WO2021156213A1 - Lipid nanoparticles for delayed delivery of fragrance with enhanced water solubility, their preparation and use - Google Patents

Lipid nanoparticles for delayed delivery of fragrance with enhanced water solubility, their preparation and use Download PDF

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Publication number
WO2021156213A1
WO2021156213A1 PCT/EP2021/052339 EP2021052339W WO2021156213A1 WO 2021156213 A1 WO2021156213 A1 WO 2021156213A1 EP 2021052339 W EP2021052339 W EP 2021052339W WO 2021156213 A1 WO2021156213 A1 WO 2021156213A1
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component
carbon atoms
group
alkyl
mixtures
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PCT/EP2021/052339
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French (fr)
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Siddheshwar Bhaskar JAGTAP
Jayavant Ratan SHIRKE
Nagesh Appasaheb WAGDARE
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Clariant International Ltd
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Publication of WO2021156213A1 publication Critical patent/WO2021156213A1/en

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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0295Liquid crystals
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/14Liposomes; Vesicles
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/37Esters of carboxylic acids
    • A61K8/375Esters of carboxylic acids the alcohol moiety containing more than one hydroxy group
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q13/00Formulations or additives for perfume preparations
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions
    • C11D11/0094Process for making liquid detergent compositions, e.g. slurries, pastes or gels
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0013Liquid compositions with insoluble particles in suspension
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005Other compounding ingredients characterised by their effect
    • C11D3/001Softening compositions
    • C11D3/0015Softening compositions liquid
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/50Perfumes
    • C11D3/502Protected perfumes
    • C11D3/505Protected perfumes encapsulated or adsorbed on a carrier, e.g. zeolite or clay
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/41Particular ingredients further characterized by their size
    • A61K2800/412Microsized, i.e. having sizes between 0.1 and 100 microns
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/41Particular ingredients further characterized by their size
    • A61K2800/413Nanosized, i.e. having sizes below 100 nm

Definitions

  • Lipid nanoparticles for delayed delivery of fragrance with enhanced water solubility their preparation and use
  • the invention relates to lipid nanoparticles comprising fragrance and to the use thereof in cosmetic formulations or in laundry applications.
  • fragrances are usually mixed directly into the compositions, for example shampoos, shower gels, face cleansers, solid or liquid soaps or creams and lotions and leave on products in haircare.
  • This procedure has the disadvantage that in most cases upon use only small amounts of the fragrance remain on the skin, on the hair or on the fabric, which can develop their effect there.
  • the majority of the fragrances is usually washed off during use. This leads to large amounts of costly fragrances having to be incorporated into the formulations in order to achieve a desired effect.
  • Fragrances are volatile substances.
  • Various approaches of encapsulation have already been used to avoid premature delivery of fragrances. Examples thereof are polymeric encapsulation or inorganic encapsulation. These approaches have been carried out for the development of long-lasting fragrance delivery systems.
  • Polymeric capsules such as melamine formaldehyde, polyacrylates or polyurethanes usually result in microcapsules with particle size above 1 micron with pressure triggered release in laundry applications.
  • the pressure-triggered capsules rather release the fragrances quickly with friction hence fragrance long-lasting is not prolonged. Diffusion controlled-release would be desired for the prolonged fragrance long-lasting in laundry, cosmetics and hair care products.
  • EP 1 964544 A1 discloses sensitive skin perfumes. These may be encapsulated within a water-insoluble aminoplast capsule.
  • WO 2008/061384 A1 discloses a batch process for preparation of an emulsion comprising lamellar liquid crystal particles containing fragrance.
  • the process comprises blending the fragrance with emulsifiers capable of forming liquid- crystalline structures, at least one fatty alcohol co-emulsifier having at least 22 carbon atoms, an amphiphilic reinforcing material and a selected wax and adding water slowly to the fragrance mixture thus formed and mixing under shear conditions to obtain a stable emulsion.
  • a selected surfactant system is used.
  • compositions for the targeted release of fragrances and aromas In the encapsulation process a polyol phase A is used in combination with a phase B comprising fragrance, carrier and emulsifier. In the encapsulation process solid lipid nanoparticle dispersions (SLN) are formed.
  • SSN lipid nanoparticle dispersions
  • WO 1999/055819 A1 discloses encapsulation of perfume oil for delivery of high impact accord perfume ingredients with modified starch and starch as shell by spray drying method.
  • the high impact perfume ingredients have a boiling point of 275°C or lower and a calculated log P value of 2 or higher. These encapsulated particles are useful in laundry compositions especially for detergent compositions.
  • WO 2019/115621 A1 discloses the encapsulation of fragrances in a multilamellar vesicle.
  • Vesicles having a particle size e.g. in the range from 100 to 800 nm are produced which contain two or more concentric lipid double layers and fragrance.
  • the double layer of the vesicles comprise at least one surfactant having an HLB value of greater than 6 and an amphiphilic compound having a log P value of 1 or above.
  • the vesicles with encapsulated fragrance provide a long-lasting fragrance- release in cosmetic formulations and in laundry formulations.
  • Encapsulation of fragrances and especially water-soluble fragrances in aqueous media is always a challenge.
  • the water-soluble ingredients of the fragrances diffuse through the encapsulating membrane into the aqueous medium. Such diffusion of ingredients results in a phase separation in the formulation.
  • fragrances having components with log P values of less than 1 comprise water-soluble ingredients which can diffuse through shell membranes into the surrounding aqueous medium or can even avoid the formation of shell membranes.
  • Fragrances with enhanced water-solubility comprise - besides water-insoluble components - also water-soluble ingredients. Said ingredients are added to alter the olfactory characteristics of a fragrance.
  • Water-soluble diluents have multiple advantages in the fragrance like to dilute the fragrance strength, as viscosifier (see EP 0816484 A2), or to reduce and mask the odor of the blend (see US 3,759,806).
  • fragrances comprising water-soluble components
  • it would be possible to use smaller amounts of fragrance meaning that the cosmetic or laundry formulations could be produced more cost- efficient.
  • fragrance compositions comprising water- soluble diluents and odor forming compounds over a broad range of partition coefficients (“log P”) can be encapsulated in lipid nanoparticles comprising selected additives.
  • These lipid nanoparticles are preferably sub-micron particles with narrow particle size distribution and with high encapsulation efficiency of fragrance.
  • the encapsulated fragrance is stable under storage conditions and will have long-lasting fragrance release on use thereof.
  • the lipid nanoparticles can encapsulate fragrances with enhanced water-solubility and also offer its long-lasting release on use. The long-lasting release of fragrances is a key requirement of laundry, cosmetic and hair care products.
  • the present invention relates to lipid nanoparticles, preferably to vesicles in the shape of a rotational body comprising at least one, preferably two or more, preferably concentric, lipid double layers and fragrance, wherein the lipid nanoparticle comprises a) one or more surfactants having an HLB value of greater than 6, and b) one or more amphiphilic compounds having a log P value of 1 or greater than 1 , and c) one or more odor forming compounds, and d) one or more diluents selected from the group consisting of aliphatic C1-C6 alcohols, polyols having 3 to 6 carbon atoms and 3 to 6 hydroxy groups, alkylene glycols having 2 to 6 carbon atoms, polyalkylene glycols having alkyleneoxy units of 2 to 6 carbon atoms and from 2 to 6, preferably 2 to 4 repeating units, wherein one or more of the hydroxyl groups of the aforementioned alcohols, polyols, alkylene glycols and poly
  • the lipid nanoparticles of the present invention preferably are sub-micron particles with narrow particle size distribution and with high encapsulation efficiency of fragrance.
  • the encapsulated fragrance is stable under storage conditions and has long-lasting fragrance release on use thereof. Since the effectiveness of fragrances contained in the lipid nanoparticles according to the present invention can be increased during use, it is possible to use smaller amounts of fragrance, meaning that cosmetic or laundry compositions can be produced more cost- efficient.
  • Surfactant of component a) is characterized by its HLB value of greater than 6.
  • hydrophilic-lipophilic balance The nature of a surfactant is represented by the hydrophilic-lipophilic balance of the molecule.
  • the degree of this hydrophilic-lipophilic balance can be determined by calculating values for the different regions of the molecule, as described by Griffin in 1949 and 1954. Griffin's method has been primarily developed for non ionic surfactants as described in 1954 and works as follows:
  • M h is the molecular mass of the hydrophilic portion of the molecule, and M is the molecular mass of the whole molecule, giving a result on a scale of 0 to 20.
  • An HLB value of 0 corresponds to a completely lipophilic molecule, and a value of 20 corresponds to a completely hydrophilic molecule.
  • HLB HLB as used in this specification for nonionic surfactants is calculated by the above formula. The method of Griffin is published, for example, in Journal of the Society of Cosmetic Chemists, 5 (4), 249-256 (1954).
  • HLB as used in this specification for anionic, cationic or amphoteric surfactants is calculated by the method of Davies. This method is published, for example, in Gas/Liquid and Liquid/Liquid Interfaces, Proceedings of 2 nc * International Congress Surface Activity, pp. 426-438, Butterworths, London 1957.
  • Amphiphilic compound of component b) is characterized by its log P value of > 1.
  • the amphiphilic character of component b) can be determined by its partition coefficient between octanol and water.
  • the octanol-water partition coefficient (log P) is a measure of the distribution of a substance between the aqueous and the organic octanol phase and is defined as follows
  • the vesicles of the present invention are multilamellar vesicles in the shape of a rotational body comprising two or more concentric lipid double layers.
  • the shape of the vesicles of the present invention is spherical, ellipsoidal or disk-like.
  • the vesicles of the present invention may also have another shape of a solid of revolution.
  • the mean diameter of the lipid nanoparticles of the present invention preferably is from 80 to 800 nm, more preferably from 100 to 700 nm, even more preferably from 120 to 500 nm, particularly preferably from 150 to 480 nm, and especially preferably from 210 to 460 nm.
  • the mean diameter is determined by laser diffraction analysis, for example by using a Horiba LA 940 or Mastersizer 3000 from Malvern using the “Mie Scattering Theory” evaluation.
  • lipid nanoparticles having axes of different length such as lipid nanoparticles having the shape of an ellipsoid or of a disk
  • the largest axis determines the mean diameter
  • the lipid nanoparticles of the present invention have a narrow particle size distribution of Gaussian shape.
  • the standard deviation of the particle size distribution is between 10% and 90% of the mean diameter.
  • the lipid nanoparticles of the present invention contain at least one fragrance which comprises at least one odor forming compound c) and at least one selected diluent, component d).
  • Preferred ingredients of the fragrance encapsulated in the vesicles of the present invention are one or more odor forming compounds c) having a log P value of 1 or greater than 1 and/or one or more odor forming compounds c) having a log P value smaller than 1.
  • the term “log P” has been defined above.
  • the fragrance comprising components c) and d) is an additional component present in the vesicles besides components a), b) and e).
  • the lipid nanoparticles of the present invention may incorporate high amounts of one or more fragrances comprising components c) and d) discussed in detail below, for example more than 25 % by weight, based on the total weight of the vesicle. But lipid nanoparticles having lower amounts of fragrance(s) are also possible.
  • the lipid nanoparticles of the present invention may optionally contain co-surfactants as component f) in addition to components a) to e) and optional components g) and/or h) described below.
  • Co-surfactants are surfactants which are not capable of forming micelles.
  • a co-surfactant is any amphiphilic substance having an HLB value ⁇ 6.
  • Preferred co-surfactants have an HLB value from 2 to 6.
  • the lipid nanoparticles of the present invention may optionally contain waxes as component g) in addition to components a) to e) and optional components f) and/or h) described below.
  • the lipid nanoparticles of the present invention in addition to components a) to e) and optional components f) and/or g) may optionally contain as component h) one or more humectants selected from the group consisting of polyols having 3 to 6 carbon atoms and 3 to 6 hydroxyl groups, hydroxy carboxylic acids, esters from polyols having 3 to 6 carbon atoms and 3 to 6 hydroxyl groups, wherein at least one hydroxyl group of the polyol is esterified with an aliphatic monocarboxylic acid having 1 to 4 carbon atoms and mixtures thereof.
  • humectants selected from the group consisting of polyols having 3 to 6 carbon atoms and 3 to 6 hydroxyl groups, hydroxy carboxylic acids, esters from polyols having 3 to 6 carbon atoms and 3 to 6 hydroxyl groups, wherein at least one hydroxyl group of the polyol is esterified with an aliphatic monocarboxylic acid having 1 to
  • humectants g) are glycerol, trimethylolpropane, pentaerythritol, sugar alcohols, such as sorbitol, xylitol, malitol, glycolic acid, lactic acid, citric acid, mandelic acid, glycerol triacetate, trimethylolpropane triacetate and/or pentaerythritol tetraacetate.
  • Preferred humectant is glycerol.
  • the vesicles of the present invention comprise at least one lipid double layer, preferably several concentric lipid double layers. Although while not being bound by theoretical considerations it is believed that in multilamellar vesicles the lipid double layers are arranged in the form of onion shells. As the fragrance molecules contained in the vesicles of the present invention can only leave the vesicle via the outer surface, this arrangement provides for the increased storage-stability and retarded release of the fragrance from the vesicles.
  • the layer(s) of the lipid nanoparticles of the present invention can adopt a solid gel phase state at lower temperatures but may undergo phase transition to a fluid state at higher temperatures, and the chemical properties of the amphiphilic compounds contained in the lipid nanoparticles influence at which temperature this will happen.
  • a solid gel state of the layer(s) is preferred.
  • the temperature for the phase transition depends very much on the solidification point of the amphiphilic components.
  • the temperature for the phase transition can be determined, for example, by differential scanning calorimetry (DSC).
  • the temperature for the phase transition from a solid gel phase state to a fluid state may be modified within a broad temperature range.
  • lipid nanoparticles of the present invention having a phase transition from a solid gel phase state to a fluid state within a range from 30°C to 130°C, preferably from 40°C to 120°C. This temperature range is preferably chosen for optimum release kinetics and protection of the lipid nanoparticle against heat.
  • the lipid nanoparticles of the present invention are formed from a selected combination of fragrances with surfactants of component a) and compounds defined above as components b) to e) which may optionally contain in addition components f) and/or g) and/or h).
  • mixtures of fragrances comprising components c) and d) with selected components a), b) and e) and optionally with components f) and/or g) and/or h) form lipid nanoparticles, preferably vesicles having lamellar liquid-crystalline structures.
  • Such structures can be determined by means of optical microscopy using a polarization microscope.
  • lamellar liquid-crystalline structures can be determined by TEM or TEM-freeze fracture technology. Appropriate techniques are known to the person skilled in the art.
  • the mixtures of fragrances comprising components c) and d) with components a), b) and e) and optionally with components f) and/or g) and/or h) forming the lipid nanoparticles of the present invention are chosen so that preferably a lamellar structure is formed.
  • suitable amounts of the fragrances comprising components c) and d) and components a), b) and e) and optionally with components f) and/or g) and/or h) is possible through simple manual experiments.
  • the mixtures of fragrances comprising components c) and d) with components a), b) and e) and optionally with components f) and/or g) and/or h) forming the lipid nanoparticles of the invention are chosen so that in water or selected aqueous media lipid nanoparticles, preferably lamellar vesicles are obtainable which preferably have an average diameter of 800 nm or less than 800 nm.
  • the aqueous media may contain additional additives, such as electrolytes, polyols such as glycerol, polyethylene glycol or propylene glycol, water-soluble vitamins or rheology modifiers, such as natural biopolymers, preferably one or more natural biopolymers selected from the group consisting of xanthan gum, guar gum, gellan gum, gum arabic and mixtures thereof.
  • additional additives such as electrolytes, polyols such as glycerol, polyethylene glycol or propylene glycol, water-soluble vitamins or rheology modifiers, such as natural biopolymers, preferably one or more natural biopolymers selected from the group consisting of xanthan gum, guar gum, gellan gum, gum arabic and mixtures thereof.
  • the lipid nanoparticles of the present invention contain fragrances comprising components c) and d) and components a), b) and e) and optionally components f) and/or g) and/or h) which are believed to form lyotropic lamellar liquid-crystalline phases. It is believed that the formation of liquid-crystalline structures is essentially dependent on the geometry of components a) to e) and optional components f) and/or g) and/or h), which can be expressed by the packing parameter PP.
  • a packing parameter PP can be assigned to a chemical species, for example to a component a), b) or e) or to a component c) or d) present in the fragrance.
  • a packing parameter of a mixture is defined by the following formula:
  • PPi is the packing parameter of the single species i
  • ci is the concentration of the single species i in weight percent
  • ctotal is the total concentration of all i species in the mixture.
  • lyotropic spherical lamellar liquid-crystalline structures are required for entrapping fragrances comprising components c) and d) and are formed by components a), b) and e) optionally in combination with components f) and/or g) and/or h) at a resulting packing parameter PPmixture of at least 0.5 and preferably in the range from 0.5 to 1.
  • Preferred lipid nanoparticles of the present invention are vesicles comprising components a) to e) and optionally component f) and/or component g) and/or component h) and wherein the packing parameter of the mixture of components a) to e) and optionally component f) and/or component g) and/or component h) has a value of 0.5 or greater than 0.5 and preferably is in the range from 0.5 to 1.
  • components a), b) and e) and optionally components f) and/or g) and/or h) maybe present in lyotropic lamellar liquid- crystalline phases and in the lyotropic state, fragrance molecules are stored, for example, between the components forming the required vesicle structure.
  • the hydrophilic moiety of a component can be varied according to the desired adhesion to a later substrate.
  • the hydrophilic moiety can be varied for adhesion to the human skin or to textile fibers.
  • Lipid nanoparticles of the present invention are preferably formed when the packing parameter of the mixture of all participating surfactants and amphiphilic molecules is 0.5 or greater than 0.5, more preferably in the range from 0.5 to 1. This range is valid for spherical lipid nanoparticles, preferably spherical vesicles. If the shape of the lipid nanoparticles is ellipsoid or disk like the packing parameter value shifts to higher values.
  • HLB values may be correlated to the packing parameter and to log P values.
  • fragrances into the lamellar structure of the vesicles will modify the value of the packing parameter of the mixture of the vesicle loaded with the fragrance.
  • the packing of lipids within the double-layer also affects its mechanical properties, including its resistance to stretching and bending and including the release kinetics and/or release concentration of the encapsulated fragrances.
  • the lipid nanoparticles preferably the vesicles of the present invention can encapsulate components c) and d) of fragrances with a very broad log P range.
  • lipid nanoparticles preferably of vesicles with entrapped component c) and d) comprising fragrances
  • components a), b) and e) and optionally f) and/or g) and/or h) are required having a sufficient high packing parameter.
  • the used surfactants of component a) can be of nonionic, anionic, cationic or amphoteric structure. Hence, it is possible to adapt the surface charge of the lipid nanoparticles to the surface charge of the application area of the fragrance. This allows a maximum deposition of fragrances.
  • the one or more surfactants of component a) preferably are selected from the group consisting of nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants and mixtures thereof, provided these have an HLB value of greater than 6.
  • the packing parameter of the one or more surfactants of component a) has a value of 0.5 or greater than 0.5 and more preferably is in the range from 0.5 to 1 .
  • the one or more nonionic surfactants of component a) are selected from the group consisting of polyoxyethylene sorbitan esters, polyoxyethylene sorbitol esters, polyoxyalkylene fatty alcohol ethers, polyoxyalkylene fatty acid esters, alkoxylated glycerides, polyoxyethylene methyl glucoside esters, alkyl polyglucosides, EO-PO blockpolymers (EO: ethylene oxide; PO: propylene oxide), and mixtures thereof.
  • the one or more anionic surfactants of component a) are selected from the group consisting of alkylbenzenesulfonates, alkanesulfonates, olefinsulfonates, alkyl ether sulfates, alkyl sulfates, sulfosuccinates, alkyl phosphates, alkyl ether phosphates, protein fatty acid condensates, preferably collagen hydrolysates modified with fatty acid, amino acid-based surfactants, isethionates, taurides, acyl lactylates, neutralized fatty acids, and mixtures thereof.
  • the one or more cationic surfactants of component a) are selected from the group consisting of esterquats, ditallow dimethyl ammonium chloride, C12/14 alkyl dimethyl benzyl ammonium chloride, alkyl dimethyl benzyl ammonium chlorides, cetyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, behenyl trimethyl ammonium chloride, alkyl hydroxyethyl dimethyl ammonium chlorides, distearyl dimethyl ammonium chloride, dihydrogenated tallow fatty alkyl dimethyl ammonium chloride, and mixtures thereof.
  • the one or more amphoteric surfactants of component a) are selected from the group consisting of alkyl amphoacetates, alkyl amidopropyl betaines, alkyl amidopropyl dimethylamine betaines, undecylenamidopropyl betaine, alkyl dimethyl amine oxides, and mixtures thereof.
  • the lipid nanoparticles of the present invention contain as component a) one or more nonionic surfactants having an HLB value of greater than 6, even more preferably selected from the group consisting of polyoxyalkylene fatty alcohol ethers, polyoxyalkylene fatty acid esters, collagen hydrolysates modified with fatty acid, and mixtures thereof, and particularly preferably selected from the group consisting of polyoxyalkylene C8-C24-fatty alcohol ethers, polyoxyalkylene C8-C24-fatty acid esters, collagen hydrolysates modified with Cs-C24-fatty acid, and mixtures thereof.
  • the one or more surfactants of component a) are selected from polyoxyalkylene Cs-C24-fatty alcohol ethers.
  • the polyoxyalkylene groups preferably are polyoxyethylene groups, preferably with ethoxylation degrees from 5 to 150, more preferably with ethoxylation degrees from 10 to 130 and even more preferably with ethoxylation degrees from 15 to 120 and the fatty alcohol preferably is a Ci2-Ci8-fatty alcohol.
  • the fatty alcohol preferably is linear and preferably is saturated.
  • ethoxylated lauryl alcohol and ethoxylated stearyl alcohol are preferred.
  • the one or more surfactants of component a) are selected from the group consisting of ethoxylated lauryl alcohol with ethoxylation degrees from 20 to 24 or from 90 to 110, preferably from 20 to 24, and more preferably of approximately 23 and ethoxylated stearyl alcohol with ethoxylation degrees from 20 to 24 or from 90 to 110, preferably from 90 to 110, and more preferably of approximately 100, and mixtures thereof.
  • the term “from ... to ...” shall mean that all single values encompassed by this term may be realized but it shall not mean that all values encompassed by this term have to be realized.
  • amphiphilic compounds b) are specific esters of fatty acids, preferably specific triglycerides of fatty acids or specific esters of fatty acids and fatty alcohols or mixtures thereof.
  • Triglycerides of fatty acids or esters of fatty acids and fatty alcohols are amphiphilic components which are not capable of forming micelles.
  • Their amphiphilic character is expressed by the log P value of 1 or greater than 1 , and preferably their log P value is from 1 to 5. For a caprylic/capric acid triglyceride, for example, the log P is 4.
  • Examples of tryglycerides of fatty acids are glycerol esters of one or more fatty acids having 6 to 10 carbon atoms.
  • Examples of esters of fatty acids and fatty alcohols are esters of fatty acids having 8 to 24 carbon atoms and fatty alcohols having 8 to 28 carbon atoms.
  • the fatty acid portions of these esters can be derived from saturated and/or from ethylenically unsaturated aliphatic fatty acids.
  • Unsaturated fatty acids may have one or more ethylenically unsaturated carbon- carbon bonds.
  • the triglycerides comprise fatty acid groups from different fatty acids.
  • the one or more amphiphilic compounds of component b) are selected from the group consisting of triglycerides of one or more fatty acids having 6 to 10 carbon atoms, esters of fatty acids and fatty alcohols, preferably esters of fatty acids having 8 to 24 carbon atoms and fatty alcohols having 8 to 24 carbon atoms, preferably 10 to 18 carbon atoms, and mixtures thereof.
  • amphiphilic compounds b) are cetyl palmitate and/or triglycerides of glycerol with fatty acids selected from the group consisting of caprylic acid, capric acid and mixtures thereof.
  • fragrances are understood as meaning compositions comprising at least one odor forming compound c) and at least one diluent d).
  • mixtures of two or more compounds c) are contained in the fragrances used in this invention.
  • Odor forming compounds c) are generally essential oils, flower oils, extracts from plant and animal drugs, odorants isolated from natural products, chemically modified (semisynthetic) odorants, and odorants obtained by purely synthetic means.
  • the odor forming compounds c) can originate from a large number of herbal starting materials.
  • flowers for example lavender, rose, jasmine, neroli
  • stems and leaves for example from geranium, patchouli, petit grain, fruits such as anis, coriander, caroway, juniper
  • fruit peels for example from agrumes, such as bergamot, lemon, orange
  • seeds such as mace, angelica, celery, cardamom
  • roots such as angelica, costus, iris, calmus
  • wood such as sandalwood, guaiac wood, cedar wood, rosewood
  • herbs and grasses such as tarragon, lemongrass, sage, thyme
  • needles and branches for example from spruce, fir, pine, dwarf-pine
  • resins and balsams for example from galvanum, elemi, benzoin, myrrh, olibanum, opoponax.
  • Animal raw materials for odor forming compounds c) are, for example, ambergris, musk, civet and castoreum.
  • Examples of semisynthetic odor forming compounds c) are isoeugenol, vanillin, hydroxycitronellal, citronellol, geranyl acetate, ionones and methylionones.
  • the completely synthetic odorants or fragrances are very diverse and often orientate themselves to natural substances.
  • Further suitable odor forming compounds c) used in fragrances are known to the person skilled in the art.
  • the odor forming compounds c) in the fragrances used to manufacture the lipid nanoparticles of the present invention preferably contain functional groups of aldehyde, ketone, ester, alcohol, ether or a combination of two or more of these groups.
  • one or more odor forming compounds c) of the fragrance used in the manufacture of the lipid nanoparticles of the present invention have a log P value from 1 to 10, more preferably from 1 to 8.5.
  • Preferred odor forming compounds c) of this type are selected from the group consisting of ethyl butyrate, ethyl 2-methyl butyrate, isoamyl acetate, prenyl acetate, cis-3-hexenyl acetate, hexyl acetate, dextro-limonene, dihydromyrcenol, allyl hexanoate, linalool, 2-phenylethanol, benzyl acetate, heptanoic acid 2-propenyl ester, citronellol, nerol, woody acetate, dimethyl benzyl carbinyl acetate, 3-phenylpropionaldehyde, aldehyde C-14, dimethyl benzy
  • component c) consists of one or more odor forming compounds each having a log P value of 1 or greater than 1 and preferably each having a log P value from 1 to 8.5, or component c) comprises one or more odor forming compounds each having a log P value of 1 or greater than 1 and preferably each having a log P value from 1 to 8.5.
  • component c) comprises one or more odor forming compounds each having a log P value of 1 or greater than 1 and preferably each having a log P value from 1 to 8.5 and in addition comprises one or more odor forming compounds each having a log P value of smaller than 1 and preferably each having a log P value from 0.9 to -4.
  • the lipid nanoparticles of the present invention comprise one or more odor forming compounds c) having a log P value smaller than 1 and preferably from 0.9 to -4.
  • the one or more odor forming compounds c) of this type are selected from the group consisting of ethyl maltol, apple ketal, maltol, maltyl acetate, maple furanone, methyl acetate, acetaldehyde diethyl acetal, acetoin, acetoin acetate, butyric acid, 1 -acetoxyacetone, 2-acetyl furan, 2-furyl methyl ketone, diethyl malate and mixtures thereof.
  • the fragrances comprising odor forming compounds c) and diluents d) are stored in the lipid nanoparticles of the invention.
  • the fragrances are dissolved, and crystallization of the fragrances is prevented.
  • This permits, inter alia, the preparation of cosmetic or laundry formulations with a skin-friendly pH, and by preventing the fragrances from crystallization, the skin friendliness of the composition is increased further.
  • the mixtures of components used according to the invention having the fragrances dissolved therein spread upon application to the skin, meaning that application of the fragrance to the skin is improved.
  • the one or more diluents of component d) are preferably selected from the group consisting of aliphatic C1-C4 alcohols, dialkyl ethers having 3 to 8 carbon atoms, alkylene glycols having 2 to 6 carbon atoms, dialkylene glycols having alkyleneoxy units of 2 to 6 carbon atoms, trialkylene glycols having alkyleneoxy units of 2 to 6 carbon atoms, tetraalkylene glycols having alkyleneoxy units of 2 to 6 carbon atoms, partly or totally Ci-C4-alkyl etherified alkylene glycols having 2 to 6 carbon atoms, partly or totally Ci-C4-alkyl etherified dialkylene glycols having alkyleneoxy units of 2 to 6 carbon atoms, partly or totally Ci-C4-alkyl etherified trialkylene glycols having alkyleneoxy units of 2 to 6 carbon atoms, partly or totally Ci-C4-alkyl etherified tetraalkylene
  • diluents d) are used comprising alkyleneoxy units of 2 to 4 carbon atoms.
  • component d) examples are monohydric aliphatic C1 -C4 alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol and isobutanol or the corresponding alkyl ethers thereof, such as the corresponding methyl ethers or ethyl ethers thereof.
  • Ethanol is a preferred component d).
  • component d) are hydroxyl-terminated ethylene glycols having 2 to 6 carbon atoms, such as ethylene glycol, di-ethylene glycol or tri ethylene glycol; or hydroxyl-terminated propylene glycols having 2 to 9 carbon atoms, such as propylene glycol, di-propylene glycol or tri-propylene glycol; or hydroxyl-terminated butylene glycols having 2 to 12 carbon atoms, such as butylene glycol, di-butylene glycol ortri- butylene glycol; or hydroxyl-terminated pentylene glycols having 2 to 15 carbon atoms, such as pentylene glycol, di-pentylene glycol or tri-pentylene glycol; or hydroxyl- terminated hexylene glycols having 2 to 18 carbon atoms, such as hexylene glycol, di-hexylene glycol or tri-hexylene glycol; or the corresponding mono- ordi-Ci-C
  • Ci-C4-aliphatic alcohol substituted with a 1 ,3-dioxolane ring as component d) is 2,2,4-trimethyl-1,3-dioxolane-2-ethanol.
  • the diluent d) has a log P value of smaller than 1 , more preferably from 0 to -1.
  • the one or more diluents of component d) are selected from the group consisting of monohydric aliphatic C1-C4 alcohols, propylene glycol, di-propylene glycol, tri-propylene glycol, propylene glycol mono-methyl ether, di-propylene glycol mono-methyl ether, tri-propylene glycol mono-methyl ether, propylene glycol mono-ethyl ether, di-propylene glycol mono-ethyl ether, tri-propylene glycol mono-ethyl ether and mixtures thereof.
  • the one or more diluents of component d) are selected from the group consisting of monohydric aliphatic C1-C4 alcohols, propylene glycol, dipropylene glycol, propylene glycol mono methyl ether, propylene glycol mono ethyl ether, dipropylene glycol mono methyl ether, dipropylene glycol mono ethyl ether and mixtures thereof.
  • the fragrance used in the manufacture of the lipid nanoparticles of the present invention is preferably a mixture of one or more compounds c) having a log P value of 1 or greater than 1 and preferably from 1 to 8.5, with one or more diluents d) or in the alternative is preferably a mixture of one or more compounds c) having a log P value of 1 or greater than 1 and preferably from 1 to 8.5, with one or more compounds c) having a log P value smaller than 1 and preferably from 0.9 to -4, with one or more diluents d).
  • the amount of component c) in the fragrance used in the manufacture of the lipid nanoparticles of the present invention preferably is from 40 to 95 % by weight and more preferably from 60 to 90 % by weight, in each case based on the total weight of the fragrance.
  • the amount of component d) in the fragrance used in the manufacture of the lipid nanoparticles of the present invention preferably is from 5 to 60 % by weight and more preferably from 10 to 40 % by weight, in each case based on the total weight of the fragrance.
  • the fragrance comprising components c) and d) which is used in the manufacture of the lipid nanoparticles of the present invention preferably has an interfacial tension of 1 mN/m or greater than 1 mN/m, more preferably from 1 to 60 mN/m and even more preferably from 5 to 30 mN/m.
  • Interfacial tension occurs at the boundary of two immiscible liquids due to the imbalance of intermolecular forces. Interfacial tension is the tendency of an interface to become spherical to make its surface energy as low as possible. Interfacial tension measurement of fragrance samples can be carried out using Kruss GmbH instrument with model no. DSA100S by pendant drop method. An average of three measurements is noted as interfacial tension unit milli-Newtons per meter (mN/m).
  • additives e preferably of those additives e having a log P value from 10 to 50, stabilizes the lipid nanoparticles of the present invention.
  • These lipid nanoparticles contain fragrances with enhanced water- solubility, but they do not show phase separation and have an improved storage- stability in aqueous media.
  • Component e) contained in the lipid nanoparticles of the present invention is an additive being selected from the group consisting of Ci2-C26-fatty acid esters from polyols having 2 to 6 carbon atoms and 2 to 4 hydroxyl groups, wherein at least two hydroxyl groups of the polyols are esterified and the polyols are partly or totally esterified, Ci2-C26-fatty acid esters from polyols having 2 to 6 carbon atoms, 2 to 4 hydroxyl groups and one ether group, wherein at least two hydroxyl groups of the polyols are esterified and the polyols are partly or totally esterified, and mixtures thereof.
  • Ci2-C26-fatty acids used to prepare the esters of component e) may be unsaturated or preferably saturated compounds.
  • unsaturated fatty acids are myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linoleadic acid, alpha-linolenic acid, arachidonic acid, eicosapaentaneonic aicd, erucic acid and docosahexaenoic acid.
  • saturated fatty acids are lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, arachidic acid, behenic acid, lignoceric acid and cerotic acid.
  • Polyols having 2 to 6 carbon atoms and 2 to 4 hydroxyl groups used to prepare the esters of component e) may be unsaturated or preferably saturated compounds, more preferred saturated aliphatic compounds.
  • Examples of polyols are ethylene glycol, propane-1 ,2-diol, propane-1 ,3-diol, butane-1 , 2-diol, butane-1 ,3-diol, butane-1 ,4-diol, butane-2, 3-diol, pentane-1 ,5-diol, hexane-1 ,6-diol, hexane-1 , 2,6- triol, trimethylol- propane, 2, 2-dimethylpropane-1 ,3-diol, glycerol or penthaerithritol.
  • Polyols having 2 to 6 carbon atoms and 2 to 4 hydroxyl groups used to prepare the esters of component e) may have one ether group which may form part of a heterocyclic ring. Examples of these polyols are diglycerol or sorbitan.
  • the esters of component e) have between 2 and 4 ester groups.
  • the one or more additives of component e) are selected from fatty acid esters from polyols, wherein the fatty acid residue comprises 12 to 22, preferably 16 to 20 and more preferably 18 carbon atoms and the polyol has 2 to 6 carbon atoms, 2 to 4 hydroxyl groups and contains either no or one ether group and wherein at least two of the hydroxyl groups of the polyols are esterified and the polyols are partly or totally esterified, and mixtures thereof.
  • the polyol part of the one or more additives of component e) contains one ether group the polyol preferably is diglycerol.
  • the one or more additives of component e) are selected from fatty acid esters of polyols, wherein the fatty acid residue comprises 12 to 22, preferably 16 to 20 and more preferably 18 carbon atoms and the polyol is selected from ethylene glycol, glycerol, diglycerol and/or pentaerythritol and wherein at least two of the hydroxyl groups of the polyols are esterified and the polyols are partly or totally esterified, and mixtures thereof.
  • the fatty acid esters of glycerol are preferably selected from glycerol esters wherein all three hydroxyl groups of the glycerol are esterified (triglycerides).
  • the single additives of the one or more additives of component e) comprise from 38 to 77 carbon atoms.
  • the fatty acid underlying the fatty acid part of the one or more additives of component e) is selected from the group consisting of stearic acid, isostearic acid and mixtures thereof.
  • the one or more additives of component e) have a log P value from 10 to 50 and more preferably from 14 to 40.
  • the additive of component e) is pentaerythritol tetrastearate.
  • lipid nanoparticles of the present invention comprising a) one or more surfactants having an HLB value of greater than 6 and being selected from polyoxyethylene Ci2-Ci8-fatty alcohol ethers with ethoxylation degrees from 10 to 150 and preferably from 15 to 120 and more preferably being selected from the group consisting of ethoxylated lauryl alcohol and ethoxylated stearyl alcohol, each with ethoxylation degrees from 15 to 120 and mixtures thereof, and b) one or more amphiphilic compounds having a log P value from 1 to 5 and being selected from the group consisting of triglycerides of glycerol with one or more fatty acids having 8 to 10 carbon atoms, esters of fatty acids having 8 to 24 carbon atoms and fatty alcohols having 10 to 18 carbon atoms and mixtures thereof, and preferably being selected from the group consisting of cetyl palmitate and triglycerides of glycerol with caprylic acid and/or capric acid, and mixture
  • Suitable co-surfactants of component f) are sorbitan esters, citric esters, lactic esters, partial fatty acid glycerides, polyglycerides, glycerol esters, polyglycerol esters, sorbitol esters, fatty alcohols, propylene glycol esters, methyl glucoside esters, alkyl polyglucosides, sugar esters or mixtures of two or more thereof.
  • Examples of preferred co-surfactants f) are glycerol monostearate, glycerol monopalm itate, glycerol mono-dipalmitate, glycerol monobehenate, glycerol mono- dibehenate, glycerol monooleate, glycerol mono-dioleate, sorbitan tristearate, sorbitan monooleate, sorbitan trioleate, sorbitan tribehenate, propylene glycol monolaurate, propylene glycol monopalm itate, propylene glycol monostearate, propylene glycol monooleate, propylene glycol monobehenate, sorbitan sesquioleate, glycerol stearate, sorbitan monostearate, sorbitan stearate, sorbitan isostearate, glycerol laurateand mixtures thereof. These compounds have HLB- values from 2.5 to 5.2.
  • Suitable waxes of component g) are waxes of the mono ester type.
  • waxes are amphiphilic their amphiphilic behavior may be specified by log P values.
  • Preferred waxes have log P values of 4.7 or greater than 4.7, more preferably of 6 or greater than 6.
  • log P values As their hydrocarbon number increases above C 13 , as is the case for the majority of the wax constituents, log P values of 6 or greater than 6 are found.
  • Waxes are furthermore characterized by their solidification point, which is typically between 30 and 100°C. Waxes are organic compounds that characteristically consist of long alkyl chains. They may also include various functional groups such as fatty acids, primary and secondary long chain alcohols, unsaturated bonds, aromatics, amides, ketones, and aldehydes. They frequently contain fatty acid esters as well.
  • Waxes used as component g) in the present invention can be synthetic ones, animal or plant derived or montan waxes.
  • the amount of surfactant(s) of component a) of the lipid nanoparticles of the present invention can vary over a broad range. Typical amounts of these surfactant(s) in the lipid nanoparticles of the present invention may be from 1 to 95 % by weight and preferably from 10 to 40 % by weight, in each case based on the total weight of the lipid nanoparticles.
  • the amount of amphiphilic compounds of component b) of the lipid nanoparticles of the present invention can vary over a broad range. Typical amounts of amphiphilic compounds of component b) in the lipid nanoparticles of the present invention may be from 1 to 95 % by weight and preferably from 10 to 40 % by weight, in each case based on the total weight of the lipid nanoparticles.
  • the amount of fragrance comprising components c) and d) in the lipid nanoparticles of the present invention can vary over a broad range.
  • the amount of the fragrance in the lipid nanoparticles of the present invention is from 1 to 60 % by weight, more preferably from 10 to 50 % by weight and even more preferably from 15 to 40 % weight, in each case based on the total weight of the lipid nanoparticles.
  • the amount of odor forming compounds c) in the lipid nanoparticles of the present invention can vary over a broad range.
  • Typical amounts of compounds c) in the lipid nanoparticles of the present invention may be from 0.4 to 57 % by weight and preferably from 6 to 45 % by weight, in each case based on the total weight of the lipid nanoparticles.
  • the amount of diluent(s) d) in the lipid nanoparticles of the present invention can vary over a broad range. Typical amounts of diluent(s) d) in the lipid nanoparticles of the present invention may be from 0.05 to 36 % by weight and preferably from 1 to 20 % by weight, in each case based on the total weight of the lipid nanoparticles.
  • the amount of the one or more additives of component e) in the lipid nanoparticles of the present invention can vary over a broad range.
  • the amount of the one or more additives e) in the lipid nanoparticles of the present invention may be from 1 to 20 % by weight and more preferably from 1 to 12 % by weight, in each case based on the total weight of the lipid nanoparticles.
  • the amount of co-surfactants, component f), in the lipid nanoparticles of the present invention also can vary over a broad range. Typical amounts of co-surfactants in the lipid nanoparticles of the present invention may be from 0 to 50 % by weight and preferably from 1 to 10 % by weight, in each case based on the total weight of the lipid nanoparticles.
  • the amount of waxes, component g), in the lipid nanoparticles of the present invention also can vary over a broad range. Typical amounts of these waxes in the lipid nanoparticles of the present invention may be from 0 to 50 % by weight and preferably from 3 to 10 % by weight, in each case based on the total weight of the lipid nanoparticles.
  • the amount of humectants, component h), in the lipid nanoparticles of the present invention also can vary over a broad range. Typical amounts of these humectants in the lipid nanoparticles of the present invention may be from 0 to 10 % by weight, preferably from 2 to 7 % by weight and more preferably from 3 to 7 % by weight in each case based on the total weight of the lipid nanoparticles.
  • lipid nanoparticles of the present invention wherein the amount of component a) is from 1 to 95 % by weight, and the amount of component b) is from 1 to 95 % by weight, and the amount of component c) is from 0.4 to 57 % by weight, and the amount of component d) is from 0.05 to 36 % by weight, and the amount of component e) is from 1 to 20 % by weight, wherein the weight percentages in each case are based on the total weight of the lipid nanoparticle.
  • the fragrances comprising components c) and d) can be introduced in high amounts into the lipid nanoparticles comprising components a), b) and e) and optionally f) and/or g) and/or h) and be stored there.
  • the fragrances are dissolved, and crystallizing out of the fragrances is prevented.
  • This permits, inter alia, the preparation of cosmetic or laundry formulations with a skin-friendly pH, and by preventing the fragrances from crystallizing out, the skin friendliness of the composition is increased further.
  • the mixtures of components used according to the invention having the fragrances dissolved therein spread upon application to the skin, meaning that application of the fragrance to the skin is improved.
  • the lipid nanoparticles of the present invention are provided in aqueous compositions with amounts of the lipid nanoparticles preferably from 0.1 to 60 % by weight, more preferably from 1 to 50 % by weight and even more preferably from 5 to 20 % by weight, in each case based on the total weight of the aqueous composition.
  • the present invention also relates to aqueous compositions comprising one or more lipid nanoparticles of the present invention and water, wherein the amount of the one or more lipid nanoparticles preferably is from 0.1 to 60 % by weight, more preferably from 1 to 50 % by weight and even more preferably from 5 to 20 % by weight, in each case based on the total weight of the aqueous composition.
  • the aqueous composition may consist of only water, or may consist of water and adjuvants, such as electrolytes, alcohols, including polyols, rheology modifiers, surfactants or mixtures comprising two or more of said adjuvants.
  • the polyols may comprise propylene glycol, polyethylene glycol, glycerol, polyglycerol, sorbitol, isosorbide or dimethyl isosorbide.
  • the aqueous compositions of the present invention comprise one or more rheology modifiers, more preferably one or more natural biopolymers and even more preferably one or more natural biopolymers selected from the group consisting of xanthan gum, guar gum, gellan gum, gum arabic and mixtures thereof.
  • the amount of the adjuvants in the aqueous compositions of the present invention preferably is from 1 to 8 % by weight and more preferably from 1.5 to 5 % by weight, in each case based on the total weight of the aqueous composition.
  • the amount of fragrance in the aqueous compositions of the present invention is from 1 to 35 % by weight, based on the total weight of the aqueous composition.
  • the lipid nanoparticles of the present invention may be prepared by mixing selected components constituting the lipid nanoparticles in different containers and by combining said mixtures or by feeding the components constituting the lipid nanoparticles to an emulsification device for manufacture of nano-emulsions.
  • An example of such emulsification device is disclosed in US 2013/0201785 A1 .
  • an emulsifying device for continuous production of emulsions and/or dispersions which comprises a) at least one mixing apparatus comprising a rotationally symmetric chamber sealed airtight on all sides, at least one inlet line for introduction of free- flowing components, at least one outlet line for discharge of the mixed free- flowing components, a stirrer unit which ensures laminar flow and comprises stirrer elements secured on a stirrer shaft, the axis of rotation of which runs along the axis of symmetry of the chamber and the stirrer shaft of which is guided on at least one side, wherein the at least one inlet line is arranged upstream of or below the at least one outlet line, wherein the ratio between the distance between inlet and outlet lines and the diameter of the chamber is > 2:1 , wherein the ratio between the distance between inlet and outlet lines and the length of the stirrer arms of the stirrer elements is 3:1 to 50:1 , and wherein the ratio of the diameter of the stirrer shaft, based on the internal diameter of the chamber
  • the present invention also relates to a first method of manufacturing the lipid nanoparticles of the present invention or an aqueous composition of the present invention comprising the steps: i) forming a composition A by combining one or more surfactants of component a) and water in a first container, ii) forming a composition B by combining one or more amphiphilic compounds of component b), a fragrance comprising component c) and component d) as well as one or more additives of component e) in a second container, iii) combining compositions A and B by adding component B to component A under agitation, and iv) adding water as composition C to the combined compositions A and B from step iii).
  • composition A in step i) and/or components of composition B in step ii) are heated in order to melt the components in said compositions.
  • Preferred heating temperatures are from 30 to 130°C and preferably from 30 to 80°C.
  • composition C comprising one or more surfactants and/or one or more rheology modifiers is used.
  • the present invention also relates to a second method of manufacturing the lipid nanoparticles of the present invention comprising the steps: ia) feeding a composition A comprising one or more surfactants of component a) and water to a first inlet line of an emulsification device, iia) feeding a composition B comprising one or more amphiphilic compounds of component b), fragrance comprising components c) and d) and one or more additives of component e) to a second inlet line of an emulsification device, iiia) combining compositions A and B in a turbulent mixing zone in the emulsification device, iva) transporting the mixed compositions within the emulsification device towards an outlet line, whereby laminar flow of the mixed components is established in the zone preceding the outlet line thereby vesicles are formed, and va) discharging the lipid nanoparticles via the outlet line from the emulsification device.
  • the lipid nanoparticles formed in the emulsification device are diluted with water or with an aqueous phase comprising adjuvants. This can be performed in a separate device by introducing the lipid nanoparticles into water which optionally contains one or more additional surfactants and/or optionally contains one or more rheology modifiers.
  • the lipid nanoparticles and the aqueous compositions of the present invention may preferably be used in cosmetic formulations or in laundry formulations.
  • Cosmetic formulations are preferably skin-treatment compositions or hair- treatment compositions.
  • Laundry formulations are preferably laundry additives, washing agents or fabric softeners.
  • Cosmetic formulations or laundry formulations usually comprise further ingredients typical of these formulations.
  • the combination of fragrance-containing lipid nanoparticles, water and optionally other substances can, however, also like the lipid nanoparticles and water itself, be used for producing hair- and/or skin cleansing compositions or for producing washing agents and/or fabric softeners.
  • hair- and/or skin-cleansing compositions may be present in any desired suitable form, for example as shampoos, shower gels, face cleansers or soaps.
  • washing agents or fabric softeners may be present in any desired suitable form, for example as powders or concentrates.
  • the lipid nanoparticles of the present invention permit also extensive protection of the fragrances against oxidative decomposition. If appropriate, further antioxidants can also be added.
  • the fragrances in the lipid nanoparticles of the present invention or in the cosmetic or laundry compositions of the present invention are significantly better protected against oxidation than in conventional application forms.
  • the present invention also relates to the use of the lipid nanoparticles of the present invention or the aqueous compositions of the present invention in cosmetic and hair care compositions, preferably in compositions for skin treatment or for hair treatment.
  • the present invention furthermore relates to the use of the lipid nanoparticles of the present invention or the aqueous compositions of the present invention in laundry compositions, preferably in washing agents or in fabric softeners.
  • the present invention furthermore relates to the use of the lipid nanoparticles of the present invention or the aqueous compositions of the present invention for providing prolonged fragrance release by slow diffusion in cosmetic or hair care compositions or in laundry compositions, preferably in washing agents or in fabric softeners.
  • the invention furthermore relates to a composition, in particular cosmetic composition or fabric conditioner composition, comprising the lipid nanoparticles described herein and one or more further components (F).
  • Cosmetic conditioner as used in this description also means “fabric softener”.
  • the composition of the invention is a cosmetic composition or a fabric conditioner composition.
  • the composition of the invention is a cosmetic composition.
  • the composition of the invention is a fabric conditioner composition.
  • composition of the invention may be a cosmetic composition selected from the group consisting of shampoo, hair conditioner, body wash, bubble bath, bath oil, facial cleanser, cleansing mask, cleansing milk, micellar water, make-up remover, cleansing wipes, perfume, soaps, shaving soaps, shaving foams and cleansing foams.
  • Preferred cosmetic compositions are hair care compositions or skin care compositions.
  • the composition of the invention is a hair care composition or a skin care composition. More preferred cosmetic compositions are hair care compositions, such as shampoo compositions or hair conditioner compositions. More preferably, the composition of the invention is a hair care composition, such as a shampoo composition or a hair conditioner composition.
  • the composition of the invention is a shampoo composition.
  • the shampoo composition can be in the form of rinse-off products or ‘dry shampoo’ products, can be opaque or transparent, and can be formulated in a wide variety of product forms, including creams, gels, emulsions, mousses and sprays.
  • the shampoo composition of the present invention is in the form of a rinse-off product.
  • the shampoo composition is, for example, suitable for cleansing human hair or animal hair, preferably human hair.
  • the composition of the invention is a hair conditioner composition.
  • the hair conditioner composition can be in the form of rinse-off products or leave-on products, can be opaque or transparent, and can be formulated in a wide variety of product forms, including creams, gels, emulsions, mousses and sprays.
  • the hair conditioner composition is in the form of a rinse-off product.
  • the composition of the invention in particular cosmetic composition or fabric conditioner composition, comprises from 0.1 to 20 wt.-%, preferably from 0.2 to 15 wt.-%, more preferably from 0.3 to 10 wt.-%, even more preferably from 0.5 to 5 wt.-%, particularly preferably from 1 to 3 wt.-% of the lipid nanoparticles described herein, based on the total weight of the composition.
  • the composition of the invention, in particular cosmetic composition or fabric conditioner composition comprises 1 wt.-%, 2 wt.-%, 3 wt.-%, 4 wt.-%, 5 wt.-%,
  • the composition of the invention in particular cosmetic composition or fabric conditioner composition, comprises one or more further components (F), which can be in an amount of at least 0.01% by weight, preferably at least 0.05% by weight, more preferably at least 0.1% by weight, even more preferably at least 0.5% by weight, such as 0.5 to 20% by weight of the composition.
  • the component (F) is selected from the group consisting of acidity regulators, colorants, conditioning agents, emulsifiers, film formers, fragrances, glossers, humectants, lubricants, moisturizers, pigments, preservatives, skin penetration enhancers, stabilizers, surfactants, thickeners, and viscosity modifiers. More preferably, the component (F) is selected from the group consisting of acidity regulators, glossers, lubricants, and surfactants.
  • Suitable lubricants are, for example, fatty alcohol components having 6 to 18 carbon atoms.
  • the surfactants may, for example, be selected from non polymeric, cationic quaternary ammonium compounds, in particular cetrimonium chloride (CTAC).
  • Suitable classical cationic conditioning agents include cationic quaternary ammonium salts.
  • the component (F) is a cationic quaternary ammonium salt.
  • quaternary ammonium salts include benzyl triethyl ammonium chloride, cetyl trimethylammonium chloride (cetrimonium chloride, CTAC), behentrimonium chloride (BTAC) or cetylpyridinium chloride.
  • cationic components a variety of further cationic polymers are suitable, including quaternized cellulose ethers, copolymers of vinylpyrrolidone, acrylic polymers, including homopolymers or copolymers of dimethyldiallylammonium chloride or acrylamide. Also suitable are various types of homo- or copolymers derived from acrylic or methacrylic acid, acrylamide, methylacrylamide, diacetone- acrylamide.
  • the component (F) is a glosser.
  • Typical glossers are silicones. Suitable as silicones are volatile or nonvolatile nonionic silicone fluids, silicone resins, and silicone semisolids or solids. Volatile silicones are linear or cyclic silicones having a measureable vapor pressure, which is defined as a vapor pressure of at least 2 mm of mercury at 20°C. Also suitable are water insoluble nonvolatile silicone fluids including polyalkyl siloxanes, polyaryl siloxanes, polyalkylaryl siloxanes, polyether siloxane copolymers, amine-functional silicones, or mixtures thereof.
  • the composition of the invention may contain from 0.05 to 5%, preferably 0.5 to 5% by weight of at least one oil component.
  • Typical oils are organic oils, which often are esters.
  • the oil component may comprise glyceryl esters of fatty acids, or triglycerides, coconut oil, almond oil, apricot kernel oil, avocado oil, babassu oil, evening primrose oil, camelina sativa seed oil, grape seed oil, macadamia ternifolia seed oil, corn oil, meadowfoam seed oil, mink oil, olive oil, palm kernel oil, safflower oil, sesame oil, soybean oil, sunflower oil, wheat germ oil, and camellia reticulata seed oil.
  • sorbitan esters are also suitable as the oil component.
  • the composition of the invention can contain from 0.1 to 10% by weight, preferably from 0.2 to 5% by weight, more preferably from 0.2 to 3% by weight, also more preferably from 0.5 to 5% by weight of at least one rheology modifying agent, in particular a gelling and thickening agent.
  • rheology modifying agent in particular a gelling and thickening agent.
  • cellulosic thickeners for example, hydroxyethylcellulose, hydroxypropylcellulose, and carboxymethylcellulose, guar gum, such as hydroxypropylguar, gums of microbial origin, such as xanthan gum and scleroglucan gum, and synthetic thickeners, such as crosslinked homo- or copolymers of acrylic acid and/or of acrylamidopropanesulphonic acid.
  • Other rheology modifying agents include fatty acid amides such as coconut diethanolamide and monoethanolamide, and oxyethylenated monoethanolamide of carboxylic acid alkyl ether
  • Rheology modifying agents are also known as structuring materials.
  • Common structuring materials include polymeric materials known as “carbomers”, including, for example the cross-linked polyacrylic acid polymers available from Lubrizol Corporation under the trademark Carbopol®.
  • Another class of (meth)acylic acid polymers are alkali-swellable emulsion (ASE) polymers.
  • ASE polymers include, for example, Aculyn ® 38 copolymer from Dow.
  • Carbomers and ASE polymers belong to a class of materials known as hydrodynamic thickeners. These hydrodynamic thickeners include acid groups in their polymeric structure that, when deprotonated, form anionic charges that repel each other, causing the polymer chains to expand and entangle.
  • Expansion and chain entanglement can give rise to thickening and suspending effects provided by the deprotonated polymers.
  • the properties of these hydrodynamic thickeners are impacted by their molecular weight, acid group content, degree of cross-linking, and extent of swelling. These thickeners are also known as "space filling” or “volume excluding”, and tend to increase both viscosity and yield point as the concentration thereof is increased.
  • hydrodynamic polymers commonly give rise to compositions that exhibit shear thinning or non-Newtonian behavior.
  • Another class of (meth)acrylic acid based rheology modifiers are hydrophobically modified alkali swellable (HASE) polymers.
  • the HASE polymers include acid groups, the deprotonation of which gives rise to polymer swelling. Additionally, the HASE polymers include hydrophobic side groups, chains or blocks that give rise to associative interactions with each other, as well as with other hydrophobic species present in the compositions in which they are employed, for example, hydrophobic groups of surfactants, fatty acids, other thickening agents, and the like.
  • Aculyn ® 22 and Aculyn ® 28 copolymers from Dow and Aqua SF 1 ® copolymer from Lubrizol Corporation are among the commonly used HASE materials.
  • the polymers are formed from the copolymerization of a monomer system that includes: (1 ) methacrylic or acrylic acid, (2) methacrylic or acrylic acid ester of a C8-C30 alkyl or, as therein more particularly described, a hydrocarbyl monoether of polyethylene glycol, (3) a C1-C4 alkyl acrylate or methacrylate, and, optionally, (4) a small amount of a polyethylenically unsaturated monomer.
  • a monomer system that includes: (1 ) methacrylic or acrylic acid, (2) methacrylic or acrylic acid ester of a C8-C30 alkyl or, as therein more particularly described, a hydrocarbyl monoether of polyethylene glycol, (3) a C1-C4 alkyl acrylate or methacrylate, and, optionally, (4) a small amount of a polyethylenically unsaturated monomer.
  • the composition of the invention can also comprise as component (F) a fatty compound.
  • the fatty compound may be included in the composition at a level of from 0.1 to 20 % by weight, preferably from 1 .0 to 10 % by weight.
  • the fatty compound is selected from the group consisting of fatty alcohols (e.g. cetyl alcohol, stearyl alcohol or cetearyl alcohol), fatty acids, fatty alcohol derivatives, fatty acid derivatives, or mixtures thereof.
  • fatty alcohols have 14 to 30 or 16 to 22 carbon atoms. These fatty alcohols are saturated and can be linear or branched. Examples of fatty alcohols are cetyl alcohol, stearyl alcohol, behenyl alcohol, and mixtures thereof. Preferred fatty acids have from 10 to 30 or from 12 to 22 carbon atoms.
  • fatty acids can be saturated and can be linear or branched. Also included herein are salts of these fatty acids. Examples of fatty acids are lauric acid, palmitic acid, stearic acid, behenic acid, sebacic acid, or mixtures thereof.
  • the fatty alcohol derivatives and fatty acid derivatives useful herein include alkyl ethers of fatty alcohols, alkoxylated fatty alcohols, alkyl ethers of alkoxylated fatty alcohols, esters of fatty alcohols, fatty acid esters of compounds having esterifiable hydroxy groups, hydroxy-substituted fatty acids, or mixtures thereof.
  • fatty alcohol derivatives and fatty acid derivatives include methyl stearyl ether, polyoxyethylene ethers of behenyl alcohol, ethyl stearate, cetyl stearate, cetyl palmitate, stearyl stearate, myristyl myristate, polyoxyethylene cetyl ether stearate, polyoxyethylene stearyl ether stearate, polyoxyethylene lauryl ether stearate, ethyleneglycol monostearate, polyoxyethylene monostearate, polyoxyethylene distearate, propyleneglycol monostearate, propyleneglycol distearate, trimethylolpropane distearate, sorbitan stearate, poly glyceryl stearate, glyceryl monostearate, glyceryl distearate, glyceryl tristearate, or mixtures thereof.
  • the composition of the invention may comprise an aqueous carrier.
  • the level and species of the aqueous carrier are selected according to the compatibility with other components and other desired characteristic of the composition.
  • the aqueous carrier may, for example, be water or water solutions of lower alkyl alcohols or polyhydric alcohols.
  • the lower alkyl alcohols may, for example, be monohydric alcohols having 1 to 6 carbons, often ethanol and/or isopropanol.
  • the polyhydric alcohols may, for example, be propylene glycol, hexylene glycol, glycerin, and/or propane diol.
  • the aqueous carrier is substantially water. Deionized water is preferably used. Water from natural sources, including minerals can also be used, depending on the desired characteristic of the composition.
  • the composition of the invention can comprise up to 80 %, often even up to 95 % by weight of water.
  • compositions of the invention may also include as a further component (F), other components being suitable for rendering the compositions more cosmetically or aesthetically acceptable or to provide them with additional usage benefits.
  • a further component (F) other components being suitable for rendering the compositions more cosmetically or aesthetically acceptable or to provide them with additional usage benefits.
  • Such other components can generally be used individually at levels of from 0.001 % to 5 % by weight.
  • a wide variety of further components (F) can be formulated into the composition of the invention.
  • conditioning agents such as hydrolysed collagen, vitamin E, panthenol, panthenyl ethyl ether, hydrolysed keratin, proteins, plant extracts, nutrients; emollients, such as PPG-3 myristyl ether, trimethyl pentanol hydroxyethyl ether; hair-fixative polymers, such as amphoteric fixative polymers, cationic fixative polymers, anionic fixative polymers, nonionic fixative polymers, silicone grafted copolymers; preservatives, such as benzyl alcohol, methyl paraben, propyl paraben, imidazolidinyl urea; pH adjusting agents, such as citric acid, sodium citrate, succinic acid, phosphoric acid, sodium hydroxide, sodium carbonate; salts, in general, such as potassium acetate or sodium chloride; coloring agents; hair oxidizing (bleaching) agents, such as hydrogen peroxide, perborate or persulfate salts
  • the composition of the invention comprises an anti fungal substance.
  • the anti-fungal substance is selected from the group consisting of ketoconazole, oxiconazole, bifonazole, butoconazole, cloconazole, clotrimazole, econazole, enilconazole, fenticonazole, isoconazole, miconazole, sulconazole, tioconazole, fluconazole, itraconazole, terconazole, naftifine, terbinafine, zinc pyrithione, piroctone olamine (octopirox), and combinations thereof.
  • the composition of the invention comprises a total amount of anti-fungal substance in the composition of from 0.1 wt.-% to 1 wt.-%.
  • the composition of the invention comprises piroctone olamine.
  • the composition of the invention comprises a pyridinethione anti-dandruff particulate.
  • 1-hydroxy-2-pyridinethione salts are highly preferred particulate anti dandruff agents.
  • the concentration of pyridinethione anti-dandruff particulate may range from 0.1 % to 4% by weight of the formulation, preferably from 0.1 % to 3%, more preferably from 0.3% to 2%.
  • Preferred pyridinethione salts include those formed from heavy metals such as zinc, tin, cadmium, magnesium, aluminum and zirconium, preferably zinc, more preferably the zinc salt of 1 -hydroxy-2- pyridinethione (known as "zinc pyridinethione" or "ZPT"), more preferably 1-hydroxy-2-pyridinethione salts in platelet particle form. Salts formed from other cations, such as sodium, may also be suitable.
  • Pyridinethione anti-dandruff agents are described, for example, in U.S. Pat. No. 2,809,971; U.S. Pat. No. 3,236,733; U.S. Pat. No. 3,753,196; U.S. Pat. No. 3,761,418; U.S. Pat. No. 4,345,080;
  • salt is present at levels from 0.1 to 1 wt.-% of the total composition to adjust the product viscosity.
  • NaOH is present at levels from 0.1 to 1 wt.-% of the total composition to adjust the pH of the formulation.
  • composition of the invention may contain as a further component (F) a polysorbate for adjusting rheology, for example, polysorbate-20, polysorbate-21 , polysorbate-40, polysorbate-60, or mixtures thereof.
  • a polysorbate for adjusting rheology for example, polysorbate-20, polysorbate-21 , polysorbate-40, polysorbate-60, or mixtures thereof.
  • the polysorbate can be contained in the composition in amounts up to 5% (e.g. 0.1 to 5%) by weight.
  • the composition of the invention can also contain as a further component (F) a polypropylene glycol.
  • Preferred polypropylene glycols are those having a weight average molecular weight of from 200 to 100000 g/mol.
  • the polypropylene glycol may be either water-soluble, water-insoluble, or may have a limited solubility in water, depending upon the degree of polymerization and whether other moieties are attached thereto.
  • the desired solubility of the polypropylene glycol in water will depend in large part upon the form of the composition (e.g., leave-on hair care composition, rinse-off hair care composition).
  • the polypropylene glycol can be included in the composition of the invention at a level of up to 10% by weight.
  • the polypropylene glycol has a solubility in water at 25°C of less than about 1 g/100 g water, more preferably a solubility in water of less than about 0.5 g/100 g water, and even more preferably a solubility in water of less than about 0.1 g/100 g water.
  • the polypropylene glycol can be included in the composition of the invention at a level of up to 10% by weight.
  • composition of the invention can also contain, as a further component (F), low melting point oil selected from the group consisting of hydrocarbons having from 10 to 40 carbon atoms; unsaturated fatty alcohols having from 10 to 30 carbon atoms such as oleyl alcohol; unsaturated fatty acids having from about 10 to about 30 carbon atoms; fatty acid derivatives; fatty alcohol derivatives; ester oils such as pentaerythritol ester oils, trimethylol ester oils, citrate ester oils, or glyceryl ester oils; poly [alpha]-olefin oils; and mixtures thereof.
  • low melting point oil selected from the group consisting of hydrocarbons having from 10 to 40 carbon atoms; unsaturated fatty alcohols having from 10 to 30 carbon atoms such as oleyl alcohol; unsaturated fatty acids having from about 10 to about 30 carbon atoms; fatty acid derivatives; fatty alcohol derivatives; ester oils such as pentaerythritol ester oils, trimethylo
  • Preferred low melting point oils are selected from the group consisting of ester oils such as pentaerythritol ester oils, trimethylol ester oils, citrate ester oils, or glyceryl ester oils; poly [alpha]-olefin oils; and mixtures thereof.
  • ester oils such as pentaerythritol ester oils, trimethylol ester oils, citrate ester oils, or glyceryl ester oils
  • Particularly useful pentaerythritol ester oils and trimethylol ester oils are pentaerythritol tetraisostearate, pentaerythritol tetraoleate, trimethylolpropane triisostearate, trimethylolpropane trioleate, or mixtures thereof.
  • Particularly useful glyceryl esters are triisostearin, triolein or trilinolein.
  • composition of the invention can also contain, as a further component (F), a cationic polymer.
  • Cationic polymers may be present in the composition of the invention for further enhancing deposition performance.
  • Suitable cationic polymers may be homopolymers which are cationically substituted or may be formed from two or more types of monomers.
  • the weight average (Mw) molecular weight of the polymers will generally be between 100 000 and 2 million g/mol.
  • the polymers will have cationic nitrogen containing groups such as quaternary ammonium or protonated amino groups, or a mixture thereof.
  • the cationic nitrogen-containing group will generally be present as a substituent on a fraction of the total monomer units of the cationic polymer.
  • the polymer when it is not a homopolymer it can contain non-cationic spacer monomer units.
  • Such polymers are described in the CTFA Cosmetic Ingredient Directory, 3rd edition.
  • the ratio of the cationic to non-cationic monomer units is selected to give polymers having a cationic charge density in the required range, which is generally from 0.2 to 3.0 meq/gm.
  • the cationic charge density of the polymer is suitably determined via the Kjeldahl method as described in the US Pharmacopoeia under chemical tests for nitrogen determination.
  • Suitable cationic polymers include, for example, copolymers of vinyl monomers having cationic amine or quaternary ammonium functionalities with water soluble spacer monomers such as (meth)acrylamide, alkyl and dialkyl (meth)acrylamides, alkyl (meth)acrylate, vinyl caprolactone and vinyl pyrrolidine.
  • the alkyl and dialkyl substituted monomers preferably have C1-C7 alkyl groups, more preferably C1-3 alkyl groups.
  • Other suitable spacers include vinyl esters, vinyl alcohol, maleic anhydride, propylene glycol and ethylene glycol.
  • the cationic amines can be primary, secondary or tertiary amines, depending upon the particular species and the pH of the composition. In general, secondary and tertiary amines, especially tertiary, are preferred.
  • Amine substituted vinyl monomers and amines can be polymerized in the amine form and then converted to ammonium by quaternization.
  • the cationic polymers can comprise mixtures of monomer units derived from amine- and/or quaternary ammonium-substituted monomer and/or compatible spacer monomers.
  • Suitable cationic polymers include, for example cationic diallyl quaternary ammonium- containing polymers including, for example, dimethyldiallylammonium chloride homopolymer and copolymers of acrylamide and dimethyldiallylammonium chloride, referred to in the industry (CTFA) as Polyquaternium 6 and Polyquaternium 7, respectively; mineral acid salts of amino- alkyl esters of homo- and co-polymers of unsaturated carboxylic acids having from 3 to 5 carbon atoms, (as described in US4009256A1 from NAT STARCH CHEM CORP); cationic polyacrylamides (as described in W095/22311A1 Unilever PLC).
  • CTFA cationic diallyl quaternary ammonium- containing polymers
  • CCTFA cationic diallyl quaternary ammonium- containing polymers
  • Cationic polysaccharide polymers suitable for use in compositions of the invention include monomers of the formula: A-0-[R-N + (R1)(R2)(R3)X ], wherein: A is an anhydroglucose residual group, such as a starch or cellulose anhydroglucose residual.
  • R is an alkylene, oxyalkylene, polyoxyalkylene, or hydroxyalkylene group, or combination thereof.
  • R1 , R2 and R3 independently represent alkyl, aryl, alkylaryl, arylalkyl, alkoxyalkyl, or alkoxyaryl groups, each group containing up to about 18 carbon atoms. The total number of carbon atoms for each cationic moiety (i.e.
  • cationic cellulose includes the polymeric quaternary ammonium salts of hydroxyethyl cellulose reacted with lauryl dimethyl ammonium- substituted epoxide, referred to in the industry (CTFA) as Polyquaternium 24. These materials are available from the Amerchol Corporation, for instance under the trade name Polymer LM-200.
  • CTFA lauryl dimethyl ammonium- substituted epoxide
  • Suitable cationic polysaccharide polymers include quaternary nitrogen-containing cellulose ethers (e.g. as described in US-3962418 from L’Oreal), and copolymers of etherified cellulose and starch (e.g. as described in US-3958581 from L’Oreal).
  • a particularly suitable type of cationic polysaccharide polymer that can be used is a cationic guar gum derivative, such as guar hydroxypropyltrimethylammonium chloride (commercially available from Solvay in their JAGUAR trade named series).
  • a cationic guar gum derivative such as guar hydroxypropyltrimethylammonium chloride (commercially available from Solvay in their JAGUAR trade named series).
  • examples of such materials are JAGUAR C13S, JAGUAR C14, JAGUAR C15, JAGUAR C17 and JAGUAR C16 Jaguar CHT and JAGUAR C162.
  • Mixtures of any of the above cationic polymers may be used.
  • Cationic polymer may be present in the composition of the invention at levels of from 0.01 to 5 wt.-%, preferably from 0.05 to 1 wt.-%, more preferably from 0.08 to 0.5 wt.-% by total weight of cationic polymer based on the total weight of the composition.
  • the cationic polymers have a number average molecular weight of at least about 5000 g/mol, typically from 10000 g/mol to 10 million g/mol and are selected from the group consisting of copolymers of vinyl monomers having cationic amine or quaternary ammonium functionalities with water soluble spacer monomers such as acrylamide, methacrylamide, alkyl and dialkyl acrylamides, alkyl and dialkyl methacrylamides, alkyl acrylate, alkyl methacrylate, vinyl caprolactone, and vinyl pyrrolidone.
  • Other suitable spacer monomers include vinyl esters, vinyl alcohol, maleic anhydride, propylene glycol, and ethylene glycol.
  • Preferred cationic polymers are cationic celluloses, cationic starches, and cationic guar gums. Commercially available cationic guar polymers are e.g. Jaguar ® from Solvay.
  • the composition of the invention comprises a surfactant system.
  • the surfactant system comprises a surfactant selected from the group consisting of anionic surfactants, cationic surfactants, non-ionic surfactants, zwitterionic surfactants and/or amphoteric surfactants.
  • the composition of the invention comprises a total amount of surfactant of from 0.01 wt.-% to 70 wt.-%, from 0.1 wt.-% to 40%, from 1 wt.-% to 30%, from 2 wt.-% to 20 wt.-%.
  • the composition of the invention comprises an anionic surfactant.
  • the anionic surfactant is selected from the group consisting of (Cio-C2o)-alkyl and alkylene carboxylates, alkyl ether carboxylates, fatty alcohol sulfates, fatty alcohol ether sulfates, alkylamide sulfates and sulfonates, fatty acid alkylamide polyglycol ether sulfates, alkanesulfonates and hydroxyalkanesulfonates, olefinsulfonates, acyl esters of isethionates, alpha- sulfo fatty acid esters, alkylbenzenesulfonates, alkylphenol glycol ether sulfonates, sulfosuccinates, sulfosuccinic monoesters and diesters, fatty alcohol ether phosphates, protein/fatty acid condensation products, al
  • the anionic surfactants can be used in the form of their water-soluble or water-dispersible salts, examples being the sodium, potassium, magnesium, ammonium, mono-, di-, and triethanolammonium, and analogous alkylammonium salts.
  • the anionic surfactant is the salt of an anionic surfactant comprising 12 to 14 carbon atoms.
  • the anionic surfactant is selected from the group consisting of sodium lauryl sulfate, sodium laureth sulfate, sodium tridecyl sulfate, sodium trideceth sulfate, sodium myristyl sulfate, sodium myreth sulfate, and mixtures thereof.
  • Typical anionic surfactants for use in compositions of the invention include sodium oleyl succinate, ammonium lauryl sulphosuccinate, sodium lauryl sulphate, sodium lauryl ether sulphate, sodium lauryl ether sulphosuccinate, ammonium lauryl sulphate, ammonium lauryl ether sulphate, sodium dodecyl benzene sulphonate, triethanolamine dodecylbenzene sulphonate, sodium cocoyl isethionate, sodium lauryl isethionate, lauryl ether carboxylic acid and sodium N-lauryl sarcosinate.
  • the level of alkyl ether sulphate is from 0.5 wt.-% to 25 wt.-% of the total composition, more preferably from 3 wt.-% to 18 wt.-%, most preferably from 6 wt.-% to 15 wt.-% of the total composition.
  • the total amount of anionic surfactant in compositions of the invention may range from 0.5 wt.-% to 45 wt.-%, more preferably from 1.5 wt.-% to 20 wt.-%.
  • compositions of the invention may comprise fatty acyl isethionate, if present preferably at a level of from 1 to 10 wt.-%, more preferably from 2 to 8 wt.-%, most preferably from 2.5 to 7.5 wt.-%.
  • a preferred fatty acyl isethionate product comprises fatty acyl isethionate surfactant at a level of from 40 to 80 wt.-% of the product, as well as free fatty acid and/or fatty acid salt at a level of from 15 to 50%.
  • greater than 20 wt.-% and less than 45 wt.-%, more preferably greater than 25 wt.-% and less than 45 wt.-% of the fatty acyl isethionate are of chain length greater than or equal to Ci6; and greater than 50 wt.-%, preferably greater than 60 wt.-% of the free fatty acid/soap is of chain length Ci6 to C20.
  • the product may contain isethionate salts, which are present typically at levels less than 5 wt.-%, and traces (less than 2 wt.-%) of other impurities.
  • a mixture of aliphatic fatty acids is used for the preparation of commercial fatty acyl isethionate surfactants.
  • the resulting fatty acyl isethionate surfactants e.g., resulting from reaction of alkali metal isethionate and aliphatic fatty acid
  • These longer chain fatty acyl isethionate surfactants and fatty acids i.e. fatty acyl group and fatty acid with 16 or more carbons, can typically form insoluble surfactant/fatty acid crystals in water at ambient temperatures.
  • the composition of the invention comprises an acylglycinate surfactant.
  • the acylglycinate surfactant conforms to the formula (Y): wherein
  • R ⁇ a is a linear or branched, saturated alkyl group having 6 to 30, preferably 8 to 22, particularly preferably 8 to 18, carbon atoms or is a linear or branched, mono- or polyunsaturated alkenyl group having 6 to 30, preferably 8 to 22 and particularly preferably 12 to 18 carbon atoms, and
  • Qa + is a cation
  • Qa + is selected from the group consisting of Li + , Na + , K + , Mg ++ , Ca ++ , A ++ , NH4 + , a monoalkylammmonium ion, a dialkylammonium ion, a trialkylammonium ion and a tetraalkylammonium ion, or combinations thereof.
  • the acylglycinate surfactant is selected from sodium cocoylglycinate and potassium cocoylglycinate.
  • the acylglycinate surfactant is selected from those conforming to formula (Y), wherein R is C12 alkyl or C14 alkyl.
  • the acylglycinate surfactant is selected from those conforming to formula (Y), wherein R is C16 alkyl or C18 alkyl.
  • the composition comprises from 0.01 wt.-% to 30 wt. -%, or 1 wt.-% to 25 wt.-%, preferably from 5 wt.-% to 20 wt.-%, more preferably from 12 wt.-% to 18 wt.-% anionic surfactant.
  • composition of the invention comprises a glutamate surfactant corresponding to formula (Z) or a salt thereof: wherein
  • R’ is HOOC-CH2-CH2- or M + OOC-CH2-CH2- wherein M + is a cation; and wherein R is a linear or branched, saturated alkyl group having 6 to 30, preferably 8 to 22, more preferably 8 to 18, carbon atoms or is a linear or branched, mono- or polyunsaturated alkenyl group having 6 to 30, preferably 8 to 22 and more preferably 12 to 18 carbon atoms.
  • M + is a metal cation.
  • M + is selected from the group consisting of
  • the glutamate surfactant is selected from sodium cocoyl glutamate and potassium cocoyl glutamate. In at least one embodiment, the glutamate surfactant is selected from those conforming to formula (Z), wherein R is C12 alkyl or C14 alkyl. In at least one embodiment, the glutamate surfactant is selected from those conforming to formula (Z), wherein R is C16 alkyl or C18 alkyl.
  • the composition of the invention comprises a non-ionic surfactant.
  • the non-ionic surfactants may be present in the range 0 to 5 wt.-%.
  • Nonionic surfactants that can be included in compositions of the invention include condensation products of aliphatic primary or secondary linear or branched chain alcohols or phenols with alkylene oxides, usually ethylene oxide and generally having from 6 to 30 ethylene oxide groups.
  • Alkyl ethoxylates are particularly preferred. Most preferred are alky ethoxylates having the formula
  • R is an alkyl chain of C12 to C15, and n is 5 to 9.
  • suitable nonionic surfactants include mono- or di-alkyl alkanolamides. Examples include coco mono- or di- ethanolamide and coco mono-isopropanolamide.
  • APG alkyl polyglycosides
  • APG is one which comprises an alkyl group connected (optionally via a bridging group) to a block of one or more glycosyl groups.
  • Preferred APGs are defined by the following formula:
  • R is a branched or straight chain alkyl group which may be saturated or unsaturated and G is a saccharide group.
  • R may represent a mean alkyl chain length of from about Cs to about C20.
  • R represents a mean alkyl chain length of from about C9 to about C12.
  • G may be selected from Cs or C6 monosaccharide residues, and is preferably a glucoside.
  • G may be selected from the group comprising glucose, xylose, lactose, fructose, mannose and derivatives thereof.
  • Preferably G is glucose.
  • the degree of polymerisation, n may have a value of from about 1 to about 10 or more. Most preferably the value of n lies from about 1.3 to about 1.5.
  • Suitable alkyl polyglycosides for use in the invention are commercially available and include for example those materials identified as: Oramix NS10 ex Seppic; Plantaren 1200 and Plantaren 2000 ex Henkel.
  • sugar-derived nonionic surfactants which can be included in compositions of the invention include the fatty (e.g. C10-C18) N-alkyl (C1-C6) polyhydroxy fatty acid amides, such as the C12-C18 N-methyl glucamides, as described for example in WO-9206154 and US-5194639, and the N-alkoxy polyhydroxy fatty acid amides.
  • the non-ionic surfactant has an HLB (Hydrophilic Lipophilic Balance) of greater than 12.
  • the non-ionic surfactant is selected from the group consisting of ethoxylated or ethoxylated/propoxylated fatty alcohols with a fatty chain comprising from 12 to 22 carbon atoms, ethoxylated sterols, such as stearyl- or lauryl alcohol (EO-7), PEG-16 soya sterol or PEG-10 soya sterol, polyoxyethylene polyoxypropylene block polymers (poloxamers), and mixtures thereof.
  • HLB Hydrophilic Lipophilic Balance
  • the non-ionic surfactant is selected from the group consisting of ethoxylated fatty alcohols, fatty acids, fatty acid glycerides or alkylphenols, in particular addition products of from 2 to 30 mol of ethylene oxide and/or 1 to 5 mol of propylene oxide onto Cs- to C22-fatty alcohols, onto C12- to C22-fatty acids or onto alkyl phenols having 8 to 15 carbon atoms in the alkyl group, C12- to C22-fatty acid mono- and diesters of addition products of from 1 to 30 mol of ethylene oxide onto glycerol, addition products of from 5 to 60 mol of ethylene oxide onto castor oil or onto hydrogenated castor oil, fatty acid sugar esters, in particular esters of sucrose and one or two Cs- to C22-fatty acids, INCI: Sucrose Cocoate, Sucrose Dilaurate, Sucrose Distearate, Sucrose Laurate, Sucrose Myristate, Su
  • the non-ionic surfactant is selected from the group consisting of fatty alcohol ethoxylates (alkylpolyethylene glycols), alkylphenol polyethylene glycols, alkylmercaptan polyethylene glycols, fatty amine ethoxylates (alkylaminopolyethylene glycols), fatty acid ethoxylates (acylpolyethylene glycols), polypropylene glycol ethoxylates (Pluronics ® ), fatty acid alkylol amides, (fatty acid amide polyethylene glycols), N-alkyl-, N-alkoxypoly-hydroxy-fatty acid amide, sucrose esters, sorbitol esters, polyglycol ethers, and mixtures thereof.
  • fatty alcohol ethoxylates alkylpolyethylene glycols
  • alkylphenol polyethylene glycols alkylmercaptan polyethylene glycols
  • fatty amine ethoxylates alkylamino
  • the composition of the invention comprises a fatty N-methyl-N-glucamide surfactant.
  • the fatty N-methyl- N-glucamide surfactant conforms to the formula (X): wherein
  • R is a linear or branched alkyl or alkenyl group having from 3 to 30 carbon atoms.
  • R is an alkyl group having from 3 to 30 carbon atoms.
  • R is a saturated aliphatic hydrocarbon group which can be linear or branched and can have from 3 to 20 carbon atoms in the hydrocarbon chain, preferably linear or branched. Branched means that a lower alkyl group such as methyl, ethyl or propyl is present as substituent on a linear alkyl chain.
  • R is selected from the group consisting of 1 -propyl, 2-propyl, 1 butyl, 2-butyl, 2-methyl-1 -propyl (isobutyl), 2-methyl-2-propyl (tert-butyl), 1 -pentyl, 2-pentyl, 3-pentyl, 2-methyl-1- butyl, 3-methyl-1 -butyl,
  • N-methyl-N- glucamide surfactant is selected from those conforming to formula (X), wherein R isCi2 alkyl or Ci4 alkyl. In at least one embodiment, the N-methyl-N-glucamide surfactant is selected from those conforming to formula (X), wherein R is Ci6 alkyl or Cie alkyl.
  • the composition of the invention comprises from 1 wt.-% to 20 wt.-%, more preferably from 2 wt.-% to 10 wt.-%, even more preferably from 3 wt.-% to 7 wt.-% non-ionic surfactant.
  • Amphoteric or zwitterionic surfactant can be included in the composition of the invention in an amount ranging from 0.5 wt.-% to about 8 wt.-%, preferably from 1 wt.-% to 4 wt.-% of the total composition.
  • the amphoteric surfactants are selected from the group consisting of N-(Ci2-Ci8)-alkyl-beta-aminopropionates and N-(Ci2-Ci8)-alkyl- beta- iminodipropionates as alkali metal salts and mono-, di-, and trialkylammonium salts; N- acylaminoalkyl-N,N-dimethylacetobetaine, preferably N-(C 8 -Ci 8 )-acylaminopropyl-N,N-dimethylacetobetaine, (Ci2-Ci8)-alkyl-dimethyl- sulfopropylbetaine, amphosurfactants based on imidazoline (trade name: Miranol ® , Steinapon ® ), preferably the sodium salt of 1-(beta-carboxymethyloxyethyl)-1- (carboxymethyl)-2-laurylimidazolinium;
  • the composition of the invention comprises a betaine surfactant.
  • the betaine surfactant is selected from Cs- to Ci8-alkylbetaines.
  • the betaine surfactant is selected from the group consisting of cocodimethylcarboxymethylbetaine, lauryldimethylcarboxymethylbetaine, lauryldimethylalphacarboxyethylbetaine, cetyldimethylcarboxymethylbetaine, oleyldimethylgammacarboxypropylbetaine and laurylbis(2-hydroxypropyl)alphacarboxyethylbetaine and combinations thereof.
  • the betaine surfactant is selected from Cs- to Ci8-sulfobetaines.
  • the betaine surfactant is selected from the group consisting of cocodimethylsulfopropylbetaine, stearyldimethylsulfopropylbetaine, lauryldimethylsulfoethylbetaine, laurylbis(2-hydroxyethyl)sulfopropylbetaine, and combinations thereof.
  • the betaine surfactant is selected from carboxyl derivatives of imidazole, the Cs- to Ci8-alkyldimethylammonium acetates, the Os- to Ci8 alkyldimethylcarbonylmethylammonium salts, and the Cs- to Ci8-fatty acid alkylamidobetaines, and mixtures thereof.
  • the Cs- to Ci8-fatty acid alkylamidobetaine is selected from coconut fatty acid amidopropylbetaine, N-coconut fatty acid amidoethyl-N-[2-(carboxymethoxy)ethyl]glycerol (CTFA name: cocoamphocarboxyglycinate), and mixtures thereof.
  • a particularly preferred amphoteric or zwitterionic surfactant is cocam idopropyl betaine. Mixtures of any of the foregoing amphoteric or zwitterionic surfactants may also be suitable.
  • Preferred mixtures are those of cocam idopropyl betaine with further amphoteric or zwitterionic surfactants as described above.
  • a preferred further amphoteric or zwitterionic surfactant is sodium cocoamphoacetate.
  • the composition of the invention comprises from 0.5 wt.-% to 20 wt.-%, preferably from 1 wt.-% to 10 wt.-% amphoteric surfactant.
  • the composition of the invention comprises a surfactant system.
  • the surfactant system comprises at least one surfactant selected from the group consisting of lauryl sulfate, laureth sulfate, cocam idopropyl betaine, sodium cocoylglutamate, lauroamphoacetate, and mixtures thereof.
  • the surfactant system comprises sodium laureth sulfate, sodium lauryl sulfate, and optionally cocam idopropyl betaine.
  • the surfactant system comprises sodium laureth sulfate, potassium cocoylglutamate, and cocam idopropyl betaine.
  • the composition of the invention contains as a further component a silicone compound.
  • the composition can comprise up to 5% (e.g.
  • Suitable silicone compounds include polyalkyl or polyaryl siloxanes.
  • the preferred silicone compounds are polydimethylsiloxane, polydiethylsiloxane, and polymethylphenylsiloxane, e.g. available from Wacker (Germany) or Dow Corning, such as Xiameter PMX DC 200. Silicone compounds can be available as silicone oils or emulsions.
  • the silicone compounds may further be incorporated in the present composition in the form of an emulsion, wherein the emulsion is pre-made and added to the formulation, or made during the formulation process by mechanical mixing with or without the aid of an additional surfactant selected from anionic surfactants, nonionic surfactants, cationic surfactants, and mixtures thereof.
  • the composition of the invention contains silicone conditioning agents.
  • these are emulsified droplets of a silicone conditioning agent. These are for enhancing conditioning performance.
  • Suitable silicones include polydiorganosiloxanes, in particular polydimethylsiloxanes, which have the CTFA designation dimethicone. Also suitable for use in the compositions of the invention (particularly shampoos and hair conditioners) are polydimethyl siloxanes having hydroxyl end groups, which have the CTFA designation dimethiconol. Also suitable for use in the compositions of the invention (particularly shampoos and hair conditioners) are silicone gums having a slight degree of cross-linking, as are described for example in WO-96/31188. The viscosity of the emulsified silicone itself (not the emulsion or the final composition) is typically at least 10,000 cSt at 25°C.
  • the viscosity of the silicone itself is preferably at least 60,000 cSt, most preferably at least 500,000 cSt, ideally at least 1 ,000,000 cSt. Preferably, the viscosity does not exceed 1x10 ⁇ cSt for ease of formulation.
  • Emulsified silicones for use in the compositions of the invention will typically have an average silicone droplet size in the composition of less than 30, preferably less than 20, more preferably less than 10 micron, ideally from 0.01 to 1 micron. Silicone emulsions having an average silicone droplet size of less than 0.15 micron are generally termed microemulsions.
  • Silicone particle size may be measured by means of a laser light scattering technique, for example using a 2600D Particle Sizer from Malvern Instruments.
  • suitable pre-formed emulsions include Xiameter MEM 1785 and microemulsion DC2- 1865 available from Dow Corning. These are emulsions / microemulsions of dimethiconol.
  • Cross-linked silicone gums are also available in a pre-emulsified form, which is advantageous for ease of formulation.
  • a further preferred class of silicones for inclusion in the compositions of the invention are amino functional silicones.
  • amino functional silicone is meant a silicone containing at least one primary, secondary or tertiary amine group, or a quaternary ammonium group.
  • suitable amino functional silicones include polysiloxanes having the CTFA designation "amodimethicone”.
  • amino functional silicones suitable for use in the compositions of the invention are the aminosilicone oils DC2-8220, DC2-8166 and DC2-8566 (all ex Dow Corning).
  • Suitable quaternary silicone polymers are described in EP-A-0530974.
  • a preferred quaternary silicone polymer is K3474, ex Goldschmidt.
  • emulsions of amino functional silicone oils with non-ionic and/or cationic surfactant are also suitable from suppliers of silicone oils such as Dow Corning and General Electric. Specific examples include DC939 Cationic Emulsion and the non-ionic emulsions DC2- 7224, DC2- 8467, DC2-8177 and DC2-8154 (all ex Dow Corning).
  • the total amount of silicone is preferably from 0.01 wt.-% to 10 wt.-% of the total composition, more preferably from 0.1 wt.-% to 5 wt.-%, most preferably from 0.5 wt.-% to 3 wt.-%.
  • the composition of the invention comprises a preservative or preservative system.
  • suitable preservatives include benzyl alcohol, piroctone olamine, phenoxyethanol, parabens, pentanediol, benzoic acid/sodium benzoate, sorbic acid/potassium sorbate, and other organic acids used to provide antimicrobial protection.
  • preservation boosting ingredients include anisic acid, lactic acid, sorbitan caprylate, ethylhexylglycerin, caprylyl glycol, octanediol, and similar substances.
  • the composition comprises 0.01 to 5 wt.-%, particularly preferably from 0.05 to 1 wt.-% of at least one preservative.
  • Suitable preservatives are the substances listed in the International Cosmetic Ingredient Dictionary and Handbook, 9th Edition with the function "preservatives".
  • the preservative is selected from the group consisting of phenoxyethanol, benzyl paraben, butyl paraben, ethyl paraben, isobutyl paraben, isopropyl paraben, methyl paraben, propyl paraben, iodopropynyl butylcarbamate, methyldibromoglutaronitrile, DMDM hydantoin and combinations thereof.
  • the composition comprises a preservative selected from the group consisting of cetyltrimethyl ammonium chloride, cetylpyridinium chloride, benzethonium chloride, diisobutylethoxyethyldimethyl benzylammonium chloride, sodium N-lauryl sarcosinate, sodium-N-palmethylsarcosinate, lauroylsarcosine, N-myristoylglycine, potassium-N-laurylsarcosine, trimethylammonium chloride, sodium aluminium chlorohydroxylactate, triethylcitrate, tricetylmethylammonium chloride, 2,4,4'-trichloro-2'- hydroxydiphenylether (Triclosan), phenoxyethanol, 1,5-pentandiol, 1 ,6-hexandiol, 3,4,4'- trichlorocarbanilide (Triclocarban), diaminoalkylamide, L-
  • the preservative is selected from the group consisting of phenoxyethanol, benzyl paraben, butyl paraben, ethyl paraben, isobutyl paraben, isopropyl paraben, methyl paraben, propyl paraben, iodopropynyl butylcarbamate, methyldibromoglutaronitrile, DMDM hydantoin and combinations thereof.
  • the composition is substantially free of parabens.
  • composition of the invention may also comprise a dispersed, non-volatile, water- insoluble oily conditioning agent.
  • insoluble is meant that the material is not soluble in water (distilled or equivalent) at a concentration of 0.1 % (w/w), at 25°C.
  • Suitable oily or fatty materials are selected from hydrocarbon oils, fatty esters and mixtures thereof.
  • Straight chain hydrocarbon oils will preferably contain from about 12 to about 30 carbon atoms.
  • polymeric hydrocarbons of alkenyl monomers such as C2-C6 alkenyl monomers.
  • suitable hydrocarbon oils include paraffin oil, mineral oil, saturated and unsaturated dodecane, saturated and unsaturated tridecane, saturated and unsaturated tetradecane, saturated and unsaturated pentadecane, saturated and unsaturated hexadecane, and mixtures thereof.
  • Branched-chain isomers of these compounds, as well as of higher chain length hydrocarbons, can also be used.
  • Suitable fatty esters are characterised by having at least 10 carbon atoms, and include esters with hydrocarbyl chains derived from fatty acids or alcohols, Monocarboxylic acid esters include esters of alcohols and/or acids of the formula R'COOR in which R' and R independently denote alkyl or alkenyl radicals and the sum of carbon atoms in R' and R is at least 10, preferably at least 20. Di- and trialkyl and alkenyl esters of carboxylic acids can also be used.
  • Particularly preferred fatty esters are mono-, di- and triglycerides, more specifically the mono-, di-, and tri-esters of glycerol and long chain carboxylic acids such as C8-C22 carboxylic acids.
  • Preferred materials include cocoa butter, palm stearin, sunflower oil, soybean oil and coconut oil.
  • the oily or fatty material may be present at a level of from 0.05 to 10 wt.-%, preferably from 0.2 to 5 wt.-%, more preferably from 0.5 to 3 wt.-%, based on the total weight of the composition.
  • the composition of the invention is a shampoo composition.
  • the shampoo composition comprises from 1 to 99%, preferably from 5 to 95%, more preferably from 10 to 90% by weight of the total composition of water, and from 0.1 to 99%, preferably from 1 to 95%, more preferably from 5 to 90%, often 5 to 25% by weight of the total composition of a cleansing surfactant.
  • Suitable cleansing surfactants are generally anionic, amphoteric, betaine, or zwitterionic surfactants.
  • the anionic surfactants are alkyl ether or alkyl ether sulfates, such as sodium lauryl sulfate, or other compounds described above.
  • the shampoo composition comprises one or more further cosmetically acceptable components (F), which can be present in an amount of at least 0.5% by weight, or from 0.5 to 20% by weight, by total weight of the shampoo composition.
  • the component (F) is selected from the group consisting of cleansing ingredients, acidity regulators, colorants, conditioning agents, emulsifiers, film formers, fragrances, glossers, humectants, lubricants, moisturizers, pigments, preservatives, hair penetration enhancers, scalp actives, stabilizers, surfactants, thickeners, viscosity modifiers, and combinations thereof. More preferably, the component (F) is selected from the group consisting of surfactants, viscosity-modifying polymers and conditioning ingredients.
  • the shampoo composition comprises from 0.3 to 10% by weight of the vesicles described herein and further comprises at least 0.5% by weight of one or more further components (F) selected from the group consisting of surfactants, polymers, conditioning agents, actives, acidity regulators, lubricants, moisturisers, oils, preservatives, sequestrants, strengtheners, sun protectors, and combinations thereof.
  • F further components
  • the shampoo composition comprises further cosmetically acceptable components (F) being cleansing ingredients.
  • the shampoo composition comprises from 0.05% to 20% cleansing ingredients.
  • the level of cleansing ingredient is from 1 % to 20% by total weight of the active ingredient in the composition, preferably 5% to 18%, more preferably 8% to 16%.
  • the cleansing ingredient is selected from the group consisting of non-polymeric surfactants, saponins, polymeric surfactants, and combinations thereof.
  • the cleansing ingredient comprises or consists of surfactants.
  • the shampoo composition comprises from 0.3 to 10 % by weight of the vesicles described herein and at least 0.5 % by weight of surfactants, preferably cleansing anionic or nonionic surfactants, such as sodium laureth sulphate, sodium lauryl sulphate, ammonium laureth sulphate, ammonium lauryl sulphate, olefin sulfonates, olefin sulfates, laureth-3 or 4, cocamide DEA, glucosides, cocam idopropyl betaine, coco betaine, cocoamphodipropionate, sodium methyl 2-sulfolaurate and other laurates, sulfoacetates, sulfosuccinates, lactylates, sultaines, caprylates/ caprates, isethionates, glutamates, taurates, sarcosinates, glucamides, and combinations thereof.
  • surfactants preferably cleansing
  • the shampoo composition is silicone-free. In at least one embodiment, the shampoo composition is sulfate-free. In at least one embodiment, the shampoo composition is silicone-free and sulfate-free.
  • the shampoo composition comprises: (i) from 0.3 wt.-% to 10 wt.-% of the lipid nanoparticles described herein;
  • At least one further cosmetically acceptable component (F) selected from the group consisting of silicone, cationic polymer, rheology modifiying agent, and an amphoteric or zwitterionic surfactant.
  • the shampoo composition comprises:
  • the shampoo composition consists of:
  • At least one further cosmetically acceptable component (F) selected from the group consisting of conditioning agents, such as hydrolysed collagen, vitamin E, or panthenol, panthenyl ethyl ether, hydrolysed keratin, proteins, plant extracts, nutrients; and emollients such as PPG-3 myristyl ether, trimethyl pentanol hydroxyethyl ether; hair-fixative polymers such as amphoteric fixative polymers, cationic fixative polymers, anionic fixative polymers, nonionic fixative polymers, and silicone grafted copolymers; preservatives such as benzyl alcohol, methyl paraben, propyl paraben and imidazolidinyl urea; pH adjusting agents, such as citric acid, sodium citrate, succinic acid, phosphoric acid, sodium hydroxide, sodium carbonate; salts, in general, such as potassium acetate and sodium chloride; coloring agents; hair oxidizing (bleaching) agents
  • the composition of the invention may comprise as component (F) a cationic softening agent.
  • a cationic softening agent e.g. may be fabric conditioner compositions.
  • the cationic softening agent is usually present in the compositions of the invention at a level of 2 to 75% by weight, preferably 10 to 50% by weight, more preferably 20 to 35% by weight of the total composition. Also preferably, the level of the cationic softening agent is 10 to 30% by weight of the total composition.
  • the level of the cationic softening agent is 0.5 to 8% by weight of the total composition.
  • the cationic softening agent is preferably one that is able to form a lamellar phase dispersion in water, in particular a dispersion of liposomes.
  • the cationic softening agent is preferably a quaternary ammonium compound, in particular one having two C12-28 groups connected to the nitrogen head group, preferably being connected to the nitrogen head group by at least one ester link, and more preferably by two ester links.
  • the C12-28 groups may independently be alkyl or alkenyl groups.
  • the average chain length of the alkyl and/or alkenyl groups is preferably at least C14 and more preferably at least C16. It is particularly preferred that at least half of the groups have a chain length of C18. In general, the alkyl and/or alkenyl groups are predominantly linear.
  • the cationic softening agent is preferably an ester-linked quaternary ammonium compound.
  • the quaternary ammonium compound has fatty acid chains.
  • the fatty acid chains of the quaternary ammonium compound preferably comprise from 10 to 50 wt.-%, preferably from 20 to 35 wt.-% of saturated Ci8 chains and from 10 to 50 wt.-%, preferably from 20 to 35 wt.-% of monounsaturated Ci8 chains by weight of total fatty acid chains.
  • the quaternary ammonium compound is derived from palm or tallow feedstocks. These feedstocks may be pure or predominantly palm or tallow based. Blends of different feedstocks may be used.
  • the fatty acid chains of the quaternary ammonium compound comprise from 25 to 30 wt.-%, preferably from 26 to 28 wt.-% of saturated Cis chains and from 25 to 30 wt.-%, preferably from 26 to 28 wt.-% of monounsaturated Cis chains, by weight of total fatty acid chains.
  • the fatty acid chains of the quaternary ammonium compound comprise from 30 to 35 wt.-%, preferably from 33 to 35 wt.-% of saturated Cis chains and from 24 to 35 wt.-%, preferably from 27 to 32 wt.-% of monounsaturated Cis chains, by weight of total fatty acid chains.
  • the cationic softening agent is preferably an ester-linked triethanolamine (TEA) based quaternary ammonium compound.
  • Ester-linked TEA based quaternary ammonium compounds preferably comprise a mixture of mono-, di- and tri-ester linked components.
  • the tri-ester content is preferably below 10 wt.-%, more preferably from 5 to 9 wt.-% by total weight of the quaternary active component.
  • Preferred ester-linked TEA based quaternary ammonium compounds have a diester content of from 50 to 60 wt.-%, more preferably from 52 to 59 wt.-% by total weight of the quaternary active component.
  • ester-linked TEA based quaternary ammonium compounds having a monoester content of from 30 to 45 wt.-%, more preferably from 32 to 42 wt.-% by total weight of the quaternary active component.
  • a preferred ester-linked TEA based quaternary ammonium compound comprises from 32 to 42 wt.-% of monoester, from 52 to 59 wt.-% of diester and from 5 to 9 wt.-% of triester compounds, by total weight of the quaternary active; more preferably from 35 to 39 wt.-% of monoester, from 54 to 58 wt.-% of diester and from 7 to 8 wt.-% of triester compounds, by total weight of the quaternary active component.
  • the quaternary ammonium compounds are also known as "soft" materials.
  • Iodine value refers to the measurement of the degree of unsaturation present in a material by a method of NMR spectroscopy as described in Anal. Chem., 34, 1136 (1962), Johnson and Shoolery.
  • the quaternary ammonium compounds are derived from feedstock having an overall iodine value of from 30 to 45, more preferably from 30 to 42 and most preferably 36.
  • a first group of quaternary ammonium compounds suitable for use in the present invention is represented by formula (I):
  • R 1 represents a C 1-4 alkyl, C 2-4 alkenyl or a C 1-4 hydroxyalkyl group
  • T is generally O-CO (i.e. an ester group bound to R via its carbon atom), but may alternatively be CO-O (i.e. an ester group bound to R via its oxygen atom);
  • n is a number selected from 1 to 4;
  • m is a number selected from 1 , 2, or 3; and
  • X is an anionic counter-ion, such as a halide or alkyl sulphate, e.g. chloride or methylsulphate.
  • Especially preferred agents are di-esters of triethanolammonium methylsulphate.
  • Commercial examples include Prapagen TQL, ex Clariant, and Tetranyl AHT-1, ex Kao, (both di-[hardened tallow ester]of triethanolammonium methylsulphate), AT-1 (di-[tallow ester]of triethanolammonium methylsulphate), and L5/90 (di-[palm ester] of triethanolammonium methylsulphate), both ex Kao, and Rewoquat WE15 (a di-ester of triethanolammonium methylsulphate having fatty acyl residues deriving from C10-20 and C16-18 unsaturated fatty acids), ex Witco Corporation.
  • the second group of quaternary ammonium compounds suitable for use in the invention is represented by formula (II): wherein each R 1 group is independently selected from C 1-4 alkyl, hydroxyalkyl or C 2-4 alkenyl groups; and wherein each R 2 group is independently selected from Cs- 28 alkyl or alkenyl groups; and wherein n, T, and X are as defined above.
  • Preferred materials of this second group include 1 ,2 bis[tallowoyloxy]-3- trimethylammonium propane chloride, 1,2 bis[hardened tallowoyloxy]-3- trimethylammonium propane chloride, 1,2-bis[oleoyloxy]-3-trimethylammonium propane chloride, and 1,2 bis[stearoyloxy]-3-trimethylammonium propane chloride.
  • Such materials are described in US 4,137,180 (Lever Brothers).
  • these materials also comprise an amount of the corresponding mono-ester.
  • a third group of quaternary ammonium compounds suitable for use in the invention is represented by formula (III): fill) wherein each R 1 group is independently selected from C1-4 alkyl, or C2-4 alkenyl groups; and wherein each R 2 group is independently selected from Cs-28 alkyl or alkenyl groups; and n, T, and X are as defined above.
  • Preferred materials of this third group include bis(2-tallowoyloxyethyl)dimethyl ammonium chloride and hardened versions thereof.
  • a fourth group of quaternary ammonium compounds suitable for use in the invention is represented by formula (IV): wherein each R 1 group is independently selected from C 1-4 alkyl, or C 2-4 alkenyl groups; and wherein each R 2 group is independently selected from Cs- 28 alkyl or alkenyl groups; and X is as defined above.
  • Preferred materials of this fourth group include di(hardened tallow)dimethylammonium chloride.
  • the composition of the invention may comprise as component (F) a hydrophobic agent.
  • a hydrophobic agent is usually present in an amount of from 0.05 to 1.0 wt.-%, preferably from 0.1 to 0.8 wt.-%, more preferably from 0.2 to 0.7 wt.-% and most preferably from 0.4 to 0.7 wt.-% by weight of the total composition, for example from 0.2 to 0.5 wt.-% by weight of the total composition.
  • Suitable hydrophobic agents include esters derived from the reaction of a fatty acid with an alcohol.
  • the fatty acid preferably has a carbon chain length of from Cs to C22 and may be saturated or unsaturated, preferably saturated. Some examples include stearic acid, palmitic acid, lauric acid and myristic acid.
  • the alcohol may be linear, branched or cyclic. Linear or branched alcohols have a preferred carbon chain length of from 1 to 6.
  • Preferred alcohols include methanol, ethanol, propanol, isopropanol, sorbitol.
  • Preferred hydrophobic agents include methyl esters, ethyl esters, propyl esters, isopropyl esters and sorbitan esters derived from such fatty acids and alcohols.
  • Non-limiting examples of suitable hydrophobic agents include methyl esters derived from fatty acids having a carbon chain length of from at least Cio, ethyl esters derived from fatty acids having a carbon chain length of from at least Cio, propyl esters derived from fatty acids having a carbon chain length of from at least C8, isopropyl esters derived from fatty acids having a carbon chain length of from at least Cs, sorbitan esters derived from fatty acids having a carbon chain length of from at least Ci6, and alcohols with a carbon chain length greater than Cio.
  • Naturally occurring fatty acids commonly have a carbon chain length of up to C22.
  • Some preferred materials include methyl undecanoate, ethyl decanoate, propyl octanoate, isopropyl myristate, sorbitan stearate and 2-methyl undecanol, ethyl myristate, methyl myristate, methyllaurate, isopropyl palmitate and ethyl stearate; more preferably methyl undecanoate, ethyl decanoate, isopropyl myristate, sorbitan stearate, 2-methyl undecanol, ethyl myristate, methyl myristate, methyl laurate and isopropyl palmitate.
  • Non-limiting examples of such materials include methyl undecanoate, ethyl decanoate, propyl octanoate, isopropyl myristate, sorbitan stearate and 2-methyl undecanol; preferably methyl undecanoate, ethyl decanoate, isopropyl myristate, sorbitan stearate and 2-methyl undecanol.
  • the hydrophobic agent is isopropyl myristate.
  • the composition of the invention may comprise as component (F) a non-ionic alkoxylated material.
  • a non-ionic alkoxylated material reduces the occurrence of flocculation when the composition is added to water, such as rinse water.
  • the non-ionic alkoxylated material may be present in an amount of from 0.01 to 0.5 wt.-%, preferably from 0.02 to 0.4 wt.-%, more preferably from 0.05 to 0.25 wt.-% and most preferably 0.1 wt.-% by total weight of the composition.
  • Suitable non-ionic alkoxylated materials include non-ionic surfactants.
  • Suitable non-ionic surfactants include addition products of ethylene oxide and/or propylene oxide with fatty alcohols, fatty acids and fatty amines.
  • the non-ionic alkoxylated material is preferably selected from addition products of (a) an alkoxide selected from ethylene oxide, propylene oxide and mixtures thereof with (b) a fatty material selected from fatty alcohols, fatty acids and fatty amines.
  • Suitable surfactants are, for example, substantially water-soluble surfactants of the general formula:
  • R is selected from the group consisting of primary, secondary and branched chain alkyl and/or acyl hydrocarbyl groups; primary, secondary and branched chain alkenyl hydrocarbyl groups; and primary, secondary and branched chain alkenyl substituted phenolic hydrocarbyl groups; the hydrocarbyl groups having a chain length of from 10 to 60, preferably 10 to 25, e.g. 14 to 20 carbon atoms.
  • Y is typically:
  • R has the meaning given above or can be hydrogen
  • Z is at least about 6, preferably at least about 10 or 11.
  • LutensolTM AT25 (BASF) based on coco chain and 25 EO groups is an example of a suitable nonionic surfactant.
  • suitable surfactants include Renex 36 (Trideceth-6), ex Uniqema; Tergitoi 15-S3, ex Dow Chemical Co.; Dihydrol LT7, ex Thai Ethoxylate ltd; Cremophor CO40, ex BASF and Neodol 91-8, ex Shell.
  • the composition of the invention may comprise as component (F) a polymeric thickening agent, also referred to as thickening polymer.
  • Thickening polymers may be added to the compositions of the invention for further thickening. Any suitable thickener polymer may be used. If present, the amount of thickening polymer used in the compositions of the invention is typically from 0.001 to 0.5 wt.-%, preferably from 0.005 to 0.4 wt.-%, more preferably from 0.05 to 0.35 wt.-% and most preferably from 0.1 to 0.25 wt.-%, by weight of the total composition.
  • Suitable polymers are water soluble or dispersable.
  • the polymer is cationic.
  • Polymers particularly useful in the compositions of the invention include those described in WO 2010/078959 (SNF S.A.S.). These are crosslinked water- swellable cationic copolymers having at least one cationic monomer and optionally other non-ionic and/or anionic monomers. Preferred polymers of this type are copolymers of acrylamide and trimethylaminoethylacrylate chloride.
  • Preferred polymers comprise less than 25 % of water-soluble polymers by weight of the total polymer, preferably less than 20 %, and most preferably less than 15%, and a cross-linking agent concentration of from 500 ppm to 5000 ppm relative to the polymer, preferably from 750 ppm to 5000 ppm, more preferably from 1000 to 4500 ppm (as determined by a suitable metering method such as that described on page 8 of patent EP 343840).
  • the cross-linking agent concentration must be higher than about 500 ppm relative to the polymer and preferably higher than about 750 ppm when the crosslinking agent used is the methylene bisacrylamide, or other cross-linking agents at concentrations that lead to equivalent cross-linking levels of from 10 to 10,000 ppm.
  • Suitable cationic monomers are selected from the group consisting of the following monomers and derivatives and their quaternary or acid salts: dimethylaminopropylmethacrylamide, dimethylaminopropylacrylamide, diallylamine, methyldiallylamine, dialky lam inoalkyl-acrylates and methacrylates, dialkylaminoalkyl- acrylamides or -methacrylamides.
  • the monomers may also contain hydrophobic groups.
  • cross-linking agents methylene bisacrylamide (MBA), ethylene glycol diacrylate, polyethylene glycol dimethacrylate, diacrylamide, triallylamine, cyanomethylacrylate, vinyl oxyethylacrylate or methacrylate and formaldehyde, glyoxal, compounds of the glycidyl ether type such as ethyleneglycol diglycidyl ether, or the epoxides or any other means familiar to the expert permitting cross-linking.
  • MFA methylene bisacrylamide
  • ethylene glycol diacrylate polyethylene glycol dimethacrylate
  • diacrylamide diacrylamide
  • triallylamine cyanomethylacrylate
  • vinyl oxyethylacrylate or methacrylate and formaldehyde glyoxal
  • compounds of the glycidyl ether type such as ethyleneglycol diglycidyl ether, or the epoxides or any other means familiar to the expert permitting cross-linking.
  • the cross-linking rate preferably ranges from 800 to 5000 ppm (on the basis of methylene bisacrylamide) relative to the polymer or equivalent cross-linking with a cross-linking agent of different efficiency.
  • the degree of non- linearity can additionally be controlled by the inclusion of chain transfer agents (such as isopropyl alcohol, sodium hypophosphite, mercaptoethanol) in the polymerisation mixture in order to control the polymeric chain's length and the cross-linking density.
  • chain transfer agents such as isopropyl alcohol, sodium hypophosphite, mercaptoethanol
  • An example of a preferred polymer is Flosoft 270LS ex SNF. Further polymeric thickening agents or thickening polymers are described further above.
  • the composition of the invention may comprise as component (F) a non-cationic softening material, preferably non-ionic softening material, which is preferably an oily sugar derivative.
  • a non-cationic softening material preferably non-ionic softening material, which is preferably an oily sugar derivative.
  • An oily sugar derivative is a liquid or soft solid derivative of a cyclic polyol (CPE) or of a reduced saccharide (RSE), said derivative resulting from 35 to 100% of the hydroxyl groups in said polyol or in said saccharide being esterified or etherified.
  • the derivative has two or more ester or ether groups independently attached to a C8-C22 alkyl or alkenyl chain.
  • the CPE or RSE does not have any substantial crystalline character at 20°C. Instead it is preferably in a liquid or soft solid state at 20°C.
  • liquid or soft solid CPEs or RSEs suitable for use in the present invention result from 35 to 100% of the hydroxyl groups of the starting cyclic polyol or reduced saccharide being esterified or etherified with groups such that the CPEs or RSEs are in the required liquid or soft solid state.
  • These groups typically contain unsaturation, branching or mixed chain lengths.
  • the CPEs or RSEs have 3 or more ester or ether groups or mixtures thereof, for example 3 to 8, especially 3 to 5. It is preferred if two or more of the ester or ether groups of the CPE or RSE are independently of one another attached to a C8-C22 alkyl or alkenyl chain.
  • the C8-C22 alkyl or alkenyl groups may be branched or linear carbon chains.
  • 35-85% of the hydroxyl groups, most preferably 40-80%, even more preferably 45-75%, such as 45-70% are esterified or etherified.
  • the CPE or RSE contains at least 35% tri or higher esters, e.g. at least 40%.
  • the CPE or RSE has at least one of the chains independently attached to the ester or ether groups having at least one unsaturated bond. This provides a cost- effective way of making the CPE or RSE a liquid or a soft solid. It is preferred if predominantly unsaturated fatty chains, derived from, for example, rape oil, cotton seed oil, soybean oil, oleic, tallow, palmitoleic, linoleic, erucic or other sources of unsaturated vegetable fatty acids, are attached to the ester/ether groups.
  • ester or ether chains of the CPE or RSE.
  • the ester or ether chains of the CPE or RSE are preferably predominantly unsaturated.
  • Preferred CPEs or RSEs include sucrose tetratallowate, sucrose tetrarapeate, sucrose tetraoleate, sucrose tetraesters of soybean oil or cotton seed oil, cellobiose tetraoleate, sucrose trioleate, sucrose triapeate, sucrose pentaoleate, sucrose pentarapeate, sucrose hexaoleate, sucrose hexarapeate, sucrose triesters, pentaesters and hexaesters of soybean oil or cotton seed oil, glucose trioleate, glucose tetraoleate, xylose trioleate, or sucrose tetra-, tri-, penta- or hexa-esters with any mixture of predominantly unsaturated fatty acid chains.
  • CPEs or RSEs are those with monosaturated fatty acid chains, i.e. where any polyunsaturation has been removed by partial hydrogenation.
  • CPEs or RSEs based on polyunsaturated fatty acid chains e.g. sucrose tetralinoleate, may be used provided most of the polyunsaturation has been removed by partial hydrogenation.
  • liquid CPEs or RSEs are any of the above but where the polyunsaturation has been removed through partial hydrogenation.
  • the fatty acid chains Preferably 40% or more of the fatty acid chains contain an unsaturated bond, more preferably 50% or more, most preferably 60% or more. In most cases 65% to 100%, e.g. 65% to 95% contain an unsaturated bond.
  • CPEs are preferred for use with the present invention.
  • Inositol is a preferred example of a cyclic polyol. Inositol derivatives are especially preferred.
  • cyclic polyol encompasses all forms of saccharides. Indeed, saccharides are especially preferred for use with this invention. Examples of preferred saccharides for the CPEs or RSEs to be derived from are monosaccharides and disaccharides.
  • Examples of monosaccharides include xylose, arabinose, galactose, fructose, sorbose and glucose. Glucose is especially preferred.
  • Examples of disaccharides include maltose, lactose, cellobiose and sucrose. Sucrose is especially preferred.
  • An example of a reduced saccharide is sorbitan.
  • the liquid or soft solid CPEs can be prepared by methods well known to those skilled in the art. These include acylation of the cyclic polyol or reduced saccharide with an acid chloride; trans-esterification of the cyclic polyol or reduced saccharide fatty acid esters using a variety of catalysts; acylation of the cyclic polyol or reduced saccharide with an acid anhydride and acylation of the cyclic polyol or reduced saccharide with a fatty acid. See for instance US 4 386 213 and AU 14416/88 (both P&G).
  • the CPE or RSE has 3 or more, preferably 4 or more ester or ether groups. If the CPE is a disaccharide, it is preferred if the disaccharide has 3 or more ester or ether groups. Particularly preferred CPEs are esters with a degree of esterification of 3 to 5, for example, sucrose tri, tetra and penta esters.
  • each ring of the CPE has one ether or ester group, preferably at the C1 position.
  • Suitable examples of such compounds include methyl glucose derivatives.
  • CPEs examples include esters of alkyl(poly)glucosides, in particular alkyl glucoside esters having a degree of polymerisation from 1 to 2.
  • the length of the unsaturated (and saturated if present) chains in the CPE or RSE is C8-C22, preferably C12-C22. It is possible to include one or more chains of C-i-Cs.
  • the liquid or soft solid CPEs or RSEs which are suitable for use in the present invention are characterised as materials having a solid: liquid ratio of between 50:50 and 0:100 at 20°C as determined by T2 relaxation time NMR, preferably between 43:57 and 0:100, most preferably between 40:60 and 0:100, such as, 20:80 and 0:100.
  • the T2 NMR relaxation time is commonly used for characterising solid: liquid ratios in soft solid products such as fats and margarines.
  • any component of the signal with a T2 of less than 100 ps is considered to be a solid component and any component with T2 > 100 ps is considered to be a liquid component.
  • the prefixes e.g. tetra and penta
  • the compounds exist as a mixture of materials ranging from the monoester to the fully esterified ester. It is the average degree of esterification which is used herein to define the CPEs and RSEs.
  • the CPE or RSE is preferably present in the composition in an amount of 0.5 - 50% by weight, based upon the total weight of the composition, more preferably 1 - 30% by weight, such as 2 - 25%, e.g. 2 - 20%.
  • Particularly preferred CPEs and RSEs for use in the compositions of the invention include sucrose tetraoleate, sucrose pentaerucate, sucrose tetraerucate and sucrose pentaoleate.
  • composition of the invention may comprise as component (F) a co-softener.
  • component (F) a co-softener.
  • they are typically present at from 0.1 to 20% and particularly at from 0.5 to 10%, based on the total weight of the composition.
  • Suitable co-softeners include fatty acids.
  • Preferred co-softeners include fatty esters and fatty N-oxides.
  • Fatty esters that may be employed include fatty monoesters, such as glycerol monostearate, fatty sugar esters, such as those disclosed WO 01/46361 (Unilever).
  • Preferred fatty acids include hardened tallow fatty acid (available under the tradename PristereneTM, ex Uniqema).
  • Preferred fatty alcohols include hardened tallow alcohol (available under the tradenames StenolTM and FlydrenolTM, ex Cognis and LaurexTM CS, ex Albright and Wilson).
  • the composition of the invention may comprise as component (F) a fatty complexing agent.
  • Especially suitable fatty complexing agents include fatty alcohols.
  • Fatty complexing material may be used to improve the viscosity profile of the composition.
  • the fatty complexing agent is preferably present in an amount greater than 0.3 to 5% by weight based on the total weight of the composition. More preferably, the fatty component is present in an amount of from 0.4 to 4%.
  • the weight ratio of the mono-ester component of the quaternary ammonium fabric softening material to the fatty complexing agent is preferably from 5:1 to 1 :5, more preferably 4: 1 to 1 :4, most preferably 3:1 to 1:3, e.g. 2:1 to 1 :2.
  • the composition of the invention may comprise as component (F) shading dyes.
  • suitable shading dyes are disclosed in WO 2012/072368, on pages 17 to 22.
  • Preferred overall ranges, suitable for the present invention are from 0.00001 to 0.1 wt.-%, more preferably 0.0001 to 0.01 wt.-%, most preferably 0.0005 to 0.005 wt.-% by weight of the total composition.
  • composition of the invention may comprise additional fragrances and perfumes.
  • fragrances and perfumes are described further above.
  • suitable fragrances and perfumes are also disclosed in WO 2012/072368, on pages 22 to 26.
  • composition of the invention may comprise one or more further ingredients.
  • additional ingredients include preservatives (e.g. bactericides), pH buffering agents, perfume carriers, hydrotropes, anti-redeposition agents, soil- release agents, polyelectrolytes, anti-shrinking agents, anti-wrinkle agents, anti-oxidants, sunscreens, anti-corrosion agents, drape imparting agents, anti static agents, ironing aids, pearlisers and/or opacifiers, natural oils/extracts, processing aids, e.g. electrolytes, hygiene agents, e.g. anti-bacterials and anti- fungals and skin benefit agents.
  • the composition of the invention is a fabric conditioner composition.
  • the fabric conditioner composition comprises a cationic softening agent.
  • Preferred cationic softening agents are quaternary ammonium compounds.
  • the fabric conditioner composition comprises a hydrophobic agent. In at least one embodiment, the fabric conditioner composition comprises a non- ionic alkoxylated material. In at least one embodiment, the fabric conditioner composition comprises a polymeric thickening agent. In at least one embodiment, the fabric conditioner composition comprises a non-ionic softener. In at least one embodiment, the fabric conditioner composition comprises a co-softener. In at least one embodiment, the fabric conditioner composition comprises a fatty complexing agent. The fabric conditioner composition may further comprise shading dyes, additional fragrances and perfumes, and/or further ingredients.
  • the fabric conditioner composition comprises:
  • the fabric conditioner composition comprises:
  • At least one further component (F) selected from the group consisting of hydrophobic agents, non-ionic alkoxylated materials, polymeric thickening agents, non- cationic softeners, preferably non-ionic softeners, co-softeners, fatty complexing agents.
  • the invention further relates to a method of preparing the composition of the invention, in particular a cosmetic composition or a fabric conditioner composition, comprising the step of preparing the lipid nanoparticles described herein, and mixing the lipid nanoparticles with one or more further components (F) and preferably water.
  • the compositions can be prepared by any conventional method well known in the art.
  • the invention further relates to a method of treating hair, comprising: a) applying a shampoo composition and/or hair conditioner composition according to the invention onto wet hair and then b) removing the shampoo composition and/or hair conditioner composition from the hair.
  • the invention further relates to the use of the lipid nanoparticles described herein in cosmetic compositions.
  • Preferred cosmetic compositions are described further above.
  • Preferred components are described further above.
  • the invention further relates to the use of the lipid nanoparticles described herein in fabric conditioner compositions.
  • Preferred fabric conditioner compositions are described further above.
  • Preferred components are described further above.
  • Accelerated stability analysis of formulations was performed using dispersion analyzer LUMiSizer® 611.3-79, (LUM GmbFI, Germany) which involves centrifugation method with photometric detection at 865 nm.
  • LUMiSizer® 611.3-79 LUM GmbFI, Germany
  • samples were filled in polyamide cuvettes and centrifuged at 4000 rpm for up to 2.5 hours at 45°C. Then, phase separation and instability were indicated by the included software (SepView 6.0; LUM).
  • phase A and of phase B are introduced into the inlet lines of an emulsification device as disclosed in US 2013/0201785 A1.
  • the product from this emulsification device is a composition consisting essentially of lipid nanoparticles comprising fragrance.
  • PSD measurement method The product obtained from the emulsification device is introduced under stirring into a vessel containing phase C. An aqueous composition comprising vesicles is formed. PSD measurement method:
  • the average particle size of the lipid nanoparticles is measured by Malvern mastersizer- 3000 particle size analyser. D50 (nm) of the stable sample is reported in respective examples.
  • fragrance formulations were used (weight percentages refer to total fragrance mass):
  • Comparative Example 1 lipid nanoparticles without additives
  • Comparative Example 2 lipid nanoparticles with rheology modifier - Xanthan Gum
  • Comparative Example 3 lipid nanoparticles without additives
  • Example 5 lipid nanoparticles with additives - Hostacerin DGI
  • Example 6 lipid nanoparticles with additive - Genapol PMS
  • Inventive Example 7 lipid nanoparticles with additive - Monecol DSE - and with rheology modifier - Xanthan Gum
  • Inventive Example 8 lipid nanoparticles with additive - Monegyl T-18 and with rheology modifier - Xanthan Gum
  • Example 9 lipid nanoparticles with additive - Moxilub-518
  • Inventive Example 10 lipid nanoparticles with additive - Moxilub-518
  • Inventive Example 11 lipid nanoparticles with additive - Moxilub-518
  • Inventive Example 12 lipid nanoparticles with additive - Moxilub-518

Abstract

Disclosed is a lipid nanoparticle comprising a) one or more surfactants having an HLB value of greater than 6, and b) one or more amphiphilic compounds having a logP value of 1 or greater than 1, and c) one or more odor forming compounds, and d) one or more selected diluents, and e) one or more selected additives. The fragrance with enhanced water-solubility is encapsulated in the nanoparticles. The encapsulated fragrance is stable during storage conditions and the nanoparticles have long-lasting fragrance release on use thereof. The nanoparticles may be used in cosmetic formulations or in laundry formulations.

Description

Lipid nanoparticles for delayed delivery of fragrance with enhanced water solubility, their preparation and use
Description
The invention relates to lipid nanoparticles comprising fragrance and to the use thereof in cosmetic formulations or in laundry applications.
Many cosmetic and laundry compositions comprise fragrances. These are usually mixed directly into the compositions, for example shampoos, shower gels, face cleansers, solid or liquid soaps or creams and lotions and leave on products in haircare. This procedure has the disadvantage that in most cases upon use only small amounts of the fragrance remain on the skin, on the hair or on the fabric, which can develop their effect there. The majority of the fragrances is usually washed off during use. This leads to large amounts of costly fragrances having to be incorporated into the formulations in order to achieve a desired effect.
However, when suitably high amounts of fragrances are used in cosmetic or laundry formulations this may lead to an undesired skin irritation when the formulations are used.
Fragrances are volatile substances. Various approaches of encapsulation have already been used to avoid premature delivery of fragrances. Examples thereof are polymeric encapsulation or inorganic encapsulation. These approaches have been carried out for the development of long-lasting fragrance delivery systems. Polymeric capsules such as melamine formaldehyde, polyacrylates or polyurethanes usually result in microcapsules with particle size above 1 micron with pressure triggered release in laundry applications. There still exist challenges to encapsulate a broad range of fragrances with different partition coefficients, especially water-soluble fragrances. The pressure-triggered capsules rather release the fragrances quickly with friction hence fragrance long-lasting is not prolonged. Diffusion controlled-release would be desired for the prolonged fragrance long-lasting in laundry, cosmetics and hair care products. EP 1 964544 A1 discloses sensitive skin perfumes. These may be encapsulated within a water-insoluble aminoplast capsule.
WO 2008/061384 A1 discloses a batch process for preparation of an emulsion comprising lamellar liquid crystal particles containing fragrance. The process comprises blending the fragrance with emulsifiers capable of forming liquid- crystalline structures, at least one fatty alcohol co-emulsifier having at least 22 carbon atoms, an amphiphilic reinforcing material and a selected wax and adding water slowly to the fragrance mixture thus formed and mixing under shear conditions to obtain a stable emulsion. In the formation of this emulsion a selected surfactant system is used.
US 2007/0105746 A1 discloses compositions for the targeted release of fragrances and aromas. In the encapsulation process a polyol phase A is used in combination with a phase B comprising fragrance, carrier and emulsifier. In the encapsulation process solid lipid nanoparticle dispersions (SLN) are formed.
WO 1999/055819 A1 discloses encapsulation of perfume oil for delivery of high impact accord perfume ingredients with modified starch and starch as shell by spray drying method. The high impact perfume ingredients have a boiling point of 275°C or lower and a calculated log P value of 2 or higher. These encapsulated particles are useful in laundry compositions especially for detergent compositions.
WO 2019/115621 A1 discloses the encapsulation of fragrances in a multilamellar vesicle. Vesicles having a particle size e.g. in the range from 100 to 800 nm are produced which contain two or more concentric lipid double layers and fragrance. The double layer of the vesicles comprise at least one surfactant having an HLB value of greater than 6 and an amphiphilic compound having a log P value of 1 or above. The vesicles with encapsulated fragrance provide a long-lasting fragrance- release in cosmetic formulations and in laundry formulations.
Encapsulation of fragrances and especially water-soluble fragrances in aqueous media is always a challenge. The water-soluble ingredients of the fragrances diffuse through the encapsulating membrane into the aqueous medium. Such diffusion of ingredients results in a phase separation in the formulation.
Thus, encapsulation of fragrances having components with log P values of less than 1 is still a challenge as such fragrances comprise water-soluble ingredients which can diffuse through shell membranes into the surrounding aqueous medium or can even avoid the formation of shell membranes.
Fragrances with enhanced water-solubility comprise - besides water-insoluble components - also water-soluble ingredients. Said ingredients are added to alter the olfactory characteristics of a fragrance. Water-soluble diluents have multiple advantages in the fragrance like to dilute the fragrance strength, as viscosifier (see EP 0816484 A2), or to reduce and mask the odor of the blend (see US 3,759,806).
There is still demand for cosmetic or laundry formulations which, on the one hand, allow the amount of fragrances comprising water-soluble components used to be kept low and thus to reduce costs, but which, on the other hand, nevertheless allow a very good effectiveness of the fragrances comprising water-soluble components and providing storage-stable formulations.
If the effectiveness of the fragrances comprising water-soluble components could be increased during use, it would be possible to use smaller amounts of fragrance, meaning that the cosmetic or laundry formulations could be produced more cost- efficient.
Surprisingly, it has been found that fragrance compositions comprising water- soluble diluents and odor forming compounds over a broad range of partition coefficients (“log P”) can be encapsulated in lipid nanoparticles comprising selected additives. These lipid nanoparticles are preferably sub-micron particles with narrow particle size distribution and with high encapsulation efficiency of fragrance. The encapsulated fragrance is stable under storage conditions and will have long-lasting fragrance release on use thereof. The lipid nanoparticles can encapsulate fragrances with enhanced water-solubility and also offer its long-lasting release on use. The long-lasting release of fragrances is a key requirement of laundry, cosmetic and hair care products.
The present invention relates to lipid nanoparticles, preferably to vesicles in the shape of a rotational body comprising at least one, preferably two or more, preferably concentric, lipid double layers and fragrance, wherein the lipid nanoparticle comprises a) one or more surfactants having an HLB value of greater than 6, and b) one or more amphiphilic compounds having a log P value of 1 or greater than 1 , and c) one or more odor forming compounds, and d) one or more diluents selected from the group consisting of aliphatic C1-C6 alcohols, polyols having 3 to 6 carbon atoms and 3 to 6 hydroxy groups, alkylene glycols having 2 to 6 carbon atoms, polyalkylene glycols having alkyleneoxy units of 2 to 6 carbon atoms and from 2 to 6, preferably 2 to 4 repeating units, wherein one or more of the hydroxyl groups of the aforementioned alcohols, polyols, alkylene glycols and polyalkylene glycols may be partly or totally etherified with Ci-C4-alkyl groups or may be partly or totally esterified with Ci-C4-acyl groups or may be etherified with C1-C4- alkyl groups and esterified with Ci-C4-acyl groups and these etherified and esterified substances may either contain no hydroxy group or at least one hydroxy group, Ci-C6-aliphatic alcohols substituted with a dioxolane ring, and mixtures thereof, and e) one or more additives being selected from the group consisting of C12-C26- fatty acid esters of polyols having 2 to 6 carbon atoms and 2 to 4 hydroxyl groups, wherein at least two hydroxyl groups of the polyols are esterified and the polyols are partly or totally esterified, Ci2-C26-fatty acid esters from polyols having 2 to 6 carbon atoms, 2 to 4 hydroxyl groups and one ether group, wherein at least two hydroxyl groups of the polyols are esterified and the polyols are partly or totally esterified, and mixtures thereof. The lipid nanoparticles of the present invention preferably are sub-micron particles with narrow particle size distribution and with high encapsulation efficiency of fragrance. The encapsulated fragrance is stable under storage conditions and has long-lasting fragrance release on use thereof. Since the effectiveness of fragrances contained in the lipid nanoparticles according to the present invention can be increased during use, it is possible to use smaller amounts of fragrance, meaning that cosmetic or laundry compositions can be produced more cost- efficient.
Surfactant of component a) is characterized by its HLB value of greater than 6.
The nature of a surfactant is represented by the hydrophilic-lipophilic balance of the molecule. The degree of this hydrophilic-lipophilic balance can be determined by calculating values for the different regions of the molecule, as described by Griffin in 1949 and 1954. Griffin's method has been primarily developed for non ionic surfactants as described in 1954 and works as follows:
HLB = 20 * Aft /If where
Mh is the molecular mass of the hydrophilic portion of the molecule, and M is the molecular mass of the whole molecule, giving a result on a scale of 0 to 20. An HLB value of 0 corresponds to a completely lipophilic molecule, and a value of 20 corresponds to a completely hydrophilic molecule.
The term “HLB” as used in this specification for nonionic surfactants is calculated by the above formula. The method of Griffin is published, for example, in Journal of the Society of Cosmetic Chemists, 5 (4), 249-256 (1954).
The term “HLB” as used in this specification for anionic, cationic or amphoteric surfactants is calculated by the method of Davies. This method is published, for example, in Gas/Liquid and Liquid/Liquid Interfaces, Proceedings of 2nc* International Congress Surface Activity, pp. 426-438, Butterworths, London 1957.
Amphiphilic compound of component b) is characterized by its log P value of > 1. The amphiphilic character of component b) can be determined by its partition coefficient between octanol and water. The octanol-water partition coefficient (log P) is a measure of the distribution of a substance between the aqueous and the organic octanol phase and is defined as follows
Figure imgf000007_0001
Examples of calculated and measured log P values are found in A. Leo, C.
Hansch, D. Elkins, Chemical Reviews, Volume 71, no. 6, (1971).
Preferably, the vesicles of the present invention are multilamellar vesicles in the shape of a rotational body comprising two or more concentric lipid double layers.
Preferably, the shape of the vesicles of the present invention is spherical, ellipsoidal or disk-like. However, the vesicles of the present invention may also have another shape of a solid of revolution.
The mean diameter of the lipid nanoparticles of the present invention preferably is from 80 to 800 nm, more preferably from 100 to 700 nm, even more preferably from 120 to 500 nm, particularly preferably from 150 to 480 nm, and especially preferably from 210 to 460 nm.
The mean diameter is determined by laser diffraction analysis, for example by using a Horiba LA 940 or Mastersizer 3000 from Malvern using the “Mie Scattering Theory” evaluation.
In case of lipid nanoparticles having axes of different length, such as lipid nanoparticles having the shape of an ellipsoid or of a disk, the largest axis determines the mean diameter.
The lipid nanoparticles of the present invention have a narrow particle size distribution of Gaussian shape. Preferably, the standard deviation of the particle size distribution is between 10% and 90% of the mean diameter.
The lipid nanoparticles of the present invention contain at least one fragrance which comprises at least one odor forming compound c) and at least one selected diluent, component d). Preferred ingredients of the fragrance encapsulated in the vesicles of the present invention are one or more odor forming compounds c) having a log P value of 1 or greater than 1 and/or one or more odor forming compounds c) having a log P value smaller than 1. The term “log P” has been defined above. The fragrance comprising components c) and d) is an additional component present in the vesicles besides components a), b) and e).
It has been found that the lipid nanoparticles of the present invention may incorporate high amounts of one or more fragrances comprising components c) and d) discussed in detail below, for example more than 25 % by weight, based on the total weight of the vesicle. But lipid nanoparticles having lower amounts of fragrance(s) are also possible.
The lipid nanoparticles of the present invention may optionally contain co-surfactants as component f) in addition to components a) to e) and optional components g) and/or h) described below. Co-surfactants are surfactants which are not capable of forming micelles. A co-surfactant is any amphiphilic substance having an HLB value < 6. Preferred co-surfactants have an HLB value from 2 to 6.
The lipid nanoparticles of the present invention may optionally contain waxes as component g) in addition to components a) to e) and optional components f) and/or h) described below.
The lipid nanoparticles of the present invention in addition to components a) to e) and optional components f) and/or g) may optionally contain as component h) one or more humectants selected from the group consisting of polyols having 3 to 6 carbon atoms and 3 to 6 hydroxyl groups, hydroxy carboxylic acids, esters from polyols having 3 to 6 carbon atoms and 3 to 6 hydroxyl groups, wherein at least one hydroxyl group of the polyol is esterified with an aliphatic monocarboxylic acid having 1 to 4 carbon atoms and mixtures thereof.
Examples of humectants g) are glycerol, trimethylolpropane, pentaerythritol, sugar alcohols, such as sorbitol, xylitol, malitol, glycolic acid, lactic acid, citric acid, mandelic acid, glycerol triacetate, trimethylolpropane triacetate and/or pentaerythritol tetraacetate.
Preferred humectant is glycerol.
The vesicles of the present invention comprise at least one lipid double layer, preferably several concentric lipid double layers. Although while not being bound by theoretical considerations it is believed that in multilamellar vesicles the lipid double layers are arranged in the form of onion shells. As the fragrance molecules contained in the vesicles of the present invention can only leave the vesicle via the outer surface, this arrangement provides for the increased storage-stability and retarded release of the fragrance from the vesicles.
The layer(s) of the lipid nanoparticles of the present invention can adopt a solid gel phase state at lower temperatures but may undergo phase transition to a fluid state at higher temperatures, and the chemical properties of the amphiphilic compounds contained in the lipid nanoparticles influence at which temperature this will happen. For controlling the retarded release of the fragrance, a solid gel state of the layer(s) is preferred. The temperature for the phase transition depends very much on the solidification point of the amphiphilic components. The temperature for the phase transition can be determined, for example, by differential scanning calorimetry (DSC).
For the use in fabric softeners a high transition temperature is required, because laundry is often dried at high temperatures in a tumble-drier.
Surprisingly, by proper choice of the above-mentioned substances forming the lipid nanoparticles of the present invention the temperature for the phase transition from a solid gel phase state to a fluid state may be modified within a broad temperature range.
Preferred are lipid nanoparticles of the present invention having a phase transition from a solid gel phase state to a fluid state within a range from 30°C to 130°C, preferably from 40°C to 120°C. This temperature range is preferably chosen for optimum release kinetics and protection of the lipid nanoparticle against heat.
The lipid nanoparticles of the present invention are formed from a selected combination of fragrances with surfactants of component a) and compounds defined above as components b) to e) which may optionally contain in addition components f) and/or g) and/or h).
Although while not being bound by theoretical considerations it is believed that mixtures of fragrances comprising components c) and d) with selected components a), b) and e) and optionally with components f) and/or g) and/or h) form lipid nanoparticles, preferably vesicles having lamellar liquid-crystalline structures. Such structures can be determined by means of optical microscopy using a polarization microscope. In addition, lamellar liquid-crystalline structures can be determined by TEM or TEM-freeze fracture technology. Appropriate techniques are known to the person skilled in the art.
The mixtures of fragrances comprising components c) and d) with components a), b) and e) and optionally with components f) and/or g) and/or h) forming the lipid nanoparticles of the present invention are chosen so that preferably a lamellar structure is formed. The selection of suitable amounts of the fragrances comprising components c) and d) and components a), b) and e) and optionally with components f) and/or g) and/or h) is possible through simple manual experiments.
The mixtures of fragrances comprising components c) and d) with components a), b) and e) and optionally with components f) and/or g) and/or h) forming the lipid nanoparticles of the invention are chosen so that in water or selected aqueous media lipid nanoparticles, preferably lamellar vesicles are obtainable which preferably have an average diameter of 800 nm or less than 800 nm. The aqueous media may contain additional additives, such as electrolytes, polyols such as glycerol, polyethylene glycol or propylene glycol, water-soluble vitamins or rheology modifiers, such as natural biopolymers, preferably one or more natural biopolymers selected from the group consisting of xanthan gum, guar gum, gellan gum, gum arabic and mixtures thereof.
The lipid nanoparticles of the present invention contain fragrances comprising components c) and d) and components a), b) and e) and optionally components f) and/or g) and/or h) which are believed to form lyotropic lamellar liquid-crystalline phases. It is believed that the formation of liquid-crystalline structures is essentially dependent on the geometry of components a) to e) and optional components f) and/or g) and/or h), which can be expressed by the packing parameter PP.
PP=V0 / (ae * I0)
VO surfactant tail volume ae equilibrium area per molecule at the aggregate interface I0 tail length
A packing parameter PP can be assigned to a chemical species, for example to a component a), b) or e) or to a component c) or d) present in the fragrance.
If several chemical species are present in certain concentrations to form a mixture of these species, a packing parameter of this mixture PPmixture can be calculated.
A packing parameter of a mixture is defined by the following formula:
PPmixture = (å ci * PPi) / ctotal, wherein
PPi is the packing parameter of the single species i, ci is the concentration of the single species i in weight percent, and ctotal is the total concentration of all i species in the mixture.
Depending on their packing parameter components a), b) and e) are forming different aggregates. It is believed that lyotropic spherical lamellar liquid-crystalline structures are required for entrapping fragrances comprising components c) and d) and are formed by components a), b) and e) optionally in combination with components f) and/or g) and/or h) at a resulting packing parameter PPmixture of at least 0.5 and preferably in the range from 0.5 to 1.
Preferred lipid nanoparticles of the present invention are vesicles comprising components a) to e) and optionally component f) and/or component g) and/or component h) and wherein the packing parameter of the mixture of components a) to e) and optionally component f) and/or component g) and/or component h) has a value of 0.5 or greater than 0.5 and preferably is in the range from 0.5 to 1.
Compounds with packing parameters PP or PPmixture < 0.5 are forming micelles. However, micelles are present in a dynamic equilibrium and continually breakdown and build up again. For this reason, micelles are not very suitable as storage media for other ingredients. As the packing parameter is shifting into a range from 0.3 to 0.5, the compounds or mixtures of compounds form rod-like micelles. Compounds or compound blends with packing parameters > 0.5 to < 1 are forming preferably vesicles. Sandwich double layers are preferably formed at packing parameters around 1. It is believed that components a), b) and e) and optionally components f) and/or g) and/or h) maybe present in lyotropic lamellar liquid- crystalline phases and in the lyotropic state, fragrance molecules are stored, for example, between the components forming the required vesicle structure. The hydrophilic moiety of a component can be varied according to the desired adhesion to a later substrate. For example, the hydrophilic moiety can be varied for adhesion to the human skin or to textile fibers.
Lipid nanoparticles of the present invention are preferably formed when the packing parameter of the mixture of all participating surfactants and amphiphilic molecules is 0.5 or greater than 0.5, more preferably in the range from 0.5 to 1. This range is valid for spherical lipid nanoparticles, preferably spherical vesicles. If the shape of the lipid nanoparticles is ellipsoid or disk like the packing parameter value shifts to higher values.
HLB values may be correlated to the packing parameter and to log P values.
The incorporation of fragrances into the lamellar structure of the vesicles will modify the value of the packing parameter of the mixture of the vesicle loaded with the fragrance.
The packing of lipids within the double-layer also affects its mechanical properties, including its resistance to stretching and bending and including the release kinetics and/or release concentration of the encapsulated fragrances.
Surprisingly, the lipid nanoparticles, preferably the vesicles of the present invention can encapsulate components c) and d) of fragrances with a very broad log P range.
For matching the required packing parameter of greater than 0.5, preferably from 0.5 to 1.5 and more preferably from 0.5 to 1 for the formation of lipid nanoparticles, preferably of vesicles with entrapped component c) and d) comprising fragrances, components a), b) and e) and optionally f) and/or g) and/or h) are required having a sufficient high packing parameter. The used surfactants of component a) can be of nonionic, anionic, cationic or amphoteric structure. Hence, it is possible to adapt the surface charge of the lipid nanoparticles to the surface charge of the application area of the fragrance. This allows a maximum deposition of fragrances.
The one or more surfactants of component a) preferably are selected from the group consisting of nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants and mixtures thereof, provided these have an HLB value of greater than 6. Preferably, the packing parameter of the one or more surfactants of component a) has a value of 0.5 or greater than 0.5 and more preferably is in the range from 0.5 to 1 .
Preferably, the one or more nonionic surfactants of component a) are selected from the group consisting of polyoxyethylene sorbitan esters, polyoxyethylene sorbitol esters, polyoxyalkylene fatty alcohol ethers, polyoxyalkylene fatty acid esters, alkoxylated glycerides, polyoxyethylene methyl glucoside esters, alkyl polyglucosides, EO-PO blockpolymers (EO: ethylene oxide; PO: propylene oxide), and mixtures thereof.
Preferably, the one or more anionic surfactants of component a) are selected from the group consisting of alkylbenzenesulfonates, alkanesulfonates, olefinsulfonates, alkyl ether sulfates, alkyl sulfates, sulfosuccinates, alkyl phosphates, alkyl ether phosphates, protein fatty acid condensates, preferably collagen hydrolysates modified with fatty acid, amino acid-based surfactants, isethionates, taurides, acyl lactylates, neutralized fatty acids, and mixtures thereof.
Preferably, the one or more cationic surfactants of component a) are selected from the group consisting of esterquats, ditallow dimethyl ammonium chloride, C12/14 alkyl dimethyl benzyl ammonium chloride, alkyl dimethyl benzyl ammonium chlorides, cetyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, behenyl trimethyl ammonium chloride, alkyl hydroxyethyl dimethyl ammonium chlorides, distearyl dimethyl ammonium chloride, dihydrogenated tallow fatty alkyl dimethyl ammonium chloride, and mixtures thereof.
Preferably, the one or more amphoteric surfactants of component a) are selected from the group consisting of alkyl amphoacetates, alkyl amidopropyl betaines, alkyl amidopropyl dimethylamine betaines, undecylenamidopropyl betaine, alkyl dimethyl amine oxides, and mixtures thereof.
More preferably, the lipid nanoparticles of the present invention contain as component a) one or more nonionic surfactants having an HLB value of greater than 6, even more preferably selected from the group consisting of polyoxyalkylene fatty alcohol ethers, polyoxyalkylene fatty acid esters, collagen hydrolysates modified with fatty acid, and mixtures thereof, and particularly preferably selected from the group consisting of polyoxyalkylene C8-C24-fatty alcohol ethers, polyoxyalkylene C8-C24-fatty acid esters, collagen hydrolysates modified with Cs-C24-fatty acid, and mixtures thereof.
Especially preferably, the one or more surfactants of component a) are selected from polyoxyalkylene Cs-C24-fatty alcohol ethers. In these surfactants, the polyoxyalkylene groups preferably are polyoxyethylene groups, preferably with ethoxylation degrees from 5 to 150, more preferably with ethoxylation degrees from 10 to 130 and even more preferably with ethoxylation degrees from 15 to 120 and the fatty alcohol preferably is a Ci2-Ci8-fatty alcohol. The fatty alcohol preferably is linear and preferably is saturated. Among these surfactants ethoxylated lauryl alcohol and ethoxylated stearyl alcohol are preferred. Extraordinarily preferably, the one or more surfactants of component a) are selected from the group consisting of ethoxylated lauryl alcohol with ethoxylation degrees from 20 to 24 or from 90 to 110, preferably from 20 to 24, and more preferably of approximately 23 and ethoxylated stearyl alcohol with ethoxylation degrees from 20 to 24 or from 90 to 110, preferably from 90 to 110, and more preferably of approximately 100, and mixtures thereof.
In the context of this specification the term “from ... to ...” (e.g. used to describe ethoxylation degrees) shall mean that all single values encompassed by this term may be realized but it shall not mean that all values encompassed by this term have to be realized. Thus, the term “a substance having an ethoxylation degree from 10 to 150”, e.g. might describe a substance having an ethoxylation degree of 22 and it might be that this substance also comprises other components having ethoxylation degrees in the given range (but different from 22) but it might also be that this substance does not comprise other components having ethoxylation degrees different from 22.
Examples of amphiphilic compounds b) are specific esters of fatty acids, preferably specific triglycerides of fatty acids or specific esters of fatty acids and fatty alcohols or mixtures thereof. Triglycerides of fatty acids or esters of fatty acids and fatty alcohols are amphiphilic components which are not capable of forming micelles. Their amphiphilic character is expressed by the log P value of 1 or greater than 1 , and preferably their log P value is from 1 to 5. For a caprylic/capric acid triglyceride, for example, the log P is 4.
Examples of tryglycerides of fatty acids are glycerol esters of one or more fatty acids having 6 to 10 carbon atoms. Examples of esters of fatty acids and fatty alcohols are esters of fatty acids having 8 to 24 carbon atoms and fatty alcohols having 8 to 28 carbon atoms. The fatty acid portions of these esters can be derived from saturated and/or from ethylenically unsaturated aliphatic fatty acids. Unsaturated fatty acids may have one or more ethylenically unsaturated carbon- carbon bonds. Preferably, the triglycerides comprise fatty acid groups from different fatty acids.
Preferably, the one or more amphiphilic compounds of component b) are selected from the group consisting of triglycerides of one or more fatty acids having 6 to 10 carbon atoms, esters of fatty acids and fatty alcohols, preferably esters of fatty acids having 8 to 24 carbon atoms and fatty alcohols having 8 to 24 carbon atoms, preferably 10 to 18 carbon atoms, and mixtures thereof.
Examples for particularly preferred amphiphilic compounds b) are cetyl palmitate and/or triglycerides of glycerol with fatty acids selected from the group consisting of caprylic acid, capric acid and mixtures thereof.
According to the invention, fragrances are understood as meaning compositions comprising at least one odor forming compound c) and at least one diluent d). Preferably, mixtures of two or more compounds c) are contained in the fragrances used in this invention. Odor forming compounds c) are generally essential oils, flower oils, extracts from plant and animal drugs, odorants isolated from natural products, chemically modified (semisynthetic) odorants, and odorants obtained by purely synthetic means. The odor forming compounds c) can originate from a large number of herbal starting materials. Examples which may be specified are: flowers, for example lavender, rose, jasmine, neroli; stems and leaves, for example from geranium, patchouli, petit grain, fruits such as anis, coriander, caroway, juniper; fruit peels, for example from agrumes, such as bergamot, lemon, orange; seeds, such as mace, angelica, celery, cardamom; roots, such as angelica, costus, iris, calmus; wood, such as sandalwood, guaiac wood, cedar wood, rosewood; herbs and grasses, such as tarragon, lemongrass, sage, thyme; needles and branches, for example from spruce, fir, pine, dwarf-pine; resins and balsams, for example from galvanum, elemi, benzoin, myrrh, olibanum, opoponax.
Animal raw materials for odor forming compounds c) are, for example, ambergris, musk, civet and castoreum.
Examples of semisynthetic odor forming compounds c) are isoeugenol, vanillin, hydroxycitronellal, citronellol, geranyl acetate, ionones and methylionones. The completely synthetic odorants or fragrances are very diverse and often orientate themselves to natural substances. For a description of the fragrances, reference may be made, for example, to Rompp, Chemielexikon, 9^ edition, keywords "Parfums [perfumes]", "Riechstoffe [odorants]", "Duftstoffe [fragrances]". Further suitable odor forming compounds c) used in fragrances are known to the person skilled in the art.
The odor forming compounds c) in the fragrances used to manufacture the lipid nanoparticles of the present invention preferably contain functional groups of aldehyde, ketone, ester, alcohol, ether or a combination of two or more of these groups.
Preferably, one or more odor forming compounds c) of the fragrance used in the manufacture of the lipid nanoparticles of the present invention have a log P value from 1 to 10, more preferably from 1 to 8.5. Preferred odor forming compounds c) of this type are selected from the group consisting of ethyl butyrate, ethyl 2-methyl butyrate, isoamyl acetate, prenyl acetate, cis-3-hexenyl acetate, hexyl acetate, dextro-limonene, dihydromyrcenol, allyl hexanoate, linalool, 2-phenylethanol, benzyl acetate, heptanoic acid 2-propenyl ester, citronellol, nerol, woody acetate, dimethyl benzyl carbinyl acetate, 3-phenylpropionaldehyde, aldehyde C-14, dimethyl benzyl carbinyl butyrate, musk indanone, phenoxyethyl isobutyrate, sandalrome, hedione, (Z)-3-hexen-1 -yl salicylate, versalide, galaxolide, musk ketone, rose acetate, ethyl vanillin, cedrol, patchouli ethanone, phantolid, laevo-rose oxide, eugenol, raspberry ketone, lilial, methyl cinnamate, geranyl acetate, nerolidol, eugenyl acetate, linalyl acetate, citral, verdyl acetate, aldehyde C-10, methyl linoleate and mixtures thereof.
Preferably, component c) consists of one or more odor forming compounds each having a log P value of 1 or greater than 1 and preferably each having a log P value from 1 to 8.5, or component c) comprises one or more odor forming compounds each having a log P value of 1 or greater than 1 and preferably each having a log P value from 1 to 8.5.
Furthermore preferably, component c) comprises one or more odor forming compounds each having a log P value of 1 or greater than 1 and preferably each having a log P value from 1 to 8.5 and in addition comprises one or more odor forming compounds each having a log P value of smaller than 1 and preferably each having a log P value from 0.9 to -4.
Preferably, the lipid nanoparticles of the present invention comprise one or more odor forming compounds c) having a log P value smaller than 1 and preferably from 0.9 to -4. More preferably, the one or more odor forming compounds c) of this type are selected from the group consisting of ethyl maltol, apple ketal, maltol, maltyl acetate, maple furanone, methyl acetate, acetaldehyde diethyl acetal, acetoin, acetoin acetate, butyric acid, 1 -acetoxyacetone, 2-acetyl furan, 2-furyl methyl ketone, diethyl malate and mixtures thereof. The fragrances comprising odor forming compounds c) and diluents d) are stored in the lipid nanoparticles of the invention. As a result, the fragrances are dissolved, and crystallization of the fragrances is prevented. This permits, inter alia, the preparation of cosmetic or laundry formulations with a skin-friendly pH, and by preventing the fragrances from crystallization, the skin friendliness of the composition is increased further. The mixtures of components used according to the invention having the fragrances dissolved therein spread upon application to the skin, meaning that application of the fragrance to the skin is improved.
The one or more diluents of component d) are preferably selected from the group consisting of aliphatic C1-C4 alcohols, dialkyl ethers having 3 to 8 carbon atoms, alkylene glycols having 2 to 6 carbon atoms, dialkylene glycols having alkyleneoxy units of 2 to 6 carbon atoms, trialkylene glycols having alkyleneoxy units of 2 to 6 carbon atoms, tetraalkylene glycols having alkyleneoxy units of 2 to 6 carbon atoms, partly or totally Ci-C4-alkyl etherified alkylene glycols having 2 to 6 carbon atoms, partly or totally Ci-C4-alkyl etherified dialkylene glycols having alkyleneoxy units of 2 to 6 carbon atoms, partly or totally Ci-C4-alkyl etherified trialkylene glycols having alkyleneoxy units of 2 to 6 carbon atoms, partly or totally Ci-C4-alkyl etherified tetraalkylene glycols having alkyleneoxy units of 2 to 6 carbon atoms, partly or totally Ci-C4-acyl esterified alkylene glycols having 2 to 6 carbon atoms, partly or totally Ci-C4-acyl esterified dialkylene glycols having alkyleneoxy units of 2 to 6 carbon atoms, partly or totally Ci-C4-acyl esterified trialkylene glycols having alkyleneoxy units of 2 to 6 carbon atoms, partly or totally Ci-C4-acyl esterified tetraalkylene glycols having alkyleneoxy units of 2 to 6 carbon atoms, Ci-C4-alkyl etherified and Ci-C4-acyl esterified alkylene glycols having 2 to 6 carbon atoms, Ci-C4-alkyl etherified and Ci-C4-acyl esterified dialkylene glycols having alkyleneoxy units of 2 to 6 carbon atoms, Ci-C4-alkyl etherified and Ci-C4-acyl esterified trialkylene glycols having alkyleneoxy units of 2 to 6 carbon atoms, Ci-C4-alkyl etherified and Ci-C4-acyl esterified tetraalkylene glycols having alkyleneoxy units of 2 to 6 carbon atoms, Ci-C4-aliphatic alcohols substituted with an 1 ,3-dioxolane ring and mixtures thereof.
More preferably, diluents d) are used comprising alkyleneoxy units of 2 to 4 carbon atoms.
Thus, these are diluents d) selected from the group consisting of alkylene glycols having 2 to 4 carbon atoms, dialkylene glycols having alkyleneoxy units of 2 to 4 carbon atoms, trialkylene glycols having alkyleneoxy units of 2 to 4 carbon atoms, tetraalkylene glycols having alkyleneoxy units of 2 to 4 carbon atoms, partly or totally Ci-C4-alkyl etherified alkylene glycols having 2 to 4 carbon atoms, partly or totally Ci-C4-alkyl etherified dialkylene glycols having alkyleneoxy units of 2 to 4 carbon atoms, partly or totally Ci-C4-alkyl etherified trialkylene glycols having alkyleneoxy units of 2 to 4 carbon atoms, partly or totally Ci-C4-alkyl etherified tetraalkylene glycols having alkyleneoxy units of 2 to 4 carbon atoms, partly or totally Ci-C4-acyl esterified alkylene glycols having 2 to 4 carbon atoms, partly or totally Ci-C4-acyl esterified dialkylene glycols having alkyleneoxy units of 2 to 4 carbon atoms, partly or totally Ci-C4-acyl esterified trialkylene glycols having alkyleneoxy units of 2 to 4 carbon atoms, partly or totally Ci-C4-acyl esterified tetraalkylene glycols having alkyleneoxy units of 2 to 4 carbon atoms, Ci-C4-alkyl etherified and Ci-C4-acyl esterified alkylene glycols having 2 to 4 carbon atoms, Ci-C4-alkyl etherified and Ci-C4-acyl esterified dialkylene glycols having alkyleneoxy units of 2 to 4 carbon atoms, Ci-C4-alkyl etherified and Ci-C4-acyl esterified trialkylene glycols having alkyleneoxy units of 2 to 4 carbon atoms, Ci-C4-alkyl etherified and Ci-C4-acyl esterified tetraalkylene glycols having alkyleneoxy units of 2 to 4 carbon atoms and mixtures thereof.
Examples of component d) are monohydric aliphatic C1 -C4 alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol and isobutanol or the corresponding alkyl ethers thereof, such as the corresponding methyl ethers or ethyl ethers thereof. Ethanol is a preferred component d).
Further examples of component d) are hydroxyl-terminated ethylene glycols having 2 to 6 carbon atoms, such as ethylene glycol, di-ethylene glycol or tri ethylene glycol; or hydroxyl-terminated propylene glycols having 2 to 9 carbon atoms, such as propylene glycol, di-propylene glycol or tri-propylene glycol; or hydroxyl-terminated butylene glycols having 2 to 12 carbon atoms, such as butylene glycol, di-butylene glycol ortri- butylene glycol; or hydroxyl-terminated pentylene glycols having 2 to 15 carbon atoms, such as pentylene glycol, di-pentylene glycol or tri-pentylene glycol; or hydroxyl- terminated hexylene glycols having 2 to 18 carbon atoms, such as hexylene glycol, di-hexylene glycol or tri-hexylene glycol; or the corresponding mono- ordi-Ci-C4-alkyl ethers thereof, such as the corresponding mono-methyl ethers, di-methyl ethers, mono- ethyl ethers or di-ethyl ethers thereof; or the corresponding mono- or di-Ci-C4- acylesters thereof, such as the corresponding mono-acetyl esters or di-acetyl esters; or the corresponding Ci-C4-acylesters and Ci-C4-alkyl ethers thereof, such as the corresponding acetyl esters and methyl ethers or acetyl esters and ethyl ethers.
A preferred example of a Ci-C4-aliphatic alcohol substituted with a 1 ,3-dioxolane ring as component d) is 2,2,4-trimethyl-1,3-dioxolane-2-ethanol.
Preferably, the diluent d) has a log P value of smaller than 1 , more preferably from 0 to -1.
Particularly preferably, the one or more diluents of component d) are selected from the group consisting of monohydric aliphatic C1-C4 alcohols, propylene glycol, di-propylene glycol, tri-propylene glycol, propylene glycol mono-methyl ether, di-propylene glycol mono-methyl ether, tri-propylene glycol mono-methyl ether, propylene glycol mono-ethyl ether, di-propylene glycol mono-ethyl ether, tri-propylene glycol mono-ethyl ether and mixtures thereof.
Extraordinarily preferably, the one or more diluents of component d) are selected from the group consisting of monohydric aliphatic C1-C4 alcohols, propylene glycol, dipropylene glycol, propylene glycol mono methyl ether, propylene glycol mono ethyl ether, dipropylene glycol mono methyl ether, dipropylene glycol mono ethyl ether and mixtures thereof.
The fragrance used in the manufacture of the lipid nanoparticles of the present invention is preferably a mixture of one or more compounds c) having a log P value of 1 or greater than 1 and preferably from 1 to 8.5, with one or more diluents d) or in the alternative is preferably a mixture of one or more compounds c) having a log P value of 1 or greater than 1 and preferably from 1 to 8.5, with one or more compounds c) having a log P value smaller than 1 and preferably from 0.9 to -4, with one or more diluents d).
The amount of component c) in the fragrance used in the manufacture of the lipid nanoparticles of the present invention preferably is from 40 to 95 % by weight and more preferably from 60 to 90 % by weight, in each case based on the total weight of the fragrance.
The amount of component d) in the fragrance used in the manufacture of the lipid nanoparticles of the present invention preferably is from 5 to 60 % by weight and more preferably from 10 to 40 % by weight, in each case based on the total weight of the fragrance.
The fragrance comprising components c) and d) which is used in the manufacture of the lipid nanoparticles of the present invention preferably has an interfacial tension of 1 mN/m or greater than 1 mN/m, more preferably from 1 to 60 mN/m and even more preferably from 5 to 30 mN/m.
Interfacial tension occurs at the boundary of two immiscible liquids due to the imbalance of intermolecular forces. Interfacial tension is the tendency of an interface to become spherical to make its surface energy as low as possible. Interfacial tension measurement of fragrance samples can be carried out using Kruss GmbH instrument with model no. DSA100S by pendant drop method. An average of three measurements is noted as interfacial tension unit milli-Newtons per meter (mN/m).
It has been found that the addition of additives e), preferably of those additives e) having a log P value from 10 to 50, stabilizes the lipid nanoparticles of the present invention. These lipid nanoparticles contain fragrances with enhanced water- solubility, but they do not show phase separation and have an improved storage- stability in aqueous media.
Component e) contained in the lipid nanoparticles of the present invention is an additive being selected from the group consisting of Ci2-C26-fatty acid esters from polyols having 2 to 6 carbon atoms and 2 to 4 hydroxyl groups, wherein at least two hydroxyl groups of the polyols are esterified and the polyols are partly or totally esterified, Ci2-C26-fatty acid esters from polyols having 2 to 6 carbon atoms, 2 to 4 hydroxyl groups and one ether group, wherein at least two hydroxyl groups of the polyols are esterified and the polyols are partly or totally esterified, and mixtures thereof.
Ci2-C26-fatty acids used to prepare the esters of component e) may be unsaturated or preferably saturated compounds. Examples of unsaturated fatty acids are myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linoleadic acid, alpha-linolenic acid, arachidonic acid, eicosapaentaneonic aicd, erucic acid and docosahexaenoic acid. Examples of saturated fatty acids are lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, arachidic acid, behenic acid, lignoceric acid and cerotic acid.
Polyols having 2 to 6 carbon atoms and 2 to 4 hydroxyl groups used to prepare the esters of component e) may be unsaturated or preferably saturated compounds, more preferred saturated aliphatic compounds. Examples of polyols are ethylene glycol, propane-1 ,2-diol, propane-1 ,3-diol, butane-1 , 2-diol, butane-1 ,3-diol, butane-1 ,4-diol, butane-2, 3-diol, pentane-1 ,5-diol, hexane-1 ,6-diol, hexane-1 , 2,6- triol, trimethylol- propane, 2, 2-dimethylpropane-1 ,3-diol, glycerol or penthaerithritol.
Polyols having 2 to 6 carbon atoms and 2 to 4 hydroxyl groups used to prepare the esters of component e) may have one ether group which may form part of a heterocyclic ring. Examples of these polyols are diglycerol or sorbitan.
The esters of component e) have between 2 and 4 ester groups.
Preferably, the one or more additives of component e) are selected from fatty acid esters from polyols, wherein the fatty acid residue comprises 12 to 22, preferably 16 to 20 and more preferably 18 carbon atoms and the polyol has 2 to 6 carbon atoms, 2 to 4 hydroxyl groups and contains either no or one ether group and wherein at least two of the hydroxyl groups of the polyols are esterified and the polyols are partly or totally esterified, and mixtures thereof.
In case the polyol part of the one or more additives of component e) contains one ether group the polyol preferably is diglycerol.
Preferably, the one or more additives of component e) are selected from fatty acid esters of polyols, wherein the fatty acid residue comprises 12 to 22, preferably 16 to 20 and more preferably 18 carbon atoms and the polyol is selected from ethylene glycol, glycerol, diglycerol and/or pentaerythritol and wherein at least two of the hydroxyl groups of the polyols are esterified and the polyols are partly or totally esterified, and mixtures thereof.
In case the polyol is glycerol, the fatty acid esters of glycerol are preferably selected from glycerol esters wherein all three hydroxyl groups of the glycerol are esterified (triglycerides).
More preferably, the single additives of the one or more additives of component e) comprise from 38 to 77 carbon atoms.
Even more preferably, the fatty acid underlying the fatty acid part of the one or more additives of component e) is selected from the group consisting of stearic acid, isostearic acid and mixtures thereof.
Preferably, the one or more additives of component e) have a log P value from 10 to 50 and more preferably from 14 to 40.
Particularly preferably, the one or more additives of component e) are selected from the group consisting of ethylene glycol distearate (log P = 16.53), glycerol tristearate (log P = 25.27), diglycerol diisostearate (log P = 14.01), pentaerythritol tetrastearate (log P = 34.01) and mixtures thereof.
Especially preferably, the additive of component e) is pentaerythritol tetrastearate.
Very preferred are lipid nanoparticles of the present invention comprising a) one or more surfactants having an HLB value of greater than 6 and being selected from polyoxyethylene Ci2-Ci8-fatty alcohol ethers with ethoxylation degrees from 10 to 150 and preferably from 15 to 120 and more preferably being selected from the group consisting of ethoxylated lauryl alcohol and ethoxylated stearyl alcohol, each with ethoxylation degrees from 15 to 120 and mixtures thereof, and b) one or more amphiphilic compounds having a log P value from 1 to 5 and being selected from the group consisting of triglycerides of glycerol with one or more fatty acids having 8 to 10 carbon atoms, esters of fatty acids having 8 to 24 carbon atoms and fatty alcohols having 10 to 18 carbon atoms and mixtures thereof, and preferably being selected from the group consisting of cetyl palmitate and triglycerides of glycerol with caprylic acid and/or capric acid, and mixtures thereof, and c) one or more odor forming compounds having a log P value from 1 to 8.5, and d) one or more diluents being selected from the group consisting of aliphatic C1-C4 alcohols, propylene glycol, dipropylene glycol, propylene glycol mono-methyl ether, propylene glycol mono-ethyl ether, dipropylene glycol mono-methyl ether, dipropylene glycol mono-ethyl ether, and mixtures thereof, and e) one or more additives being selected from fatty acid esters of polyols, wherein the fatty acid residue comprises 12 to 22, preferably 16 to 20 and more preferably 18 carbon atoms and the polyol is selected from ethylene glycol, glycerol, diglycerol and/or pentaerythritol and wherein at least two of the hydroxyl groups of the polyols are esterified and the polyols are partly or totally esterified, and mixtures thereof, and more preferably, the one or more additives of component e) are selected from the group consisting of ethylene glycol distearate, glycerol tristearate, diglycerol di isostearate, pentaerythritol tetrastearate and mixtures thereof.
Examples of suitable co-surfactants of component f) are sorbitan esters, citric esters, lactic esters, partial fatty acid glycerides, polyglycerides, glycerol esters, polyglycerol esters, sorbitol esters, fatty alcohols, propylene glycol esters, methyl glucoside esters, alkyl polyglucosides, sugar esters or mixtures of two or more thereof.
Examples of preferred co-surfactants f) are glycerol monostearate, glycerol monopalm itate, glycerol mono-dipalmitate, glycerol monobehenate, glycerol mono- dibehenate, glycerol monooleate, glycerol mono-dioleate, sorbitan tristearate, sorbitan monooleate, sorbitan trioleate, sorbitan tribehenate, propylene glycol monolaurate, propylene glycol monopalm itate, propylene glycol monostearate, propylene glycol monooleate, propylene glycol monobehenate, sorbitan sesquioleate, glycerol stearate, sorbitan monostearate, sorbitan stearate, sorbitan isostearate, glycerol laurateand mixtures thereof. These compounds have HLB- values from 2.5 to 5.2.
Examples of suitable waxes of component g) are waxes of the mono ester type.
As waxes are amphiphilic their amphiphilic behavior may be specified by log P values. Preferred waxes have log P values of 4.7 or greater than 4.7, more preferably of 6 or greater than 6. As their hydrocarbon number increases above C 13 , as is the case for the majority of the wax constituents, log P values of 6 or greater than 6 are found. Waxes are furthermore characterized by their solidification point, which is typically between 30 and 100°C. Waxes are organic compounds that characteristically consist of long alkyl chains. They may also include various functional groups such as fatty acids, primary and secondary long chain alcohols, unsaturated bonds, aromatics, amides, ketones, and aldehydes. They frequently contain fatty acid esters as well.
Waxes used as component g) in the present invention can be synthetic ones, animal or plant derived or montan waxes. Preferred are lipid nanoparticles comprising besides components a) to e) and optional components f) and/or g) at least one humectant as component h), preferably glycerol, and more preferably glycerol in an amount from 2 to 7 % by weight, based on the total weight of the lipid nanoparticle.
The amount of surfactant(s) of component a) of the lipid nanoparticles of the present invention can vary over a broad range. Typical amounts of these surfactant(s) in the lipid nanoparticles of the present invention may be from 1 to 95 % by weight and preferably from 10 to 40 % by weight, in each case based on the total weight of the lipid nanoparticles.
The amount of amphiphilic compounds of component b) of the lipid nanoparticles of the present invention can vary over a broad range. Typical amounts of amphiphilic compounds of component b) in the lipid nanoparticles of the present invention may be from 1 to 95 % by weight and preferably from 10 to 40 % by weight, in each case based on the total weight of the lipid nanoparticles.
The amount of fragrance comprising components c) and d) in the lipid nanoparticles of the present invention can vary over a broad range. Preferably, the amount of the fragrance in the lipid nanoparticles of the present invention is from 1 to 60 % by weight, more preferably from 10 to 50 % by weight and even more preferably from 15 to 40 % weight, in each case based on the total weight of the lipid nanoparticles.
The amount of odor forming compounds c) in the lipid nanoparticles of the present invention can vary over a broad range. Typical amounts of compounds c) in the lipid nanoparticles of the present invention may be from 0.4 to 57 % by weight and preferably from 6 to 45 % by weight, in each case based on the total weight of the lipid nanoparticles.
The amount of diluent(s) d) in the lipid nanoparticles of the present invention can vary over a broad range. Typical amounts of diluent(s) d) in the lipid nanoparticles of the present invention may be from 0.05 to 36 % by weight and preferably from 1 to 20 % by weight, in each case based on the total weight of the lipid nanoparticles.
The amount of the one or more additives of component e) in the lipid nanoparticles of the present invention can vary over a broad range. Preferably, the amount of the one or more additives e) in the lipid nanoparticles of the present invention may be from 1 to 20 % by weight and more preferably from 1 to 12 % by weight, in each case based on the total weight of the lipid nanoparticles.
The amount of co-surfactants, component f), in the lipid nanoparticles of the present invention also can vary over a broad range. Typical amounts of co-surfactants in the lipid nanoparticles of the present invention may be from 0 to 50 % by weight and preferably from 1 to 10 % by weight, in each case based on the total weight of the lipid nanoparticles.
The amount of waxes, component g), in the lipid nanoparticles of the present invention also can vary over a broad range. Typical amounts of these waxes in the lipid nanoparticles of the present invention may be from 0 to 50 % by weight and preferably from 3 to 10 % by weight, in each case based on the total weight of the lipid nanoparticles.
The amount of humectants, component h), in the lipid nanoparticles of the present invention also can vary over a broad range. Typical amounts of these humectants in the lipid nanoparticles of the present invention may be from 0 to 10 % by weight, preferably from 2 to 7 % by weight and more preferably from 3 to 7 % by weight in each case based on the total weight of the lipid nanoparticles.
Preferred are lipid nanoparticles of the present invention, wherein the amount of component a) is from 1 to 95 % by weight, and the amount of component b) is from 1 to 95 % by weight, and the amount of component c) is from 0.4 to 57 % by weight, and the amount of component d) is from 0.05 to 36 % by weight, and the amount of component e) is from 1 to 20 % by weight, wherein the weight percentages in each case are based on the total weight of the lipid nanoparticle. The fragrances comprising components c) and d) can be introduced in high amounts into the lipid nanoparticles comprising components a), b) and e) and optionally f) and/or g) and/or h) and be stored there. As a result, the fragrances are dissolved, and crystallizing out of the fragrances is prevented. This permits, inter alia, the preparation of cosmetic or laundry formulations with a skin-friendly pH, and by preventing the fragrances from crystallizing out, the skin friendliness of the composition is increased further. The mixtures of components used according to the invention having the fragrances dissolved therein spread upon application to the skin, meaning that application of the fragrance to the skin is improved.
Preferably, the lipid nanoparticles of the present invention are provided in aqueous compositions with amounts of the lipid nanoparticles preferably from 0.1 to 60 % by weight, more preferably from 1 to 50 % by weight and even more preferably from 5 to 20 % by weight, in each case based on the total weight of the aqueous composition.
The present invention also relates to aqueous compositions comprising one or more lipid nanoparticles of the present invention and water, wherein the amount of the one or more lipid nanoparticles preferably is from 0.1 to 60 % by weight, more preferably from 1 to 50 % by weight and even more preferably from 5 to 20 % by weight, in each case based on the total weight of the aqueous composition.
The aqueous composition may consist of only water, or may consist of water and adjuvants, such as electrolytes, alcohols, including polyols, rheology modifiers, surfactants or mixtures comprising two or more of said adjuvants. The polyols may comprise propylene glycol, polyethylene glycol, glycerol, polyglycerol, sorbitol, isosorbide or dimethyl isosorbide.
Preferably, the aqueous compositions of the present invention comprise one or more rheology modifiers, more preferably one or more natural biopolymers and even more preferably one or more natural biopolymers selected from the group consisting of xanthan gum, guar gum, gellan gum, gum arabic and mixtures thereof.
The amount of the adjuvants in the aqueous compositions of the present invention preferably is from 1 to 8 % by weight and more preferably from 1.5 to 5 % by weight, in each case based on the total weight of the aqueous composition.
Preferably, the amount of fragrance in the aqueous compositions of the present invention is from 1 to 35 % by weight, based on the total weight of the aqueous composition.
The lipid nanoparticles of the present invention may be prepared by mixing selected components constituting the lipid nanoparticles in different containers and by combining said mixtures or by feeding the components constituting the lipid nanoparticles to an emulsification device for manufacture of nano-emulsions. An example of such emulsification device is disclosed in US 2013/0201785 A1 .
In this document an emulsifying device for continuous production of emulsions and/or dispersions is disclosed which comprises a) at least one mixing apparatus comprising a rotationally symmetric chamber sealed airtight on all sides, at least one inlet line for introduction of free- flowing components, at least one outlet line for discharge of the mixed free- flowing components, a stirrer unit which ensures laminar flow and comprises stirrer elements secured on a stirrer shaft, the axis of rotation of which runs along the axis of symmetry of the chamber and the stirrer shaft of which is guided on at least one side, wherein the at least one inlet line is arranged upstream of or below the at least one outlet line, wherein the ratio between the distance between inlet and outlet lines and the diameter of the chamber is > 2:1 , wherein the ratio between the distance between inlet and outlet lines and the length of the stirrer arms of the stirrer elements is 3:1 to 50:1 , and wherein the ratio of the diameter of the stirrer shaft, based on the internal diameter of the chamber, is 0.25 to 0.75 times the internal diameter of the chamber, such that the components introduced into the mixing apparatus via the at least one inlet line are stirred and continuously transported by means of a turbulent mixing area on the inlet side, in which the components are mixed turbulently by the shear forces exerted by the stirrer units, a downstream percolating mixing area in which the components are mixed further and the turbulent flow decreases, a laminar mixing area on the outlet side, in which a lyotropic, liquid-crystalline phase is established in the mixture of the components, in the direction of the outlet line, b) at least one drive for the stirrer unit and c) at least one conveying device per component or per component mixture.
The present invention also relates to a first method of manufacturing the lipid nanoparticles of the present invention or an aqueous composition of the present invention comprising the steps: i) forming a composition A by combining one or more surfactants of component a) and water in a first container, ii) forming a composition B by combining one or more amphiphilic compounds of component b), a fragrance comprising component c) and component d) as well as one or more additives of component e) in a second container, iii) combining compositions A and B by adding component B to component A under agitation, and iv) adding water as composition C to the combined compositions A and B from step iii).
In a preferred variant of this first method components of composition A in step i) and/or components of composition B in step ii) are heated in order to melt the components in said compositions. Preferred heating temperatures are from 30 to 130°C and preferably from 30 to 80°C.
In still another preferred variant of this first method a composition C comprising one or more surfactants and/or one or more rheology modifiers is used.
The present invention also relates to a second method of manufacturing the lipid nanoparticles of the present invention comprising the steps: ia) feeding a composition A comprising one or more surfactants of component a) and water to a first inlet line of an emulsification device, iia) feeding a composition B comprising one or more amphiphilic compounds of component b), fragrance comprising components c) and d) and one or more additives of component e) to a second inlet line of an emulsification device, iiia) combining compositions A and B in a turbulent mixing zone in the emulsification device, iva) transporting the mixed compositions within the emulsification device towards an outlet line, whereby laminar flow of the mixed components is established in the zone preceding the outlet line thereby vesicles are formed, and va) discharging the lipid nanoparticles via the outlet line from the emulsification device.
In a preferred embodiment of the second inventive method the lipid nanoparticles formed in the emulsification device are diluted with water or with an aqueous phase comprising adjuvants. This can be performed in a separate device by introducing the lipid nanoparticles into water which optionally contains one or more additional surfactants and/or optionally contains one or more rheology modifiers.
The lipid nanoparticles and the aqueous compositions of the present invention may preferably be used in cosmetic formulations or in laundry formulations.
Cosmetic formulations are preferably skin-treatment compositions or hair- treatment compositions. Laundry formulations are preferably laundry additives, washing agents or fabric softeners.
Cosmetic formulations or laundry formulations usually comprise further ingredients typical of these formulations. The combination of fragrance-containing lipid nanoparticles, water and optionally other substances can, however, also like the lipid nanoparticles and water itself, be used for producing hair- and/or skin cleansing compositions or for producing washing agents and/or fabric softeners. Such hair- and/or skin-cleansing compositions may be present in any desired suitable form, for example as shampoos, shower gels, face cleansers or soaps.
In particular, the washing agents or fabric softeners may be present in any desired suitable form, for example as powders or concentrates.
In addition to the storage effect, the lipid nanoparticles of the present invention permit also extensive protection of the fragrances against oxidative decomposition. If appropriate, further antioxidants can also be added.
Even without the addition of antioxidants, the fragrances in the lipid nanoparticles of the present invention or in the cosmetic or laundry compositions of the present invention are significantly better protected against oxidation than in conventional application forms.
The present invention also relates to the use of the lipid nanoparticles of the present invention or the aqueous compositions of the present invention in cosmetic and hair care compositions, preferably in compositions for skin treatment or for hair treatment.
The present invention furthermore relates to the use of the lipid nanoparticles of the present invention or the aqueous compositions of the present invention in laundry compositions, preferably in washing agents or in fabric softeners.
The present invention furthermore relates to the use of the lipid nanoparticles of the present invention or the aqueous compositions of the present invention for providing prolonged fragrance release by slow diffusion in cosmetic or hair care compositions or in laundry compositions, preferably in washing agents or in fabric softeners.
The invention furthermore relates to a composition, in particular cosmetic composition or fabric conditioner composition, comprising the lipid nanoparticles described herein and one or more further components (F). “Fabric conditioner” as used in this description also means “fabric softener”. Preferably, the composition of the invention is a cosmetic composition or a fabric conditioner composition. In a preferred embodiment, the composition of the invention is a cosmetic composition. In another preferred embodiment, the composition of the invention is a fabric conditioner composition.
For example, the composition of the invention may be a cosmetic composition selected from the group consisting of shampoo, hair conditioner, body wash, bubble bath, bath oil, facial cleanser, cleansing mask, cleansing milk, micellar water, make-up remover, cleansing wipes, perfume, soaps, shaving soaps, shaving foams and cleansing foams.
Preferred cosmetic compositions are hair care compositions or skin care compositions. Preferably, the composition of the invention is a hair care composition or a skin care composition. More preferred cosmetic compositions are hair care compositions, such as shampoo compositions or hair conditioner compositions. More preferably, the composition of the invention is a hair care composition, such as a shampoo composition or a hair conditioner composition.
Particularly preferably, the composition of the invention is a shampoo composition. The shampoo composition can be in the form of rinse-off products or ‘dry shampoo’ products, can be opaque or transparent, and can be formulated in a wide variety of product forms, including creams, gels, emulsions, mousses and sprays. Preferably, the shampoo composition of the present invention is in the form of a rinse-off product. The shampoo composition is, for example, suitable for cleansing human hair or animal hair, preferably human hair.
Also particularly preferably, the composition of the invention is a hair conditioner composition. The hair conditioner composition can be in the form of rinse-off products or leave-on products, can be opaque or transparent, and can be formulated in a wide variety of product forms, including creams, gels, emulsions, mousses and sprays. Preferably, the hair conditioner composition is in the form of a rinse-off product. Typically, the composition of the invention, in particular cosmetic composition or fabric conditioner composition, comprises from 0.1 to 20 wt.-%, preferably from 0.2 to 15 wt.-%, more preferably from 0.3 to 10 wt.-%, even more preferably from 0.5 to 5 wt.-%, particularly preferably from 1 to 3 wt.-% of the lipid nanoparticles described herein, based on the total weight of the composition. For example, the composition of the invention, in particular cosmetic composition or fabric conditioner composition, comprises 1 wt.-%, 2 wt.-%, 3 wt.-%, 4 wt.-%, 5 wt.-%,
6 wt.-%, 7 wt.-%, 8 wt.-%, 9 wt.-%, or 10 wt.-% of the lipid nanoparticles described herein, based on the total weight of the composition.
The composition of the invention, in particular cosmetic composition or fabric conditioner composition, comprises one or more further components (F), which can be in an amount of at least 0.01% by weight, preferably at least 0.05% by weight, more preferably at least 0.1% by weight, even more preferably at least 0.5% by weight, such as 0.5 to 20% by weight of the composition. Preferably, the component (F) is selected from the group consisting of acidity regulators, colorants, conditioning agents, emulsifiers, film formers, fragrances, glossers, humectants, lubricants, moisturizers, pigments, preservatives, skin penetration enhancers, stabilizers, surfactants, thickeners, and viscosity modifiers. More preferably, the component (F) is selected from the group consisting of acidity regulators, glossers, lubricants, and surfactants.
Suitable lubricants are, for example, fatty alcohol components having 6 to 18 carbon atoms. The surfactants may, for example, be selected from non polymeric, cationic quaternary ammonium compounds, in particular cetrimonium chloride (CTAC).
Suitable classical cationic conditioning agents include cationic quaternary ammonium salts. In at least one embodiment, the component (F) is a cationic quaternary ammonium salt. Examples of such quaternary ammonium salts include benzyl triethyl ammonium chloride, cetyl trimethylammonium chloride (cetrimonium chloride, CTAC), behentrimonium chloride (BTAC) or cetylpyridinium chloride. As cationic components, a variety of further cationic polymers are suitable, including quaternized cellulose ethers, copolymers of vinylpyrrolidone, acrylic polymers, including homopolymers or copolymers of dimethyldiallylammonium chloride or acrylamide. Also suitable are various types of homo- or copolymers derived from acrylic or methacrylic acid, acrylamide, methylacrylamide, diacetone- acrylamide.
In at least one embodiment, the component (F) is a glosser. Typical glossers are silicones. Suitable as silicones are volatile or nonvolatile nonionic silicone fluids, silicone resins, and silicone semisolids or solids. Volatile silicones are linear or cyclic silicones having a measureable vapor pressure, which is defined as a vapor pressure of at least 2 mm of mercury at 20°C. Also suitable are water insoluble nonvolatile silicone fluids including polyalkyl siloxanes, polyaryl siloxanes, polyalkylaryl siloxanes, polyether siloxane copolymers, amine-functional silicones, or mixtures thereof.
The composition of the invention may contain from 0.05 to 5%, preferably 0.5 to 5% by weight of at least one oil component. Typical oils are organic oils, which often are esters. The oil component may comprise glyceryl esters of fatty acids, or triglycerides, coconut oil, almond oil, apricot kernel oil, avocado oil, babassu oil, evening primrose oil, camelina sativa seed oil, grape seed oil, macadamia ternifolia seed oil, corn oil, meadowfoam seed oil, mink oil, olive oil, palm kernel oil, safflower oil, sesame oil, soybean oil, sunflower oil, wheat germ oil, and camellia reticulata seed oil. Also suitable as the oil component are sorbitan esters.
The composition of the invention can contain from 0.1 to 10% by weight, preferably from 0.2 to 5% by weight, more preferably from 0.2 to 3% by weight, also more preferably from 0.5 to 5% by weight of at least one rheology modifying agent, in particular a gelling and thickening agent. Examples are cellulosic thickeners, for example, hydroxyethylcellulose, hydroxypropylcellulose, and carboxymethylcellulose, guar gum, such as hydroxypropylguar, gums of microbial origin, such as xanthan gum and scleroglucan gum, and synthetic thickeners, such as crosslinked homo- or copolymers of acrylic acid and/or of acrylamidopropanesulphonic acid. Other rheology modifying agents include fatty acid amides such as coconut diethanolamide and monoethanolamide, and oxyethylenated monoethanolamide of carboxylic acid alkyl ether.
Rheology modifying agents are also known as structuring materials. Common structuring materials include polymeric materials known as "carbomers", including, for example the cross-linked polyacrylic acid polymers available from Lubrizol Corporation under the trademark Carbopol®. Another class of (meth)acylic acid polymers are alkali-swellable emulsion (ASE) polymers. ASE polymers include, for example, Aculyn® 38 copolymer from Dow. Carbomers and ASE polymers belong to a class of materials known as hydrodynamic thickeners. These hydrodynamic thickeners include acid groups in their polymeric structure that, when deprotonated, form anionic charges that repel each other, causing the polymer chains to expand and entangle. Expansion and chain entanglement can give rise to thickening and suspending effects provided by the deprotonated polymers. The properties of these hydrodynamic thickeners are impacted by their molecular weight, acid group content, degree of cross-linking, and extent of swelling. These thickeners are also known as "space filling" or "volume excluding", and tend to increase both viscosity and yield point as the concentration thereof is increased. In use, hydrodynamic polymers commonly give rise to compositions that exhibit shear thinning or non-Newtonian behavior. Another class of (meth)acrylic acid based rheology modifiers are hydrophobically modified alkali swellable (HASE) polymers. Like ASE polymers, the HASE polymers include acid groups, the deprotonation of which gives rise to polymer swelling. Additionally, the HASE polymers include hydrophobic side groups, chains or blocks that give rise to associative interactions with each other, as well as with other hydrophobic species present in the compositions in which they are employed, for example, hydrophobic groups of surfactants, fatty acids, other thickening agents, and the like.
Association creates hydrophobic regions distributed throughout the polymer chain network. This can also help to enhance the properties of the materials as solubilizing agents. Aculyn® 22 and Aculyn® 28 copolymers from Dow and Aqua SF 1® copolymer from Lubrizol Corporation are among the commonly used HASE materials.
U.S. Patent 4,529,773 (Witiak et al.) reports alkali-soluble emulsion polymers activated by neutralization to a pH above 6.5, and subsequently acidified in the presence of a surfactant. These are described as useful thickeners in acidic compositions. The polymers are formed from the copolymerization of a monomer system that includes: (1 ) methacrylic or acrylic acid, (2) methacrylic or acrylic acid ester of a C8-C30 alkyl or, as therein more particularly described, a hydrocarbyl monoether of polyethylene glycol, (3) a C1-C4 alkyl acrylate or methacrylate, and, optionally, (4) a small amount of a polyethylenically unsaturated monomer.
The composition of the invention can also comprise as component (F) a fatty compound. The fatty compound may be included in the composition at a level of from 0.1 to 20 % by weight, preferably from 1 .0 to 10 % by weight. The fatty compound is selected from the group consisting of fatty alcohols (e.g. cetyl alcohol, stearyl alcohol or cetearyl alcohol), fatty acids, fatty alcohol derivatives, fatty acid derivatives, or mixtures thereof.
It is understood that the components disclosed can in some instances fall into more than one classification, e.g., some fatty alcohol derivatives can also be classified as fatty acid derivatives. However, a given classification, is not intended to be a limitation on that particular compound but is done so for convenience of classification and nomenclature. Non-limiting examples are found in International Cosmetic Ingredient Dictionary and Handbook, Fourteenth Edition (2014), and CTFA Cosmetic Ingredient Handbook, Second Edition, 1992. Preferably, fatty alcohols have 14 to 30 or 16 to 22 carbon atoms. These fatty alcohols are saturated and can be linear or branched. Examples of fatty alcohols are cetyl alcohol, stearyl alcohol, behenyl alcohol, and mixtures thereof. Preferred fatty acids have from 10 to 30 or from 12 to 22 carbon atoms. These fatty acids can be saturated and can be linear or branched. Also included herein are salts of these fatty acids. Examples of fatty acids are lauric acid, palmitic acid, stearic acid, behenic acid, sebacic acid, or mixtures thereof. The fatty alcohol derivatives and fatty acid derivatives useful herein include alkyl ethers of fatty alcohols, alkoxylated fatty alcohols, alkyl ethers of alkoxylated fatty alcohols, esters of fatty alcohols, fatty acid esters of compounds having esterifiable hydroxy groups, hydroxy-substituted fatty acids, or mixtures thereof. Examples of fatty alcohol derivatives and fatty acid derivatives include methyl stearyl ether, polyoxyethylene ethers of behenyl alcohol, ethyl stearate, cetyl stearate, cetyl palmitate, stearyl stearate, myristyl myristate, polyoxyethylene cetyl ether stearate, polyoxyethylene stearyl ether stearate, polyoxyethylene lauryl ether stearate, ethyleneglycol monostearate, polyoxyethylene monostearate, polyoxyethylene distearate, propyleneglycol monostearate, propyleneglycol distearate, trimethylolpropane distearate, sorbitan stearate, poly glyceryl stearate, glyceryl monostearate, glyceryl distearate, glyceryl tristearate, or mixtures thereof.
The composition of the invention may comprise an aqueous carrier. The level and species of the aqueous carrier are selected according to the compatibility with other components and other desired characteristic of the composition. The aqueous carrier may, for example, be water or water solutions of lower alkyl alcohols or polyhydric alcohols. The lower alkyl alcohols may, for example, be monohydric alcohols having 1 to 6 carbons, often ethanol and/or isopropanol. The polyhydric alcohols may, for example, be propylene glycol, hexylene glycol, glycerin, and/or propane diol. Preferably, the aqueous carrier is substantially water. Deionized water is preferably used. Water from natural sources, including minerals can also be used, depending on the desired characteristic of the composition. Generally, the composition of the invention can comprise up to 80 %, often even up to 95 % by weight of water.
The compositions of the invention may also include as a further component (F), other components being suitable for rendering the compositions more cosmetically or aesthetically acceptable or to provide them with additional usage benefits. Such other components can generally be used individually at levels of from 0.001 % to 5 % by weight. A wide variety of further components (F) can be formulated into the composition of the invention. These include conditioning agents, such as hydrolysed collagen, vitamin E, panthenol, panthenyl ethyl ether, hydrolysed keratin, proteins, plant extracts, nutrients; emollients, such as PPG-3 myristyl ether, trimethyl pentanol hydroxyethyl ether; hair-fixative polymers, such as amphoteric fixative polymers, cationic fixative polymers, anionic fixative polymers, nonionic fixative polymers, silicone grafted copolymers; preservatives, such as benzyl alcohol, methyl paraben, propyl paraben, imidazolidinyl urea; pH adjusting agents, such as citric acid, sodium citrate, succinic acid, phosphoric acid, sodium hydroxide, sodium carbonate; salts, in general, such as potassium acetate or sodium chloride; coloring agents; hair oxidizing (bleaching) agents, such as hydrogen peroxide, perborate or persulfate salts; hair reducing agents such as thioglycolates; perfumes; sequestering agents, such as disodium ethylene- diamine tetraacetate; ultraviolet and infrared screening and absorbing agents, such as octyl salicylate; anti-dandruff agents, such as zinc pyrithione, piroctone olamine or salicylic acid.
In at least one embodiment, the composition of the invention comprises an anti fungal substance. In at least one embodiment, the anti-fungal substance is selected from the group consisting of ketoconazole, oxiconazole, bifonazole, butoconazole, cloconazole, clotrimazole, econazole, enilconazole, fenticonazole, isoconazole, miconazole, sulconazole, tioconazole, fluconazole, itraconazole, terconazole, naftifine, terbinafine, zinc pyrithione, piroctone olamine (octopirox), and combinations thereof. In at least one embodiment, the composition of the invention comprises a total amount of anti-fungal substance in the composition of from 0.1 wt.-% to 1 wt.-%. In at least one embodiment, the composition of the invention comprises piroctone olamine. In at least one embodiment, the composition of the invention comprises a pyridinethione anti-dandruff particulate. For example, 1-hydroxy-2-pyridinethione salts are highly preferred particulate anti dandruff agents. The concentration of pyridinethione anti-dandruff particulate may range from 0.1 % to 4% by weight of the formulation, preferably from 0.1 % to 3%, more preferably from 0.3% to 2%. Preferred pyridinethione salts include those formed from heavy metals such as zinc, tin, cadmium, magnesium, aluminum and zirconium, preferably zinc, more preferably the zinc salt of 1 -hydroxy-2- pyridinethione (known as "zinc pyridinethione" or "ZPT"), more preferably 1-hydroxy-2-pyridinethione salts in platelet particle form. Salts formed from other cations, such as sodium, may also be suitable. Pyridinethione anti-dandruff agents are described, for example, in U.S. Pat. No. 2,809,971; U.S. Pat. No. 3,236,733; U.S. Pat. No. 3,753,196; U.S. Pat. No. 3,761,418; U.S. Pat. No. 4,345,080;
U.S. Pat. No. 4,323,683; U.S. Pat. No.4,379,753; and U.S. Pat. No. 4,470,982. It is contemplated that when ZPT is used as the anti- dandruff particulate in the compositions herein, that the growth or regrowth of hair may be stimulated or regulated, or both, or that hair loss may be reduced or inhibited, orthat hair may appear thicker or fuller.
Preferably, salt is present at levels from 0.1 to 1 wt.-% of the total composition to adjust the product viscosity. Preferably, NaOH is present at levels from 0.1 to 1 wt.-% of the total composition to adjust the pH of the formulation.
The composition of the invention may contain as a further component (F) a polysorbate for adjusting rheology, for example, polysorbate-20, polysorbate-21 , polysorbate-40, polysorbate-60, or mixtures thereof. The polysorbate can be contained in the composition in amounts up to 5% (e.g. 0.1 to 5%) by weight.
The composition of the invention can also contain as a further component (F) a polypropylene glycol. Preferred polypropylene glycols are those having a weight average molecular weight of from 200 to 100000 g/mol. The polypropylene glycol may be either water-soluble, water-insoluble, or may have a limited solubility in water, depending upon the degree of polymerization and whether other moieties are attached thereto. The desired solubility of the polypropylene glycol in water will depend in large part upon the form of the composition (e.g., leave-on hair care composition, rinse-off hair care composition). The polypropylene glycol can be included in the composition of the invention at a level of up to 10% by weight.
For example, in a rinse-off hair care composition, it is preferred that the polypropylene glycol has a solubility in water at 25°C of less than about 1 g/100 g water, more preferably a solubility in water of less than about 0.5 g/100 g water, and even more preferably a solubility in water of less than about 0.1 g/100 g water. The polypropylene glycol can be included in the composition of the invention at a level of up to 10% by weight.
The composition of the invention can also contain, as a further component (F), low melting point oil selected from the group consisting of hydrocarbons having from 10 to 40 carbon atoms; unsaturated fatty alcohols having from 10 to 30 carbon atoms such as oleyl alcohol; unsaturated fatty acids having from about 10 to about 30 carbon atoms; fatty acid derivatives; fatty alcohol derivatives; ester oils such as pentaerythritol ester oils, trimethylol ester oils, citrate ester oils, or glyceryl ester oils; poly [alpha]-olefin oils; and mixtures thereof. Preferred low melting point oils are selected from the group consisting of ester oils such as pentaerythritol ester oils, trimethylol ester oils, citrate ester oils, or glyceryl ester oils; poly [alpha]-olefin oils; and mixtures thereof. Particularly useful pentaerythritol ester oils and trimethylol ester oils are pentaerythritol tetraisostearate, pentaerythritol tetraoleate, trimethylolpropane triisostearate, trimethylolpropane trioleate, or mixtures thereof. Particularly useful glyceryl esters are triisostearin, triolein or trilinolein.
The composition of the invention can also contain, as a further component (F), a cationic polymer. Cationic polymers may be present in the composition of the invention for further enhancing deposition performance.
Suitable cationic polymers may be homopolymers which are cationically substituted or may be formed from two or more types of monomers. The weight average (Mw) molecular weight of the polymers will generally be between 100 000 and 2 million g/mol. The polymers will have cationic nitrogen containing groups such as quaternary ammonium or protonated amino groups, or a mixture thereof.
If the molecular weight of the polymer is too low, then the conditioning effect is poor. If too high, then there may be problems of high extensional viscosity leading to stringiness of the composition when it is poured.
The cationic nitrogen-containing group will generally be present as a substituent on a fraction of the total monomer units of the cationic polymer. Thus, when the polymer is not a homopolymer it can contain non-cationic spacer monomer units. Such polymers are described in the CTFA Cosmetic Ingredient Directory, 3rd edition. The ratio of the cationic to non-cationic monomer units is selected to give polymers having a cationic charge density in the required range, which is generally from 0.2 to 3.0 meq/gm. The cationic charge density of the polymer is suitably determined via the Kjeldahl method as described in the US Pharmacopoeia under chemical tests for nitrogen determination.
Suitable cationic polymers include, for example, copolymers of vinyl monomers having cationic amine or quaternary ammonium functionalities with water soluble spacer monomers such as (meth)acrylamide, alkyl and dialkyl (meth)acrylamides, alkyl (meth)acrylate, vinyl caprolactone and vinyl pyrrolidine. The alkyl and dialkyl substituted monomers preferably have C1-C7 alkyl groups, more preferably C1-3 alkyl groups. Other suitable spacers include vinyl esters, vinyl alcohol, maleic anhydride, propylene glycol and ethylene glycol.
The cationic amines can be primary, secondary or tertiary amines, depending upon the particular species and the pH of the composition. In general, secondary and tertiary amines, especially tertiary, are preferred.
Amine substituted vinyl monomers and amines can be polymerized in the amine form and then converted to ammonium by quaternization.
The cationic polymers can comprise mixtures of monomer units derived from amine- and/or quaternary ammonium-substituted monomer and/or compatible spacer monomers.
Suitable cationic polymers include, for example cationic diallyl quaternary ammonium- containing polymers including, for example, dimethyldiallylammonium chloride homopolymer and copolymers of acrylamide and dimethyldiallylammonium chloride, referred to in the industry (CTFA) as Polyquaternium 6 and Polyquaternium 7, respectively; mineral acid salts of amino- alkyl esters of homo- and co-polymers of unsaturated carboxylic acids having from 3 to 5 carbon atoms, (as described in US4009256A1 from NAT STARCH CHEM CORP); cationic polyacrylamides (as described in W095/22311A1 Unilever PLC). Other cationic polymers that can be used include cationic polysaccharide polymers, such as cationic cellulose derivatives, cationic starch derivatives, and cationic guar gum derivatives.
Cationic polysaccharide polymers suitable for use in compositions of the invention include monomers of the formula: A-0-[R-N+(R1)(R2)(R3)X ], wherein: A is an anhydroglucose residual group, such as a starch or cellulose anhydroglucose residual. R is an alkylene, oxyalkylene, polyoxyalkylene, or hydroxyalkylene group, or combination thereof. R1 , R2 and R3 independently represent alkyl, aryl, alkylaryl, arylalkyl, alkoxyalkyl, or alkoxyaryl groups, each group containing up to about 18 carbon atoms. The total number of carbon atoms for each cationic moiety (i.e. , the sum of carbon atoms in R1 , R2 and R3) is preferably about 20 or less, and X is an anionic counterion. Another type of cationic cellulose includes the polymeric quaternary ammonium salts of hydroxyethyl cellulose reacted with lauryl dimethyl ammonium- substituted epoxide, referred to in the industry (CTFA) as Polyquaternium 24. These materials are available from the Amerchol Corporation, for instance under the trade name Polymer LM-200. Other suitable cationic polysaccharide polymers include quaternary nitrogen-containing cellulose ethers (e.g. as described in US-3962418 from L’Oreal), and copolymers of etherified cellulose and starch (e.g. as described in US-3958581 from L’Oreal).
A particularly suitable type of cationic polysaccharide polymer that can be used is a cationic guar gum derivative, such as guar hydroxypropyltrimethylammonium chloride (commercially available from Solvay in their JAGUAR trade named series). Examples of such materials are JAGUAR C13S, JAGUAR C14, JAGUAR C15, JAGUAR C17 and JAGUAR C16 Jaguar CHT and JAGUAR C162.
Mixtures of any of the above cationic polymers may be used.
Cationic polymer may be present in the composition of the invention at levels of from 0.01 to 5 wt.-%, preferably from 0.05 to 1 wt.-%, more preferably from 0.08 to 0.5 wt.-% by total weight of cationic polymer based on the total weight of the composition.
In at least one embodiment, the cationic polymers have a number average molecular weight of at least about 5000 g/mol, typically from 10000 g/mol to 10 million g/mol and are selected from the group consisting of copolymers of vinyl monomers having cationic amine or quaternary ammonium functionalities with water soluble spacer monomers such as acrylamide, methacrylamide, alkyl and dialkyl acrylamides, alkyl and dialkyl methacrylamides, alkyl acrylate, alkyl methacrylate, vinyl caprolactone, and vinyl pyrrolidone. Other suitable spacer monomers include vinyl esters, vinyl alcohol, maleic anhydride, propylene glycol, and ethylene glycol. Preferred cationic polymers are cationic celluloses, cationic starches, and cationic guar gums. Commercially available cationic guar polymers are e.g. Jaguar® from Solvay.
In at least one embodiment, the composition of the invention comprises a surfactant system. In at least one embodiment, the surfactant system comprises a surfactant selected from the group consisting of anionic surfactants, cationic surfactants, non-ionic surfactants, zwitterionic surfactants and/or amphoteric surfactants.
In at least one embodiment, the composition of the invention comprises a total amount of surfactant of from 0.01 wt.-% to 70 wt.-%, from 0.1 wt.-% to 40%, from 1 wt.-% to 30%, from 2 wt.-% to 20 wt.-%.
In at least one embodiment, the composition of the invention comprises an anionic surfactant. In at least one embodiment, the anionic surfactant is selected from the group consisting of (Cio-C2o)-alkyl and alkylene carboxylates, alkyl ether carboxylates, fatty alcohol sulfates, fatty alcohol ether sulfates, alkylamide sulfates and sulfonates, fatty acid alkylamide polyglycol ether sulfates, alkanesulfonates and hydroxyalkanesulfonates, olefinsulfonates, acyl esters of isethionates, alpha- sulfo fatty acid esters, alkylbenzenesulfonates, alkylphenol glycol ether sulfonates, sulfosuccinates, sulfosuccinic monoesters and diesters, fatty alcohol ether phosphates, protein/fatty acid condensation products, alkyl monoglyceride sulfates and sulfonates, alkylglyceride ether sulfonates, fatty acid methyltaurides, fatty acid sarcosinates, sulforicinoleates, acylglutamates, and mixtures thereof. The anionic surfactants (and their mixtures) can be used in the form of their water-soluble or water-dispersible salts, examples being the sodium, potassium, magnesium, ammonium, mono-, di-, and triethanolammonium, and analogous alkylammonium salts. In at least one embodiment, the anionic surfactant is the salt of an anionic surfactant comprising 12 to 14 carbon atoms. In at least one embodiment, the anionic surfactant is selected from the group consisting of sodium lauryl sulfate, sodium laureth sulfate, sodium tridecyl sulfate, sodium trideceth sulfate, sodium myristyl sulfate, sodium myreth sulfate, and mixtures thereof. Typical anionic surfactants for use in compositions of the invention include sodium oleyl succinate, ammonium lauryl sulphosuccinate, sodium lauryl sulphate, sodium lauryl ether sulphate, sodium lauryl ether sulphosuccinate, ammonium lauryl sulphate, ammonium lauryl ether sulphate, sodium dodecyl benzene sulphonate, triethanolamine dodecylbenzene sulphonate, sodium cocoyl isethionate, sodium lauryl isethionate, lauryl ether carboxylic acid and sodium N-lauryl sarcosinate. Preferred anionic surfactants are selected from sodium lauryl sulphate and sodium lauryl ether sulphate(n)EO, (where n is from 1 to 3); more preferably sodium lauryl ether sulphate(n)EO, (where n is from 1 to 3); most preferably sodium lauryl ether sulphate(n)EO where n=1. Preferably the level of alkyl ether sulphate is from 0.5 wt.-% to 25 wt.-% of the total composition, more preferably from 3 wt.-% to 18 wt.-%, most preferably from 6 wt.-% to 15 wt.-% of the total composition.
The total amount of anionic surfactant in compositions of the invention may range from 0.5 wt.-% to 45 wt.-%, more preferably from 1.5 wt.-% to 20 wt.-%.
Compositions of the invention may comprise fatty acyl isethionate, if present preferably at a level of from 1 to 10 wt.-%, more preferably from 2 to 8 wt.-%, most preferably from 2.5 to 7.5 wt.-%. A preferred fatty acyl isethionate product comprises fatty acyl isethionate surfactant at a level of from 40 to 80 wt.-% of the product, as well as free fatty acid and/or fatty acid salt at a level of from 15 to 50%. Preferably, greater than 20 wt.-% and less than 45 wt.-%, more preferably greater than 25 wt.-% and less than 45 wt.-% of the fatty acyl isethionate are of chain length greater than or equal to Ci6; and greater than 50 wt.-%, preferably greater than 60 wt.-% of the free fatty acid/soap is of chain length Ci6 to C20. In addition, the product may contain isethionate salts, which are present typically at levels less than 5 wt.-%, and traces (less than 2 wt.-%) of other impurities.
Preferably, a mixture of aliphatic fatty acids is used for the preparation of commercial fatty acyl isethionate surfactants. The resulting fatty acyl isethionate surfactants (e.g., resulting from reaction of alkali metal isethionate and aliphatic fatty acid) preferably should have more than 20 wt.-%, preferably more than 25 wt.-%, but no more than 45 wt.-%, preferably 35 % (on basis of fatty acyl isethionate reaction product) of fatty acyl group with 16 or greater carbon atoms to provide both excellent lather and mildness of the resulting fatty acyl isethionate product. These longer chain fatty acyl isethionate surfactants and fatty acids, i.e. fatty acyl group and fatty acid with 16 or more carbons, can typically form insoluble surfactant/fatty acid crystals in water at ambient temperatures.
In at least one embodiment, the composition of the invention comprises an acylglycinate surfactant. In at least one embodiment, the acylglycinate surfactant conforms to the formula (Y):
Figure imgf000047_0001
wherein
R^a is a linear or branched, saturated alkyl group having 6 to 30, preferably 8 to 22, particularly preferably 8 to 18, carbon atoms or is a linear or branched, mono- or polyunsaturated alkenyl group having 6 to 30, preferably 8 to 22 and particularly preferably 12 to 18 carbon atoms, and
Qa+ is a cation.
In at least one embodiment, Qa+ is selected from the group consisting of Li+, Na+, K+, Mg++, Ca++, A ++, NH4+, a monoalkylammmonium ion, a dialkylammonium ion, a trialkylammonium ion and a tetraalkylammonium ion, or combinations thereof. In at least one embodiment, the acylglycinate surfactant is selected from sodium cocoylglycinate and potassium cocoylglycinate. In at least one embodiment, the acylglycinate surfactant is selected from those conforming to formula (Y), wherein R is C12 alkyl or C14 alkyl. In at least one embodiment, the acylglycinate surfactant is selected from those conforming to formula (Y), wherein R is C16 alkyl or C18 alkyl.
In at least one embodiment, the composition comprises from 0.01 wt.-% to 30 wt. -%, or 1 wt.-% to 25 wt.-%, preferably from 5 wt.-% to 20 wt.-%, more preferably from 12 wt.-% to 18 wt.-% anionic surfactant.
In at least one embodiment, the composition of the invention comprises a glutamate surfactant corresponding to formula (Z) or a salt thereof:
Figure imgf000048_0001
wherein
R’ is HOOC-CH2-CH2- or M+ OOC-CH2-CH2- wherein M+ is a cation; and wherein R is a linear or branched, saturated alkyl group having 6 to 30, preferably 8 to 22, more preferably 8 to 18, carbon atoms or is a linear or branched, mono- or polyunsaturated alkenyl group having 6 to 30, preferably 8 to 22 and more preferably 12 to 18 carbon atoms. In at least one embodiment, M+ is a metal cation. In at least one embodiment, M+ is selected from the group consisting of
Li+, Na+, K+, Mg++, Ca++, Al+++, NH4+, a monoalkylammmonium ion, a dialkylammonium ion, a trialkylammonium ion and a tetraalkylammonium ion, or combinations thereof. In at least one embodiment, the glutamate surfactant is selected from sodium cocoyl glutamate and potassium cocoyl glutamate. In at least one embodiment, the glutamate surfactant is selected from those conforming to formula (Z), wherein R is C12 alkyl or C14 alkyl. In at least one embodiment, the glutamate surfactant is selected from those conforming to formula (Z), wherein R is C16 alkyl or C18 alkyl.
In at least one embodiment, the composition of the invention comprises a non-ionic surfactant. The non-ionic surfactants may be present in the range 0 to 5 wt.-%. Nonionic surfactants that can be included in compositions of the invention include condensation products of aliphatic primary or secondary linear or branched chain alcohols or phenols with alkylene oxides, usually ethylene oxide and generally having from 6 to 30 ethylene oxide groups. Alkyl ethoxylates are particularly preferred. Most preferred are alky ethoxylates having the formula
R-(OCH2CH2)nOH, where
R is an alkyl chain of C12 to C15, and n is 5 to 9. Other suitable nonionic surfactants include mono- or di-alkyl alkanolamides. Examples include coco mono- or di- ethanolamide and coco mono-isopropanolamide.
Further nonionic surfactants which can be included in compositions of the invention are the alkyl polyglycosides (APGs). Typically, APG is one which comprises an alkyl group connected (optionally via a bridging group) to a block of one or more glycosyl groups. Preferred APGs are defined by the following formula:
RO-(G)n wherein
R is a branched or straight chain alkyl group which may be saturated or unsaturated and G is a saccharide group. R may represent a mean alkyl chain length of from about Cs to about C20. Preferably R represents a mean alkyl chain length of from about C9 to about C12. G may be selected from Cs or C6 monosaccharide residues, and is preferably a glucoside. G may be selected from the group comprising glucose, xylose, lactose, fructose, mannose and derivatives thereof. Preferably G is glucose. The degree of polymerisation, n, may have a value of from about 1 to about 10 or more. Most preferably the value of n lies from about 1.3 to about 1.5. Suitable alkyl polyglycosides for use in the invention are commercially available and include for example those materials identified as: Oramix NS10 ex Seppic; Plantaren 1200 and Plantaren 2000 ex Henkel.
Other sugar-derived nonionic surfactants which can be included in compositions of the invention include the fatty (e.g. C10-C18) N-alkyl (C1-C6) polyhydroxy fatty acid amides, such as the C12-C18 N-methyl glucamides, as described for example in WO-9206154 and US-5194639, and the N-alkoxy polyhydroxy fatty acid amides.
In at least one embodiment, the non-ionic surfactant has an HLB (Hydrophilic Lipophilic Balance) of greater than 12. Optionally, the non-ionic surfactant is selected from the group consisting of ethoxylated or ethoxylated/propoxylated fatty alcohols with a fatty chain comprising from 12 to 22 carbon atoms, ethoxylated sterols, such as stearyl- or lauryl alcohol (EO-7), PEG-16 soya sterol or PEG-10 soya sterol, polyoxyethylene polyoxypropylene block polymers (poloxamers), and mixtures thereof.
In at least one embodiment, the non-ionic surfactant is selected from the group consisting of ethoxylated fatty alcohols, fatty acids, fatty acid glycerides or alkylphenols, in particular addition products of from 2 to 30 mol of ethylene oxide and/or 1 to 5 mol of propylene oxide onto Cs- to C22-fatty alcohols, onto C12- to C22-fatty acids or onto alkyl phenols having 8 to 15 carbon atoms in the alkyl group, C12- to C22-fatty acid mono- and diesters of addition products of from 1 to 30 mol of ethylene oxide onto glycerol, addition products of from 5 to 60 mol of ethylene oxide onto castor oil or onto hydrogenated castor oil, fatty acid sugar esters, in particular esters of sucrose and one or two Cs- to C22-fatty acids, INCI: Sucrose Cocoate, Sucrose Dilaurate, Sucrose Distearate, Sucrose Laurate, Sucrose Myristate, Sucrose Oleate, Sucrose Palmitate, Sucrose Ricinoleate, Sucrose Stearate, esters of sorbitan and one, two or three Cs-to C22-fatty acids and a degree of ethoxylation of from 4 to 20, polyglyceryl fatty acid esters, in particular of one, two or more Cs- to C22-fatty acids and polyglycerol having preferably 2 to 20 glyceryl units, alkyl glucosides, alkyl oligoglucosides and alkyl polyglucosides having Cs to C22-alkyl groups, e.g. decylglucoside or laurylglucoside, and mixtures thereof.
In at least one embodiment, the non-ionic surfactant is selected from the group consisting of fatty alcohol ethoxylates (alkylpolyethylene glycols), alkylphenol polyethylene glycols, alkylmercaptan polyethylene glycols, fatty amine ethoxylates (alkylaminopolyethylene glycols), fatty acid ethoxylates (acylpolyethylene glycols), polypropylene glycol ethoxylates (Pluronics®), fatty acid alkylol amides, (fatty acid amide polyethylene glycols), N-alkyl-, N-alkoxypoly-hydroxy-fatty acid amide, sucrose esters, sorbitol esters, polyglycol ethers, and mixtures thereof.
In at least one embodiment, the composition of the invention comprises a fatty N-methyl-N-glucamide surfactant. In at least one embodiment, the fatty N-methyl- N-glucamide surfactant conforms to the formula (X):
Figure imgf000051_0001
wherein
R is a linear or branched alkyl or alkenyl group having from 3 to 30 carbon atoms. In at least one embodiment, R is an alkyl group having from 3 to 30 carbon atoms. In at least one embodiment, R is a saturated aliphatic hydrocarbon group which can be linear or branched and can have from 3 to 20 carbon atoms in the hydrocarbon chain, preferably linear or branched. Branched means that a lower alkyl group such as methyl, ethyl or propyl is present as substituent on a linear alkyl chain. In at least one embodiment, R is selected from the group consisting of 1 -propyl, 2-propyl, 1 butyl, 2-butyl, 2-methyl-1 -propyl (isobutyl), 2-methyl-2-propyl (tert-butyl), 1 -pentyl, 2-pentyl, 3-pentyl, 2-methyl-1- butyl, 3-methyl-1 -butyl,
2 methyl-2-butyl, 3-methyl-2-butyl, 2, 2-dimethyl-1 -propyl, 1- hexyl, 2-hexyl,
3-hexyl, 2-methyl-1 -pentyl, 3-methyl-1 -pentyl, 4-methyl-1 -pentyl, 2- methyl-2 - pentyl, 3 methyl-2-pentyl, 4-methyl-2-pentyl, 2 methyl-3-pentyl, 3-methyl-3- pentyl, 2,2 dimethyl-1 -butyl, 2,3-dimethyl-1 -butyl, 3,3 dimethyl-1 -butyl, 2-ethyl-1 -butyl, 2,3-dimethyl-2-butyl, 3,3-dimethyl-2-butyl, 1 heptyl, 1 -octyl, 1-nonyl, 1-decyl,
1 undecyl, 1-dodecyl, 1-tetradecyl, 1-hexadecyl and 1-octadecyl. Suitable fatty N methyl-N- glucamide surfactants are described in WO-2013/178700 and EP 0 550 637, which are incorporated herein by reference. In at least one embodiment, the N-methyl-N- glucamide surfactant is selected from those conforming to formula (X), wherein R isCi2 alkyl or Ci4 alkyl. In at least one embodiment, the N-methyl-N-glucamide surfactant is selected from those conforming to formula (X), wherein R is Ci6 alkyl or Cie alkyl.
In at least one embodiment, the composition of the invention comprises from 1 wt.-% to 20 wt.-%, more preferably from 2 wt.-% to 10 wt.-%, even more preferably from 3 wt.-% to 7 wt.-% non-ionic surfactant.
Amphoteric or zwitterionic surfactant can be included in the composition of the invention in an amount ranging from 0.5 wt.-% to about 8 wt.-%, preferably from 1 wt.-% to 4 wt.-% of the total composition.
In at least one embodiment, the amphoteric surfactants are selected from the group consisting of N-(Ci2-Ci8)-alkyl-beta-aminopropionates and N-(Ci2-Ci8)-alkyl- beta- iminodipropionates as alkali metal salts and mono-, di-, and trialkylammonium salts; N- acylaminoalkyl-N,N-dimethylacetobetaine, preferably N-(C8-Ci8)-acylaminopropyl-N,N-dimethylacetobetaine, (Ci2-Ci8)-alkyl-dimethyl- sulfopropylbetaine, amphosurfactants based on imidazoline (trade name: Miranol®, Steinapon®), preferably the sodium salt of 1-(beta-carboxymethyloxyethyl)-1- (carboxymethyl)-2-laurylimidazolinium; amine oxide, e.g., (Ci2-Ci8)-alkyl- dimethylamine oxide, fatty acid amidoalkyldimethylamine oxide, and mixtures thereof.
In at least one embodiment, the composition of the invention comprises a betaine surfactant. Optionally, the betaine surfactant is selected from Cs- to Ci8-alkylbetaines. In at least one embodiment, the betaine surfactant is selected from the group consisting of cocodimethylcarboxymethylbetaine, lauryldimethylcarboxymethylbetaine, lauryldimethylalphacarboxyethylbetaine, cetyldimethylcarboxymethylbetaine, oleyldimethylgammacarboxypropylbetaine and laurylbis(2-hydroxypropyl)alphacarboxyethylbetaine and combinations thereof.
Optionally, the betaine surfactant is selected from Cs- to Ci8-sulfobetaines. In at least one embodiment, the betaine surfactant is selected from the group consisting of cocodimethylsulfopropylbetaine, stearyldimethylsulfopropylbetaine, lauryldimethylsulfoethylbetaine, laurylbis(2-hydroxyethyl)sulfopropylbetaine, and combinations thereof. Optionally, the betaine surfactant is selected from carboxyl derivatives of imidazole, the Cs- to Ci8-alkyldimethylammonium acetates, the Os- to Ci8 alkyldimethylcarbonylmethylammonium salts, and the Cs- to Ci8-fatty acid alkylamidobetaines, and mixtures thereof. Optionally, the Cs- to Ci8-fatty acid alkylamidobetaine is selected from coconut fatty acid amidopropylbetaine, N-coconut fatty acid amidoethyl-N-[2-(carboxymethoxy)ethyl]glycerol (CTFA name: cocoamphocarboxyglycinate), and mixtures thereof. A particularly preferred amphoteric or zwitterionic surfactant is cocam idopropyl betaine. Mixtures of any of the foregoing amphoteric or zwitterionic surfactants may also be suitable.
Preferred mixtures are those of cocam idopropyl betaine with further amphoteric or zwitterionic surfactants as described above. A preferred further amphoteric or zwitterionic surfactant is sodium cocoamphoacetate.
In at least one embodiment, the composition of the invention comprises from 0.5 wt.-% to 20 wt.-%, preferably from 1 wt.-% to 10 wt.-% amphoteric surfactant.
In at least one embodiment, the composition of the invention comprises a surfactant system. In at least one embodiment, the surfactant system comprises at least one surfactant selected from the group consisting of lauryl sulfate, laureth sulfate, cocam idopropyl betaine, sodium cocoylglutamate, lauroamphoacetate, and mixtures thereof. In at least one embodiment, the surfactant system comprises sodium laureth sulfate, sodium lauryl sulfate, and optionally cocam idopropyl betaine. In at least one embodiment, the surfactant system comprises sodium laureth sulfate, potassium cocoylglutamate, and cocam idopropyl betaine.
In at least one embodiment, the composition of the invention contains as a further component a silicone compound. The composition can comprise up to 5% (e.g.
0.1 to 5%) by weight of a silicone compound. Suitable silicone compounds include polyalkyl or polyaryl siloxanes. The preferred silicone compounds are polydimethylsiloxane, polydiethylsiloxane, and polymethylphenylsiloxane, e.g. available from Wacker (Germany) or Dow Corning, such as Xiameter PMX DC 200. Silicone compounds can be available as silicone oils or emulsions. The silicone compounds may further be incorporated in the present composition in the form of an emulsion, wherein the emulsion is pre-made and added to the formulation, or made during the formulation process by mechanical mixing with or without the aid of an additional surfactant selected from anionic surfactants, nonionic surfactants, cationic surfactants, and mixtures thereof.
In at least one embodiment, the composition of the invention contains silicone conditioning agents. Preferably, these are emulsified droplets of a silicone conditioning agent. These are for enhancing conditioning performance.
Suitable silicones include polydiorganosiloxanes, in particular polydimethylsiloxanes, which have the CTFA designation dimethicone. Also suitable for use in the compositions of the invention (particularly shampoos and hair conditioners) are polydimethyl siloxanes having hydroxyl end groups, which have the CTFA designation dimethiconol. Also suitable for use in the compositions of the invention (particularly shampoos and hair conditioners) are silicone gums having a slight degree of cross-linking, as are described for example in WO-96/31188. The viscosity of the emulsified silicone itself (not the emulsion or the final composition) is typically at least 10,000 cSt at 25°C. The viscosity of the silicone itself is preferably at least 60,000 cSt, most preferably at least 500,000 cSt, ideally at least 1 ,000,000 cSt. Preferably, the viscosity does not exceed 1x10^ cSt for ease of formulation. Emulsified silicones for use in the compositions of the invention (particularly shampoos) will typically have an average silicone droplet size in the composition of less than 30, preferably less than 20, more preferably less than 10 micron, ideally from 0.01 to 1 micron. Silicone emulsions having an average silicone droplet size of less than 0.15 micron are generally termed microemulsions.
Silicone particle size may be measured by means of a laser light scattering technique, for example using a 2600D Particle Sizer from Malvern Instruments. Examples of suitable pre-formed emulsions include Xiameter MEM 1785 and microemulsion DC2- 1865 available from Dow Corning. These are emulsions / microemulsions of dimethiconol. Cross-linked silicone gums are also available in a pre-emulsified form, which is advantageous for ease of formulation. A further preferred class of silicones for inclusion in the compositions of the invention (particularly shampoos and hair conditioners) are amino functional silicones. By "amino functional silicone" is meant a silicone containing at least one primary, secondary or tertiary amine group, or a quaternary ammonium group. Examples of suitable amino functional silicones include polysiloxanes having the CTFA designation "amodimethicone".
Specific examples of amino functional silicones suitable for use in the compositions of the invention are the aminosilicone oils DC2-8220, DC2-8166 and DC2-8566 (all ex Dow Corning).
Suitable quaternary silicone polymers are described in EP-A-0530974. A preferred quaternary silicone polymer is K3474, ex Goldschmidt.
Also suitable are emulsions of amino functional silicone oils with non-ionic and/or cationic surfactant. Pre-formed emulsions of amino functional silicones are also available from suppliers of silicone oils such as Dow Corning and General Electric. Specific examples include DC939 Cationic Emulsion and the non-ionic emulsions DC2- 7224, DC2- 8467, DC2-8177 and DC2-8154 (all ex Dow Corning).
Combination of amino and non-amino functional silicones may also be used.
The total amount of silicone is preferably from 0.01 wt.-% to 10 wt.-% of the total composition, more preferably from 0.1 wt.-% to 5 wt.-%, most preferably from 0.5 wt.-% to 3 wt.-%.
In at least one embodiment, the composition of the invention comprises a preservative or preservative system. Examples of suitable preservatives include benzyl alcohol, piroctone olamine, phenoxyethanol, parabens, pentanediol, benzoic acid/sodium benzoate, sorbic acid/potassium sorbate, and other organic acids used to provide antimicrobial protection. Preservation boosting ingredients include anisic acid, lactic acid, sorbitan caprylate, ethylhexylglycerin, caprylyl glycol, octanediol, and similar substances. In at least one embodiment, the composition comprises 0.01 to 5 wt.-%, particularly preferably from 0.05 to 1 wt.-% of at least one preservative. Suitable preservatives are the substances listed in the International Cosmetic Ingredient Dictionary and Handbook, 9th Edition with the function "preservatives". In at least one embodiment, the preservative is selected from the group consisting of phenoxyethanol, benzyl paraben, butyl paraben, ethyl paraben, isobutyl paraben, isopropyl paraben, methyl paraben, propyl paraben, iodopropynyl butylcarbamate, methyldibromoglutaronitrile, DMDM hydantoin and combinations thereof. In at least one embodiment, the composition comprises a preservative selected from the group consisting of cetyltrimethyl ammonium chloride, cetylpyridinium chloride, benzethonium chloride, diisobutylethoxyethyldimethyl benzylammonium chloride, sodium N-lauryl sarcosinate, sodium-N-palmethylsarcosinate, lauroylsarcosine, N-myristoylglycine, potassium-N-laurylsarcosine, trimethylammonium chloride, sodium aluminium chlorohydroxylactate, triethylcitrate, tricetylmethylammonium chloride, 2,4,4'-trichloro-2'- hydroxydiphenylether (Triclosan), phenoxyethanol, 1,5-pentandiol, 1 ,6-hexandiol, 3,4,4'- trichlorocarbanilide (Triclocarban), diaminoalkylamide, L-lysine hexadecylamide, heavy metal citrate salts, salicylate, piroctose, zinc salts, pyrithione and its heavy metal salts, zinc pyrithione, zinc phenol sulfate, farnesol, ketoconazol, oxiconazol, bifonazole, butoconazole, cloconazole, clotrimazole, econazole, enilconazole, fenticonazole, isoconazole, miconazole, sulconazole, tioconazole, fluconazole, itraconazole, terconazole, naftifine, terbinafine, selenium disulfide, Octopirox®, methylchloroisothiazolinone, methylisothiazolinone, methyldibromo glutaronitrile, AgCI, chloroxylenol, sodium salts of diethylhexylsulfosuccinate, sodiumbenzoate, phenoxyethanol, benzylalkohol, phenoxyisopropanol, paraben, such as butyl-, ethyl-, methyl- und propylparaben, and their salts, pentandiol, 1,2-octanediol, ethylhexylglycerinw, benzylalcohol, sorbic acid, benzoic acid, lactic acid, imidazolidinyl urea, diazolidinyl urea, dimethylol dimethyl hydantoin (DMDMH), sodium salts of hydroxymethyl glycinate, hydroxyethylglycine of sorbic acid and combinations thereof. In at least one embodiment, the preservative is selected from the group consisting of phenoxyethanol, benzyl paraben, butyl paraben, ethyl paraben, isobutyl paraben, isopropyl paraben, methyl paraben, propyl paraben, iodopropynyl butylcarbamate, methyldibromoglutaronitrile, DMDM hydantoin and combinations thereof. In at least one embodiment, the composition is substantially free of parabens.
The composition of the invention may also comprise a dispersed, non-volatile, water- insoluble oily conditioning agent. By "insoluble" is meant that the material is not soluble in water (distilled or equivalent) at a concentration of 0.1 % (w/w), at 25°C.
Suitable oily or fatty materials are selected from hydrocarbon oils, fatty esters and mixtures thereof. Straight chain hydrocarbon oils will preferably contain from about 12 to about 30 carbon atoms. Also suitable are polymeric hydrocarbons of alkenyl monomers, such as C2-C6 alkenyl monomers. Specific examples of suitable hydrocarbon oils include paraffin oil, mineral oil, saturated and unsaturated dodecane, saturated and unsaturated tridecane, saturated and unsaturated tetradecane, saturated and unsaturated pentadecane, saturated and unsaturated hexadecane, and mixtures thereof. Branched-chain isomers of these compounds, as well as of higher chain length hydrocarbons, can also be used.
Suitable fatty esters are characterised by having at least 10 carbon atoms, and include esters with hydrocarbyl chains derived from fatty acids or alcohols, Monocarboxylic acid esters include esters of alcohols and/or acids of the formula R'COOR in which R' and R independently denote alkyl or alkenyl radicals and the sum of carbon atoms in R' and R is at least 10, preferably at least 20. Di- and trialkyl and alkenyl esters of carboxylic acids can also be used.
Particularly preferred fatty esters are mono-, di- and triglycerides, more specifically the mono-, di-, and tri-esters of glycerol and long chain carboxylic acids such as C8-C22 carboxylic acids. Preferred materials include cocoa butter, palm stearin, sunflower oil, soybean oil and coconut oil.
The oily or fatty material may be present at a level of from 0.05 to 10 wt.-%, preferably from 0.2 to 5 wt.-%, more preferably from 0.5 to 3 wt.-%, based on the total weight of the composition.
In a particularly preferred embodiment, the composition of the invention is a shampoo composition.
In at least one embodiment, the shampoo composition comprises from 1 to 99%, preferably from 5 to 95%, more preferably from 10 to 90% by weight of the total composition of water, and from 0.1 to 99%, preferably from 1 to 95%, more preferably from 5 to 90%, often 5 to 25% by weight of the total composition of a cleansing surfactant. Suitable cleansing surfactants are generally anionic, amphoteric, betaine, or zwitterionic surfactants. For example, the anionic surfactants are alkyl ether or alkyl ether sulfates, such as sodium lauryl sulfate, or other compounds described above.
In at least one embodiment, the shampoo composition comprises one or more further cosmetically acceptable components (F), which can be present in an amount of at least 0.5% by weight, or from 0.5 to 20% by weight, by total weight of the shampoo composition. Preferably, the component (F) is selected from the group consisting of cleansing ingredients, acidity regulators, colorants, conditioning agents, emulsifiers, film formers, fragrances, glossers, humectants, lubricants, moisturizers, pigments, preservatives, hair penetration enhancers, scalp actives, stabilizers, surfactants, thickeners, viscosity modifiers, and combinations thereof. More preferably, the component (F) is selected from the group consisting of surfactants, viscosity-modifying polymers and conditioning ingredients. In at least one embodiment, the shampoo composition comprises from 0.3 to 10% by weight of the vesicles described herein and further comprises at least 0.5% by weight of one or more further components (F) selected from the group consisting of surfactants, polymers, conditioning agents, actives, acidity regulators, lubricants, moisturisers, oils, preservatives, sequestrants, strengtheners, sun protectors, and combinations thereof.
In at least one embodiment, the shampoo composition comprises further cosmetically acceptable components (F) being cleansing ingredients. In at least one embodiment, the shampoo composition comprises from 0.05% to 20% cleansing ingredients. In at least one embodiment of the shampoo composition, the level of cleansing ingredient is from 1 % to 20% by total weight of the active ingredient in the composition, preferably 5% to 18%, more preferably 8% to 16%.
In at least one embodiment, the cleansing ingredient is selected from the group consisting of non-polymeric surfactants, saponins, polymeric surfactants, and combinations thereof. Preferably the cleansing ingredient comprises or consists of surfactants.
In at least one embodiment, the shampoo composition comprises from 0.3 to 10 % by weight of the vesicles described herein and at least 0.5 % by weight of surfactants, preferably cleansing anionic or nonionic surfactants, such as sodium laureth sulphate, sodium lauryl sulphate, ammonium laureth sulphate, ammonium lauryl sulphate, olefin sulfonates, olefin sulfates, laureth-3 or 4, cocamide DEA, glucosides, cocam idopropyl betaine, coco betaine, cocoamphodipropionate, sodium methyl 2-sulfolaurate and other laurates, sulfoacetates, sulfosuccinates, lactylates, sultaines, caprylates/ caprates, isethionates, glutamates, taurates, sarcosinates, glucamides, and combinations thereof.
In at least one embodiment, the shampoo composition is silicone-free. In at least one embodiment, the shampoo composition is sulfate-free. In at least one embodiment, the shampoo composition is silicone-free and sulfate-free.
In at least one embodiment, the shampoo composition comprises: (i) from 0.3 wt.-% to 10 wt.-% of the lipid nanoparticles described herein;
(ii) from 5 wt.-% to 20 wt.-% of one or more anionic surfactants;
(iii) at least 50 wt.-% water; and
(iv) at least one further cosmetically acceptable component (F) selected from the group consisting of silicone, cationic polymer, rheology modifiying agent, and an amphoteric or zwitterionic surfactant.
In at least one embodiment, the shampoo composition comprises:
(i) from 0.3 wt.-% to 10 wt.-% of the lipid nanoparticles described herein; (ii) from 5 wt.-% to 20 wt.-% of one or more anionic surfactants;
(iii) at least 50 wt.-% water; and
(iv) at least one further component selected from the group consisting of silicone, cationic polymer, rheology modifiying agent, and an amphoteric or zwitterionic surfactant; (v) at least one further cosmetically acceptable component (F).
In at least one embodiment, the shampoo composition consists of:
(i) from 0.3 wt.-% to 10 wt.-% of the lipid nanoparticles described herein;
(ii) from 5 wt.-% to 20 wt.-% of one or more anionic surfactants; (iii) at least 50 wt.-% water; and
(iv) at least one further component selected from the group consisting of silicone, cationic polymer, rheology modifiying agent, and an amphoteric or zwitterionic surfactant;
(v) at least one further cosmetically acceptable component (F) selected from the group consisting of conditioning agents, such as hydrolysed collagen, vitamin E, or panthenol, panthenyl ethyl ether, hydrolysed keratin, proteins, plant extracts, nutrients; and emollients such as PPG-3 myristyl ether, trimethyl pentanol hydroxyethyl ether; hair-fixative polymers such as amphoteric fixative polymers, cationic fixative polymers, anionic fixative polymers, nonionic fixative polymers, and silicone grafted copolymers; preservatives such as benzyl alcohol, methyl paraben, propyl paraben and imidazolidinyl urea; pH adjusting agents, such as citric acid, sodium citrate, succinic acid, phosphoric acid, sodium hydroxide, sodium carbonate; salts, in general, such as potassium acetate and sodium chloride; coloring agents; hair oxidizing (bleaching) agents, such as hydrogen peroxide, perborate and persulfate salts; hair reducing agents such as the thioglycolates; perfumes; and sequestering agents, such as disodium ethylene-diamine tetraacetate; ultraviolet and infrared screening and absorbing agents such as octyl salicylate; and anti-dandruff agents such as zinc pyrithione, piroctone olamine and salicylic acid.
The composition of the invention may comprise as component (F) a cationic softening agent. Such compositions e.g. may be fabric conditioner compositions. If present, the cationic softening agent is usually present in the compositions of the invention at a level of 2 to 75% by weight, preferably 10 to 50% by weight, more preferably 20 to 35% by weight of the total composition. Also preferably, the level of the cationic softening agent is 10 to 30% by weight of the total composition.
Also preferably, the level of the cationic softening agent is 0.5 to 8% by weight of the total composition.
The cationic softening agent is preferably one that is able to form a lamellar phase dispersion in water, in particular a dispersion of liposomes.
The cationic softening agent is preferably a quaternary ammonium compound, in particular one having two C12-28 groups connected to the nitrogen head group, preferably being connected to the nitrogen head group by at least one ester link, and more preferably by two ester links. The C12-28 groups may independently be alkyl or alkenyl groups.
The average chain length of the alkyl and/or alkenyl groups is preferably at least C14 and more preferably at least C16. It is particularly preferred that at least half of the groups have a chain length of C18. In general, the alkyl and/or alkenyl groups are predominantly linear.
The cationic softening agent is preferably an ester-linked quaternary ammonium compound. Preferably, the quaternary ammonium compound has fatty acid chains. The fatty acid chains of the quaternary ammonium compound preferably comprise from 10 to 50 wt.-%, preferably from 20 to 35 wt.-% of saturated Ci8 chains and from 10 to 50 wt.-%, preferably from 20 to 35 wt.-% of monounsaturated Ci8 chains by weight of total fatty acid chains.
Preferably, the quaternary ammonium compound is derived from palm or tallow feedstocks. These feedstocks may be pure or predominantly palm or tallow based. Blends of different feedstocks may be used.
In a preferred embodiment, the fatty acid chains of the quaternary ammonium compound comprise from 25 to 30 wt.-%, preferably from 26 to 28 wt.-% of saturated Cis chains and from 25 to 30 wt.-%, preferably from 26 to 28 wt.-% of monounsaturated Cis chains, by weight of total fatty acid chains.
In another preferred embodiment, the fatty acid chains of the quaternary ammonium compound comprise from 30 to 35 wt.-%, preferably from 33 to 35 wt.-% of saturated Cis chains and from 24 to 35 wt.-%, preferably from 27 to 32 wt.-% of monounsaturated Cis chains, by weight of total fatty acid chains.
The cationic softening agent is preferably an ester-linked triethanolamine (TEA) based quaternary ammonium compound. Ester-linked TEA based quaternary ammonium compounds preferably comprise a mixture of mono-, di- and tri-ester linked components. The tri-ester content is preferably below 10 wt.-%, more preferably from 5 to 9 wt.-% by total weight of the quaternary active component. Preferred ester-linked TEA based quaternary ammonium compounds have a diester content of from 50 to 60 wt.-%, more preferably from 52 to 59 wt.-% by total weight of the quaternary active component. Also preferred are ester-linked TEA based quaternary ammonium compounds having a monoester content of from 30 to 45 wt.-%, more preferably from 32 to 42 wt.-% by total weight of the quaternary active component. A preferred ester-linked TEA based quaternary ammonium compound comprises from 32 to 42 wt.-% of monoester, from 52 to 59 wt.-% of diester and from 5 to 9 wt.-% of triester compounds, by total weight of the quaternary active; more preferably from 35 to 39 wt.-% of monoester, from 54 to 58 wt.-% of diester and from 7 to 8 wt.-% of triester compounds, by total weight of the quaternary active component.
The quaternary ammonium compounds are also known as "soft" materials. Iodine value as used in the context of the present invention refers to the measurement of the degree of unsaturation present in a material by a method of NMR spectroscopy as described in Anal. Chem., 34, 1136 (1962), Johnson and Shoolery. In preferred embodiments, the quaternary ammonium compounds are derived from feedstock having an overall iodine value of from 30 to 45, more preferably from 30 to 42 and most preferably 36.
A first group of quaternary ammonium compounds suitable for use in the present invention is represented by formula (I):
KCHzln(TR)ln i
R1-N+-[(CHZ)B(OHJ;: „ CG (1} wherein each R is independently selected from a Cs^s alkyl or alkenyl group;
R1 represents a C1-4 alkyl, C2-4 alkenyl or a C1-4 hydroxyalkyl group;
T is generally O-CO (i.e. an ester group bound to R via its carbon atom), but may alternatively be CO-O (i.e. an ester group bound to R via its oxygen atom); n is a number selected from 1 to 4; m is a number selected from 1 , 2, or 3; and
X is an anionic counter-ion, such as a halide or alkyl sulphate, e.g. chloride or methylsulphate. Di-ester variants of formula I (i.e. m = 2) are preferred and typically have mono- and tri ester analogues associated with them. Such materials are particularly suitable for use in the present invention.
Especially preferred agents are di-esters of triethanolammonium methylsulphate. Commercial examples include Prapagen TQL, ex Clariant, and Tetranyl AHT-1, ex Kao, (both di-[hardened tallow ester]of triethanolammonium methylsulphate), AT-1 (di-[tallow ester]of triethanolammonium methylsulphate), and L5/90 (di-[palm ester] of triethanolammonium methylsulphate), both ex Kao, and Rewoquat WE15 (a di-ester of triethanolammonium methylsulphate having fatty acyl residues deriving from C10-20 and C16-18 unsaturated fatty acids), ex Witco Corporation.
The second group of quaternary ammonium compounds suitable for use in the invention is represented by formula (II):
Figure imgf000064_0001
wherein each R1 group is independently selected from C1-4 alkyl, hydroxyalkyl or C2-4 alkenyl groups; and wherein each R2 group is independently selected from Cs-28 alkyl or alkenyl groups; and wherein n, T, and X are as defined above.
Preferred materials of this second group include 1 ,2 bis[tallowoyloxy]-3- trimethylammonium propane chloride, 1,2 bis[hardened tallowoyloxy]-3- trimethylammonium propane chloride, 1,2-bis[oleoyloxy]-3-trimethylammonium propane chloride, and 1,2 bis[stearoyloxy]-3-trimethylammonium propane chloride. Such materials are described in US 4,137,180 (Lever Brothers). Preferably, these materials also comprise an amount of the corresponding mono-ester.
A third group of quaternary ammonium compounds suitable for use in the invention is represented by formula (III):
Figure imgf000064_0002
fill) wherein each R1 group is independently selected from C1-4 alkyl, or C2-4 alkenyl groups; and wherein each R2 group is independently selected from Cs-28 alkyl or alkenyl groups; and n, T, and X are as defined above. Preferred materials of this third group include bis(2-tallowoyloxyethyl)dimethyl ammonium chloride and hardened versions thereof.
A fourth group of quaternary ammonium compounds suitable for use in the invention is represented by formula (IV):
Figure imgf000065_0001
wherein each R1 group is independently selected from C1-4 alkyl, or C2-4 alkenyl groups; and wherein each R2 group is independently selected from Cs-28 alkyl or alkenyl groups; and X is as defined above. Preferred materials of this fourth group include di(hardened tallow)dimethylammonium chloride.
Further quaternary ammonium compounds are described further above.
The composition of the invention may comprise as component (F) a hydrophobic agent. If present, the hydrophobic agent is usually present in an amount of from 0.05 to 1.0 wt.-%, preferably from 0.1 to 0.8 wt.-%, more preferably from 0.2 to 0.7 wt.-% and most preferably from 0.4 to 0.7 wt.-% by weight of the total composition, for example from 0.2 to 0.5 wt.-% by weight of the total composition.
Suitable hydrophobic agents include esters derived from the reaction of a fatty acid with an alcohol. The fatty acid preferably has a carbon chain length of from Cs to C22 and may be saturated or unsaturated, preferably saturated. Some examples include stearic acid, palmitic acid, lauric acid and myristic acid. The alcohol may be linear, branched or cyclic. Linear or branched alcohols have a preferred carbon chain length of from 1 to 6. Preferred alcohols include methanol, ethanol, propanol, isopropanol, sorbitol. Preferred hydrophobic agents include methyl esters, ethyl esters, propyl esters, isopropyl esters and sorbitan esters derived from such fatty acids and alcohols.
Non-limiting examples of suitable hydrophobic agents include methyl esters derived from fatty acids having a carbon chain length of from at least Cio, ethyl esters derived from fatty acids having a carbon chain length of from at least Cio, propyl esters derived from fatty acids having a carbon chain length of from at least C8, isopropyl esters derived from fatty acids having a carbon chain length of from at least Cs, sorbitan esters derived from fatty acids having a carbon chain length of from at least Ci6, and alcohols with a carbon chain length greater than Cio. Naturally occurring fatty acids commonly have a carbon chain length of up to C22.
Some preferred materials include methyl undecanoate, ethyl decanoate, propyl octanoate, isopropyl myristate, sorbitan stearate and 2-methyl undecanol, ethyl myristate, methyl myristate, methyllaurate, isopropyl palmitate and ethyl stearate; more preferably methyl undecanoate, ethyl decanoate, isopropyl myristate, sorbitan stearate, 2-methyl undecanol, ethyl myristate, methyl myristate, methyl laurate and isopropyl palmitate.
Non-limiting examples of such materials include methyl undecanoate, ethyl decanoate, propyl octanoate, isopropyl myristate, sorbitan stearate and 2-methyl undecanol; preferably methyl undecanoate, ethyl decanoate, isopropyl myristate, sorbitan stearate and 2-methyl undecanol. Most preferably, the hydrophobic agent is isopropyl myristate.
The composition of the invention may comprise as component (F) a non-ionic alkoxylated material. The addition of such a non-ionic material reduces the occurrence of flocculation when the composition is added to water, such as rinse water. If present, the non-ionic alkoxylated material may be present in an amount of from 0.01 to 0.5 wt.-%, preferably from 0.02 to 0.4 wt.-%, more preferably from 0.05 to 0.25 wt.-% and most preferably 0.1 wt.-% by total weight of the composition.
Suitable non-ionic alkoxylated materials include non-ionic surfactants. Suitable non- ionic surfactants include addition products of ethylene oxide and/or propylene oxide with fatty alcohols, fatty acids and fatty amines. The non-ionic alkoxylated material is preferably selected from addition products of (a) an alkoxide selected from ethylene oxide, propylene oxide and mixtures thereof with (b) a fatty material selected from fatty alcohols, fatty acids and fatty amines.
Suitable surfactants are, for example, substantially water-soluble surfactants of the general formula:
R-Y-(C2H40)Z-CH2-CH2-0H where
R is selected from the group consisting of primary, secondary and branched chain alkyl and/or acyl hydrocarbyl groups; primary, secondary and branched chain alkenyl hydrocarbyl groups; and primary, secondary and branched chain alkenyl substituted phenolic hydrocarbyl groups; the hydrocarbyl groups having a chain length of from 10 to 60, preferably 10 to 25, e.g. 14 to 20 carbon atoms.
In the general formula for the ethoxylated non-ionic surfactant, Y is typically:
-O- , -C(0)0- , -C(0)N(R)- or -C(0)N(R)R- in which
R has the meaning given above or can be hydrogen; and
Z is at least about 6, preferably at least about 10 or 11.
Lutensol™ AT25 (BASF) based on coco chain and 25 EO groups is an example of a suitable nonionic surfactant. Other suitable surfactants include Renex 36 (Trideceth-6), ex Uniqema; Tergitoi 15-S3, ex Dow Chemical Co.; Dihydrol LT7, ex Thai Ethoxylate ltd; Cremophor CO40, ex BASF and Neodol 91-8, ex Shell.
Further non-ionic surfactants are described further above. The composition of the invention may comprise as component (F) a polymeric thickening agent, also referred to as thickening polymer. Thickening polymers may be added to the compositions of the invention for further thickening. Any suitable thickener polymer may be used. If present, the amount of thickening polymer used in the compositions of the invention is typically from 0.001 to 0.5 wt.-%, preferably from 0.005 to 0.4 wt.-%, more preferably from 0.05 to 0.35 wt.-% and most preferably from 0.1 to 0.25 wt.-%, by weight of the total composition.
Suitable polymers are water soluble or dispersable. A high M.Wt, (for example, in the region of about 100,000 to 5,000,000), which can be achieved by crosslinking, is advantageous. Preferably, the polymer is cationic.
Polymers particularly useful in the compositions of the invention include those described in WO 2010/078959 (SNF S.A.S.). These are crosslinked water- swellable cationic copolymers having at least one cationic monomer and optionally other non-ionic and/or anionic monomers. Preferred polymers of this type are copolymers of acrylamide and trimethylaminoethylacrylate chloride.
Preferred polymers comprise less than 25 % of water-soluble polymers by weight of the total polymer, preferably less than 20 %, and most preferably less than 15%, and a cross-linking agent concentration of from 500 ppm to 5000 ppm relative to the polymer, preferably from 750 ppm to 5000 ppm, more preferably from 1000 to 4500 ppm (as determined by a suitable metering method such as that described on page 8 of patent EP 343840). The cross-linking agent concentration must be higher than about 500 ppm relative to the polymer and preferably higher than about 750 ppm when the crosslinking agent used is the methylene bisacrylamide, or other cross-linking agents at concentrations that lead to equivalent cross-linking levels of from 10 to 10,000 ppm.
Suitable cationic monomers are selected from the group consisting of the following monomers and derivatives and their quaternary or acid salts: dimethylaminopropylmethacrylamide, dimethylaminopropylacrylamide, diallylamine, methyldiallylamine, dialky lam inoalkyl-acrylates and methacrylates, dialkylaminoalkyl- acrylamides or -methacrylamides.
Following is a non-restrictive list of monomers performing a non-ionic function: acrylamide, methacrylamide, N-alkyl acrylamide, N-vinyl pyrrolidone, N-vinyl formamide, N-vinyl acetamide, vinylacetate, vinyl alcohol, acrylate esters, allyl alcohol.
Following is a non-restrictive list of monomers performing an anionic function: acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, as well as monomers performing a sulfonic acid or phosphonic acid functions, such as 2- acrylamido-2-methyl propane sulfonic acid (ATBS) etc.
The monomers may also contain hydrophobic groups.
Following is a non-restrictive list of cross-linking agents: methylene bisacrylamide (MBA), ethylene glycol diacrylate, polyethylene glycol dimethacrylate, diacrylamide, triallylamine, cyanomethylacrylate, vinyl oxyethylacrylate or methacrylate and formaldehyde, glyoxal, compounds of the glycidyl ether type such as ethyleneglycol diglycidyl ether, or the epoxides or any other means familiar to the expert permitting cross-linking.
By way of preeminent preference, the cross-linking rate preferably ranges from 800 to 5000 ppm (on the basis of methylene bisacrylamide) relative to the polymer or equivalent cross-linking with a cross-linking agent of different efficiency.
As described in US 2002/0132749 and Research Disclosure 429116, the degree of non- linearity can additionally be controlled by the inclusion of chain transfer agents (such as isopropyl alcohol, sodium hypophosphite, mercaptoethanol) in the polymerisation mixture in order to control the polymeric chain's length and the cross-linking density.
An example of a preferred polymer is Flosoft 270LS ex SNF. Further polymeric thickening agents or thickening polymers are described further above.
The composition of the invention may comprise as component (F) a non-cationic softening material, preferably non-ionic softening material, which is preferably an oily sugar derivative. An oily sugar derivative is a liquid or soft solid derivative of a cyclic polyol (CPE) or of a reduced saccharide (RSE), said derivative resulting from 35 to 100% of the hydroxyl groups in said polyol or in said saccharide being esterified or etherified. The derivative has two or more ester or ether groups independently attached to a C8-C22 alkyl or alkenyl chain.
Advantageously, the CPE or RSE does not have any substantial crystalline character at 20°C. Instead it is preferably in a liquid or soft solid state at 20°C.
The liquid or soft solid CPEs or RSEs suitable for use in the present invention result from 35 to 100% of the hydroxyl groups of the starting cyclic polyol or reduced saccharide being esterified or etherified with groups such that the CPEs or RSEs are in the required liquid or soft solid state. These groups typically contain unsaturation, branching or mixed chain lengths.
Typically, the CPEs or RSEs have 3 or more ester or ether groups or mixtures thereof, for example 3 to 8, especially 3 to 5. It is preferred if two or more of the ester or ether groups of the CPE or RSE are independently of one another attached to a C8-C22 alkyl or alkenyl chain. The C8-C22 alkyl or alkenyl groups may be branched or linear carbon chains. Preferably, 35-85% of the hydroxyl groups, most preferably 40-80%, even more preferably 45-75%, such as 45-70% are esterified or etherified. Preferably, the CPE or RSE contains at least 35% tri or higher esters, e.g. at least 40%.
The CPE or RSE has at least one of the chains independently attached to the ester or ether groups having at least one unsaturated bond. This provides a cost- effective way of making the CPE or RSE a liquid or a soft solid. It is preferred if predominantly unsaturated fatty chains, derived from, for example, rape oil, cotton seed oil, soybean oil, oleic, tallow, palmitoleic, linoleic, erucic or other sources of unsaturated vegetable fatty acids, are attached to the ester/ether groups.
These chains are referred to below as the ester or ether chains (of the CPE or RSE).
The ester or ether chains of the CPE or RSE are preferably predominantly unsaturated. Preferred CPEs or RSEs include sucrose tetratallowate, sucrose tetrarapeate, sucrose tetraoleate, sucrose tetraesters of soybean oil or cotton seed oil, cellobiose tetraoleate, sucrose trioleate, sucrose triapeate, sucrose pentaoleate, sucrose pentarapeate, sucrose hexaoleate, sucrose hexarapeate, sucrose triesters, pentaesters and hexaesters of soybean oil or cotton seed oil, glucose trioleate, glucose tetraoleate, xylose trioleate, or sucrose tetra-, tri-, penta- or hexa-esters with any mixture of predominantly unsaturated fatty acid chains.
The most preferred CPEs or RSEs are those with monosaturated fatty acid chains, i.e. where any polyunsaturation has been removed by partial hydrogenation. However, some CPEs or RSEs based on polyunsaturated fatty acid chains, e.g. sucrose tetralinoleate, may be used provided most of the polyunsaturation has been removed by partial hydrogenation.
The most highly preferred liquid CPEs or RSEs are any of the above but where the polyunsaturation has been removed through partial hydrogenation.
Preferably 40% or more of the fatty acid chains contain an unsaturated bond, more preferably 50% or more, most preferably 60% or more. In most cases 65% to 100%, e.g. 65% to 95% contain an unsaturated bond.
CPEs are preferred for use with the present invention. Inositol is a preferred example of a cyclic polyol. Inositol derivatives are especially preferred.
In the context of the present invention, the term cyclic polyol encompasses all forms of saccharides. Indeed, saccharides are especially preferred for use with this invention. Examples of preferred saccharides for the CPEs or RSEs to be derived from are monosaccharides and disaccharides.
Examples of monosaccharides include xylose, arabinose, galactose, fructose, sorbose and glucose. Glucose is especially preferred. Examples of disaccharides include maltose, lactose, cellobiose and sucrose. Sucrose is especially preferred. An example of a reduced saccharide is sorbitan.
The liquid or soft solid CPEs can be prepared by methods well known to those skilled in the art. These include acylation of the cyclic polyol or reduced saccharide with an acid chloride; trans-esterification of the cyclic polyol or reduced saccharide fatty acid esters using a variety of catalysts; acylation of the cyclic polyol or reduced saccharide with an acid anhydride and acylation of the cyclic polyol or reduced saccharide with a fatty acid. See for instance US 4 386 213 and AU 14416/88 (both P&G).
It is preferred if the CPE or RSE has 3 or more, preferably 4 or more ester or ether groups. If the CPE is a disaccharide, it is preferred if the disaccharide has 3 or more ester or ether groups. Particularly preferred CPEs are esters with a degree of esterification of 3 to 5, for example, sucrose tri, tetra and penta esters.
Where the cyclic polyol is a reducing sugar, it is advantageous if each ring of the CPE has one ether or ester group, preferably at the C1 position. Suitable examples of such compounds include methyl glucose derivatives.
Examples of suitable CPEs include esters of alkyl(poly)glucosides, in particular alkyl glucoside esters having a degree of polymerisation from 1 to 2.
The length of the unsaturated (and saturated if present) chains in the CPE or RSE is C8-C22, preferably C12-C22. It is possible to include one or more chains of C-i-Cs.
The liquid or soft solid CPEs or RSEs which are suitable for use in the present invention are characterised as materials having a solid: liquid ratio of between 50:50 and 0:100 at 20°C as determined by T2 relaxation time NMR, preferably between 43:57 and 0:100, most preferably between 40:60 and 0:100, such as, 20:80 and 0:100. The T2 NMR relaxation time is commonly used for characterising solid: liquid ratios in soft solid products such as fats and margarines. For the purpose of the present invention, any component of the signal with a T2 of less than 100 ps is considered to be a solid component and any component with T2 > 100 ps is considered to be a liquid component.
For the CPEs and RSEs, the prefixes (e.g. tetra and penta) only indicate the average degrees of esterification. The compounds exist as a mixture of materials ranging from the monoester to the fully esterified ester. It is the average degree of esterification which is used herein to define the CPEs and RSEs.
If present, the CPE or RSE is preferably present in the composition in an amount of 0.5 - 50% by weight, based upon the total weight of the composition, more preferably 1 - 30% by weight, such as 2 - 25%, e.g. 2 - 20%.
Particularly preferred CPEs and RSEs for use in the compositions of the invention include sucrose tetraoleate, sucrose pentaerucate, sucrose tetraerucate and sucrose pentaoleate.
The composition of the invention may comprise as component (F) a co-softener. When employed, they are typically present at from 0.1 to 20% and particularly at from 0.5 to 10%, based on the total weight of the composition.
Suitable co-softeners include fatty acids. Preferred co-softeners include fatty esters and fatty N-oxides. Fatty esters that may be employed include fatty monoesters, such as glycerol monostearate, fatty sugar esters, such as those disclosed WO 01/46361 (Unilever).
Preferred fatty acids include hardened tallow fatty acid (available under the tradename Pristerene™, ex Uniqema). Preferred fatty alcohols include hardened tallow alcohol (available under the tradenames Stenol™ and Flydrenol™, ex Cognis and Laurex™ CS, ex Albright and Wilson). The composition of the invention may comprise as component (F) a fatty complexing agent. Especially suitable fatty complexing agents include fatty alcohols. Fatty complexing material may be used to improve the viscosity profile of the composition.
If present, the fatty complexing agent is preferably present in an amount greater than 0.3 to 5% by weight based on the total weight of the composition. More preferably, the fatty component is present in an amount of from 0.4 to 4%. The weight ratio of the mono-ester component of the quaternary ammonium fabric softening material to the fatty complexing agent is preferably from 5:1 to 1 :5, more preferably 4: 1 to 1 :4, most preferably 3:1 to 1:3, e.g. 2:1 to 1 :2.
The composition of the invention may comprise as component (F) shading dyes. Examples of suitable shading dyes are disclosed in WO 2012/072368, on pages 17 to 22. The level of shading dye present in the compositions of the invention, if present, depends on the type of shading dye. Preferred overall ranges, suitable for the present invention are from 0.00001 to 0.1 wt.-%, more preferably 0.0001 to 0.01 wt.-%, most preferably 0.0005 to 0.005 wt.-% by weight of the total composition.
In addition to the fragrance comprised in the lipid nanoparticles described herein, the composition of the invention may comprise additional fragrances and perfumes.
Examples of suitable fragrances and perfumes are described further above. Examples of suitable fragrances and perfumes are also disclosed in WO 2012/072368, on pages 22 to 26.
The composition of the invention may comprise one or more further ingredients. Such optional further ingredients include preservatives (e.g. bactericides), pH buffering agents, perfume carriers, hydrotropes, anti-redeposition agents, soil- release agents, polyelectrolytes, anti-shrinking agents, anti-wrinkle agents, anti-oxidants, sunscreens, anti-corrosion agents, drape imparting agents, anti static agents, ironing aids, pearlisers and/or opacifiers, natural oils/extracts, processing aids, e.g. electrolytes, hygiene agents, e.g. anti-bacterials and anti- fungals and skin benefit agents.
In a particularly preferred embodiment, the composition of the invention is a fabric conditioner composition. Typically, the fabric conditioner composition comprises a cationic softening agent. Preferred cationic softening agents are quaternary ammonium compounds.
In at least one embodiment, the fabric conditioner composition comprises a hydrophobic agent. In at least one embodiment, the fabric conditioner composition comprises a non- ionic alkoxylated material. In at least one embodiment, the fabric conditioner composition comprises a polymeric thickening agent. In at least one embodiment, the fabric conditioner composition comprises a non-ionic softener. In at least one embodiment, the fabric conditioner composition comprises a co-softener. In at least one embodiment, the fabric conditioner composition comprises a fatty complexing agent. The fabric conditioner composition may further comprise shading dyes, additional fragrances and perfumes, and/or further ingredients.
In at least one embodiment, the fabric conditioner composition comprises:
(i) from 0.3 wt.-% to 10 wt.-% of the lipid nanoparticles described herein;
(ii) from 10 wt.-% to 50 wt.-%, preferably from 20 wt.-% to 35 wt.-% of one or more cationic softening agents, preferably quaternary ammonium compounds; and
(iii) at least 40 wt.-% water.
In at least one embodiment, the fabric conditioner composition comprises:
(i) from 0.3 wt.-% to 10 wt.-% of the lipid nanoparticles described herein;
(ii) from 10 wt.-% to 50 wt.-%, preferably from 20 wt.-% to 35 wt.-% of one or more cationic softening agents, preferably quaternary ammonium compounds; (iii) at least 40 wt.-% water; and
(iv) at least one further component (F) selected from the group consisting of hydrophobic agents, non-ionic alkoxylated materials, polymeric thickening agents, non- cationic softeners, preferably non-ionic softeners, co-softeners, fatty complexing agents.
The invention further relates to a method of preparing the composition of the invention, in particular a cosmetic composition or a fabric conditioner composition, comprising the step of preparing the lipid nanoparticles described herein, and mixing the lipid nanoparticles with one or more further components (F) and preferably water. The compositions can be prepared by any conventional method well known in the art.
The invention further relates to a method of treating hair, comprising: a) applying a shampoo composition and/or hair conditioner composition according to the invention onto wet hair and then b) removing the shampoo composition and/or hair conditioner composition from the hair.
The invention further relates to the use of the lipid nanoparticles described herein in cosmetic compositions. Preferred cosmetic compositions are described further above. Preferred components are described further above.
The invention further relates to the use of the lipid nanoparticles described herein in fabric conditioner compositions. Preferred fabric conditioner compositions are described further above. Preferred components are described further above.
The invention is illustrated in more detail by the examples below without, however, limiting it thereto.
In the following examples accelerated stability analysis was carried out as follows: Accelerated stability analysis of formulations was performed using dispersion analyzer LUMiSizer® 611.3-79, (LUM GmbFI, Germany) which involves centrifugation method with photometric detection at 865 nm. To perform a stability study, samples were filled in polyamide cuvettes and centrifuged at 4000 rpm for up to 2.5 hours at 45°C. Then, phase separation and instability were indicated by the included software (SepView 6.0; LUM).
EXAMPLES
The following abbreviations are used: rpm revolutions per minute
RT room temperature (25°C) wt.-% percent by weight
Encapsulation process:
In the following comparative examples 1 to 4 and inventive examples 5 to 12 ingredients of phase A were mixed together in a beaker and heated at 40°C to melt. Similarly, ingredients of phase B were mixed together in another beaker and heated to 70°C to melt. Then, melted phase B was added to melted phase A slowly with continuous stirring to form vesicles. Then, phase C was added while stirring to dilute the encapsulated formulation.
An alternative process for the preparation of the comparative examples 1 to 4 and inventive examples 5 to 12 is as follows:
The ingredients of phase A and of phase B are introduced into the inlet lines of an emulsification device as disclosed in US 2013/0201785 A1. The product from this emulsification device is a composition consisting essentially of lipid nanoparticles comprising fragrance.
The product obtained from the emulsification device is introduced under stirring into a vessel containing phase C. An aqueous composition comprising vesicles is formed. PSD measurement method:
The average particle size of the lipid nanoparticles is measured by Malvern mastersizer- 3000 particle size analyser. D50 (nm) of the stable sample is reported in respective examples.
In the examples the following fragrance formulations were used (weight percentages refer to total fragrance mass):
Fragrance A:
29.95 % by weight of 1-(2-methoxy-1-methylethoxy)-2-propanol (dipropylene glycol monomethyl ether) = diluent d) having logP -0.342
70.05 % by weight of different water-insoluble olfactory substances having log P values between 1.36 and 7.25
Fragrance B:
14.41 % by weight of 1 ,T-oxybis-2-propanol (dipropylene glycol) = diluent d) having logP -0.589
1.48 % by weight of different water-soluble olfactory substances having log P values between -0.9 and -1.34
84.11 % by weight of different water-insoluble olfactory substances having log P values between 1.35 and 8.5
Fragrance C:
12.43 % by weight of 1 ,T-oxybis-2-propanol (dipropylene glycol) = diluent d) having logP -0.589
87.57 % by weight of different water-insoluble olfactory substances having log P values between 1.40 and 6.60 Comparative Example 1 (lipid nanoparticles without additives)
Figure imgf000079_0001
Comparative Example 2 (lipid nanoparticles with rheology modifier - Xanthan Gum)
Figure imgf000080_0001
Comparative Example 3 (lipid nanoparticles without additives)
Figure imgf000081_0001
Comparative Example 4 (lipid nanoparticles without additives)
Figure imgf000082_0001
Inventive Example 5 (lipid nanoparticles with additives - Hostacerin DGI)
Figure imgf000083_0001
Inventive Example 6 (lipid nanoparticles with additive - Genapol PMS)
Figure imgf000084_0001
Inventive Example 7 (lipid nanoparticles with additive - Monecol DSE - and with rheology modifier - Xanthan Gum)
Figure imgf000085_0001
Inventive Example 8 (lipid nanoparticles with additive - Monegyl T-18 and with rheology modifier - Xanthan Gum)
Figure imgf000086_0001
Inventive Example 9 (lipid nanoparticles with additive - Moxilub-518)
Figure imgf000087_0001
Inventive Example 10 (lipid nanoparticles with additive - Moxilub-518)
Figure imgf000088_0001
Inventive Example 11 (lipid nanoparticles with additive - Moxilub-518)
Figure imgf000089_0001
Inventive Example 12 (lipid nanoparticles with additive - Moxilub-518)
Figure imgf000090_0001

Claims

Patent claims
1. A lipid nanoparticle comprising a) one or more surfactants having an HLB value of greater than 6, and b) one or more amphiphilic compounds having a log P value of 1 or greater than 1 , and c) one or more odor forming compounds, and d) one or more diluents selected from the group consisting of aliphatic
Ci-C6 alcohols, polyols having 3 to 6 carbon atoms and 3 to 6 hydroxy groups, alkylene glycols having 2 to 6 carbon atoms, polyalkylene glycols having alkyleneoxy units of 2 to 6 carbon atoms and from 2 to 6, preferably 2 to 4 repeating units, wherein one or more of the hydroxyl groups of the aforementioned alcohols, polyols, alkylene glycols and polyalkylene glycols may be partly or totally etherified with Ci-C4-alkyl groups or may be partly or totally esterified with Ci-C4-acyl groups or may be etherified with Ci-C4-alkyl groups and esterified with Ci-C4-acyl groups and these etherified and esterified substances may either contain no hydroxy group or at least one hydroxy group, Ci-C6-aliphatic alcohols substituted with a dioxolane ring, and mixtures thereof, and e) one or more additives being selected from the group consisting of C12-C26- fatty acid esters of polyols having 2 to 6 carbon atoms and 2 to 4 hydroxyl groups, wherein at least two hydroxyl groups of the polyols are esterified and the polyols are partly or totally esterified, Ci2-C26-fatty acid esters from polyols having 2 to 6 carbon atoms, 2 to 4 hydroxyl groups and one ether group, wherein at least two hydroxyl groups of the polyols are esterified and the polyols are partly or totally esterified, and mixtures thereof.
2. The lipid nanoparticle according to claim 1 , wherein this is a vesicle in the shape of a rotational body comprising at least one lipid double layer and fragrance wherein the vesicle comprises components a) to e) defined in claim 1.
3. The lipid nanoparticle according to claim 2, characterized in that the vesicle is multilamellar comprising two or more concentric lipid double layers.
4. The lipid nanoparticle according to claim 2 or 3, characterized in that the shape of the vesicle is spherical, ellipsoidal or disk-like.
5. The lipid nanoparticle according to one or more of claims 1 to 4, characterized in that the mean diameter of the nanoparticle is from 80 to 800 nm, preferably from 100 to 700 nm, more preferably from 120 to 500 nm and even more preferably from 150 to 480 nm.
6. The lipid nanoparticle according to one or more of claims 1 to 5, characterized in that the one or more surfactants of component a) are selected from the group consisting of nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants and mixtures thereof, and wherein the packing parameter of the one of more surfactants of component a) preferably has a value of 0.5 or greater than 0.5 and more preferably is in the range from 0.5 to 1.
7. The lipid nanoparticle according to claim 6, characterized in that the one or more nonionic surfactants of component a) are selected from the group consisting of polyoxyethylene sorbitan esters, polyoxyethylene sorbitol esters, polyoxyalkylene fatty alcohol ethers, polyoxyalkylene fatty acid esters, alkoxylated glycerides, polyoxyethylene methyl glucoside esters, alkyl polyglucosides, EO-PO blockpolymers and mixtures thereof, or wherein the one or more anionic surfactants of component a) are selected from the group consisting of alkylbenzenesulfonates, alkanesulfonates, olefinsulfonates, alkyl ether sulfates, alkyl sulfates, sulfosuccinates, alkyl phosphates, alkyl ether phosphates, protein fatty acid condensates, amino acid-based surfactants, isethionates, taurides, acyl lactylates, neutralized fatty acids and mixtures thereof, or wherein the one or more cationic surfactants of component a) are selected from the group consisting of esterquats, ditallow dimethyl ammonium chloride, C12/14 alkyl dimethyl benzyl ammonium chloride, alkyl dimethyl benzyl ammonium chlorides, cetyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, behenyl trimethyl ammonium chloride, alkyl hydroxyethyl dimethyl ammonium chlorides, distearyl dimethyl ammonium chloride, dihydrogenated tallow fatty alkyl dimethyl ammonium chloride and mixtures thereof.
8. The lipid nanoparticle according to one or more of claims 1 to 7, characterized in that the one or more surfactants of component a) are selected from polyoxyalkylene C8-C24-fatty alcohol ethers, preferably selected from ethoxylated Ci2-Ci8-fatty alcohol ethers with ethoxylation degrees from 5 to 150 and more preferably are selected from the group consisting of ethoxylated lauryl alcohol with ethoxylation degrees from 20 to 24 or from 90 to 110, preferably from 20 to 24, and ethoxylated stearyl alcohol with ethoxylation degrees from 20 to 24 or from 90 to 110, preferably from 90 to 110, and mixtures thereof.
9. The lipid nanoparticle according to one or more of claims 1 to 8, characterized in that the one or more amphiphilic compounds of component b) are selected from the group consisting of triglycerides of one or more fatty acids having 6 to 10 carbon atoms, esters of a fatty acid and a fatty alcohol, preferably esters of a fatty acid having 8 to 24 carbon atoms and a fatty alcohol having 8 to 24 carbon atoms, and mixtures thereof.
10. The lipid nanoparticle according to one or more of claims 1 to 9, characterized in that component c) consists of one or more odor forming compounds each having a log P value of 1 or greater than 1 and preferably each having a log P value from 1 to 8.5, or comprises one or more odor forming compounds each having a log P value of 1 or greater than 1 and preferably each having a log P value from 1 to 8.5.
11. The lipid nanoparticle according to claim 10, characterized in that component c) comprises one or more odor forming compounds each having a log P value of 1 or greater than 1 and preferably each having a log P value from 1 to 8.5 and in addition comprises one or more odor forming compounds each having a log P value of smaller than 1 and preferably each having a log P value from
0.9 to -4.
12. The lipid nanoparticle according to one or more of claims 1 to 11 , characterized in that it comprises one or more odor forming compounds c) having a log P value smaller than 1 , preferably from 0.9 to -4, and more preferably one or more odor forming compounds c) selected from the group consisting of ethyl maltol, apple ketal, maltol, maltyl acetate, maple furanone, methyl acetate, acetaldehyde diethyl acetal, acetoin, acetoin acetate, butyric acid, 1-acetoxyacetone, 2-acetyl furan, 2-furyl methyl ketone, diethyl malate and mixtures thereof.
13. The lipid nanoparticle according to one or more of claims 1 to 12, characterized in that the one or more diluents of component d) are selected from the group consisting of aliphatic C1-C4 alcohols, dialkyl ethers having 3 to 8 carbon atoms, alkylene glycols having 2 to 6 carbon atoms, dialkylene glycols having alkyleneoxy units of 2 to 6 carbon atoms, trialkylene glycols having alkyleneoxy units of 2 to 6 carbon atoms, tetraalkylene glycols having alkyleneoxy units of 2 to 6 carbon atoms, partly or totally Ci-C4-alkyl etherified alkylene glycols having 2 to 6 carbon atoms, partly or totally Ci-C4-alkyl etherified dialkylene glycols having alkyleneoxy units of 2 to 6 carbon atoms, partly or totally Ci-C4-alkyl etherified trialkylene glycols having alkyleneoxy units of 2 to 6 carbon atoms, partly or totally Ci-C4-alkyl etherified tetraalkylene glycols having alkyleneoxy units of 2 to 6 carbon atoms, partly or totally Ci-C4-acyl esterified alkylene glycols having 2 to 6 carbon atoms, partly or totally Ci-C4-acyl esterified dialkylene glycols having alkyleneoxy units of 2 to 6 carbon atoms, partly or totally Ci-C4-acyl esterified trialkylene glycols having alkyleneoxy units of 2 to 6 carbon atoms, partly or totally Ci-C4-acyl esterified tetraalkylene glycols having alkyleneoxy units of 2 to 6 carbon atoms, Ci-C4-alkyl etherified and Ci-C4-acyl esterified alkylene glycols having 2 to 6 carbon atoms, Ci-C4-alkyl etherified and Ci-C4-acyl esterified dialkylene glycols having alkyleneoxy units of 2 to 6 carbon atoms, Ci-C4-alkyl etherified and Ci-C4-acyl esterified trialkylene glycols having alkyleneoxy units of 2 to 6 carbon atoms, Ci-C4-alkyl etherified and Ci-C4-acyl esterified tetraalkylene glycols having alkyleneoxy units of 2 to 6 carbon atoms, Ci-C4-aliphatic alcohols substituted with an 1 ,3-dioxolane ring, and mixtures thereof.
14. The lipid nanoparticle according to one or more of claims 1 to 13, characterized in that the one or more diluents of component d) are selected from the group consisting of monohydric aliphatic C1-C4 alcohols, propylene glycol, di-propylene glycol, tri-propylene glycol, propylene glycol mono-methyl ether, di-propylene glycol mono-methyl ether, tri-propylene glycol mono-methyl ether, propylene glycol mono-ethyl ether, di-propylene glycol mono-ethyl ether, tri-propylene glycol mono- ethyl ether and mixtures thereof.
15. The lipid nanoparticle according to one or more of claims 1 to 14, characterized in that the one or more additives of component e) are selected from fatty acid esters of polyols, wherein the fatty acid residue comprises 12 to 22, preferably 16 to 20 and more preferably 18 carbon atoms and the polyol is selected from ethylene glycol, glycerol, diglycerol and/or pentaerythritol and wherein at least two of the hydroxyl groups of the polyols are esterified and the polyols are partly or totally esterified, and mixtures thereof.
16. The lipid nanoparticle according to one or more of claims 1 to 15, characterized in that the one or more additives of component e) have a log P value from 10 to 50 and more preferably from 14 to 40.
17. The lipid nanoparticle according to claim 16, characterized in that the one or more additives of component e) are selected from the group consisting of ethylene glycol distearate, glycerol tristearate, diglycerol diisostearate, pentaerythritol tetrastearate and mixtures thereof.
18. The lipid nanoparticle according to one or more of claims 1 to 17, characterized in that it comprises a) one or more surfactants having an HLB value of greater than 6 and being selected from polyoxyethylene Ci2-Ci8-fatty alcohol ethers with ethoxylation degrees from 10 to 150 and preferably from 15 to 120 and more preferably being selected from the group consisting of ethoxylated lauryl alcohol and ethoxylated stearyl alcohol, each with ethoxylation degrees from 15 to 120 and mixtures thereof, and b) one or more amphiphilic compounds having a log P value from 1 to 5 and being selected from the group consisting of triglycerides of glycerol with one or more fatty acids having 8 to 10 carbon atoms, esters of fatty acids having 8 to 24 carbon atoms and fatty alcohols having 10 to 18 carbon atoms and mixtures thereof, and preferably being selected from the group consisting of cetyl palmitate and triglycerides of glycerol with caprylic acid and/or capric acid, and mixtures thereof, and c) one or more odor forming compounds having a log P value from 1 to 8.5, and d) one or more diluents being selected from the group consisting of aliphatic C1-C4 alcohols, propylene glycol, dipropylene glycol, propylene glycol mono- methyl ether, propylene glycol mono-ethyl ether, dipropylene glycol mono- methyl ether, dipropylene glycol mono-ethyl ether, and mixtures thereof, and e) one or more additives being selected from fatty acid esters of polyols, wherein the fatty acid residue comprises 12 to 22, preferably 16 to 20 and more preferably 18 carbon atoms and the polyol is selected from ethylene glycol, glycerol, diglycerol and/or pentaerythritol and wherein at least two of the hydroxyl groups of the polyols are esterified and the polyols are partly or totally esterified, and mixtures thereof, and more preferably, the one or more additives of component e) are selected from the group consisting of ethylene glycol distearate, glycerol tristearate, diglycerol diisostearate, pentaerythritol tetrastearate and mixtures thereof.
19. The lipid nanoparticle according to one or more of claims 1 to 18, characterized in that the nanoparticle comprises glycerol as component h) and preferably comprises glycerol in an amount from 2 to 7 % by weight, based on the total weight of the nanoparticle.
20. The lipid nanoparticle according to one or more of claims 1 to 19, characterized in that the amount of component a) is from 1 to 95 % by weight, and the amount of component b) is from 1 to 95 % by weight, and the amount of component c) is from 0.4 to 57 % by weight, and the amount of component d) is from 0.05 to 36 % by weight, and the amount of component e) is from 1 to 20 % by weight, wherein the weight percentages in each case are based on the total weight of the nanoparticle.
21. An aqueous composition comprising the lipid nanoparticles according to one or more of claims 1 to 20 and water, wherein the amount of the nanoparticles is from 0.1 to 60 % by weight, preferably from 1 to 50 % by weight and more preferably from 5 to 20 % by weight, in each case based on the total weight of the aqueous composition.
22. The aqueous composition according to claim 20, characterized in that it comprises one or more rheology modifiers, preferably one or more natural biopolymers and more preferably one or more natural biopolymers selected from the group consisting of xanthan gum, guar gum, gellan gum, gum arabic and mixtures thereof.
23. A method of manufacturing the lipid nanoparticles according to one or more of claims 1 to 20 or an aqueous composition according to claim 21 or 22 comprising the steps: i) forming a composition A by combining one or more surfactants of component a) and water in a first container, ii) forming a composition B by combining one or more amphiphilic compounds of component b), a fragrance comprising component c) and component d) as well as one or more additives of component e) in a second container, iii) combining compositions A and B by adding component B to component A under agitation, and iv) adding water as composition C to the combined compositions A and B from step iii).
24. The method according to claim 23, characterized in that the components of composition A in step i) and/or the components of composition B in step ii) are heated to temperatures from 30 to 130°C.
25. The method according to claim 23 or 24, characterized in that composition C comprises one or more surfactants and/or one or more rheology modifiers.
26. A method of manufacturing the lipid nanoparticles according to one or more of claims 1 to 20 comprising the steps: ia) feeding a composition A comprising one or more surfactants of component a) and water to a first inlet line of an emulsification device, iia) feeding a composition B comprising one or more amphiphilic compounds of component b), fragrance comprising components c) and d) and one or more additives of component e) to a second inlet line of an emulsification device, iiia) combining compositions A and B in a turbulent mixing zone in the emulsification device, iva) transporting the mixed compositions within the emulsification device towards an outlet line, whereby laminar flow of the mixed components is established in the zone preceding the outlet line thereby vesicles are formed, and va) discharging the nanoparticles via the outlet line from the emulsification device.
27. The method according to claim 26, characterized in that the nanoparticles formed in the emulsification device are diluted with water in a separate device by introducing the vesicles into water which optionally contains one or more additional surfactants and/or optionally contains one or more rheology modifiers.
28. Use of the lipid nanoparticles according to one or more of claims 1 to 20 or the aqueous compositions according to claim 21 or 22 in cosmetic and hair care compositions.
29. Use of the lipid nanoparticles according to one or more of claims 1 to 20 or the aqueous compositions according to claim 21 or 22 in laundry compositions, preferably in washing agents or in fabric softeners.
30. Use of the lipid nanoparticles according to one or more of claims 1 to 20 or the aqueous compositions according to claim 21 or 22 for providing prolonged fragrance release by slow diffusion in cosmetic or hair care compositions or in laundry compositions, preferably in washing agents or in fabric softeners.
PCT/EP2021/052339 2020-02-04 2021-02-01 Lipid nanoparticles for delayed delivery of fragrance with enhanced water solubility, their preparation and use WO2021156213A1 (en)

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