, cocoa butter, coconut oil, pumpkin seed oil, linseed oil, macadamia nut oil, corn germ oil, mallow oil, almond oil, mango kernel oil, marula oil, poppy seed oil, evening primrose oil, olive oil, palm oil, palm kernel oil, peach kernel oil, rambutan oil, rapeseed oil, rice bran oil, castor oil, sacha inchi oil, safflower oil, sea buckthorn pulp oil, sea buckthorn kernel oil, sasanqua oil, sesame oil, Shea butter, soybean oil, sunflower oil, tea tree oil, grapeseed oil, tsubaki oil, walnut oil, wheat germ oil, meadowfoam oil, rosehip oil or any mixtures thereof.

8. Silicone-free hair wash according to any of the preceding claims, comprising as c2) compounds or mixtures thereof known under the INCI names Glyceryl Oleate, Hydrogenated Ethylhexyl Olivate.

9. Silicone-free hair wash according to any of the preceding claims, comprising as c3) citrrollenol homopolymers and / or derivatives of citrrollenol homopolymers.

10. Silicone-free hair wash according to any of the preceding claims, containing 0.1–10 wt.% of at least one further conditioning agent selected from the group of (i) O2-O6 polyols (ii) Trimethylglycin (iii) cationic polymers of natural origin (iv) or mixtures thereof.

11. Silicone-free hair wash according to one of the preceding claims, comprising at least two further conditioning active ingredients selected from among the INCI names (i) Glycerines, (ii) Betaine (iii) Hydroxypropyl Guar Hydroxypropyltrinonium Chloride and / or Guar Hydroxypropyltrimonium Chloride known compounds.

12. Silicone-free hair wash according to any of the preceding claims, comprising at least one hydrogenated triglyceride in a weight fraction of 0.01 - 10 wt.% of the total weight of the hair wash.

13. Silicone-free hair wash according to claim 12, comprising a hydrogenated triglyceride known under the INCI name Hydrogenated Castor Oil.

14. Silicone-free hair wash according to any of the preceding claims, containing at least one hydroxycarboxylic acid in a weight fraction of 0.1 - 5.0 wt.% of the total weight of the product.

15. Cosmetic use of a silicone-free hair wash according to one of the preceding claims for improving the care properties of hair, in particular for improving combability and smoothness of hair and for reducing hair breakage.

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