WO2008006486A1 - Cosmetic or dermatological preparations containing folic acid, fillers and thickeners - Google Patents

Cosmetic or dermatological preparations containing folic acid, fillers and thickeners Download PDF

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Publication number
WO2008006486A1
WO2008006486A1 PCT/EP2007/005871 EP2007005871W WO2008006486A1 WO 2008006486 A1 WO2008006486 A1 WO 2008006486A1 EP 2007005871 W EP2007005871 W EP 2007005871W WO 2008006486 A1 WO2008006486 A1 WO 2008006486A1
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Prior art keywords
fillers
preparations
cosmetic
weight
folic acid
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PCT/EP2007/005871
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German (de)
French (fr)
Inventor
Rixa Dippe
Anja Drucks
Julia Eckert
Christel Meding
Jens Nielsen
Jens Treu
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Beiersdorf Ag
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Priority to EP07765018A priority Critical patent/EP2046272A1/en
Publication of WO2008006486A1 publication Critical patent/WO2008006486A1/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
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/67Vitamins
    • 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
    • A61K8/19Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/25Silicon; Compounds thereof
    • 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
    • A61K8/19Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/29Titanium; Compounds thereof
    • 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
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73Polysaccharides
    • 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
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73Polysaccharides
    • A61K8/732Starch; Amylose; Amylopectin; Derivatives thereof
    • 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
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8147Homopolymers or copolymers of acids; Metal or ammonium salts thereof, e.g. crotonic acid, (meth)acrylic acid; Compositions of derivatives of such polymers
    • 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
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8152Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
    • 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
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/88Polyamides
    • 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
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89Polysiloxanes
    • A61K8/891Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
    • 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
    • A61K8/96Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution
    • A61K8/97Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution from algae, fungi, lichens or plants; from derivatives thereof
    • A61K8/9706Algae
    • A61K8/9717Rhodophycota or Rhodophyta [red algae], e.g. Porphyra
    • 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
    • A61K8/96Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution
    • A61K8/97Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution from algae, fungi, lichens or plants; from derivatives thereof
    • A61K8/9783Angiosperms [Magnoliophyta]
    • A61K8/9789Magnoliopsida [dicotyledons]
    • 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
    • A61K8/96Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution
    • A61K8/97Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution from algae, fungi, lichens or plants; from derivatives thereof
    • A61K8/9783Angiosperms [Magnoliophyta]
    • A61K8/9794Liliopsida [monocotyledons]
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61PSPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P17/00Drugs for dermatological disorders
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • A61Q19/004Aftersun preparations

Definitions

  • Cosmetic or dermatological preparations containing folic acid, fillers and thickeners containing folic acid, fillers and thickeners
  • the present invention relates to cosmetic or dermatological preparations containing folic acid, fillers and thickeners.
  • the skin is exposed to a variety of environmental factors that can lead to their damage.
  • lipids and proteins especially the DNA is affected.
  • UVC region The damaging effect of the ultraviolet part of solar radiation on the skin is well known. While rays having a wavelength smaller than 290 nm (the so-called UVC region) are absorbed by the ozone layer in the earth's atmosphere, rays in the range between 290 nm and 320 nm, the so-called UVB region, cause erythema simple sunburn or even more or less severe burns.
  • UVA range it is important to have available filter substances, since its rays can cause reactions in photosensitive skin. It has been proven that UVA radiation leads to damage to the elastic and collagen fibers of the connective tissue, which the skin ages prematurely and that it can be seen as the cause of numerous phototoxic and photoallergic reactions. The damaging influence of UVB radiation can be amplified by UVA radiation.
  • DNA replication required in view of the large number of nucleotides that have to be copied per cell division is guaranteed, on the one hand, by the specificity of the DNA polymerases involved in replication (replicases) and, on the other hand, by their additional exonuclease activity: They catalyze the excision of inappropriate nucleotides and their replacement by the correct ones immediately after the new synthesis.
  • the damage caused by chemical action (by mutagens, some of which can intervene between two superimposed base pairs of the double helix) as well as the radiation-induced changes (eg two superimposed thymine residues can dimerize) help repair enzymes (including: Endonucleases, polymerases, ligases) that cut out and replace inappropriate nucleotides again from the DNA.
  • repair enzymes including: Endonucleases, polymerases, ligases
  • Some of these repair systems are inducible, i. H. they are synthesized only when needed. The question of which strand contains the original information and which was wrongly synthesized is apparently decided by the repair enzyme on the basis of the state of methylation.
  • Exposure to environmental influences causes damage to the DNA molecules of the cells of the body, which can, however, be remedied by cellular DNA repair mechanisms.
  • the DNA damage is detected and then the damage is repaired. If the damage is not completely eliminated shortly after it has been formed by repair processes, these accumulate in the form of permanent DNA damage in the cells and are subsequently passed on to the daughter cells.
  • This permanent damage in particular due to possible late effects (gradual loss of function), has a high potential for damage and is playing an increasingly important role in aging processes and in the initiation of damage already in childhood.
  • Object of the present invention was therefore to remedy the evils of the prior art remedy.
  • active ingredients and preparations should be provided which should ensure a reliable prophylaxis of damage to the skin's own DNA and / or in a particular embodiment should be used to repair damage already occurred to the skin's own DNA.
  • Folic acid has the following structure:
  • Folic acid occurs in liver, kidney, yeast, fungi, cereals and green leaves, predominantly as a conjugate with poly- ⁇ -L-glutamic acid (pteroylpolyglutamic acids). It has been discovered as a growth substance for various microorganisms and has a vitamin character for the human organism. Adult human needs are about 200 ⁇ g per day of bioavailable folate.
  • H 2 folate 7,8-dihydrofolic acid
  • FH 2 7,8-dihydrofolic acid
  • H 2 folate old abbreviation: FH 2
  • nicotinamide adenine dinucleotide phosphate and the enzyme dihydrofolate reductase.
  • H 2 folate in turn is produced in plants and some microorganisms via several intermediates of guanosine 5'-triphosphate (guanosine phosphates) and uses dihydrofolate reductase to convert (6S) -5,6,7,8-tetrahydrofolic acid, the actual physiologically active form of folic acid.
  • 7,8-Dihydrofolic acid has the following chemical structure:
  • derivatives of folic acid is to be understood in particular as meaning the abovementioned dihydrofolic acid and the tetrahydrofolic acid.
  • Folic acid-containing skin care products should be pleasant to use in addition to the positive effect on the skin. Powder raw materials give a pleasant silky velvet skin feeling. However, both folic acid (electrolyte) and powder raw materials destabilize an emulsion, so that the combination in an emulsion is often not storage and heat stable.
  • folic acid and / or derivatives thereof have a high potential for repairing damaged DNA. Furthermore, folic acid and / or its derivatives provide effective prophylaxis against DNA damage, especially those caused by UV radiation.
  • Fillers in the context of the present invention are particulate substances which as a rule do not produce any color effect in the cosmetic formulation in which they are used. Furthermore, fillers according to the invention usually have a low refractive index and, as a result, no or very little opacity.
  • fillers which z. B. serve as support materials in the formulation of powders or as viscosity and sensor modulators in emulsions or anhydrous formulations. Such fillers are also often used to obtain matting effects on the skin or to absorb sebum.
  • fillers generally also affects the spreadability of conventional formulations on the skin and the uniformity of a possible color effect.
  • the fillers in the context of the present invention are advantageously selected from the group of inorganic fillers, for example from the group of silicates.
  • Silicates are salts and esters (silicic acid esters) of orthosilicic acid [Si (OH) 4 ] and their condensation products.
  • the silicates are not only the most species-rich class of minerals, but also extremely important geologically and technically. Over 80% of the earth's crust is made up of silicates.
  • phyllosilicates are advantageous.
  • Layer silicates (phyllosilicates, leaf silicates) are (ideally) silicate structures with two-dimensionally infinite layers of [SiO 4 ] 4 ' tetrahedra, each tetrahedron being connected via 3 bridging oxygens with neighboring tetrahedra.
  • Chemical formulas can only be approximated for phyllosilicates because they have a large ion exchange capacity and silicon can be exchanged for aluminum and this in turn against magnesium, Fe 2+ , Fe 3+ , Zn and the like.
  • the resulting possibly negative charge of the layers is usually compensated by cations, in particular by Na + and Ca 2+ in interlayer positions.
  • Phyllosilicates can be obtained by reversible storage of water (in the 2- to 7-fold amount) and other substances such. As alcohols, glycols and the like swell. Their use as thickeners in cosmetic products is accordingly known per se. However, the prior art could not point the way to the present invention.
  • Advantageous phyllosilicates which can be used in the context of the present invention are, for example, those whose largest expansion direction in the unmodified and unswollen state has an average length of less than 10 ⁇ m.
  • the mean extents of the modified layered silicate particles used may be 1000 nm ⁇ 100 nm ⁇ 1 nm and less.
  • the effective size of the modified layered silicate particles in a cosmetic or dermatological formulation of course depends on the amount of stored substances.
  • Particularly advantageous (layered) silicates according to the invention are:
  • Kaolin Al 2 [Si 2 O 5 ] (OH) 4
  • Montmorillonite M + Al [Si 2 O 5 ] (OH), also called smectite. These include:
  • Bentonite montmorillonite with Ca (filler earth) or Na (Wyoming bentonite)
  • Mica an aluminosilicate that is easily fissile and is present in tabular crystals. Mica is transparent to translucent and has pearlescence. The most important form is muscovite: K Al 2 [AISi 3 O 10 ] (OH, F) 2 . Sericite is a special form of mica that has smaller platelets than muscovite. Magnesium silicate Mg 2 [Si 4 Oi 0 ] Also, silicon oxides (SiO 2 ) are to be used advantageously in the context of the present invention.
  • Aerosils (fumed silica), which are highly disperse silicas with frequently irregular shape, whose specific surface area is generally very large (200-400 m 2 / g) and which can be controlled by means of the production process, are preferred according to the invention. Aerosils are also referred to as: Amorphous Silica Amorphous Silicon Oxide Hydrate Silica, Amorphous Silicic Anhydride Silicon Dioxide Silicon Dioxide.
  • Aerosil 130 (Degussa Hüls), Aerosil 200 (Degussa Hüls), Aerosil 255 (Degussa Hüls), Aerosil 300 (Degussa Hellers), Aerosil 380 (Degussa Hellers), B-6C (Suzuki Yushi), CAB-O-SIL Fumed silica (Cabot), CAB-O-SIL EH-5 (Cabot), CAB-O-SIL HS-5 (Cabot), CAB-O-SIL LM-130 (Cabot), CAB-O-SIL MS-55 (Cabot), CAB-O-SIL M-5 (Cabot), E-6C (Suzuki Yushi), Fossil Flour MBK (MBK), MSS-500 (Kobo), Neosil CT 1 1 (Crosfield Co.), Ronasphere ( Rona / EM Industries), Silica, Anhydrous 31 (Whittaker, Clark & Daniels), Silica, Crystalline 216
  • Silicon oxides can also be produced in a spherical form, in which case the specific surface area is smaller than in the aerosils, since the particles are larger and round.
  • An example of this are the Ronaspheren (average particle diameter ⁇ 3 ⁇ ) from. Merck (see Figure 1).
  • Further fillers preferred according to the invention are silicas whose free OH groups on the particle surface are (completely or partially) organically modified.
  • Advantageous z the obtainable by addition of dimethylsilyl groups silica dimethyl silylates, such as Aerosil R972 (Degussa Hüls), Aerosil R974 (Degussa Hüls), CAB-O-SIL TS-610 (Cabot), CAB-O-SIL TS -720 (Cabot), Wacker HDK H15 (Wacker chemistry), Wacker HDK H18 (Wacker chemistry) and / or Wacker HDK H20 (Wacker chemistry).
  • dimethylsilyl groups silica dimethyl silylates such as Aerosil R972 (Degussa Hüls), Aerosil R974 (Degussa Hggs), CAB-O-SIL TS-610 (Cabot), CAB-O-SIL TS -720 (Cabot), Wacker HD
  • silicates obtainable by addition of trimethylsilyl groups (eg Aerosil R 812 (Degussa Hüls), CAB-O-SIL TS-530 (Cabot), Sipemat D 17 (Degussa Hüls), Wacker HDK H2000 (Wacker). Chemistry)).
  • trimethylsilyl groups eg Aerosil R 812 (Degussa Hüls), CAB-O-SIL TS-530 (Cabot), Sipemat D 17 (Degussa Hüls), Wacker HDK H2000 (Wacker). Chemistry
  • polymethylsilsesquioxanes obtainable by hydrolysis and condensation reactions of methyltrimethoxysilanes, which likewise have a round shape and whose particle size distribution can be controlled by the preparation.
  • Preferred polymethylsilsesquioxanes are available, for example, under the trade names Tospearl 2000 B from GE Bayer Silikones, Tospearl 145A from Toshiba, AEC Silicone Resin Spheres from A & E Connock and Wacker-Belsil PMS MK from Wacker-Chemie.
  • Boron nitride is isoelectronic with carbon (i.e., graphite and diamond shapes are possible). Boron nitride is characterized by its chemical inertness.
  • Wacker boron nitride BNP Wacker-Chemie Further advantageous fillers in the context of the present invention are carbonates, such as. As magnesium carbonate (MgCO 3 ) and calcium carbonate (CaCO 3 ). It is particularly advantageous for the purposes of the present invention to use the carbonates as fillers in dry powders.
  • MgCO 3 magnesium carbonate
  • CaCO 3 calcium carbonate
  • the fillers in the context of the present invention are also advantageously selected from the group of organic fillers.
  • advantageous organic fillers are, for.
  • natural polymers such as silk powder, microcrystalline cellulose and / or zinc stearates.
  • Advantageous organic fillers are also starch and starch derivatives, such as:
  • Organic fillers preferred according to the invention are also synthetic polymers, ie. H. Polymer particles which are present in the preparation in the form of solids, such as polycarbonates, polyethers, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyamides, polyurethanes, polyacrylates and the like. Particularly advantageous is z.
  • nylon polyamide 6 and polyamide 12
  • polyamide 6 for example microfine polyamide particles, in particular those available under the trade name SP-500 from TORAY.
  • polyamide 6- also: nylon 6
  • polyamide 12 also: nylon 1-2
  • Polyamide 6 is the polyamide [poly ( ⁇ -caprolactam)] synthesized from ⁇ -aminocaproic acid (6-aminohexanoic acid) or ⁇ -caprolactam
  • polyamide 12 is a poly ( ⁇ -laurinlactam) from ⁇ -laurolactam.
  • Advantageous in the sense of the present invention are, for example Orgasol ® 1002 (polyamide 6), and Orgasol ® 2002 (polyamide 12) from ELF ATOCHEM.
  • Silicone Resins Trimethylsiloxysilicate (eg SR 1000 GE Bayer Silicones)
  • silicone elastomers can be selected from the group of vinyl dimethicone crosspolymers, such as. Dow Corning 9506 Cosmetic Powder from Dow Coming (INCI: Dimethicone / Vinyl Dimethicone Crosspolymer).
  • silicone resins such as e.g. KSP-100, KSP-200 or KSP-300 from Shin Etsu, which are also listed under the INCI name Dimethicone / Vinyl Dimethicone Crosspolymer or SR 1000 from GE Bayer Silicones, which bears the INCI name Trimethylsiloxy Silicate
  • lauroyl lysine which is sold by Ajinomoto under the name Amihope LL.
  • the total amount of at least one filler in the finished cosmetic or dermatological preparations is advantageously selected from the range of 0.05-20.0% by weight, preferably 0.5-10.0% by weight, based on the total weight of the preparations.
  • Fillers preferred according to the invention come from the group of inorganic or organic silicon compounds.
  • the layer silicates are particularly preferred. Of these, kaolin, talc and mica are particularly preferred.
  • the preferred inorganic silicon compounds include the surface of the organically modified spherical particles.
  • Aerosil R 972 particularly preferred are the polymethylsilsesquioxanes and hydrophobically modified aerosils, e.g. Aerosil R 972.
  • Organic silicon compounds include the siloxane elastomers and siloxane resins. Of these, particularly preferred are the KSP types from Shin Etsu, as well as the trimethylsiloxysilicate.
  • fillers come from the group of spherical particles. More preferably, the average particle diameter is less than 20 microns. Furthermore, preference is given to choosing spherical particles of organic origin. Particularly preferred is the BPD-500 marketed by Kobo.
  • spherical particles having an average particle diameter of less than 10 ⁇ m are preferred.
  • nylon-12 e.g. sold as SP-501 or SP-500 by the company Kobo.
  • polymethyl methacrylates e.g. sold under the trade name Covabead LH 85 by LCW.
  • the preparations are characterized in that they contain 0.001% by weight to 10% by weight, preferably 0.05% by weight to 5% by weight, in particular 0.1-2, 0 wt .-%, based on the total weight of the preparations, on one or more fillers.
  • thickeners are preferably selected from the group of hydrocolloids.
  • Hydrocolloid is the technological abbreviation for the correct name.
  • Hydrocolloids are macromolecules that are largely linear in shape and have intermolecular interaction forces that allow side and major valence bonds between the individual molecules to form a reticulate structure that are partially water-soluble natural or synthetic polymers.
  • Forming gels or viscous solutions in aqueous systems they increase the viscosity of the water either by binding water molecules (hydration) or by taking up and enveloping the water in their interwoven macromolecules, while at the same time restricting the mobility of the water represent a large group of chemically very different natural and synthetic polymers whose common feature is their solubility in water or aqueous media, provided that these polymers have a solubility for water solubility have sufficient number of hydrophilic groups and are not too strongly crosslinked.
  • the hydrophilic groups may be nonionic, anionic or cati
  • the group of cosmetically and dermatologically relevant hydrocolloids can be classified as follows: organic, natural compounds, such as agar-agar, carrageenan, tragacanth,
  • Starch dextrins, gelatin, casein, organic, modified natural products such.
  • vinyl polymers polycarboxylic acids, polyethers, polyimines, polyamides, inorganic compounds such.
  • polysilicic acids clay minerals such as montmorillonites, zeolites, silicic acids.
  • Hydrocolloids which are preferred according to the invention are, for example, methylcelluloses, which are referred to as the methyl ethers of cellulose. They are characterized by the following structural formula
  • cellulose mixed ethers which are generally also referred to as methylcelluloses and, in addition to a dominating content of methyl, additionally contain 2-hydroxyethyl, 2-hydroxypropyl or 2-hydroxybutyl groups.
  • Particularly preferred are (hydroxypropyl) methylcelluloses, for example those available under the trade name Methocel E4M from Dow Chemical Comp.
  • sodium carboxymethylcellulose the sodium salt of the glycolic acid ether of cellulose, for which R in structural formula I can be a hydrogen and / or CH 2 -COONa.
  • Particularly preferred is sodium carboxymethylcellulose, also known as cellulose gum, available under the tradename Natrosol Plus 330 CS from Aqualon.
  • xanthan also called xanthan gum, which is an anionic heteropolysaccharide, which is generally formed by fermentation from corn sugar and isolated as the potassium salt. It is produced by Xanthomonas campestris and some other species under aerobic conditions with a molecular weight of 2 * 10 6 to 24 * 10 6 .
  • Xanthan comes with a chain ß-1, 4-bonded glucose (cellulose) formed with side chains. The structure of the subgroups consists of glucose, mannose, glucuronic acid, acetate and pyruvate.
  • Xanthan is the name given to the first microbial anionic heteropolysaccharide.
  • Xanthan is formed from a chain of ⁇ -1,4-linked glucose (cellulose) with side chains.
  • the structure of the subgroups consists of glucose, mannose, glucuronic acid, acetate and pyruvate.
  • the number of pyruvate units determines the viscosity of xanthan.
  • Xanthan is produced in two-day batch cultures with a yield of 70-90%, based on carbohydrate used. Yields of 25-30 g / l are achieved. The workup is carried out after killing the culture by precipitation with z.
  • B. 2-propanol. Xanthan is then dried and ground.
  • Advantageous gelling agent for the purposes of the present invention is also carrageenan, a gel-forming and similar to agar based extract of North Atlantic, to the Florideen counting red algae (Chondrus crispus and Gigartina stellata).
  • carrageenan is used for the dried algae product and carrageenan for the extract thereof.
  • the carrageenan precipitated from the hot-water extract of the algae is a colorless to sand-colored powder with a molecular weight range of 100,000-800,000 and a sulphate content of about 25%.
  • Carrageenan which dissolves very easily in warm water); Upon cooling, a thixotropic gel forms, even if the water content is 95-98%. The strength of the gel is effected by the double helix structure of the carrageenan.
  • Carrageenan has three main components:
  • the gel-forming ⁇ fraction consists of D-galactose-4-sulfate and 3,6-anhydro- ⁇ -D-galactose, which are alternately glycosidically linked in the 1, 3 and 1, 4 positions (Agar, in contrast, contains 3,6-anhydro- ⁇ -L-galactose).
  • the non-gelling ⁇ -fraction is composed of 1, 3-glycosidically linked D-galactose-2-sulfate and 1, 4-linked D-galactose-2,6-disulfate radicals u. easily soluble in cold water.
  • the ⁇ -carrageenan composed of D-galactose-4-sulfate in 1, 3-bond and 3,6-anhydro- ⁇ -D-galactose-2-sulfate in 1, 4-bond is both water-soluble and gel-forming.
  • Other types of carrageenan are also denoted by Greek letters: ⁇ , ⁇ , ⁇ , ⁇ , v, ⁇ , ⁇ , ⁇ , ⁇ .
  • the type of cations present K + , NH 4 + , Na + , Mg 2+ , Ca 2+ ) also influences the solubility of the carrageenans.
  • the use of chitosan in cosmetic preparations is known per se. Chitosan is a partially deacylated chitin.
  • X represents either the acetyl radical or hydrogen.
  • Chitosan is formed by deacetylation and partial depolymerization (hydrolysis) of chitin, which by the structural formula
  • chitosan In the range of about pH ⁇ 6 chitosan is positively charged and there also soluble in aqueous systems. It is not compatible with anionic raw materials. For this reason, the use of nonionic emulsifiers is suitable for producing chitosan-containing oil-in-water emulsions. These are known per se, for example from EP-A 776 657.
  • Preference according to the invention is given to chitosans having a degree of deacetylation of> 25%, in particular> 55 to 99% [determined by means of 1 H-NMR]).
  • chitosans with molecular weights between 10,000 and 1,000,000, especially those with molecular weights between 100,000 and 1,000,000. [determined by gel permeation chromatography].
  • Polyacrylates are also advantageously gelators to be used in the context of the present invention.
  • Polyacrylates which are advantageous according to the invention are acrylate-alkyl acrylate copolymers, in particular those selected from the group of the so-called carbomers or carbopols (Carbopol® is actually a registered trademark of B.F. Goodrich Company).
  • the acrylate copolymer (s) according to the invention are characterized by the following structure:
  • R ' represents a long-chain alkyl radical and x and y represent numbers which symbolize the respective stoichiometric proportion of the respective comonomers.
  • Particularly preferred according to the invention are acrylate copolymers and / or acrylate-alkyl acrylate copolymers, which are available under the trade names Carbopol® 1382, Carbopol® 981 and Carbopol® 5984 from the BF Goodrich Company.
  • the total amount of one or more thickeners in the finished cosmetic or dermatological preparations advantageously less than 1, 5 wt .-%, preferably between 0.1 and 1, 0 wt .-%, based on the total weight of the preparations selected.
  • the cosmetic or dermatological preparations may be composed as usual and used for the treatment, care and cleansing of the skin and / or the hair and as a make-up product in decorative cosmetics.
  • They preferably contain from 0.001% by weight to 10% by weight, preferably from 0.05% by weight to 5% by weight, in particular from 0.1% to 2.0% by weight, based on the total weight of the preparations, of folic acid and / or its derivatives.
  • Cosmetic and dermatological preparations according to the invention can be present in various forms.
  • they may contain a solution, an anhydrous preparation, an emulsion or microemulsion of the water-in-oil (W / O) type or of the oil-in-water (O / W) type, a multiple emulsion, for example water-type. in-oil-in-water (W / O / W), a gel, a solid stick, an ointment or even an aerosol.
  • folic acid and / or its derivatives in encapsulated form, for example in collagen matrices and other customary encapsulating materials, for example as encapsulated encapsulations, in gelatin, wax matrices or liposomally encapsulated.
  • wax matrices as described in DE-OS 43 08 282, have been found to be favorable.
  • the cosmetic and dermatological preparations according to the invention may comprise cosmetic adjuvants such as are conventionally used in such preparations, e.g. Preservatives, bactericides, perfumes, foaming inhibitors, colorants, pigments having a coloring effect, thickeners, surface-active substances, emulsifiers, softening, moistening and / or moisturizing substances, fats, oils, waxes or other conventional ingredients of a cosmetic or cosmetic dermatological formulation such as alcohols, polyols, polymers, foam stabilizers, electrolytes, organic solvents or silicone derivatives.
  • cosmetic adjuvants such as are conventionally used in such preparations, e.g. Preservatives, bactericides, perfumes, foaming inhibitors, colorants, pigments having a coloring effect, thickeners, surface-active substances, emulsifiers, softening, moistening and / or moisturizing substances, fats, oils, waxes or other conventional ingredients of a cosmetic or cosmetic dermatological formulation such as alcohol
  • folic acid and / or its derivatives can also be combined with other antioxidants and / or radical scavengers.
  • the amount of antioxidants (one or more compounds) in the preparations is preferably from 0.001 to 30% by weight, particularly preferably from 0.05 to 20% by weight, in particular from 1 to 10% by weight, based on the total weight of the preparation ,
  • the lipid phase can advantageously be selected from the following substance group: mineral oils, mineral waxes
  • Oils such as triglycerides of capric or caprylic acid, further natural oils such as e.g. Castor oil;
  • Fats, waxes and other natural and synthetic fats preferably esters of fatty acids with lower C-number alcohols, e.g. with isopropanol, propylene glycol or glycerol, or esters of fatty alcohols with alkanoic acids of low C number or with fatty acids; benzoates;
  • Silicone oils such as dimethylpolysiloxanes, diethylpolysiloxanes, diphenylpolysiloxanes and mixed forms thereof.
  • the oil phase of the emulsions, oleogels or hydrodispersions or lipodispersions in the context of the present invention is advantageously selected from the group of esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids having a chain length of 3 to 30 carbon atoms and saturated and / or or unsaturated, branched and / or unbranched alcohols having a chain length of 3 to 30 carbon atoms, from the group of esters of aromatic carboxylic acids and saturated and / or unsaturated, branched and / or unbranched alcohols having a chain length of 3 to 30 carbon atoms.
  • ester oils can then advantageously be selected from the group isopropyl myristate, isopropyl palmitate, isopropyl stearate, isopropyl oleate, n-butyl stearate, n-hexyl laurate, n-decyl oleate, isooctyl stearate, isononyl stearate, isononyl isononanoate, 2-ethylhexyl palmitate, 2-ethylhexyl laurate, 2-hexyldecyl stearate, 2 Octyldodecyl palmitate, oleyl oleate, oleyl erucate, erucyl oleate, erucyl erucate and also synthetic, semisynthetic and natural mixtures of such esters, eg jojoba oil.
  • the aqueous phase of the preparations according to the invention optionally advantageously contains alcohols, diols or polyols of low C number, and their ethers, preferably ethanol, isopropanol, propylene glycol, glycerol, ethylene glycol, ethylene glycol monoethyl or -mob nobutyl ether, propylene glycol monomethyl, -monoethyl- or -monobutylether , Diethylene glycol monomethyl or monoethyl ether and analogous products, furthermore lower C-number alcohols, eg Ethanol, isopropanol, 1, 2-propanediol, glycerol and in particular one or more thickening agents, which or which can be advantageously selected from the group of silica, aluminum silicates, polysaccharides or their derivatives, e.g.
  • Hyuronic acid, xanthan gum, hydroxypropylmethylcellulose particularly advantageously from the group of the polyacrylates, preferably a polyacrylate from the group of the so-called Carbopol, for example Carbopols types 980, 981, 1382, 2984, 5984, in each case individually or in combination.
  • Carbopol for example Carbopols types 980, 981, 1382, 2984, 5984, in each case individually or in combination.
  • mixtures of the abovementioned solvents are used.
  • alcoholic solvents water can be another ingredient.
  • Emulsions according to the invention are advantageous and contain, for example, the said fats, oils, waxes and other fatty substances, as well as water and an emulsifier, as is customarily used for such a type of formulation.
  • Gels according to the invention usually contain alcohols of low carbon number, for example ethanol, isopropanol, 1,2-propanediol, glycerol and water or an abovementioned oil in the presence of a thickener, which in the case of oily-alcoholic gels preferably silica or an aluminum silicate in aqueous-alcoholic or alcoholic gels is preferably a polyacrylate.
  • Suitable propellants for preparations which can be sprayed from aerosol containers according to the invention are the customary known highly volatile, liquefied propellants, for example hydrocarbons (propane, butane, isobutane), which can be used alone or mixed with one another. Also, compressed air is advantageous to use.
  • preparations according to the invention may also contain substances which absorb UV radiation in the UVB range, the total amount of filter substances being e.g. 0.1 wt .-% to 30 wt .-%, preferably 0.5 to 10 wt .-%, in particular 1, 0 to 6.0 wt .-%, based on the total weight of the preparations to cosmetic preparations for To provide the hair or the skin against the entire range of ultraviolet radiation. They can also serve as a sunscreen for hair or skin.

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Abstract

The invention relates to cosmetic or dermatological preparations containing folic acid and/or derivatives thereof, fillers and thickeners.

Description

Beschreibung description
Kosmetische oder dermatologische Zubereitungen mit einem Gehalt an Folsäure, Füllstoffen und VerdickernCosmetic or dermatological preparations containing folic acid, fillers and thickeners
Die vorliegende Erfindung betrifft kosmetische oder dermatologische Zubereitungen mit einem Gehalt an Folsäure, Füllstoffen und Verdickern.The present invention relates to cosmetic or dermatological preparations containing folic acid, fillers and thickeners.
Die Haut ist einer Vielzahl von Umwelteinflüssen ausgesetzt, die zu ihrer Schädigung führen können. Neben Lipiden und Proteinen ist dabei vor allem die DNA betroffen.The skin is exposed to a variety of environmental factors that can lead to their damage. In addition to lipids and proteins, especially the DNA is affected.
Die schädigende Wirkung des ultravioletten Teils der Sonnenstrahlung auf die Haut ist allgemein bekannt. Während Strahlen mit einer Wellenlänge, die kleiner als 290 nm ist (der sogenannte UVC-Bereich), von der Ozonschicht in der Erdatmosphäre absorbiert werden, verursachen Strahlen im Bereich zwischen 290 nm und 320 nm, dem sogenannten UVB- Bereich, ein Erythem, einen einfachen Sonnenbrand oder sogar mehr oder weniger starke Verbrennungen.The damaging effect of the ultraviolet part of solar radiation on the skin is well known. While rays having a wavelength smaller than 290 nm (the so-called UVC region) are absorbed by the ozone layer in the earth's atmosphere, rays in the range between 290 nm and 320 nm, the so-called UVB region, cause erythema simple sunburn or even more or less severe burns.
Als ein Maximum der Erythemwirksamkeit des Sonnenlichtes wird der engere Bereich um 308 nm angegeben.As a maximum of the erythema efficiency of sunlight, the narrower range around 308 nm is given.
Zum Schutz gegen UVB-Strahlung sind zahlreiche Verbindungen bekannt, bei denen es sich um Derivate des 3-Benzylidencamphers, der 4-Aminobenzoesäure, der Zimtsäure, der SaIi- cylsäure, des Benzophenons sowie auch des 2-Phenylbenzimidazols handelt.For protection against UVB radiation, numerous compounds are known which are derivatives of 3-benzylidene camphor, 4-aminobenzoic acid, cinnamic acid, acidic acid, benzophenone and also 2-phenylbenzimidazole.
Auch für den Bereich zwischen etwa 320 nm und etwa 400 nm, des sogenannten UVA- Bereich, ist es wichtig, Filtersubstanzen zur Verfügung zu haben, da dessen Strahlen Reaktionen bei lichtempfindlicher Haut hervorrufen können. Es ist erwiesen, dass UVA-Strahlung zu einer Schädigung der elastischen und kollagenen Fasern des Bindegewebes führt, was die Haut vorzeitig altern lässt, und dass sie als Ursache zahlreicher phototoxischer und photoallergischer Reaktionen zu sehen ist. Der schädigende Einfluss der UVB-Strahlung kann durch UVA-Strahlung verstärkt werden.Also for the range between about 320 nm and about 400 nm, the so-called UVA range, it is important to have available filter substances, since its rays can cause reactions in photosensitive skin. It has been proven that UVA radiation leads to damage to the elastic and collagen fibers of the connective tissue, which the skin ages prematurely and that it can be seen as the cause of numerous phototoxic and photoallergic reactions. The damaging influence of UVB radiation can be amplified by UVA radiation.
Insbesondere Hautzellen erhalten durch häufige UV-Exposition einen hohen Anteil an DNA- Schäden und benötigen deshalb besonders effiziente und leistungsfähige Reparatursysteme. Nur effiziente hauteigene DNA-Reparatursysteme sind in der Lage, Schäden schnell zu beseitigen, wodurch Hautveränderungen und ein frühzeitiges Auftreten von Hautalterungserscheinungen verhindert werden können. Effiziente DNA-Reparatur trägt damit entscheidend zum Erhalt einer gesunden, vitalen Haut bei. Stimulierung und Unterstützung hauteigener Reparatursysteme durch kosmetisch-dermatologische Inhaltsstoffe sind deshalb sehr wichtig-Skin cells in particular receive a high proportion of DNA damage as a result of frequent UV exposure and therefore require particularly efficient and efficient repair systems. Only efficient, proprietary DNA repair systems are able to quickly repair damage that can prevent skin alteration and early onset of skin aging. Efficient DNA repair thus contributes significantly to maintaining a healthy, vital skin. Stimulation and support of skin-own repair systems by cosmetic-dermatological ingredients are therefore very important-
Die angesichts der großen Anzahl Nucleotide, die pro Zellteilung kopiert werden müssen, notwendige hohe Zuverlässigkeit bei der DNA-Replikation wird einerseits durch die Spezifität der DNA-Polymerasen, die an der Replikation beteiligt sind (Replicasen), andererseits durch deren zusätzlich vorhandene Exonucleaseaktivität garantiert: Sie katalysieren das Herausschneiden unpassender Nucleotide und deren Ersatz durch die richtigen sofort nach der Neusynthese. Den durch chemische Einwirkung entstehenden Schäden (durch Mutagene, von denen einige sich zwischen zwei übereinanderliegende Basenpaare der Doppelhelix einschieben können) sowie den von Strahlungseinwirkung herrührenden Veränderungen (wobei z. B. zwei übereinanderliegende Thymin-Reste dimerisieren können) helfen Reparatur-Enzyme (darunter: Endonucleasen, Polymerasen, Ligasen) ab, die unpassende Nucleotide wieder aus den DNA herausschneiden und ersetzen. Einige dieser Reparatursysteme sind induzierbar, d. h. sie werden erst bei Bedarf synthetisiert. Die Frage, welcher Strang die Original-Information enthält und welcher falsch synthetisiert wurde, wird vom Reparaturenzym offenbar anhand des Methylierungszustands entschieden.The high reliability of DNA replication required in view of the large number of nucleotides that have to be copied per cell division is guaranteed, on the one hand, by the specificity of the DNA polymerases involved in replication (replicases) and, on the other hand, by their additional exonuclease activity: They catalyze the excision of inappropriate nucleotides and their replacement by the correct ones immediately after the new synthesis. The damage caused by chemical action (by mutagens, some of which can intervene between two superimposed base pairs of the double helix) as well as the radiation-induced changes (eg two superimposed thymine residues can dimerize) help repair enzymes (including: Endonucleases, polymerases, ligases) that cut out and replace inappropriate nucleotides again from the DNA. Some of these repair systems are inducible, i. H. they are synthesized only when needed. The question of which strand contains the original information and which was wrongly synthesized is apparently decided by the repair enzyme on the basis of the state of methylation.
Durch Exposition zu Umwelteinflüssen (z.B. UV-Strahlung, chemische und physikalische Faktoren) entstehen Schäden an den DNA-Molekülen der Zellen des Körpers, die jedoch durch zelleigene DNA-Reparaturmechanismen behoben werden können. Dabei erfolgt zuerst die Erkennung des DNA-Schadens und dann die Reparatur des vorliegenden Schadens. Werden die Schäden nicht vollständig kurz nach ihrer Entstehung durch Reparaturprozesse beseitigt, reichern sich diese in Form von permanenten DNA-Schäden in den Zellen an und werden nachfolgend an die Tochterzellen weitergegeben. Diese permanenten Schäden besitzen insbesondere durch mögliche Spätfolgen (schrittweise Funktionsausfälle) ein hohes Schadenspotential und spielen einen immer größere Rolle in Alterungsprozessen und bei der Schadensauslösung bereits im Kindesalter.Exposure to environmental influences (eg UV radiation, chemical and physical factors) causes damage to the DNA molecules of the cells of the body, which can, however, be remedied by cellular DNA repair mechanisms. First of all, the DNA damage is detected and then the damage is repaired. If the damage is not completely eliminated shortly after it has been formed by repair processes, these accumulate in the form of permanent DNA damage in the cells and are subsequently passed on to the daughter cells. This permanent damage, in particular due to possible late effects (gradual loss of function), has a high potential for damage and is playing an increasingly important role in aging processes and in the initiation of damage already in childhood.
Aufgabe der vorliegenden Erfindung war es mithin, den Übelständen des Standes der Technik Abhilfe zu schaffen. Insbesondere sollten Wirkstoffe und Zubereitungen zur Verfügung gestellt werden, die eine sichere Prophylaxe von Schäden an der hauteigenen DNA gewährleisten und/oder in einer besonderen Ausführungsform zur Reparatur bereits eingetretener Schäden an der hauteigenen DNA dienen sollte.Object of the present invention was therefore to remedy the evils of the prior art remedy. In particular, active ingredients and preparations should be provided which should ensure a reliable prophylaxis of damage to the skin's own DNA and / or in a particular embodiment should be used to repair damage already occurred to the skin's own DNA.
Folsäure weist folgende Struktur auf:Folic acid has the following structure:
Figure imgf000004_0001
Figure imgf000004_0001
Folsäure kommt in Leber, Niere, Hefe, Pilzen, Getreide und grünen Blättern, vorwiegend als Konjugat mit Poly-γ-L-glutaminsäure (Pteroylpolyglutaminsäuren) vor. Sie wurde als Wuchsstoff für verschiedene Mikroorganismen entdeckt und hat für den menschlichen Organismus Vitamincharakter. Der Bedarf des erwachsenen Menschen beträgt etwa 200 μg je Tag an bioverfügbarem Folat.Folic acid occurs in liver, kidney, yeast, fungi, cereals and green leaves, predominantly as a conjugate with poly-γ-L-glutamic acid (pteroylpolyglutamic acids). It has been discovered as a growth substance for various microorganisms and has a vitamin character for the human organism. Adult human needs are about 200 μg per day of bioavailable folate.
Folsäure steht im Organismus im Gleichgewicht mit 7,8-Dihydrofolsäure (H2Folat; alte Abkürzung: FH2) unter Beteiligung von Nicotinamid-Adenin-Dinucleotid-Phosphat und des Enzyms Dihydrofolat-Reduktase. H2Folat wiederum entsteht in Pflanzen und einigen Mikroorganismen über mehrere Zwischenstufen aus Guanosin-5'-triphosphat (Guanosinphosphate) und setzt sich mit Hilfe der Dihydrofolat-Reduktase zu (6S)-5,6,7,8-Tetrahydrofolsäure um, der eigentlichen physiologisch wirksamen Form der Folsäure.Folic acid in the organism is in equilibrium with 7,8-dihydrofolic acid (H 2 folate, old abbreviation: FH 2 ) with the participation of nicotinamide adenine dinucleotide phosphate and the enzyme dihydrofolate reductase. H 2 folate in turn is produced in plants and some microorganisms via several intermediates of guanosine 5'-triphosphate (guanosine phosphates) and uses dihydrofolate reductase to convert (6S) -5,6,7,8-tetrahydrofolic acid, the actual physiologically active form of folic acid.
7,8-Dihydrofolsäure hat folgende chemische Struktur:7,8-Dihydrofolic acid has the following chemical structure:
Figure imgf000005_0001
Figure imgf000005_0001
(6S)-5,6,7,8-Tetrahydrofolsäure hat folgende chemische Struktur:(6S) -5,6,7,8-tetrahydrofolic acid has the following chemical structure:
Figure imgf000005_0002
Figure imgf000005_0002
Unter dem Begriff der Derivate der Folsäure sind insbesondere die vorgenannte Dihydrofol- säure und die Tetrahydrofolsäure zu verstehen.The term derivatives of folic acid is to be understood in particular as meaning the abovementioned dihydrofolic acid and the tetrahydrofolic acid.
Folsäurehaltige Hautpflegeprodukte sollen neben dem positiven Effekt auf die Haut angenehm anzuwenden sein. Puderrohstoffe geben ein angenehmes seidig samtes Hautgefühl. Allerdings destabilisieren sowohl Folsäure (Elektrolyt) als auch Puderrohstoffe eine Emulsion, so dass die Kombination in einer Emulsion häufig nicht lager- und wärmestabil ist.Folic acid-containing skin care products should be pleasant to use in addition to the positive effect on the skin. Powder raw materials give a pleasant silky velvet skin feeling. However, both folic acid (electrolyte) and powder raw materials destabilize an emulsion, so that the combination in an emulsion is often not storage and heat stable.
Gelöst wird dieses Problem erfindungsgemäß durch kosmetische oder dermatologische Zubereitungen mit einem Gehalt an Folsäure und/oder deren Derivaten, Füllstoffen und Verdickern Erfindungsgemäß weisen Folsäure und/oder deren Derivate ein hohes Potential zur Reparatur geschädigter DNA auf. Ferner bieten Folsäure und/oder deren Derivate wirksame Prophylaxe gegen DNA-Schäden, insbesondere solche Schäden, die durch UV-Strahlung hervorgerufen werden.This problem is solved according to the invention by cosmetic or dermatological preparations containing folic acid and / or derivatives thereof, fillers and thickeners According to the invention, folic acid and / or derivatives thereof have a high potential for repairing damaged DNA. Furthermore, folic acid and / or its derivatives provide effective prophylaxis against DNA damage, especially those caused by UV radiation.
Füllstoffe im Sinne der vorliegenden Erfindung sind partikuläre Substanzen, die in der Regel keinen Farbeffekt in der kosmetischen Formulierung erzeugen, in der sie eingesetzt werden. Ferner haben erfindungsgemäße Füllstoffe üblicherweise einen niedrigen Brechungsindex und daraus resultierend keine oder eine nur sehr geringe Deckkraft.Fillers in the context of the present invention are particulate substances which as a rule do not produce any color effect in the cosmetic formulation in which they are used. Furthermore, fillers according to the invention usually have a low refractive index and, as a result, no or very little opacity.
Der Stand der Technik kennt eine Reihe von Füllstoffen, welche z. B. als Trägermaterialien bei der Formulierung von Pudern oder als Viskositäts- und Sensorik-Modulatoren in Emulsionen oder wasserfreien Formulierungen dienen. Derartige Füllstoffe werden häufig auch eingesetzt, um mattierende Effekte auf der Haut zu erlangen oder um Sebum zu absorbieren.The prior art knows a number of fillers, which z. B. serve as support materials in the formulation of powders or as viscosity and sensor modulators in emulsions or anhydrous formulations. Such fillers are also often used to obtain matting effects on the skin or to absorb sebum.
Darüber hinaus beeinflußt der Einsatz von Füllstoffen im allgemeinen auch die Verteilbarkeit üblicher Formulierungen auf der Haut sowie die Gleichmäßigkeit eines möglichen Farbeffektes.In addition, the use of fillers generally also affects the spreadability of conventional formulations on the skin and the uniformity of a possible color effect.
Die Füllstoffe im Sinne der vorliegenden Erfindung werden vorteilhaft aus der Gruppe der anorganische Füllstoffe gewählt, beispielsweise aus der Gruppe der Silikate.The fillers in the context of the present invention are advantageously selected from the group of inorganic fillers, for example from the group of silicates.
Silikate sind Salze und Ester (Kieselsäureester) der Orthokieselsäure [Si(OH)4] und deren Kondensationsprodukte. Die Silikate sind nicht nur die artenreichste Klasse der Mineralien, sondern auch geologisch und technisch außerordentlich wichtig. Über 80 % der Erdkruste bestehen aus Silikaten.Silicates are salts and esters (silicic acid esters) of orthosilicic acid [Si (OH) 4 ] and their condensation products. The silicates are not only the most species-rich class of minerals, but also extremely important geologically and technically. Over 80% of the earth's crust is made up of silicates.
Vorteilhaft im Sinne der vorliegenden Erfindung sind beispielsweise Schichtsilikate. Schichtsilikate (Phyllosilikate, Blattsilikate) sind (idealerweise) Silikat-Strukturen mit zweidimensional unendlichen Schichten aus [SiO4]4'-Tetraedern, wobei jedes Tetraeder über 3 Brücken- Sauerstoffe mit Nachbar-Tetraedern verbunden ist. Chemische Formeln lassen sich für Schichtsilikate nur angenähert aufstellen, da sie ein großes lonenaustausch-Vermögen besitzen und Silicium gegen Aluminium und dieses wiederum gegen Magnesium, Fe2+, Fe3+, Zn und dergleichen ausgetauscht werden kann. Die daraus möglicherweise resultierende negative Ladung der Schichten wird in der Regel durch Kationen, insbesondere durch Na+ und Ca2+ in Zwischenschicht-Positionen ausgeglichen.For the purposes of the present invention, for example, phyllosilicates are advantageous. Layer silicates (phyllosilicates, leaf silicates) are (ideally) silicate structures with two-dimensionally infinite layers of [SiO 4 ] 4 ' tetrahedra, each tetrahedron being connected via 3 bridging oxygens with neighboring tetrahedra. Chemical formulas can only be approximated for phyllosilicates because they have a large ion exchange capacity and silicon can be exchanged for aluminum and this in turn against magnesium, Fe 2+ , Fe 3+ , Zn and the like. The resulting possibly negative charge of the layers is usually compensated by cations, in particular by Na + and Ca 2+ in interlayer positions.
Schichtsilikate können durch reversible Einlagerung von Wasser (in der 2- bis 7-fachen Menge) und anderen Substanzen wie z. B. Alkoholen, Glykolen und dergleichen mehr aufquellen. Ihre Verwendung als Verdickungsmittel in kosmetischen Mitteln ist dementsprechend an sich bekannt. Allerdings konnte der Stand der Technik nicht den Weg zur vorliegenden Erfindung weisen.Phyllosilicates can be obtained by reversible storage of water (in the 2- to 7-fold amount) and other substances such. As alcohols, glycols and the like swell. Their use as thickeners in cosmetic products is accordingly known per se. However, the prior art could not point the way to the present invention.
Vorteilhafte Schichtsilikate, welche im Sinne der vorliegenden Erfindung eingesetzt werden können, sind beispielsweise solche, deren größte Ausdehnungsrichtung im unmodifizierten und ungequollenen Zustand im Mittel eine Länge von weniger als 10 μm hat. Beispielsweise können die mittleren Ausdehnungen der verwendeten modifizierten Schichtsilikatpartikel bei 1000 nm x 100 nm x 1 nm und darunter liegen. Die effektive Größe der modifizierten Schichtsilikatpartikel in einer kosmetischen oder dermatologischen Formulierung hängt selbstverständlich von der Menge an eingelagerten Substanzen ab.Advantageous phyllosilicates which can be used in the context of the present invention are, for example, those whose largest expansion direction in the unmodified and unswollen state has an average length of less than 10 μm. For example, the mean extents of the modified layered silicate particles used may be 1000 nm × 100 nm × 1 nm and less. The effective size of the modified layered silicate particles in a cosmetic or dermatological formulation of course depends on the amount of stored substances.
Erfindungsgemäß vorteilhafte (Schicht-) Silikate sind insbesondere:Particularly advantageous (layered) silicates according to the invention are:
Talkum: Mg3 [Si4O10] (OH)2,Talc: Mg 3 [Si 4 O 10 ] (OH) 2 ,
Kaolin: AI2[Si2O5] (OH)4 Kaolin: Al 2 [Si 2 O 5 ] (OH) 4
Montmorillonit: M+ Al [Si2O5](OH), auch Smektite genannt. Darunter fallen:Montmorillonite: M + Al [Si 2 O 5 ] (OH), also called smectite. These include:
• Bentonite = Montmorillonite mit Ca (Füller Erden) oder Na (Wyoming Bentonite)• Bentonite = montmorillonite with Ca (filler earth) or Na (Wyoming bentonite)
• Hektorite: MV3(Mg2JLi013)[Si4O10(OH)2], worin M+ meist Na+ darstellt,Hectorites: MV 3 (Mg 2J Li 013 ) [Si 4 O 10 (OH) 2 ], where M + is usually Na + ,
Glimmer (Mica), ein Alumosilikat, das leicht spaltbar ist und in tafeligen Kristallen vorliegt. Glimmer ist transparent bis durchscheinend und weist Perlglanz auf. Die wichtigste Form ist Muskovit: K Al2 [AISi3O10] (OH, F)2. Sericite ist eine Sonderform des Glimmers, die kleinere Plättchen als Muskovit aufweist. Magnesiumsilikat Mg2 [Si4Oi0] Auch Siliciumoxide (SiO2) sind vorteilhaft im Sinne der vorliegenden Erfindung zu verwenden. Erfindungsgemäß bevorzugt sind beispielsweise Aerosile (fumed Silica), welche hochdisperse Kieselsäuren mit häufig irregulärer Form sind, deren spezifische Oberfläche in der Regel sehr groß ist (200 - 400 m2 / g) und mit Hilfe des Herstellverfahrens gesteuert werden kann. Aerosile werden auch bezeichnet als: Amorphous Silica Amorphous Silicon Oxide Hydrate Silica, Amorphous Silicic Anhydride Silicon Dioxide Silicon Dioxide.Mica, an aluminosilicate that is easily fissile and is present in tabular crystals. Mica is transparent to translucent and has pearlescence. The most important form is muscovite: K Al 2 [AISi 3 O 10 ] (OH, F) 2 . Sericite is a special form of mica that has smaller platelets than muscovite. Magnesium silicate Mg 2 [Si 4 Oi 0 ] Also, silicon oxides (SiO 2 ) are to be used advantageously in the context of the present invention. Aerosils (fumed silica), which are highly disperse silicas with frequently irregular shape, whose specific surface area is generally very large (200-400 m 2 / g) and which can be controlled by means of the production process, are preferred according to the invention. Aerosils are also referred to as: Amorphous Silica Amorphous Silicon Oxide Hydrate Silica, Amorphous Silicic Anhydride Silicon Dioxide Silicon Dioxide.
Erfindungsgemäß vorteilhafte Aerosile sind z. B. unter den folgenden Handlesnamen erhältlich:According to the invention advantageous aerosols are z. For example, available under the following handle names:
Aerosil 130 (Degussa Hüls), Aerosil 200 (Degussa Hüls), Aerosil 255 (Degussa Hüls), Aero- sil 300 (Degussa Hüls), Aerosil 380 (Degussa Hüls), B-6C (Suzuki Yushi), CAB-O-SIL Fumed Silica (Cabot), CAB-O-SIL EH-5 (Cabot), CAB-O-SIL HS-5 (Cabot), CAB-O-SIL LM-130 (Cabot), CAB-O-SIL MS-55 (Cabot), CAB-O-SIL M-5 (Cabot), E-6C (Suzuki Yushi), Fossil Flour MBK (MBK), MSS-500 (Kobo), Neosil CT 1 1 (Crosfield Co.), Ronasphere (Rona/EM Industries), Silica, Anhydrous 31 (Whittaker, Clark & Daniels), Silica, Crystalline 216 (Whitta- ker, Clark & Daniels), Silotrat-1 (Vevy), Sorbosil AC33 (Crosfield Co.), Sorbosil AC 35 (Crosfield Co.), Sorbosil AC 37 (Crosfield Co.), Sorbosil AC 39 (Crosfield Co.), Sorbosil AC77 (Crosfield Co.), Sorbosil TC 15 (Crosfield Co.), Spherica (Ikeda), Spheriglass (Potters-Ballo- tini), Spheron L-1500 (Presperse), Spheron N-2000 (Presperse), Spheron P-1500 (Presper- se), Wacker HDK H 30 (Wacker-Chemie), Wacker HDK N 20 (Wacker-Chemie), Wacker HDK P 100 H (Wacker Silicones), Wacker HDK N 2OP (Wacker-Chemie), Wacker HDK N 25P (Wacker-Chemie), Wacker HDK S 13 (Wacker-Chemie), Wacker HDK T 30 (Wacker- Chemie), Wacker HDK V 15 (Wacker-Chemie), Wacker HDK V 15 P (Wacker-Chemie), Ze- lec Sil (DuPont).Aerosil 130 (Degussa Hüls), Aerosil 200 (Degussa Hüls), Aerosil 255 (Degussa Hüls), Aerosil 300 (Degussa Hüls), Aerosil 380 (Degussa Hüls), B-6C (Suzuki Yushi), CAB-O-SIL Fumed silica (Cabot), CAB-O-SIL EH-5 (Cabot), CAB-O-SIL HS-5 (Cabot), CAB-O-SIL LM-130 (Cabot), CAB-O-SIL MS-55 (Cabot), CAB-O-SIL M-5 (Cabot), E-6C (Suzuki Yushi), Fossil Flour MBK (MBK), MSS-500 (Kobo), Neosil CT 1 1 (Crosfield Co.), Ronasphere ( Rona / EM Industries), Silica, Anhydrous 31 (Whittaker, Clark & Daniels), Silica, Crystalline 216 (Whittaker, Clark & Daniels), Silotrat-1 (Vevy), Sorbosil AC33 (Crosfield Co.), Sorbosil AC 35 (Crosfield Co.), Sorbosil AC 37 (Crosfield Co.), Sorbosil AC 39 (Crosfield Co.), Sorbosil AC77 (Crosfield Co.), Sorbosil TC 15 (Crosfield Co.), Spherica (Ikeda), Spheriglass (Potters' Ballo- tini), Spheron L-1500 (Pres- perse), Spheron N-2000 (Pres- perese), Spheron P-1500 (Presperse), Wacker HDK H 30 (Wacker-Chemie), Wacker HDK N 20 (Wacker-Chemie) , Wacker HDK P 100 H (Wacker Silic ones), Wacker HDK N 2OP (Wacker chemistry), Wacker HDK N 25P (Wacker chemistry), Wacker HDK S 13 (Wacker chemistry), Wacker HDK T 30 (Wacker chemistry), Wacker HDK V 15 (Wacker chemistry) Chemistry), Wacker HDK V 15 P (Wacker-Chemie), Cellec Sil (DuPont).
Siliciumoxide lassen sich auch in sphärischer Form herstellen, wobei hier die spezifische Oberfläche kleiner ist als bei den Aerosilen, da die Teilchen größer und rund sind. Ein Beispiel hierfür sind die Ronaspheren (mittlerer Teilchendurchmesser < 3 μ) der Fa. Merck (siehe Fig 1 ).Silicon oxides can also be produced in a spherical form, in which case the specific surface area is smaller than in the aerosils, since the particles are larger and round. An example of this are the Ronaspheren (average particle diameter <3 μ) from. Merck (see Figure 1).
Weitere erfindungsgemäß bevorzugte Füllstoffe sind Siliciumdioxide, deren freien OH-Grup- pen an der Teilchenoberfläche (ganz oder teilweise) organisch modifiziert sind. Vorteilhaft sind z. B. die durch Addition von Dimethylsilyl-Gruppen erhältlichen Silica Di- methyl Silylate, wie beispielsweise Aerosil R972 (Degussa Hüls), Aerosil R974 (Degussa Hüls), CAB-O-SIL TS-610 (Cabot), CAB-O-SIL TS-720 (Cabot), Wacker HDK H15 (Wacker- Chemie), Wacker HDK H18 (Wacker-Chemie) und/oder Wacker HDK H20 (Wacker-Chemie).Further fillers preferred according to the invention are silicas whose free OH groups on the particle surface are (completely or partially) organically modified. Advantageous z. For example, the obtainable by addition of dimethylsilyl groups silica dimethyl silylates, such as Aerosil R972 (Degussa Hüls), Aerosil R974 (Degussa Hüls), CAB-O-SIL TS-610 (Cabot), CAB-O-SIL TS -720 (Cabot), Wacker HDK H15 (Wacker chemistry), Wacker HDK H18 (Wacker chemistry) and / or Wacker HDK H20 (Wacker chemistry).
Ferner vorteilhaft sind die durch Addition von Trimethylsilylgruppen erhältlichen Silica Silylate (z. B. Aerosil R 812 (Degussa Hüls), CAB-O-SIL TS-530 (Cabot), Sipemat D 17 (Degussa Hüls), Wacker HDK H2000 (Wacker-Chemie)).Further advantageous are the silicates obtainable by addition of trimethylsilyl groups (eg Aerosil R 812 (Degussa Hüls), CAB-O-SIL TS-530 (Cabot), Sipemat D 17 (Degussa Hüls), Wacker HDK H2000 (Wacker). Chemistry)).
Ferner vorteilhaft im Sinne der vorliegenden Erfindung sind die durch Hydrolyse- und Kondensationsreaktionen von Methyltrimethoxysilane erhältlichen Polymethylsilsesquioxane, die ebenfalls eine runde Form besitzen und deren Teilchengrößenverteilung durch die Herstellung gesteuert werden kann.Also advantageous in the context of the present invention are the polymethylsilsesquioxanes obtainable by hydrolysis and condensation reactions of methyltrimethoxysilanes, which likewise have a round shape and whose particle size distribution can be controlled by the preparation.
Bevorzugte Polymethylsilsesquioxane werden beispielsweise unter den Handelsnamen Tospearl 2000 B von GE Bayer Silikones, Tospearl 145A von Toshiba, AEC Silicone Resin Spheres von A & E Connock sowie Wacker - Belsil PMS MK von der Wacker-Chemie angeboten.Preferred polymethylsilsesquioxanes are available, for example, under the trade names Tospearl 2000 B from GE Bayer Silikones, Tospearl 145A from Toshiba, AEC Silicone Resin Spheres from A & E Connock and Wacker-Belsil PMS MK from Wacker-Chemie.
Weiterer vorteilhafter Füllstoff im Sinne der vorliegenden Erfindung ist Bornitrid. Bornitrid ist isoelektronisch mit Kohlenstoff (d. h. es sind Graphit- und Diamantform möglich). Bornitrid zeichnet sich durch seine chemische Inertheit aus.Another advantageous filler in the context of the present invention is boron nitride. Boron nitride is isoelectronic with carbon (i.e., graphite and diamond shapes are possible). Boron nitride is characterized by its chemical inertness.
Vorteilhaft im Sinne der vorliegenden Erfindung sind beispielsweise die im folgenden aufgelisteten Bornitride:For the purposes of the present invention, for example, the boron nitrides listed below are advantageous:
Handelsname erhältlich bei:Trade name available from:
Boron Nitride Powder Advanced CeramicsBoron Nitride Powder Advanced Ceramics
Boron Nitride Powder Sintec KeramikBoron Nitride Powder Sintec ceramic
Ceram Blanche KawasakiCeram Blanche Kawasaki
HCST Boron Nitride StarkHCST Boron Nitride Strong
Tres BN® CarborundumTres BN® carborundum
Wacker-Bornitrid BNP Wacker-Chemie Weitere vorteilhafte Füllstoffe im Sinne der vorliegenden Erfindung sind Carbonate, wie z. B. Magnesiumcarbonat (MgCO3) und Calciumcarbonat (CaCO3). Es ist insbesondere vorteilhaft im Sinne der vorliegenden Erfindung, die Carbonate als Füllstoffe in trockenen Pudern zu verwenden.Wacker boron nitride BNP Wacker-Chemie Further advantageous fillers in the context of the present invention are carbonates, such as. As magnesium carbonate (MgCO 3 ) and calcium carbonate (CaCO 3 ). It is particularly advantageous for the purposes of the present invention to use the carbonates as fillers in dry powders.
Die Füllstoffe im Sinne der vorliegenden Erfindung werden darüber hinaus vorteilhaft aus der Gruppe der organische Füllstoffe gewählt.The fillers in the context of the present invention are also advantageously selected from the group of organic fillers.
Erfindungsgemäß vorteilhafte organische Füllstoffe sind z. B. natürliche Polymere, wie Seidenpuder, mikrokristalline Cellulose und/oder Zinkstearate.According to the invention advantageous organic fillers are, for. As natural polymers, such as silk powder, microcrystalline cellulose and / or zinc stearates.
Vorteilhafte organische Füllstoffe sind ferner Stärke und Stärkederivate, wie:Advantageous organic fillers are also starch and starch derivatives, such as:
=> Maisstärke Zea Mays (Amidon De Mais MST (Wackherr), Argo Brand Com Starch (Com=> Corn Starch Zea Mays (Amidon De Corn MST (Wackherr), Argo Brand Com Starch (Com
Products), Pure-Dent (Grain Processing), Purity 21 C (National Starch)), => Reisstärke (D. S. A. 7 (Agrana Stärke), Oryzapearl (Ichimaru Pharcos)), => Distarch Phosphate (Com PO4 (Agrana Stärke), Com PO4 (Tn-K)), => Sodium Com Starch Octenylsuccinate (C* EmCap - Instant 12639 (Cerestar USA)), => Aluminium Starch Octenylsuccinate (Covafluid AMD (Wackherr), Dry FIo-PC (NationalProducts), Pure-Dent (Grain Processing), Purity 21 C (National Starch)), => Rice Starch (DSA 7, Oryzapearl (Ichimaru Pharcos)), => Distarch Phosphate (Com PO4 (Agrana Starch), Com PO4 (Tn-K)), => Sodium Com Starch Octenylsuccinate (C * EmCap - Instant 12639 (Cerestar USA)), => Aluminum Starch Octenylsuccinate (Covafluid AMD (Wackherr), Dry FIo-PC (National
Starch), Dry FIo Pure (National Starch), Fluidamid DF 12 (Roquette)),Starch), Dry FIo Pure (National Starch), Fluidamide DF 12 (Roquette)),
Erfindungsgemäß bevorzugte organische Füllstoffe sind auch synthetische Polymere, d. h. Polymerpartikel, welche in der Zubereitung in Form von Feststoffen vorliegen, wie beispielsweise Polycarbonate, Polyether, Polyethylen, Polypropylen, Polyvinylchlorid, Polystyrol, Polyamide, Polyurethane, Polyacrylate und dergleichen mehr. Besonders vorteilhaft ist z. B. die Substanz mit der INCI-Bezeichnung HDI / Trimethylol Hexyllactone Crosspolymer, welche unter der Bezeichnung BPD-500/Plastic Powder D von der Firma Kobo erhältlich ist.Organic fillers preferred according to the invention are also synthetic polymers, ie. H. Polymer particles which are present in the preparation in the form of solids, such as polycarbonates, polyethers, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyamides, polyurethanes, polyacrylates and the like. Particularly advantageous is z. B. the substance with the INCI name HDI / trimethylol Hexyllactone Crosspolymer, which is available under the name BPD-500 / Plastic Powder D from Kobo.
Ferner vorteilhaft im Sinne der vorliegenden Erfindung ist Nylon (Polyamid 6 und Polyamid 12), wie beispielsweise mikrofeine Polyamid-Partikel, insbesondere die unter der Handelsbezeichnung SP-500 bei der Firma TORAY erhältlichen. Ferner vorteilhaft sind Polyamid 6- (auch: Nylon 6), bzw. Polyamid 12- (auch: Nylon 1-2), Partikel. Polyamid 6 ist das aus ε-Ami- nocapronsäure (6-Aminohexansäure), oder ε-Caprolactam aufgebaute Polyamid [Poly(ε- caprolactam)], und Polyamid 12 ist ein Poly(ε-Iaurinlactam), aus ε-Laurinlactam. Vorteilhaft im Sinne der vorliegenden Erfindung sind beispielsweise Orgasol® 1002 (Polyamid 6), und Orgasol® 2002 (Polyamid 12), von der Firma ELF ATOCHEM.Also advantageous for the purposes of the present invention is nylon (polyamide 6 and polyamide 12), for example microfine polyamide particles, in particular those available under the trade name SP-500 from TORAY. Also advantageous are polyamide 6- (also: nylon 6), or polyamide 12 (also: nylon 1-2), particles. Polyamide 6 is the polyamide [poly (ε-caprolactam)] synthesized from ε-aminocaproic acid (6-aminohexanoic acid) or ε-caprolactam, and polyamide 12 is a poly (ε-laurinlactam) from ε-laurolactam. Advantageous in the sense of the present invention are, for example Orgasol ® 1002 (polyamide 6), and Orgasol ® 2002 (polyamide 12) from ELF ATOCHEM.
Weitere vorteilhafte organische Füllstoffe sind:Further advantageous organic fillers are:
=> PMMA: Polymethylmethacrylate=> PMMA: polymethyl methacrylates
=> Polyethylene Spheres=> Polyethylene spheres
=> Polyurethane=> Polyurethanes
=> Silikon Resins: Trimethylsiloxysilicate (z. B. SR 1000 GE Bayer Silicones)=> Silicone Resins: Trimethylsiloxysilicate (eg SR 1000 GE Bayer Silicones)
=> Silikonelastomere=> Silicone elastomers
So kann es z. B. von erheblichem Vorteil sein, solche Silikonelastomeren in Zubereitungen gemäß der vorliegenden Erfindung zu verwenden, wie sie beispielsweise in den US-Patenten US 4980167 oder US 4742142 beschrieben werden. Vorteilhafte Silikonelastomere sind ferner z. B. solche, welche unter den Namen KSG6 von Shin Etsu, Tefil E-505C oder Trefil E-506C von Dow Corning, Gransil von Grant Industries (SR-CYC, SR-DMF10, SR-DC556), vertrieben werden sowie solche, die in Form von vorgefertigten Gelen verkauft werden (wie z. B. KSG15, KSG17, KSG16, KSG18 von Shin Etsu, Gransil SP 5CYC Gel, Gransil SR DMF 10 Gel, Gransil SR DC 556 Gel, Gransil GCM, Gransil PM Gel, Gransil DMG-5, SF 1204 und JK 113 von Gereral Electric). Weitere vorteilhafte Silikonelastomere können gewählt werden aus der Gruppe der Vinyl Dimethicone Crosspolymere, wie z. B. das Dow Corning 9506 Cosmetic Powder von Dow Corning (INCI: Dimethicone / Vinyl Dimethicone Crosspolymer).So it may be z. For example, it may be of considerable advantage to use such silicone elastomers in formulations according to the present invention, as described, for example, in US Pat. Nos. 4,980,167 or 4,742,142. Advantageous silicone elastomers are also z. For example, those sold under the names KSG6 by Shin Etsu, Tefil E-505C or Trefil E-506C by Dow Corning, Gransil by Grant Industries (SR-CYC, SR-DMF10, SR-DC556), as well as those known in the art in the form of preformed gels (such as KSG15, KSG17, KSG16, KSG18 from Shin Etsu, Gransil SP 5CYC gel, Gransil SR DMF 10 gel, Gransil SR DC 556 gel, Gransil GCM, Gransil PM gel, Gransil DMG -5, SF 1204 and JK 113 from Gereral Electric). Further advantageous silicone elastomers can be selected from the group of vinyl dimethicone crosspolymers, such as. Dow Corning 9506 Cosmetic Powder from Dow Coming (INCI: Dimethicone / Vinyl Dimethicone Crosspolymer).
Weiterhin vorteilhaft eingesetzt werden können sogenannte Silikonharze, wie z.B. KSP-100, KSP-200 oder KSP-300 von Shin Etsu, die ebenfalls unter der INCI bezeichnung Dimethicone / Vinyl Dimethicone Crosspolymer geführt werden oder SR 1000 von GE Bayer Silicones, das die INCI Bezeichnung Trimethylsiloxy Silicate trägtSo-called silicone resins, such as e.g. KSP-100, KSP-200 or KSP-300 from Shin Etsu, which are also listed under the INCI name Dimethicone / Vinyl Dimethicone Crosspolymer or SR 1000 from GE Bayer Silicones, which bears the INCI name Trimethylsiloxy Silicate
Weiterhin bevorzugt ist auch Lauroyl Lysine, das unter der bezeichnung Amihope LL von Ajinomoto vertrieben wird.Also preferred is lauroyl lysine, which is sold by Ajinomoto under the name Amihope LL.
Die Gesamtmenge an mindestens einem Füllstoff in den fertigen kosmetischen oder dermatologischen Zubereitungen wird vorteilhaft aus dem Bereich von 0,05 - 20,0 Gew.-%, bevorzugt 0,5 - 10,0 Gew.-% gewählt, bezogen auf das Gesamtgewicht der Zubereitungen. Erfindungsgemäß bevorzugte Füllstoffe kommen aus der Gruppe der anorganischen oder organischen Siliziumverbindungen.The total amount of at least one filler in the finished cosmetic or dermatological preparations is advantageously selected from the range of 0.05-20.0% by weight, preferably 0.5-10.0% by weight, based on the total weight of the preparations. Fillers preferred according to the invention come from the group of inorganic or organic silicon compounds.
Von den anorganischen Siliziumverbindungen sind besonders bevorzugt die Schichtsilikate. Davon besonders bevorzugt sind Kaolin, Talkum und Mica.Of the inorganic silicon compounds, the layer silicates are particularly preferred. Of these, kaolin, talc and mica are particularly preferred.
Weiterhin gehören zu den bevorzugten anorganischen Siliziumverbindungen die and der Oberfläche organisch modifizierten sphärischen Partikel.Furthermore, the preferred inorganic silicon compounds include the surface of the organically modified spherical particles.
Von diesen sind besonders bevorzugt die Polymethylsilsesquioxane und hydrophob modifizierte Aerosile, wie z.B. Aerosil R 972.Of these, particularly preferred are the polymethylsilsesquioxanes and hydrophobically modified aerosils, e.g. Aerosil R 972.
Zu den organischen Siliziumverbindungen gehören die Siloxan Elastomere und Siloxan Harze. Von denen sind besonders bevorzugt die KSP-Typen von Shin Etsu, sowie das Tri- methylsiloxysilicate.Organic silicon compounds include the siloxane elastomers and siloxane resins. Of these, particularly preferred are the KSP types from Shin Etsu, as well as the trimethylsiloxysilicate.
Weitere erfindungsgemäß bevorzugte Füllstoffe kommen aus der Gruppe der sphäreischen Partikel. Besonders bevorzugt ist der mittlere Teilchendurchmesser kleiner als 20 μm. Weiterhin werden bevorzugt spärische Partikel organischen Ursprungs gewählt. Besonders bevorzugt ist davon das BPD-500, das von der Firma Kobo vertrieben wird.Further inventively preferred fillers come from the group of spherical particles. More preferably, the average particle diameter is less than 20 microns. Furthermore, preference is given to choosing spherical particles of organic origin. Particularly preferred is the BPD-500 marketed by Kobo.
Desweiteren sind bevorzugt sphärische Partikel mit einem mittlerern Teilchendurchmesser kleiner als 10 μm. Davon besonders bevorzugt sind Nylon-12, das z.B. als SP-501 oder SP- 500 von der Firma Kobo vertrieben wird. Weiterhin bevorzugt sind Polymethylmethacrylate, die z.B. unter dem Handelsnamen Covabead LH 85 von LCW vertrieben wird.Furthermore, spherical particles having an average particle diameter of less than 10 μm are preferred. Of these, particularly preferred are nylon-12, e.g. sold as SP-501 or SP-500 by the company Kobo. Further preferred are polymethyl methacrylates, e.g. sold under the trade name Covabead LH 85 by LCW.
Weiterhin bevorzugt eingesetzt werden könnenWismut Oxychlorid oder Bornitrid.It is further preferred to use bismuth oxychloride or boron nitride.
Es ist erfindungsgemäß von Vorteil, wenn die Zubereitungen, dadurch gekennzeichnet sind, dass sie 0,001 Gew.-% bis 10 Gew.-%, bevorzugt 0,05 Gew.-% bis 5 Gew.-%, insbesondere 0,1 - 2,0 Gew.-%, bezogen auf das Gesamtgewicht der Zubereitungen, an einem oder mehreren Füllstoffen enthalten.It is advantageous according to the invention if the preparations are characterized in that they contain 0.001% by weight to 10% by weight, preferably 0.05% by weight to 5% by weight, in particular 0.1-2, 0 wt .-%, based on the total weight of the preparations, on one or more fillers.
Verdicker werden erfindungsgemäß vorzugsweise gewählt aus der Gruppe der Hydrokolloi- de. „Hydrokolloid" ist die technologische Kurzbezeichnung für die an sich richtigere Bezeich- nung „hydrophiles Kolloid". Hydrokolloide sind Makromoleküle, die eine weitgehend lineare Gestalt haben und über intermolekulare Wechselwirkungskräfte verfügen, die Neben- und Hauptvalenzbindungen zwischen den einzelnen Molekülen und damit die Ausbildung eines netzartigen Gebildes ermöglichen. Sie sind teilweise wasserlösliche natürliche oder synthetische Polymere, die in wässrigen Systemen Gele oder viskose Lösungen bilden. Sie erhöhen die Viskosität des Wassers, indem sie entweder Wassermoleküle binden (Hydratation) oder aber das Wasser in ihre unter sich verflochtenen Makromoleküle aufnehmen und einhüllen, wobei sie gleichzeitig die Beweglichkeit des Wassers einschränken. Solche wasserlöslichen Polymere stellen eine große Gruppe chemisch sehr unterschiedlicher natürlicher und synthetischer Polymere dar, deren gemeinsames Merkmal ihre Löslichkeit in Wasser bzw. wäßrigen Medien ist. Voraussetzung dafür ist, dass diese Polymere über eine für die Wasserlöslichkeit ausreichende Anzahl an hydrophilen Gruppen besitzen und nicht zu stark vernetzt sind. Die hydrophilen Gruppen können nichtionischer, anionischer oder kationischer Natur sein, beispielsweise wie folgt:According to the invention, thickeners are preferably selected from the group of hydrocolloids. "Hydrocolloid" is the technological abbreviation for the correct name. "Hydrophilic colloid." Hydrocolloids are macromolecules that are largely linear in shape and have intermolecular interaction forces that allow side and major valence bonds between the individual molecules to form a reticulate structure that are partially water-soluble natural or synthetic polymers Forming gels or viscous solutions in aqueous systems, they increase the viscosity of the water either by binding water molecules (hydration) or by taking up and enveloping the water in their interwoven macromolecules, while at the same time restricting the mobility of the water represent a large group of chemically very different natural and synthetic polymers whose common feature is their solubility in water or aqueous media, provided that these polymers have a solubility for water solubility have sufficient number of hydrophilic groups and are not too strongly crosslinked. The hydrophilic groups may be nonionic, anionic or cationic in nature, for example as follows:
-NH2 — COOH -COO" M+ -NR2 -NH 2 -COOH-COO " M + -NR 2
-NH-R O -SO3 " M+ (CH2Jn -NH-R O -SO 3 " M + (CH 2 J n
—OH — NH-C- -NHo -POs' M2 " SO3 " -OH - NH-C- -NHo -POs ' M 2 " SO 3 "
-SH NH -NH3 X + -NR2 -SH NH -NH 3 X + -NR 2
— O — -NH-C-NH2 -NR2H X -- O - NH-C-NH 2 -NR 2 H X -
I (CH2Jn — N— -HNL .N. .NH2 -NR3 X' COO " I (CH 2 J n - N- -HNL .N .NH 2 -NR 3 X 'COO ".
-PR3 X-PR 3 X
N NN N
NH2 O ' NH 2 O '
+ / -CH=N+ / - CH = N
OO
Die Gruppe der kosmetisch und dermatologisch relevanten Hydrokolloide läßt sich wie folgt einteilen in: organische, natürliche Verbindungen, wie beispielsweise Agar-Agar, Carrageen, Tragant,The group of cosmetically and dermatologically relevant hydrocolloids can be classified as follows: organic, natural compounds, such as agar-agar, carrageenan, tragacanth,
Gummi arabicum, Alginate, Pektine, Polyosen, Guar-Mehl, Johannisbrotbaumkernmehl,Gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum,
Stärke, Dextrine, Gelatine, Casein, organische, abgewandelte Naturstoffe, wie z. B. Carboxymethylcellulose und andere CeIIu- loseether, Hydroxyethyl- und -propylcellulose und dergleichen, organische, vollsynthetische Verbindungen, wie z. B. Polyacryl- und Polymethacryl-Verbin- dungen, Vinylpolymere, Polycarbonsäuren, Polyether, Polyimine, Polyamide, anorganische Verbindungen, wie z. B. Polykieselsäuren, Tonmineralien wie Montmorillonite, Zeolithe, Kieselsäuren.Starch, dextrins, gelatin, casein, organic, modified natural products such. Carboxymethylcellulose and other cellulosic ethers, hydroxyethyl and propylcellulose and the like, organic, fully synthetic compounds, such. As polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides, inorganic compounds such. As polysilicic acids, clay minerals such as montmorillonites, zeolites, silicic acids.
Erfindungsgemäß bevorzugte Hydrokolloide sind beispielsweise Methylcellulosen, als welche die Methylether der Cellulose bezeichnet werden. Sie zeichnen sich durch die folgende Strukturformel ausHydrocolloids which are preferred according to the invention are, for example, methylcelluloses, which are referred to as the methyl ethers of cellulose. They are characterized by the following structural formula
Figure imgf000014_0001
Figure imgf000014_0001
Strukturformel I in der R ein Wasserstoff oder eine Methylgruppe darstellen kann.Structural formula I in which R can represent a hydrogen or a methyl group.
Insbesondere vorteilhaft im Sinne der vorliegenden Erfindung sind die im allgemeinen ebenfalls als Methylcellulosen bezeichneten Cellulosemischether, die neben einem dominierenden Gehalt an Methyl- zusätzlich 2-Hydroxyethyl-, 2-Hydroxypropyl- oder 2-Hydroxybutyl- Gruppen enthalten. Besonders bevorzugt sind (Hydroxypropyl)methylcellulosen, beispielsweise die unter der Handelsbezeichnung Methocel E4M bei der Dow Chemical Comp, erhältlichen.Particularly advantageous for the purposes of the present invention are the cellulose mixed ethers which are generally also referred to as methylcelluloses and, in addition to a dominating content of methyl, additionally contain 2-hydroxyethyl, 2-hydroxypropyl or 2-hydroxybutyl groups. Particularly preferred are (hydroxypropyl) methylcelluloses, for example those available under the trade name Methocel E4M from Dow Chemical Comp.
Erfindungsgemäß ferner vorteilhaft ist Natriumcarboxymethylcellulose, das Natrium-Salz des Glykolsäureethers der Cellulose, für welches R in Strukturformel I ein Wasserstoff und/oder CH2-COONa darstellen kann. Besonders bevorzugt ist die unter der Handelsbezeichnung Natrosol Plus 330 CS bei Aqualon erhältliche, auch als Cellulose Gum bezeichnete Natriumcarboxymethylcellulose.Also advantageous according to the invention is sodium carboxymethylcellulose, the sodium salt of the glycolic acid ether of cellulose, for which R in structural formula I can be a hydrogen and / or CH 2 -COONa. Particularly preferred is sodium carboxymethylcellulose, also known as cellulose gum, available under the tradename Natrosol Plus 330 CS from Aqualon.
Bevorzugt im Sinne der vorliegenden Erfindung ist ferner Xanthan (CAS-Nr. 11138-66-2), auch Xanthan Gummi genannt, welches ein anionisches Heteropolysaccharid ist, das in der Regel durch Fermentation aus Maiszucker gebildet und als Kaliumsalz isoliert wird. Es wird von Xanthomonas campestris und einigen anderen Species unter aeroben Bedingungen mit einem Molekulargewicht von 2*106 bis 24*106 produziert. Xanthan wird aus einer Kette mit ß-1 ,4-gebundener Glucose (Cellulose) mit Seitenketten gebildet. Die Struktur der Untergruppen besteht aus Glucose, Mannose, Glucuronsäure, Acetat und Pyruvat. Xanthan ist die Bezeichnung für das erste mikrobielle anionische Heteropolysaccharid. Es wird von Xanthomo- nas campestris und einigen anderen Species unter aeroben Bedingungen mit einem Molekulargewicht von 2-15 106 produziert. Xanthan wird aus einer Kette mit ß-1 ,4-gebundener Glucose (Cellulose) mit Seitenketten gebildet. Die Struktur der Untergruppen besteht aus Glucose, Mannose, Glucuronsäure, Acetat und Pyruvat. Die Anzahl der Pyruvat-Einheiten bestimmt die Viskosität des Xanthans. Xanthan wird in zweitägigen Batch-Kulturen mit einer Ausbeute von 70-90 %, bezogen auf eingesetztes Kohlenhydrat, produziert. Dabei werden Ausbeuten von 25-30 g/l erreicht. Die Aufarbeitung erfolgt nach Abtöten der Kultur durch Fällung mit z. B. 2-Propanol. Xanthan wird anschließend getrocknet und gemahlen.Also preferred for the purposes of the present invention is xanthan (CAS No. 11138-66-2), also called xanthan gum, which is an anionic heteropolysaccharide, which is generally formed by fermentation from corn sugar and isolated as the potassium salt. It is produced by Xanthomonas campestris and some other species under aerobic conditions with a molecular weight of 2 * 10 6 to 24 * 10 6 . Xanthan comes with a chain ß-1, 4-bonded glucose (cellulose) formed with side chains. The structure of the subgroups consists of glucose, mannose, glucuronic acid, acetate and pyruvate. Xanthan is the name given to the first microbial anionic heteropolysaccharide. It is produced by Xanthomonas campestris and some other species under aerobic conditions with a molecular weight of 2-15 10 6 . Xanthan is formed from a chain of β-1,4-linked glucose (cellulose) with side chains. The structure of the subgroups consists of glucose, mannose, glucuronic acid, acetate and pyruvate. The number of pyruvate units determines the viscosity of xanthan. Xanthan is produced in two-day batch cultures with a yield of 70-90%, based on carbohydrate used. Yields of 25-30 g / l are achieved. The workup is carried out after killing the culture by precipitation with z. B. 2-propanol. Xanthan is then dried and ground.
Vorteilhafter Gelbildner im Sinne der vorliegenden Erfindung ist ferner Carrageen, ein gelbildender und ähnlich wie Agar aufgebauter Extrakt aus nordatlantischen, zu den Florideen zählenden Rotalgen (Chondrus crispus und Gigartina stellata).Advantageous gelling agent for the purposes of the present invention is also carrageenan, a gel-forming and similar to agar based extract of North Atlantic, to the Florideen counting red algae (Chondrus crispus and Gigartina stellata).
Häufig wird die Bezeichnung Carrageen für das getrocknete Algenprodukt und Carrageenan für den Extrakt aus diesem verwendet. Das aus dem Heißwasserextrakt der Algen ausgefällte Carrageen ist ein farbloses bis sandfarbenes Pulver mit einem Molekulargewichtsbereich von 100 000-800 000 und einem Sulfat-Gehalt von ca. 25 %. Carrageen, das in warmem Wasser sehr leicht lös), ist; beim Abkühlen bildet sich ein thixotropes Gel, selbst wenn der Wassergehalt 95-98 % beträgt. Die Festigkeit des Gels wird durch die Doppelhelix-Struktur des Carrageens bewirkt . Beim Carrageenan unterscheidet man drei Hauptbestandteile: Die gelbildende κ-Fraktion besteht aus D-Galactose-4-sulfat und 3,6-Anhydro-α-D-galactose, die abwechselnd in 1 ,3- und 1 ,4-Stellung glykosidisch verbunden sind (Agar enthält demgegenüber 3,6-Anhydro-α-L-galactose). Die nicht gelierende λ-Fraktion ist aus 1 ,3-glykosidisch verknüpften D-Galactose-2-sulfat und 1 ,4-verbundenen D-Galactose-2,6-disulfat-Resten zusammengesetzt u. in kaltem Wasser leicht löslich. Das aus D-Galactose-4-sulfat in 1 ,3-Bin- dung und 3,6-Anhydro-α-D-galactose-2-sulfat in 1 ,4-Bindung aufgebaute ι-Carrageenan ist sowohl wasserlöslich als auch gelbildend. Weitere Carrageen-Typen werden ebenfalls mit griechischen Buchstaben bezeichnet: α, ß, γ, μ, v, ξ, π, ω, χ. Auch die Art vorhandener Kationen (K+, NH4 +, Na+, Mg2+, Ca2+) beeinflußt die Löslichkeit der Carrageene. Die Verwendung von Chitosan in kosmetischen Zubereitungen ist per se bekannt. Chitosan stellt ein partiell deacyliertes Chitin dar. Dieses Biopolymer hat u.a. filmbildende Eigenschaften und zeichnet sich durch ein seidiges Hautgefühl aus. Von Nachteil ist jedoch seine starke Klebrigkeit auf der Haut, die insbesondere - vorübergehend - während der Anwendung auftritt. Entsprechende Zubereitungen können dann im Einzelfalle nicht vermarktungsfähig sein, da sie vom Verbraucher nicht akzeptiert bzw. negativ beurteilt werden. Chitosan wird bekanntermaßen beispielsweise in der Haarpflege eingesetzt. Es eignet sich, besser als das ihm zugrundeliegende Chitin, als Verdicker oder Stabilisator und verbessert die Adhäsion und Wasserresistenz von polymeren Filmen. Stellvertretend für eine Vielzahl von Fundstellen des Standes der Technik: H.P.Fiedler, „Lexikon der Hilfsstoffe für Pharmazie, Kosmetik und angrenzende Gebiete", dritte Auflage 1989, Editio Cantor, Aulendorf, S. 293, Stichwort „Chitosan".Frequently, the term carrageenan is used for the dried algae product and carrageenan for the extract thereof. The carrageenan precipitated from the hot-water extract of the algae is a colorless to sand-colored powder with a molecular weight range of 100,000-800,000 and a sulphate content of about 25%. Carrageenan, which dissolves very easily in warm water); Upon cooling, a thixotropic gel forms, even if the water content is 95-98%. The strength of the gel is effected by the double helix structure of the carrageenan. Carrageenan has three main components: The gel-forming κ fraction consists of D-galactose-4-sulfate and 3,6-anhydro-α-D-galactose, which are alternately glycosidically linked in the 1, 3 and 1, 4 positions (Agar, in contrast, contains 3,6-anhydro-α-L-galactose). The non-gelling λ-fraction is composed of 1, 3-glycosidically linked D-galactose-2-sulfate and 1, 4-linked D-galactose-2,6-disulfate radicals u. easily soluble in cold water. The ι-carrageenan composed of D-galactose-4-sulfate in 1, 3-bond and 3,6-anhydro-α-D-galactose-2-sulfate in 1, 4-bond is both water-soluble and gel-forming. Other types of carrageenan are also denoted by Greek letters: α, β, γ, μ, v, ξ, π, ω, χ. The type of cations present (K + , NH 4 + , Na + , Mg 2+ , Ca 2+ ) also influences the solubility of the carrageenans. The use of chitosan in cosmetic preparations is known per se. Chitosan is a partially deacylated chitin. This biopolymer has film-forming properties and a silky feel on the skin. A disadvantage, however, is its strong stickiness on the skin, which occurs in particular - temporarily - during use. Corresponding preparations may then not be marketable in individual cases, as they are not accepted by the consumer or assessed negatively. Chitosan is known to be used for example in hair care. It is better than the underlying chitin, as a thickener or stabilizer and improves the adhesion and water resistance of polymeric films. Representative of a variety of references of the prior art: HP Fiedler, "Encyclopedia of excipients for pharmacy, cosmetics and related fields", third edition 1989, Editio Cantor, Aulendorf, p. 293, keyword "Chitosan".
Chitosan ist gekennzeichnet durch folgende Strukturformel:Chitosan is characterized by the following structural formula:
Figure imgf000016_0001
dabei nimmt n Werte bis zu ca. 10.000 an, X stellt entweder den Acetylrest oder Wasserstoff dar. Chitosan entsteht durch Deacetylierung und teilweise Depolymerisation (Hydrolyse) von Chitin, welches durch die Strukturformel
Figure imgf000016_0001
n values up to about 10,000, X represents either the acetyl radical or hydrogen. Chitosan is formed by deacetylation and partial depolymerization (hydrolysis) of chitin, which by the structural formula
Figure imgf000016_0002
gekennzeichnet ist. Chitin ist wesentlicher Bestandteil des Ektoskeletts [O χiτωv = grch.: der Panzerrock] der Gliederfüßer (z.B. Insekten, Krebse, Spinnen) und wird auch in Stützgeweben anderer Organismen (z.B. Weichtiere, Algen, Pilze) gefunden.
Figure imgf000016_0002
is marked. Chitin is an essential component of the ectoskeleton [O χiτωv = Greek: the armored skirt] of arthropods (eg insects, crabs, spiders) and is also found in supporting tissues of other organisms (eg molluscs, algae, fungi).
Im Bereich von etwa pH <6 ist Chitosan positiv geladen und dort auch in wäßrigen Systemen löslich. Es ist nicht kompatibel mit anionischen Rohstoffen. Daher bietet sich zur Herstellung chitosanhaltiger ÖI-in-Wasser-Emulsionen der Einsatz nichtionischer Emulgatoren an. Diese sind an sich bekannt, beispielsweise aus der EP-A 776 657.In the range of about pH <6 chitosan is positively charged and there also soluble in aqueous systems. It is not compatible with anionic raw materials. For this reason, the use of nonionic emulsifiers is suitable for producing chitosan-containing oil-in-water emulsions. These are known per se, for example from EP-A 776 657.
Erfindungsgemäß bevorzugt sind Chitosane mit einem Deacetylierungsgrad > 25 % , insbesondere > 55 bis 99 % [bestimmt mittels 1H-NMR]).Preference according to the invention is given to chitosans having a degree of deacetylation of> 25%, in particular> 55 to 99% [determined by means of 1 H-NMR]).
Es ist von Vorteil, Chitosane mit Molekulargewichten zwischen 10.000 und 1.000.000 zu wählen, insbesondere solches mit Molekulargewichten zwischen 100.000 und 1.000.000. [bestimmt mittels Gelpermetionschromatographie].It is advantageous to choose chitosans with molecular weights between 10,000 and 1,000,000, especially those with molecular weights between 100,000 and 1,000,000. [determined by gel permeation chromatography].
Polyacrylate sind ebenfalls vorteilhaft im sinne der vorliegenden Erfindung zu verwendende Gelatoren. Erfindungsgemäß vorteilhafte Polyacrylate sind Acrylat-Alkylacrylat-Copolymere, insbesondere solche, die aus der Gruppe der sogenannten Carbomere oder Carbopole (Car- bopol® ist eigentlich eine eingetragene Marke der B. F. Goodrich Company) gewählt werden. Insbesondere zeichnen sich das oder die erfindungsgemäß vorteilhaften Acrylat-Alkyl- acrylat-Copolymere durch die folgende Struktur aus:Polyacrylates are also advantageously gelators to be used in the context of the present invention. Polyacrylates which are advantageous according to the invention are acrylate-alkyl acrylate copolymers, in particular those selected from the group of the so-called carbomers or carbopols (Carbopol® is actually a registered trademark of B.F. Goodrich Company). In particular, the acrylate copolymer (s) according to the invention are characterized by the following structure:
Figure imgf000017_0001
Figure imgf000017_0001
Darin stellen R' einen langkettigen Alkylrest und x und y Zahlen dar, welche den jeweiligen stöchiometrischen Anteil der jeweiligen Comonomere symbolisieren. Erfindungsgemäß besonders bevorzugt sind Acrylat-Copolymere und/oder Acrylat-Alkylacry- lat-Copolymere, welche unter den Handelbezeichnungen Carbopol® 1382, Carbopol® 981 und Carbopol® 5984 von der B. F. Goodrich Company erhältlich sind.In this formula, R 'represents a long-chain alkyl radical and x and y represent numbers which symbolize the respective stoichiometric proportion of the respective comonomers. Particularly preferred according to the invention are acrylate copolymers and / or acrylate-alkyl acrylate copolymers, which are available under the trade names Carbopol® 1382, Carbopol® 981 and Carbopol® 5984 from the BF Goodrich Company.
Ferner vorteilhaft sind Copolymere aus C1o-3o-Alkylacrylaten und einem oder mehreren Monomeren der Acrylsäure, der Methacrylsäure oder deren Ester, die kreuzvernetzt sind mit einem Allylether der Saccharose oder einem Allylether des Pentaerythrit.Also advantageous are copolymers of C 1o-3 o-alkyl acrylates and one or more monomers of acrylic acid, methacrylic acid or their esters, which are cross-linked with an allyl ether of sucrose or an allyl ether of pentaerythritol.
Vorteilhaft sind Verbindungen, die die INCI-Bezeichnung „Acrylates/C 10-30 Alkyl Acrylate Crosspolymer" tragen. Insbesondere vorteilhaft sind die unter den Handelsbezeichnungen Pemulen TR1 und Pemulen TR2 bei der B. F. Goodrich Company erhältlichen.Advantageously, compounds bearing the INCI name "Acrylates / C 10-30 Alkyl Acrylate Crosspolymer." Particularly advantageous are those available under the trade names Pemulen TR1 and Pemulen TR2 from the B.F. Goodrich Company.
Die Gesamtmenge an einem oder mehreren Verdicker wird in den fertigen kosmetischen oder dermatologischen Zubereitungen vorteilhaft kleiner als 1 ,5 Gew.-%, bevorzugt zwischen 0,1 und 1 ,0 Gew.-%, bezogen auf das Gesamtgewicht der Zubereitungen, gewählt.The total amount of one or more thickeners in the finished cosmetic or dermatological preparations advantageously less than 1, 5 wt .-%, preferably between 0.1 and 1, 0 wt .-%, based on the total weight of the preparations selected.
Die kosmetischen oder dermatologischen Zubereitungen können erfindungsgemäß wie üblich zusammengesetzt sein und zur Behandlung, der Pflege und der Reinigung der Haut und/oder der Haare und als Schminkprodukt in der dekorativen Kosmetik dienen.According to the invention, the cosmetic or dermatological preparations may be composed as usual and used for the treatment, care and cleansing of the skin and / or the hair and as a make-up product in decorative cosmetics.
Sie enthalten bevorzugt 0,001 Gew.-% bis 10 Gew.-%, bevorzugt 0,05 Gew.-% bis 5 Gew.- %, insbesondere 0,1 - 2,0 Gew.-%, bezogen auf das Gesamtgewicht der Zubereitungen, an Folsäure und/oder deren Derivaten.They preferably contain from 0.001% by weight to 10% by weight, preferably from 0.05% by weight to 5% by weight, in particular from 0.1% to 2.0% by weight, based on the total weight of the preparations, of folic acid and / or its derivatives.
Erfindungsgemäße kosmetische und dermatologische Zubereitungen können in verschiedenen Formen vorliegen. So können sie z.B. eine Lösung, eine wasserfreie Zubereitung, eine Emulsion oder Mikroemulsion vom Typ Wasser-in-ÖI (W/O) oder vom Typ Öl-in-Wasser (O/W), eine multiple Emulsionen, beispielsweise vom Typ Wasser-in-ÖI-in-Wasser (W/O/W), ein Gel, einen festen Stift, eine Salbe oder auch ein Aerosol darstellen. Es ist auch erfin- dugsgemäß vorteilhaft, Folsäure und/oder deren Derivate in verkapselter Form darzureichen, z.B. in Kollagenmatrices und anderen üblichen Verkapselungsmaterialien, z.B. als CeIIuIo- severkapselungen, in Gelatine, Wachsmatrices oder liposomal verkapselt. Insbesondere Wachsmatrices wie sie in der DE-OS 43 08 282 beschrieben werden, haben sich als günstig herausgestellt. Es ist auch möglich und vorteilhaft im Sinne der vorliegenden Erfindung, Folsäure und/oder deren Derivate in wäßrige Systeme bzw. Tensidzubereitungen zur Reinigung der Haut und der Haare einzufügen.Cosmetic and dermatological preparations according to the invention can be present in various forms. For example, they may contain a solution, an anhydrous preparation, an emulsion or microemulsion of the water-in-oil (W / O) type or of the oil-in-water (O / W) type, a multiple emulsion, for example water-type. in-oil-in-water (W / O / W), a gel, a solid stick, an ointment or even an aerosol. It is also advantageous in accordance with the invention to administer folic acid and / or its derivatives in encapsulated form, for example in collagen matrices and other customary encapsulating materials, for example as encapsulated encapsulations, in gelatin, wax matrices or liposomally encapsulated. In particular wax matrices as described in DE-OS 43 08 282, have been found to be favorable. It is also possible and advantageous for the purposes of the present invention to incorporate folic acid and / or derivatives thereof into aqueous systems or surfactant preparations for cleaning the skin and hair.
Die erfindungsgemäßen kosmetischen und dermatologischen Zubereitungen können kosmetische Hilfsstoffe enthalten, wie sie üblicherweise in solchen Zubereitungen verwendet werden, z.B. Konservierungsmittel, Bakterizide, Parfüme, Substanzen zum Verhindern des Schäumens, Farbstoffe, Pigmente, die eine färbende Wirkung haben, Verdickungsmittel, oberflächenaktive Substanzen, Emulgatoren, weichmachende, anfeuchtende und/oder feuchhaltende Substanzen, Fette, Öle, Wachse oder andere übliche Bestandteile einer kosmetischen oder dermatologischen Formulierung wie Alkohole, Polyole, Polymere, Schaumstabilisatoren, Elektrolyte, organische Lösemittel oder Siliconderivate.The cosmetic and dermatological preparations according to the invention may comprise cosmetic adjuvants such as are conventionally used in such preparations, e.g. Preservatives, bactericides, perfumes, foaming inhibitors, colorants, pigments having a coloring effect, thickeners, surface-active substances, emulsifiers, softening, moistening and / or moisturizing substances, fats, oils, waxes or other conventional ingredients of a cosmetic or cosmetic dermatological formulation such as alcohols, polyols, polymers, foam stabilizers, electrolytes, organic solvents or silicone derivatives.
Insbesondere können Folsäure und/oder deren Derivate erfindungsgemäß auch mit anderen Antioxidantien und/oder Radikalfängern kombiniert werden.In particular, according to the invention, folic acid and / or its derivatives can also be combined with other antioxidants and / or radical scavengers.
Die Menge an Antioxidantien (eine oder mehrere Verbindungen) in den Zubereitungen beträgt vorzugsweise 0,001 bis 30 Gew.-%, besonders bevorzugt 0,05 - 20 Gew.-%, insbesondere 1 - 10 Gew.-%, bezogen auf das Gesamtgewicht der Zubereitung.The amount of antioxidants (one or more compounds) in the preparations is preferably from 0.001 to 30% by weight, particularly preferably from 0.05 to 20% by weight, in particular from 1 to 10% by weight, based on the total weight of the preparation ,
Die Lipidphase kann vorteilhaft gewählt werden aus folgender Substanzgruppe: Mineralöle, MineralwachseThe lipid phase can advantageously be selected from the following substance group: mineral oils, mineral waxes
Öle, wie Triglyceride der Caprin- oder der Caprylsäure, ferner natürliche Öle wie z.B. Rizinusöl;Oils such as triglycerides of capric or caprylic acid, further natural oils such as e.g. Castor oil;
Fette, Wachse und andere natürliche und synthetische Fettkörper, vorzugsweise Ester von Fettsäuren mit Alkoholen niedriger C-Zahl, z.B. mit Isopropanol, Propylenglykol oder Glycerin, oder Ester von Fettalkoholen mit Alkansäuren niedriger C-Zahl oder mit Fettsäuren; Alkylbenzoate;Fats, waxes and other natural and synthetic fats, preferably esters of fatty acids with lower C-number alcohols, e.g. with isopropanol, propylene glycol or glycerol, or esters of fatty alcohols with alkanoic acids of low C number or with fatty acids; benzoates;
Siliconöle wie Dimethylpolysiloxane, Diethylpolysiloxane, Diphenylpolysiloxane sowie Mischformen daraus. Die Ölphase der Emulsionen, Oleogele bzw. Hydrodispersionen oder Lipodispersionen im Sinne der vorliegenden Erfindung wird vorteilhaft gewählt aus der Gruppe der Ester aus gesättigten und/oder ungesättigten, verzweigten und/oder unverzweigten Alkancarbonsäuren einer Kettenlänge von 3 bis 30 C-Atomen und gesättigten und/oder ungesättigten, verzweigten und/oder unverzweigten Alkoholen einer Kettenlänge von 3 bis 30 C-Atomen, aus der Gruppe der Ester aus aromatischen Carbonsäuren und gesättigten und/oder ungesättigten, verzweigten und/oder unverzweigten Alkoholen einer Kettenlänge von 3 bis 30 C-Atomen. Solche Esteröle können dann vorteilhaft gewählt werden aus der Gruppe Isopropylmyristat, Isopropylpalmitat, Isopropylstearat, Isopropyloleat, n-Butylstearat, n-Hexyllaurat, n- Decyloleat, Isooctylstearat, Isononylstearat, Isononylisononanoat, 2-Ethylhexylpalmitat, 2- Ethylhexyllaurat, 2-Hexyldecylstearat, 2-Octyldodecylpalmitat, Oleyloleat, Oleylerucat, Eru- cyloleat, Erucylerucat sowie synthetische, halbsynthetische und natürliche Gemische solcher Ester, z.B. Jojobaöl.Silicone oils such as dimethylpolysiloxanes, diethylpolysiloxanes, diphenylpolysiloxanes and mixed forms thereof. The oil phase of the emulsions, oleogels or hydrodispersions or lipodispersions in the context of the present invention is advantageously selected from the group of esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids having a chain length of 3 to 30 carbon atoms and saturated and / or or unsaturated, branched and / or unbranched alcohols having a chain length of 3 to 30 carbon atoms, from the group of esters of aromatic carboxylic acids and saturated and / or unsaturated, branched and / or unbranched alcohols having a chain length of 3 to 30 carbon atoms. Such ester oils can then advantageously be selected from the group isopropyl myristate, isopropyl palmitate, isopropyl stearate, isopropyl oleate, n-butyl stearate, n-hexyl laurate, n-decyl oleate, isooctyl stearate, isononyl stearate, isononyl isononanoate, 2-ethylhexyl palmitate, 2-ethylhexyl laurate, 2-hexyldecyl stearate, 2 Octyldodecyl palmitate, oleyl oleate, oleyl erucate, erucyl oleate, erucyl erucate and also synthetic, semisynthetic and natural mixtures of such esters, eg jojoba oil.
Die wäßrige Phase der erfindungsgemäßen Zubereitungen enthält gegebenenfalls vorteilhaft Alkohole, Diole oder Polyole niedriger C-Zahl, sowie deren Ether, vorzugsweise Ethanol, Isopropanol, Propylenglykol, Glycerin, Ethylenglykol, Ethylenglykolmonoethyl- oder -mo- nobutylether, Propylenglykolmonomethyl, -monoethyl- oder -monobutylether, Diethy- lenglykolmonomethyl- oder -monoethylether und analoge Produkte, ferner Alkohole niedriger C-Zahl, z.B. Ethanol, Isopropanol, 1 ,2-Propandiol, Glycerin sowie insbesondere ein oder mehrere Verdickungsmittel, welches oder welche vorteilhaft gewählt werden können aus der Gruppe Siliciumdioxid, Aluminiumsilikate, Polysaccharide bzw. deren Derivate, z.B. Hyalu- ronsäure, Xanthangummi, Hydroxypropylmethylcellulose, besonders vorteilhaft aus der Gruppe der Polyacrylate, bevorzugt ein Polyacrylat aus der Gruppe der sogenannten Carbo- pole, beispielsweise Carbopole der Typen 980, 981 , 1382, 2984, 5984, jeweils einzeln oder in Kombination.The aqueous phase of the preparations according to the invention optionally advantageously contains alcohols, diols or polyols of low C number, and their ethers, preferably ethanol, isopropanol, propylene glycol, glycerol, ethylene glycol, ethylene glycol monoethyl or -mob nobutyl ether, propylene glycol monomethyl, -monoethyl- or -monobutylether , Diethylene glycol monomethyl or monoethyl ether and analogous products, furthermore lower C-number alcohols, eg Ethanol, isopropanol, 1, 2-propanediol, glycerol and in particular one or more thickening agents, which or which can be advantageously selected from the group of silica, aluminum silicates, polysaccharides or their derivatives, e.g. Hyuronic acid, xanthan gum, hydroxypropylmethylcellulose, particularly advantageously from the group of the polyacrylates, preferably a polyacrylate from the group of the so-called Carbopol, for example Carbopols types 980, 981, 1382, 2984, 5984, in each case individually or in combination.
Insbesondere werden Gemische der vorstehend genannten Lösemittel verwendet. Bei alkoholischen Lösemitteln kann Wasser ein weiterer Bestandteil sein.In particular, mixtures of the abovementioned solvents are used. For alcoholic solvents, water can be another ingredient.
Erfindungsgemäße Emulsionen sind vorteilhaft und enthalten z.B. die genannten Fette, Öle, Wachse und anderen Fettkörper, sowie Wasser und einen Emulgator, wie er üblicherweise für einen solchen Typ der Formulierung verwendet wird. Gele gemäß der Erfindung enthalten üblicherweise Alkohole niedriger C-Zahl, z.B. Ethanol, Isopropanol, 1 ,2-Propandiol, Glycerin und Wasser bzw. ein vorstehend genanntes Öl in Gegenwart eines Verdickungsmittels, das bei ölig-alkoholischen Gelen vorzugsweise Silicium- dioxid oder ein Aluminiumsilikat, bei wässrig-alkoholischen oder alkoholischen Gelen vorzugsweise ein Polyacrylat ist.Emulsions according to the invention are advantageous and contain, for example, the said fats, oils, waxes and other fatty substances, as well as water and an emulsifier, as is customarily used for such a type of formulation. Gels according to the invention usually contain alcohols of low carbon number, for example ethanol, isopropanol, 1,2-propanediol, glycerol and water or an abovementioned oil in the presence of a thickener, which in the case of oily-alcoholic gels preferably silica or an aluminum silicate in aqueous-alcoholic or alcoholic gels is preferably a polyacrylate.
Als Treibmittel für erfindungsgemäße, aus Aerosolbehältern versprühbare Zubereitungen sind die üblichen bekannten leichtflüchtigen, verflüssigten Treibmittel, beispielsweise Kohlenwasserstoffe (Propan, Butan, Isobutan) geeignet, die allein oder in Mischung miteinander eingesetzt werden können. Auch Druckluft ist vorteilhaft zu verwenden.Suitable propellants for preparations which can be sprayed from aerosol containers according to the invention are the customary known highly volatile, liquefied propellants, for example hydrocarbons (propane, butane, isobutane), which can be used alone or mixed with one another. Also, compressed air is advantageous to use.
Vorteilhaft können erfindungsgemäße Zubereitungen außerdem Substanzen enthalten, die UV-Strahlung im UVB-Bereich absorbieren, wobei die Gesamtmenge der Filtersubstanzen z.B. 0,1 Gew.-% bis 30 Gew.-%, vorzugsweise 0,5 bis 10 Gew.-%, insbesondere 1 ,0 bis 6,0 Gew.-% beträgt, bezogen auf das Gesamtgewicht der Zubereitungen, um kosmetische Zubereitungen zur Verfügung zu stellen, die das Haar bzw. die Haut vor dem gesamten Bereich der ultravioletten Strahlung schützen. Sie können auch als Sonnenschutzmittel fürs Haar oder die Haut dienen.Advantageously, preparations according to the invention may also contain substances which absorb UV radiation in the UVB range, the total amount of filter substances being e.g. 0.1 wt .-% to 30 wt .-%, preferably 0.5 to 10 wt .-%, in particular 1, 0 to 6.0 wt .-%, based on the total weight of the preparations to cosmetic preparations for To provide the hair or the skin against the entire range of ultraviolet radiation. They can also serve as a sunscreen for hair or skin.
Die nachfolgenden Beispiele sollen die vorliegende Erfindung verdeutlichen, ohne sie einzuschränken. Alle Mengenangaben, Anteile und Prozentanteile sind, soweit nicht anders angegeben, Gewichtsprozente, auf das Gewicht und die Gesamtmenge bzw. auf das Gesamtgewicht der Zubereitungen bezogen. The following examples are intended to illustrate the present invention without limiting it. All amounts, proportions and percentages are, unless otherwise stated, percentages by weight, based on the weight and the total amount or on the total weight of the preparations.
Figure imgf000022_0001
Figure imgf000022_0001

Claims

Patentansprüche claims
1. Kosmetische oder dermatologische Zubereitungen mit einem Gehalt an Folsäure und/oder deren Derivaten, Füllstoffen und Verdickern.1. Cosmetic or dermatological preparations containing folic acid and / or their derivatives, fillers and thickeners.
2. Zubereitungen nach Anspruch 1 , dadurch gekennzeichnet, dass der oder die Füllstoffe gewählt werden aus der Gruppe Nylon (Polyamid 6 und Polyamid 12), Polymethylsilsesquio- xane, Titandioxiden, Stärke (Tapiokastärke, Maissärke), Talkum, Siloxanelastomere.2. Preparations according to claim 1, characterized in that the filler or fillers are selected from the group nylon (polyamide 6 and polyamide 12), Polymethylsilsesquio- xane, titanium dioxides, starch (tapioca starch, corn starch), talc, siloxane elastomers.
3. Zubereitungen nach Anspruch 1 , dadurch gekennzeichnet, dass der oder die Verdicker gewählt werden aus der Gruppe Carbomer, Acrylate/C 10-30 Alkylacrylat Crosspolymer, Chondrus Crispus, Xanthan Gum.3. Preparations according to claim 1, characterized in that the thickener (s) are selected from the group carbomer, acrylates / C 10-30 alkyl acrylate crosspolymer, Chondrus Crispus, xanthan gum.
4. Zubereitungen nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass sie 0,001 Gew.-% bis 10 Gew.-%, bevorzugt 0,01 Gew.-% bis 1 ,0 Gew.-%, insbesondere 0,05 - 0,5 Gew.-%, bezogen auf das Gesamtgewicht der Zubereitungen, an Folsäure und/oder deren Derivaten, enthalten.4. Preparations according to one of the preceding claims, characterized in that it contains 0.001% by weight to 10% by weight, preferably 0.01% by weight to 1% by weight, in particular 0.05-0, 5 wt .-%, based on the total weight of the preparations, of folic acid and / or derivatives thereof.
5. Zubereitungen nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass sie 0,001 Gew.-% bis 10 Gew.-%, bevorzugt 0,05 Gew.-% bis 5 Gew.-%, insbesondere 0,1 - 2,0 Gew.-%, bezogen auf das Gesamtgewicht der Zubereitungen, an einem oder mehreren Füllstoffen enthalten.5. Preparations according to one of the preceding claims, characterized in that they 0.001 wt .-% to 10 wt .-%, preferably 0.05 wt .-% to 5 wt .-%, in particular 0.1 - 2.0 wt .-%, based on the total weight of the preparations, of one or more fillers.
6. Zubereitungen nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass sie weniger als 1 ,5 Gew.-%, bevorzugt zwischen 0,1 und 1 ,0 Gew.-%, bezogen auf das Gesamtgewicht der Zubereitungen, an einem oder mehreren Verdickern enthalten. 6. Preparations according to one of the preceding claims, characterized in that they contain less than 1, 5 wt .-%, preferably between 0.1 and 1, 0 wt .-%, based on the total weight of the preparations, of one or more thickeners contain.
PCT/EP2007/005871 2006-07-13 2007-07-03 Cosmetic or dermatological preparations containing folic acid, fillers and thickeners WO2008006486A1 (en)

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