Classifications

• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/90—Block copolymers
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
  • A61K8/04—Dispersions; Emulsions
  • A61K8/06—Emulsions
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
  • A61K8/0212—Face masks
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
  • A61K8/04—Dispersions; Emulsions
  • A61K8/06—Emulsions
  • A61K8/062—Oil-in-water emulsions
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q17/00—Barrier 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
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q19/00—Preparations for care of the skin
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
  • A61K2800/20—Chemical, physico-chemical or functional or structural properties of the composition as a whole
  • A61K2800/28—Rubbing or scrubbing compositions; Peeling or abrasive compositions; Containing exfoliants
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
  • A61Q1/02—Preparations containing skin colorants, e.g. pigments
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q11/00—Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q15/00—Anti-perspirants or body deodorants
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q17/00—Barrier 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
  • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q19/00—Preparations for care of the skin
  • A61Q19/001—Preparations for care of the lips
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q19/00—Preparations for care of the skin
  • A61Q19/002—Aftershave preparations
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q19/00—Preparations for care of the skin
  • A61Q19/004—Aftersun preparations
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q19/00—Preparations for care of the skin
  • A61Q19/10—Washing or bathing preparations
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q5/00—Preparations for care of the hair
  • A61Q5/02—Preparations for cleaning the hair
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q5/00—Preparations for care of the hair
  • A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q5/00—Preparations for care of the hair
  • A61Q5/12—Preparations containing hair conditioners

Definitions

• the present invention relates to cosmetic preparations comprising an oil-in-water emulsion, wherein the oil-in-water emulsion at least one amphiphilic polymer containing one or more hydrophobic units A and one or more hydrophilic units B, wherein the hydrophobic units A with terminal , polar groups modified polyisobutenes are formed, at least one suitable emulsifier component having an HLB value in the range of 8 to 20, at least one oil and / or fat phase and water.
• PIBSA polyisobutenyl substituted succinic anhydride
• WO 04/035635 relates to polymer compositions comprising at least one hydrophobic polymer and at least one modified polyisobutene, fibers, films, moldings and their further processing products composed of this polymer composition, a process for the preparation of the polymer composition according to the invention, a process for producing the fibers, films and moldings built up from the polymer composition according to the invention, colored polymer compositions containing at least one hydrophobic polymer, at least one modified polyisobutene and at least one dye; and fibers, films and moldings composed of the colored polymer composition according to the invention and the use of modified polyisobutenes for the treatment of hydrophobic polymers.
• modified polyisobutenes in cosmetics is not described.
• WO 93/029309 describes compounds based on polyisobutene and mixtures thereof which are suitable as emulsifiers for oil-in-water emulsions, processes for preparing such compounds and the emulsions themselves.
• Cosmetic preparations comprising oil-in-water emulsions comprising
• emulsifiers having an HLB value in the range from 8 to 20 are not described.
• EP-A 1 210 929 describes cosmetic and pharmaceutical compositions comprising at least one emulsifier comprising a) at least one alkyl chain obtainable by polymerization of (C 2 -C 5) -alkenes and / or alkenyl chain having at least 28 carbon atoms, which is linked to b) at least one carboxylic acid, carboxylic acid derivative, carboxylic acid anhydride, carboxylic anhydride derivative, ester and / or amide group. Alkenylsuccinic anhydrides and derivatives thereof are particularly preferred as emulsifiers. Cosmetic preparations comprising oil-in-water emulsions are not described.
• WO 02/032382 describes anhydrous pigment pastes comprising a pigment, an anhydrous solvent and a dispersant based on polyisobutene succinimide.
• EP-A 1 172 089 describes water-in-oil emulsions containing as emulsifier an oligo- or polyolefin, in particular a polyisobutene having at least 40 carbon atoms and a polar fraction. Further emulsifiers are not used.
• No. 5,980,922 describes hygiene articles water-in-oil emulsions which contain, for example, polyisobutene derivatives as emulsifiers. Oil-in-water emulsions and the use of additional emulsifiers are not described.
• O / W microemulsions comprising (a) 5 to 30, preferably 8 to 12 wt .-% of oil body, (b) 5 to 80, preferably 15 to 70 wt .-% of anionic and / or nonionic Emulsifiers and (c) 12 to 30, preferably 14 to 16 wt .-% polyols.
• the microemulsions are temperature stable and can be produced in a cold process.
• the skin is the largest organ in humans. Among its many functions (for example, for heat regulation and as a sense organ) is the barrier function, which prevents the drying of the skin (and thus ultimately the entire organism), probably the most important. At the same time, the skin acts as a protective device against the penetration and absorption of substances coming from outside.
• This barrier function is caused by the epidermis, which, as the outermost layer, forms the actual protective cover against the environment. At about one-tenth of the total thickness, it is also the thinnest layer of the skin.
• the epidermis is a stratified tissue in which the outer layer, the stratum corneum, represents the barrier function.
• the epidermal lipids In addition to their barrier effect against external chemical and physical influences, the epidermal lipids also contribute to the cohesion of the homtik and have an influence on the skin smoothness. In contrast to the sebaceous lipids, which do not form a closed film on the skin, the epidermal lipids are distributed over the entire homtik.
• cosmetics usually contain, in addition to balanced lipid mixtures and water, water-binding substances.
• the aim of skin care is also to compensate for the daily loss of fat and water loss of the skin. This is especially important when the natural regeneration capacity is insufficient.
• skin care products to protect against environmental influences, especially from the sun and wind, and delay the aging of the skin.
• Medical topical preparations usually contain one or more drugs in effective concentration.
• cosmetic and medical use and corresponding products reference is made at this point to the statutory provisions of the Federal Republic of Germany (eg Cosmetics Ordinance, Food and Medicinal Products Act).
• Emulsions are common cosmetic dosage forms. Emulsions are generally understood to mean heterogeneous systems composed of two liquids, which are immiscible with one another or have only limited miscibility, which are usually referred to as phases. One of the liquids is in the form of droplets (disperse phase), while the other liquid forms the continuous (coherent phase).
• the two liquids are water and oil and oil droplets are finely distributed in water, then it is an oil-in-water emulsion (O / W emulsion, eg milk).
• O / W emulsion oil-in-water emulsion
• the basic character of an O / W emulsion is characterized by the water.
• W / O emulsion water-in-oil emulsion
• Rarer dosage forms are multiple emulsions. These are understood as meaning those emulsions which in their droplets of the dispersed (or discontinuous) phase in turn contain droplets of a further dispersed phase, eg.
• Such "macroemulsions” usually have high viscosity.
• Microemulsions are optically isotropic, thermodynamically stable systems containing a water-insoluble oil component, emulsifiers and water.
• the clear or transparent appearance of the microemulsions is a consequence of the small particle size of the dispersed emulsion droplets.
• the droplet diameter of microemulsions is in the range of about 10 2 ⁇ m to about 10 1 ⁇ m.
• Microemulsions are trans- lucent and usually low-viscosity. The viscosity of many O / W type microemulsions is comparable to that of water.
• Microemulsions are frequently described in the literature, but their targeted production is associated with difficulties, since the areas of resistance of the microemulsion in the three-phase diagram formed from oil component, water and emulsifiers are usually very small and the location of these areas of existence to a great extent is strongly influenced by structural features of all components and all other ingredients of such systems. Microemulsions have a considerable importance in the formulation of cosmetic and pharmaceutical preparations because of their greater stability compared to macroemulsions, finer distribution of the inner phase, the usually higher effectiveness and the better transdermal penetration of the active ingredients incorporated therein. Another advantage is that they are verprüüfbar due to their low viscosity. If microemulsions are used as cosmetics, corresponding products are characterized by high cosmetic elegance.
• the so-called PIT (phase inversion temperature) method has proven.
• the emulsion components are initially charged at room temperature and heated together to about 80 0 C, wherein the lamellar liquid-crystalline phase range is passed through. After cooling to room temperature, a finely emulsified oil phase is obtained.
• the hot, anhydrous phase of oil body and emulsifier is emulsified with a portion of the amount of water at the same temperature.
• the emulsion passes through a transparent emulsion in the emulsion concentrate, which at about 85 ° C, the remaining amount of water is added. As a result, the emulsion inverts to a likewise very finely divided O / W emulsion.
• cosmetic preparations which are or contain O / W emulsions and have a high content of pigments, in addition to a cosmetically disadvantageous behavior such as the so-calledmulein, i. the formation of white spots on the skin, an insufficient and unsatisfactory distribution of active ingredients on the application surface.
• O / W emulsions Another disadvantage of prior art O / W emulsions is often their lack of stability at low or high pH (hydrolysis) and higher electrolyte concentrations. For example, this lack of stability can lead to phase separation. Although this can often be remedied by a suitable choice of the emulsifier system to some extent, but then often occur other disadvantages. Electrolytes can often not be dispensed with, since their properties are to be used. Often, the temperatures for making PIT emulsions are relatively high, and lowering the PIT of such emulsions is advantageous. It was therefore an object of the present invention to provide O / W emulsions which are stable in relation to high electrolyte concentrations or high ionic strengths for cosmetic conditions.
• Another object of the present invention was. Preparations in the field of nourishing cosmetics, decorative cosmetics and pharmacological galenics with reduced stickiness or greasiness.
• Base materials should be created for preparation forms such as cleansing emulsions, face and body care preparations, but also for medicinal-pharmaceutical and / or dermatological dosage forms. As examples may be mentioned preparations for acne and other skin manifestations.
• UVC range rays having a wavelength less than 290 nm
• UVB range rays in the range between 290 nm and 320 nm
• the narrower range around 308 nm is generally considered.
• Phenylbenzimidazoles is. Also for the range between about 320 nm and about 400 nm (UVA range), it is important to have filter substances available because even its rays can cause damage. It has been shown that UVA radiation leads to damage to the elastic and collagen fibers of the connective tissue, causing the skin to age prematurely, and that it is the cause of numerous phototoxic and photoallergic reactions. The harmful influence of UVB radiation can be amplified by UVA radiation.
• UV radiation also leads to photochemical reactions, with the photochemical reaction products interfering with skin metabolism.
• the cosmetic or dermatological formulations may additionally contain antioxidants and / or radical scavengers.
• antioxidants and / or radical scavengers are the most important inorganic pigments which are known to be used in cosmetics as UV absorbers or UV reflectors for protecting the skin from UV rays.
• the most important inorganic pigments which are known to be used in cosmetics as UV absorbers or UV reflectors for protecting the skin from UV rays are the oxides of titanium, zinc, iron, zirconium, silicon, manganese, aluminum, cerium and their mixtures.
• SPF unsun protection factor
• SPF unsun protection factor
• SPF boosters compounds which enhance the photoprotective effect of a sunscreen agent.
• Another object of the present invention was to provide compounds which increase the photoprotective effect of a sunscreen agent and thus act as SPF or SPF boosters.
• Deodorants Preparations based on O / W emulsions are also suitable as a basis for deodorants.
• Cosmetic deodorants are used to eliminate body odor that occurs when the odorless fresh sweat is decomposed by microorganisms.
• the usual cosmetic deodorants are based on different active principles.
• antiperspirants can be reduced by astringents - predominantly aluminum salts such as aluminum hydroxychloride (Aluchlorhydrat) - the formation of sweat.
• antimicrobial substances in cosmetic deodorants By using antimicrobial substances in cosmetic deodorants, the bacterial flora on the skin can be reduced. Ideally, only the odor causing microorganisms should be effectively reduced.
• the sweat flow itself is not affected by this, ideally only the microbial decomposition of the sweat is temporarily stopped.
• the combination of astringents with antimicrobial substances in the same composition is also common.
• Deodorants should fulfill the following conditions: 1) reliable deodorization; 2) no impairment of the natural biological processes of the skin;
• liquid deodorants for example aerosol sprays, roll-ons and the like
• solid preparations for example deodorant sticks (sticks), powders, powder sprays, intimate cleaners etc.
• a further object of the present invention was therefore to provide preparations which are suitable as the basis for cosmetic deodorants or antiperspirants and do not have the disadvantages of the prior art, such as excessive emulsifier quantities. Furthermore, it was an object of the invention to develop cosmetic bases for cosmetic deodorants, which are characterized by good skin compatibility.
• emulsions for moistening the skin or for stabilizing sensitive drugs such.
• vitamin C or provided by enzymes.
• a further object of the present invention is to provide hair cosmetic preparations, in particular hair cosmetic preparations for the care of the hair and the scalp, which serve, in particular, to strengthen the individual hair and / or give the hairstyle total hold and fullness.
• the human hair, especially the cuticle, but also the keratinous area between the cuticle and the cortex as the outer shell of the hair are exposed to special stress due to environmental influences, by combing and brushing, but also by hair treatment, especially hair coloring and hair deformation, eg permanent wave procedures.
• particularly aggressive stress for example bleaching with oxidants such as hydrogen peroxide, in which the pigments distributed in the cortex are oxidatively destroyed, the interior of the hair can also be affected.
• oxidative hair dyeing processes come into consideration.
• oxidatively dyed human hair similar to bleached hair, microscopic holes are detectable at sites where melanin granules were present.
• Oxidizing agents react not only with the color precursors, but also with the hair substance and may possibly cause damage to the hair.
• Even the hair washing with aggressive surfactants can stress the hair, at least reduce its appearance or the overall look of the hairstyle.
• certain water-soluble hair components eg urea, uric acid, xanthine, keratin, glycogen, citric acid, lactic acid
• water-soluble hair components eg urea, uric acid, xanthine, keratin, glycogen, citric acid, lactic acid
• some hair care cosmetics have been used for some time, which are intended to be rinsed off after exposure to the hair, some of which are to remain on the hair, the latter being able to be formulated so that they Not only to care for the individual hair, but also to improve the appearance of the hairstyle overall, for example, by giving the hair more fullness, fix the hairstyle over a longer period of time or improve his manageability.
• quaternary ammonium compounds for example, the combability of hair can be significantly improved. Such compounds are absorbed by the hair and are often detectable on the hair after several washes.
• hair styling preparations of the prior art typically include viscous components which are prone to give a feeling of stickiness which often has to be compensated for by skillful formulation.
• Numerous cosmetic preparations are in the form of creams, gels, pastes and, in general, as dosage forms which have a viscosity which is higher than water.
• the adjustment of a desired rheology and in particular a desired viscosity is achieved by the use of rheology modifiers such as thickeners.
• Conventional cosmetically acceptable thickening agents no longer ensure a sufficient effect if the electrolyte concentration in the preparations reaches or exceeds certain values.
• a further object of the present invention was thus to provide cosmetically acceptable substances which can act as thickeners in cosmetic preparations even when high electrolyte concentrations are present, in which conventional thickeners such as, for example, polyacrylic acids no longer exhibit the desired effect.
• cosmetic preparations comprising an oil-in-water emulsion, wherein the oil-in-water emulsion a) at least one amphiphilic polymer containing one or more hydrophobic units A and one or more hydrophilic units B in which the hydrophobic units A are formed from polyisobutenes modified with terminal, polar groups, b) at least one component suitable as an emulsifier having an HLB value in the range of 8 to 20, c) at least one oil and / or fat phase and d) water.
• the oil-in-water emulsion a) at least one amphiphilic polymer containing one or more hydrophobic units A and one or more hydrophilic units B in which the hydrophobic units A are formed from polyisobutenes modified with terminal, polar groups, b) at least one component suitable as an emulsifier having an HLB value in the range of 8 to 20, c) at least one oil and / or fat phase and d) water.
• amphiphilic is known to the person skilled in the art and means that a substance designated in this way has both lipophilic and hydrophilic properties.
• the hydrophobic units A are obtainable by functionalization of reactive polyisobutene having a number average molecular weight M n of 150 to 50,000.
• the hydrophobic units A are formed from a polyisobutene block whose polyisobutene macromolecules have at least 50 mol% terminally arranged double bonds. Accordingly, in a preferred embodiment of the invention, at least 50 mol%, preferably at least 60 mol%, of the functionalized polyisobutene molecules to be functionalized, based on the total number of polyisobutene molecules, contain terminal double bonds.
• amphiphilic polymers are usually technical mixtures of substances with a more or less broad molecular weight distribution.
• each hydrophobic unit A is formed from a polyisobutene block.
• polyisobutene is abbreviated to PIB in some places.
• Polyisobutenes meeting the above definition i. which are formed to at least 50 mol% of macromolecules with terminal double bonds are referred to as so-called reactive polyisobutenes.
• More preferred reactive polyisobutenes are those in which at least 60 mol%, particularly preferably at least 80 mol% of the polyisobutene macromolecules, based on the total number of polyisobutene macromolecules, have terminally arranged double bonds.
• Suitable reactive polyisobutenes can be obtained, for example, by cationic polymerization of isobutene. Pure isobutene is preferably used for the synthesis of suitable polyisobutenes. However, it is additionally possible to use cationically polymerizable comonomers. The amount of comonomer should, however, usually less than 20 wt .-%, %, preferably less than 10 wt .-% and in particular less than 5 wt .-% amount.
• the cationically polymerizable comonomers are in particular vinylaromatics, such as styrene and ⁇ -methylstyrene, C 1 -C 4 -alkylstyrenes, and also 2-, 3- and 4-methylstyrene and 4-tert-butylstyrene, C 3 - to C 6 -alkenes such as n-butene, isoolefins having 5 to 10 carbon atoms such as 2-methylbutene-1, 2-methylpentene-1, 2-methylhexene-1, 2-ethylpentene-1, 2-ethylhexene-1 and 2-propylheptene-1 into consideration ,
• Suitable isobutene-containing feedstocks for the present process are both isobutene itself and isobutene-containing C4-hydrocarbon streams, game as examples C 4 raffinates, C 4 fractions from isobutane dehydrogenation C 4 cuts from steam crackers or so-called FCC Crackers (FCC: Fluid Catalysed Cracking), provided they are largely exempt from 1, 3-butadiene contained therein.
• FCC Fluid Catalysed Cracking
• the concentration of isobutene in C 4 hydrocarbon streams is in the range of 40 to 60 weight percent.
• Suitable C 4 hydrocarbon streams should generally contain less than 500 ppm, preferably less than 200 ppm of 1,3-butadiene.
• the presence of butene-1, cis- and trans-butene-2 is largely uncritical for the polymerization and does not lead to selectivity losses.
• hydrocarbons other than isobutene assume the role of an inert solvent or are polymerized in as a comonomer.
• Suitable solvents are all organic compounds which are liquid in the selected temperature range of the preparation of the polyisobutenes and neither split off protons nor have free electron pairs. Particularly noteworthy are cyclic and aeyclic alkanes such as ethane, iso- and n-propane, n-butane and its isomers, cyclopentane and n-pentane and its isomers, cyclohexane and n-hexane and its isomers, n-heptane and its isomers and higher homologues, cyclic and acyclic alkenes such as ethene, iso- and n-propene, n-butene, cyclopentene and n-pentene, cyclohexene and n-hexene, n-heptene, aromatic hydrocarbons such as benzene, toluene or isomeric xylene.
• the hydrocarbons may also be halogenated.
• halogenated hydrocarbons include methyl chloride, methyl bromide, methylene chloride, methylene bromide, ethyl chloride, ethyl bromide, 1, 2-dichloroethane, 1, 1, 1-trichloroethane, chloroform or chlorobenzene. It is also possible to use mixtures of the solvents, provided that no undesired properties occur.
• the polymerization is usually carried out at - 80 0 C to 0 0 C, preferably -50 0 C to -5 ° C and particularly preferably at -30 0 C to -15 ° C.
• the catalyst used may be pure BF3, its complexes with electron donors or mixtures thereof.
• Electron donors (Lewis bases) are compounds that have a pair of free electrons, for example on an O, N, P or S atom, and can form complexes with Lewis acids. This complex formation is desirable in many cases because it reduces the activity of the Lewis acid and suppresses side reactions.
• Suitable electron donors are ethers such as di-isopropyl ether or tetrahydrofuran, amines such as triethylamine, amides such as di-methylacetamide, alcohols such as methanol, ethanol, i-propanol or t-butanol.
• ethers such as di-isopropyl ether or tetrahydrofuran
• amines such as triethylamine
• amides such as di-methylacetamide
• alcohols such as methanol, ethanol, i-propanol or t-butanol.
• the alcohols also act as a proton source and thus start the polymerization. Proton from ubiquitous traces of water can also activate a cationic polymerization mechanism.
• Reactive polyisobutenes which have ⁇ -olefin reactive groups at both ends of the chain or which are branched can be obtained particularly advantageously by living cationic polymerization.
• living cationic polymerization it is also possible to synthesize linear polyisobutenes which have an ⁇ -olefin group only at one chain end using this method.
• isobutene is polymerized with a suitable combination of an initiator molecule IX n with a Lewis acid S. Details of this method of polymerization are described, for example, in Kennedy et al. Ivan, "Carbocationic Macromolecular Engineering", Hanser Publishers 1992. Suitable initiator molecules IX n have one or more leaving groups X.
• the leaving group X is a Lewis base, which may also be further substituted.
• suitable leaving groups include the halogens fluorine, chlorine, bromine and iodine, straight-chain and branched alkoxy groups, such as C 2 H 5 O-, nC 3 H 7 O-, JC 3 H 7 O-, nC 4 H 9 O-, JC 4 H 9 O- , sec.-C 4 H 9 0- or tC 4 H 9 0-, as well as straight-chain and branched carboxy groups such as CH 3 CO-O-, C 2 H 5 CO-O-, nC 3 H 7 CO-O-, JC 3 H 7 CO-O-, nC 4 H 9 CO-O-, JC 4 H 9 CO-O-, sec-C 4 H 9 CO-O-, tC 4 H 9 CO-O- With or Linked to the leaving groups is the moiety I, which under reaction conditions can form sufficiently stable carbocations I + To initiate the polymerization, the leaving group is abstracte
• Suitable Lewis acids S are, for example, AlY 3 , TiY 4 , BY 3 , SnY 4 , ZnY 2 where Y is fluorine, chlorine, bromine or iodine.
• the polymerization reaction can be stopped by the destruction of the Lewis acid, for example by their reaction with Alko- hol. This forms polyisobutene which has terminal -C (CH 3 ) 2 -Z groups, which can then be converted into ⁇ - and ß-olefin end groups.
• Preferred initiator molecules are structures which can form tertiary carbocations. Particular preference is given to radicals which are derived from the lower oligomers of the isobutene H- [CH 2 -C (CH 3 ) 2 ] n -X, where n is preferably from 2 to 5. Linear reactive polyisobutenes formed with such initiator molecules have a reactive group only at one end.
• Linear polyisobutenes having reactive groups at both ends can be obtained by employing initiator molecules IXQ having two leaving groups X and Q, respectively, where X and Q may be the same or different.
• Proven in the art have compounds comprising -C (CH 3 ) 2-X groups.
• Branched polyisobutenes can be obtained by using initiator molecules IX n having 3 or more leaving groups, wherein the leaving groups may be the same or different.
• suitable initiator molecules include X- (CHS) 2 CC 6 HS- [C (CHS) 2 -Q] -C (CHS) 2 -P as 1,2,4 and / or 1,3,5-isomer, wherein the Leaving groups are preferably the same but may be different.
• Further examples of mono-, di-, tri- or polyfunctional initiator molecules are described in the cited work by Kennedy et al. Ivan and the literature cited there.
• the Glissopal BASF ® grades are, for example Aktiengesellschaft, for example, Glissopal ® 550, 1000, 1300 or 2300, as well as the Oppanol ® brands from BASF AG, as Oppanol ® B10 or B12.
• those polymers a) are particularly suitable which have a polyisobutene block having a number average molecular weight M n in the range of 150 to 50,000 g / mol, preferably in the range of 200 to 20,000 g / mol and more preferably in the range of 450 to 5000 g / mol.
• the polydispersity index (PDI) ie the ratio of weight-average and number-average molecular weight of the preferably usable polyisobutenes, is in the range from 1.05 to 10, preferably in the range from 1.05 to 5, more preferably in the range of 1.05 to 2.0.
• Suitable as amphiphilic block copolymers a) for use in the preparations according to the invention are block copolymers consisting of at least one hydrophobic unit A, formed from reactive polyisobutenes having at least one polar functional group as anchor group and at least one hydrophilic unit B, formed from a polyalkylene oxide or a polyethyleneimine. To introduce the hydrophilic unit B, the reactive polyisobutenes are functionalized by introducing polar groups.
• the functionalized polyisobutenes are reacted either with alkylene oxides such as ethylene oxide or propylene oxide or in a polymer-analogous reaction with polyalkylene oxides such as polyethylene oxide, polypropylene oxide or ethylene oxide-propylene oxide copolymers or polyethyleneimines.
• alkylene oxides such as ethylene oxide or propylene oxide
• polyalkylene oxides such as polyethylene oxide, polypropylene oxide or ethylene oxide-propylene oxide copolymers or polyethyleneimines.
• amphiphilic block copolymers a) are prepared by reaction of one or more functionalized polyisobutenes with alkylene oxides, the hydrophilic block of the described block copolymer is formed only during the reaction.
• preformed hydrophilic blocks B are used in the abovementioned polymer-analogous reactions of one or more functionalized polyisobutenes with polyalkylene oxides or polyethyleneimines.
• amphiphilic block copolymers a) are preferably prepared in a polymer-analogous reaction of the hydrophobic unit A formed from reactive polyisobutene having at least one functional group, with at least one hydrophilic unit B formed from a polyalkylene oxide.
• the invention is in principle not restricted with regard to the one or more hydrophilic units B which can be used to form the amphiphilic polymers a).
• units B which are good in water and sparingly soluble in oil.
• the reactive polyisobutenes are functionalized by introducing polar groups.
• the degree of functionalization of the modified polyisobutene derivatives having terminal, polar groups is at least 50%, preferably at least 60% and very particularly preferably at least 80%. In the case of the polymers having polar groups only at one end of the chain, this information refers only to this one end of the chain.
• the indication of the degree of functionalization refers to the total number of all chain ends.
• the nonfunctionalized chain ends are both those which have no reactive group at all and the same those which, although having a reactive group, were not reacted during the functionalization reaction.
• polar group is known to the person skilled in the art.
• the polar groups can be both protic and aprotic polar groups.
• the modified polyisobutenes thus have a hydrophobic moiety of a polyisobutene moiety and a moiety of at least some hydrophilic character from terminal polar moieties. They are preferably strongly hydrophilic groups.
• hydrophilic and “hydrophobic” are known in the art. Suitable reactions for the introduction of polar groups (functionalization) are known in principle to the person skilled in the art.
• the functionalization of the polyisobutenes used according to the invention can be carried out in one or more stages.
• the functionalization of the polyisobutene used according to the invention takes place in one or more stages and is selected from: i) reaction of the reactive polyisobutene with aromatic hydroxy compounds in the presence of an alkylation catalyst to give polyisobutenes-alkylated aromatic hydroxy compounds, ii) reaction of reactive polyisobutene with a peroxy compound to give an epoxidized polyisobutene, iii) reaction of the reactive polyisobutene with an alkene having a double bond substituted with electron-withdrawing groups (e-nophil), in an ene reaction, iv) reaction of the reactive Polyisobutene with carbon monoxide and hydrogen in the presence of a hydroformylation catalyst to obtain a hydroformylated polyisobutene, v) reaction of the reactive polyisobutene with a phosphorus halide or a phosphorus oxychloride to obtain one functionalized with phosphonic groups reaction of the
• Embodiments iii) and vi) are particularly preferred, and embodiment iii) is particularly preferred.
• the reactive polyisobutene can be reacted with an aromatic hydroxy compound in the presence of an alkylation catalyst.
• alkylation catalyst Suitable catalysts and reaction conditions of this so-called Friedel-Crafts alkylation are described, for example, in J. March, Advanced Organic Chemistry, 4th edition, published by John Wiley & Sons, pages 534-539, to which reference is hereby made.
• the aromatic hydroxy compound used for the alkylation is preferably selected from phenolic compounds having 1, 2 or 3 OH groups which may optionally have at least one further substituent.
• Preferred further substituents are C 1 -C 8 -alkyl groups and in particular methyl and ethyl. Particular preference is given to compounds of the general formula
• X 1 and X 2 are independently hydrogen, OH or CH 3.
• Particularly preferred are phenol, the cresol isomers, catechol, resorcinol, pyrogallol, fluoroglucinol and the xylenol isomers.
• phenol, o-cresol and p-cresol are used. If desired, it is also possible to use mixtures of the abovementioned compounds for the alkylation.
• the catalyst is preferably selected from Lewis acidic alkylation catalysts, which in the context of the present application is understood as meaning both individual acceptoratoms and acceptor-ligand complexes, molecules, etc., provided that they are all (outwardly) Lewis acidic ( Electron acceptor) properties. These include, for example, AICI 3 , AIBr 3 , BF 3 , BF 3 2 C 6 H 5 OH, BF 3 [O (C 2 H 5 ) 2 ] 2 , TiCl 4 , SnCl 4 , AIC 2 H 5 Cb, FeCl 3 , SbCI 5 and SbF 5 . These alkylation catalysts can be used together with a cocatalyst, for example an ether.
• Suitable ethers are di (C 1 -C 8) -alkyl ethers, such as dimethyl ether, diethyl ether, di-n- propyl ethers, and tetrahydrofuran, di (C 5 -C 8 ) cycloalkyl ethers, such as dicyclohexyl ethers and ethers having at least one aromatic hydrocarbon radical, such as anisole. If a catalyst-cocatalyst complex is used for Friedel-Crafts alkylation, the molar ratio of catalyst to cocatalyst is preferably in the range from 1:10 to 10: 1. The reaction can also be carried out with protic acids
• Sulfuric acid, phosphoric acid, trifluoromethanesulfonic acid are catalyzed.
• Organic protic acids may also be present in polymer bound form, for example as ion exchange resin.
• the alkylation can be carried out solvent-free or in a solvent.
• Suitable solvents are, for example, n-alkanes and mixtures thereof and alkyl aromatics, such as toluene, ethylbenzene and xylene, and halogenated derivatives thereof.
• the alkylation is preferably carried out at temperatures between -1O 0 C and + 100 0 C.
• the reaction is usually carried out at atmospheric pressure, but can also be carried out at higher or lower pressures.
• the proportion of alkylated products obtained and their degree of alkylation can be adjusted. So z. B substantially monoalkylated polyisobutenylphenols generally obtained with an excess of phenol or in the presence of a Lewis acidic alkylation catalyst, if in addition an ether is used as cocatalyst.
• a polyisobutenylphenol obtained in step i) can be subjected to a reaction in the Mannich reaction with at least one aldehyde, for example formaldehyde, and at least one amine having at least one primary or secondary amine function, one with Polyisobutene alkylated and additionally at least partially aminoalkylated compound. It is also possible to use reaction and / or condensation products of aldehyde and / or amine. The preparation of such compounds are described in WO 01/25293 and WO 01/25294, to which reference is hereby fully made.
• a polyisobutenylphenol obtained in step i) can be subjected to a hydrogenation step.
• the preparation of such compounds is described in unpublished German Patent Application No. 102005021093.7, to which reference is hereby made in its entirety.
• a polyisobutenylphenol obtained in step i) which optionally has one Mannich reaction or hydrogenation was reacted with alkylene oxides.
• one or more hydrophilic unit (s) B of the polymer a) are formed by graft polymerization to the terminally functionalized polyisobutene A.
• the number of hydrophilic units B depends on the number of OH groups of the polyisobutenephenol obtained in step i). If, for example, phenol is used for functionalization, a polymer a) with AB structure is obtained.
• alkylene oxides ethylene oxide or ethylene oxide / propylene oxide mixtures may preferably be used, preferably with a proportion of 0 to 50% by weight of propylene oxide, particularly preferably with a fraction of 0 to 20% by weight of propylene oxide, very particularly preferably of ethylene oxide.
• the alkylene oxide block that forms may be a random copolymer, a gradient copolymer, an alternating or a block copolymer of ethylene oxide and propylene oxide.
• the resulting polyisobutenylphenols which have optionally been subjected to a Mannich reaction or hydrogenation, are reacted with, for example, phosphorus oxychloride to form a phosphorus half ester.
• This is reacted in a subsequent step with polyethyleneimines, alkylene oxides or polyalkylene oxides to the described block copolymers a). If it is a reaction with alkylene oxides, one or more hydrophilic unit (s) B of the polymer a) are produced by graft polymerization onto the polyisobutene A terminally functionalized with phosphorus half ester groups.
• the number of hydrophilic units B depends on the number of OH groups of the resulting phosphated polyisobutenephenol. If, for example, phenol is used for the functionalization of polyisobutene and reacted with phosphorus oxychloride, a hydrophobic unit A with two OH groups is obtained, which forms the amphiphilic polymer a) with A-B2 structure by means of alkoxylation. If PIB-phenol derivatives, which were subsequently reacted further in a Mannich reaction and still contain free NH groups after the reaction, are subjected to alkoxylation, these OH groups of the phosphorus half-ester group can also react with alkylene oxides and thus form a further hydrophilic unit B.
• polyisobutenephenols reacted with, for example, phosphorus oxychloride and optionally subjected to a Mannich reaction or hydrogenation are reacted with polyethyleneimines or polyalkylene oxides, this is the case polymer-analogous reactions with a preformed hydrophilic unit B.
• the polyalkylene oxides used must contain at least one reactive group selected from the group consisting of OH, SH, NH 2 or NH.
• amphiphilic polymers a) it is preferred to use polyisobutene A which is functionalized with phosphorus halide and polyalkylene oxides having at least one OH group.
• the resulting Polyisobutenylphe- nole which were optionally subjected to a Mannich reaction or hydrogenation, with z.
• sulfuric acid or oleum to a sulfuric acid half ester As sulfuric acid or oleum to a sulfuric acid half ester. This is reacted in a subsequent step with polyethyleneimines, alkylene oxides or polyalkylene oxides to the described block copolymers a).
• hydrophilic units B depends on the number of OH groups of the resulting sulfated polyisobutenephenol. If, for example, phenol is used for the functionalization of PIB and reacted with oleum, a hydrophobic unit A with an OH group which forms the polymer a) with A-B structure by means of alkoxylation is obtained.
• PIB-phenol derivatives which were subsequently reacted further in a Mannich reaction and still contain free NH groups after the reaction, are subjected to alkoxylation, then, in addition to the OH groups of the sulfuric acid half ester group, these NH groups can also undergo a graft polymerization with alkylene oxides and thus form another hydrophilic unit B.
• polysulfated polyisobutenephenols which have previously been subjected to a Mannich reaction or hydrogenation, are reacted with polyethyleneimines or polyalkylene oxides, these are polymer-analogous reactions with a preformed hydrophilic unit B.
• the polyalkylene oxides used must have at least one group selected from OH, SH, NH 2 or NH.
• amphiphilic polymers a) from polyisobutene A functionalized with sulfuric acid half ester it is preferred to use polyalkylene oxides having at least one OH group. Which polyalkylene oxides are preferably used is described in the section "Hydrophilic units B".
• the reactive polyisobutene can be reacted with at least one peroxygen compound to give an epoxidized polyisobutene.
• peroxygen compound Suitable methods for epoxidation are described in J. March, Advanced Organic Chemistry, 4th Edition, John Wiley & Sons, pp. 826-829, incorporated herein by reference.
• the peroxy compound used is preferably at least one peracid, such as m-chloroperbenzoic acid, performic acid, peracetic acid, trifluoroperacetic acid, perfluorocarboxylic acid, benzoic acid and 3,5-dinitroperbenzoic acid used.
• the preparation of the peracids can be carried out in situ from the corresponding acids and H2O2 optionally in the presence of mineral acids.
• suitable epoxidizing reagents are, for example, alkaline hydrogen peroxide, molecular oxygen and alkyl peroxides, such as tert-butyl hydroperoxide.
• suitable solvents for the epoxidation are, for example, conventional, non-polar solvents. Particularly suitable solvents are hydrocarbons such as toluene, xylene, hexane or heptane.
• the epoxidized polyisobutenes obtained in step ii) can be reacted with ammonia to give polyisobutene amino alcohols (EP-A 0 476 785).
• the epoxidized polyisobutenes obtained are reacted with alkylene oxides in a further step.
• the reaction is a graft polymerization in which the hydrophilic units B are formed during the reaction.
• the number of hydrophilic units B depends on the number of epoxide groups per molecule of the polyisobutene epoxide. Which alkylene oxides are preferably used is described in the section "Hydrophilic units B".
• the reactive polyisobutene can furthermore be reacted with at least one alkene which has an electron-poor double bond in an ene reaction (see, for example, DE-A 195 19 042, DE-A 4 319 671, DE-A 4 319,672 or H. Mach and P. Rath in "Lubrication Science Il (1999), pp. 175-185, to which reference is made for full content).
• an alkene designated as En having an allyl-standing hydrogen atom is reacted with an electron-deficient alkene, so-called enophile, in a pericyclic reaction comprising a carbon-carbon bond, a double bond shift, and a hydrogen transfer.
• the reactive polyisobutene reacts as En.
• Suitable enophiles are compounds which are also used as dienophiles in the Diels-Alder reaction. Suitable enophiles are fumaric acid, fumaric acid, maleic acid dichloride, maleic anhydride and maleic acid, preferably maleic anhydride and maleic acid.
• the succinic acid derivatives of the general formula Ia, Ib or Ic in which X 3 is a polyisobutene group having a number average molecular weight M n of from 150 to 50,000, preferably from 200 to 20,000, particularly preferably from 450 to 5 000, are formed.
• maleic anhydride formula Ia
• PIBSA polyisobutenylsuccinic anhydride
• succinic anhydride groups succinic anhydride groups
• the ene reaction may optionally be carried out in the presence of a Lewis acid catalyst.
• a Lewis acid catalyst Suitable examples are aluminum chloride and ethylaluminum chloride.
• the polyisobutene derivatized with succinic anhydride groups is subjected to a subsequent reaction which is selected from: ⁇ ) graft polymerization with at least one abovementioned alkylene oxide to give a polyisobutene functionalized with two succinic ester groups (per succinic anhydride group), hydrolysis to give a polyisobutene functionalized with succinic groups, in which the succinic groups are reacted with alkylene oxides by graft polymerization as in a), reaction with maleic anhydride to form a product with two succinic anhydride groups at the chain end (so-called PIBBSA) a) reacting with alkylene oxides by means of graft polymerization, ⁇ ) reacting with at least one amine to obtain a polyisobutene which is at least partially functionalized
• the polyisobutenes derivatized with one succinic anhydride group per chain end can be reacted in an exhaustive ene reaction with excess maleic anhydride to form partially functionalized polyisobutenes with in part two succinic anhydride groups per chain end.
• the polyisobutenes functionalized in this way can be reacted with alkylene oxides by means of graft polymerization, in each case two succinic ester groups being formed per anhydride group.
• the succinic anhydride groups can be reacted for further functionalization, for example with polar reaction partners such as alcohols, thioalcohols or amines.
• Suitable polar reactants are preferably alcohols ROH, thio alcohols RSH or primary amines RNH 2 or secondary amines RR 1 NH, where R is a linear or branched saturated hydrocarbon radical which has at least two substituents selected from the group OH, SH , NH 2 or NH 3 + and optionally one or more CH (O) groups and optionally not adjacent -O- and / or -NH- and / or tertiary -N groups, and R 'has the same meaning independently of R.
• the succinic anhydride groups can be reacted with polyethyleneimines in a polymer-analogous manner, one or more polyisobutene chains being bonded per polyethyleneimine chain depending on the reaction procedure.
• the binding takes place via succinimide groups and / or succinamide groups.
• the polyethyleneimines are preformed hydrophilic units B.
• the succinic anhydride groups are reacted with polyalkylene oxides in a polymer-analogous manner.
• the polyalkylene oxides used must have at least one group selected from OH, SH, NH 2 or NH.
• the polyethylene oxides are preformed hydrophilic units B.
• alkylene oxides or polyalkylene oxides are preferably used is described in the section "Hydrophilic units B.” Further synthesis variants for the derivatization of succinic anhydride groups are mentioned in DE-A-101 25 158. It is also known to a person skilled in the art to use a succinic anhydride group under suitable conditions into a formic acid imide group.
• reactive polyisobutene can be free-radically copolymerized with maleic anhydride (cf., WO 95/07944, WO 01/55059, WO
• the reactive polyisobutene can be subjected to a reaction with carbon monoxide and hydrogen in the presence of a hydroformylation catalyst to give a hydroformylated polyisobutene.
• a hydroformylation catalyst are known and preferably comprise a compound or a complex of an element of Group VIII of the Periodic Table, such as Co, Rh, Ir, Ru, Pd or Pt.
• hydroformylation catalysts modified with N- or P-containing ligands are preferably used.
• Suitable salts of these metals are, for example, the hydrides, halides, nitrates, sulfates, oxides, sulfides or the salts with alkyl or arylcarboxylic acids or alkyl- or arylsulfonic acids.
• Suitable complex compounds have ligands selected, for example, from halogenated iden, amines, carboxylates, acetylacetonate, aryl or alkylsulfonates, hydride, CO, olefins, dienes, cycloolefins, nitriles, N-containing heterocycles, aromatics and heteroaromatics, ethers, PF3, phospholes, phosphabenzenes and mono-, di- and multidentate phosphine, phosphinite, phosphonite, phosphoramidite and phosphite ligands.
• ligands selected, for example, from halogenated iden, amines, carboxylates, acetylacetonate, aryl or alkylsulfonates, hydride, CO, olefins, dienes, cycloolefins, nitriles, N-containing heterocycles, aromatics
• catalytically active species of the general formula H ⁇ M y (CO) zL q are formed under hydroformylation conditions from the particular catalysts or catalyst precursors used, where M is a metal of subgroup VIII, L is a ligand and q, x, y, z is integers, depending on the valence and type of metal as well as the binding of the ligand L.
• the hydroformylation catalysts are prepared in situ in the reactor used for the hydroformylation reaction.
• Another preferred form is the use of a carbonyl generator in which prefabricated carbonyl z. B. is adsorbed on activated carbon and only the desorbed carbonyl hydroformylation is supplied, but not the salt solutions from which the carbonyl is produced.
• rhodium compounds or complexes are z.
• Rhodium (III) and rhodium (III) salts such as rhodium (III) chloride, rhodium (III) nitrate, rhodium (III) sulfate, potassium rhodium sulfate, rhodium (II). or rhodium (III) carboxylate, rhodium (II) and rhodium (III) acetate, rhodium (III) oxide, salts of rhodium (III) acid, trisammonium hexachlororhodate (III), etc.
• rhodium complexes are suitable such as rhodiumbiscarbonylacetylacetonate, acetylacetonatobisethylenrhodium (I), etc.
• ruthenium salts or compounds are, for example, ruthenium (III) chloride, ruthenium (IV), ruthenium (VI) or ruthenium (VIII) oxide, alkali metal salts of ruthenium oxygen acids such as K 2 RUO 4 or KRuO 4 or complex compounds, such as. B. RuHCl (CO) (PPh3) 3. It is also possible to use the metal carbonyls of ruthenium, such as trisruthenium dodecacarbonyl or hexaruthenium octadecacarbonyl, or mixed forms in which CO has been partially replaced by ligands of the formula PR3, such as Ru (CO) 3 (PPh3) 2.
• Suitable cobalt compounds are, for example, cobalt (II) chloride, cobalt (II) sulfate, cobalt (II) carbonate, cobalt (II) nitrate, their amine or hydrate complexes, cobalt carboxylates, such as cobalt formate, cobalt acetate, cobalt ethylhexanoate, cobalt naphthanoate, and cobalt -Caprolactamat complex.
• the carbonyl complexes of the cobalt such as dicobalt octacarbonyl, tetracobalt dodecacarbonyl and hexacobalt hexadecarbonyl, can be used.
• the above and other suitable compounds are known in principle and sufficiently described in the literature.
• Suitable activating agents which can be used for hydroformylation are, for. B. Bronsted acids, Lewis acids such as BF3, AICI3, ZnCb, and Lewis bases.
• the composition of the synthesis gas used from carbon monoxide and hydrogen can vary within wide ranges. The molar ratio of carbon monoxide and hydrogen is usually about 5:95 to 95: 5, preferably about 40:60 to 60:40.
• the temperature in the hydroformylation is generally in a range of about 20 to 200 0 C, preferably about 50 to 19O 0 C.
• the reaction is carried out usually at the partial pressure of the reaction gas at the selected reaction temperature. In general, the pressure is in a range of about 1 to 700 bar, preferably 1 to 300 bar.
• the functionalized polyisobutenes obtained by hydroformylation are advantageously suitable as intermediates for further processing by functionalizing at least part of the aldehyde functions contained in them. ⁇ ) Oxocarboxylic acids
• the hydroformylated polyisobutenes obtained in step iv) can be reacted with an oxidizing agent to give a polyisobutene which is at least partially functionalized with carboxy groups.
• oxidizing agents and processes can generally be used, e.g. In J. March, Advanced Organic Chemistry, John Wiley & Sons, 4th edition, p. 701ff. (1992). These include z.
• the oxidation with air / oxygen can be carried out both catalytically in the presence of metal salts and in the absence of catalysts.
• the metals used are preferably those which are capable of a valency change, such as Cu, Fe, Co, Mn, etc.
• the reaction usually succeeds even in the absence of a catalyst. In the case of air oxidation, the conversion can be controlled easily over the duration of the reaction.
• amphiphilic block copolymers a) from hydrophobic units A and hydrophilic units B the resulting polyisobutenes are reacted with carboxy function in a further step.
• Reactions can be with alkylene oxides, esterifications with polyalkylene oxides or amide formations with polyethylenimines.
• the reactions are carried out as described under iii) points ß) and ⁇ ) to ⁇ ).
• the hydroformylated polyisobutenes obtained in step iv) can be subjected to a reaction with hydrogen in the presence of a hydrogenation catalyst to give a polyisobutene which is at least partially functionalized with alcohol groups.
• Suitable hydrogenation catalysts are generally transition metals such as Cr, Mo, W, Fe, Rh, Co, Ni, Pd, Pt, Ru, etc., or mixtures thereof, for increasing the activity and stability on supports such as activated carbon, alumina, kieselguhr , etc., can be applied.
• Fe, Co, and preferably Ni can also be used in the form of Raney catalysts as metal sponge with a very large surface area.
• the hydrogenation of the oxo-aldehydes from stage iv) takes place, depending on the activity of the catalyst, preferably at elevated temperatures and elevated pressure.
• the reaction temperature is about 80 to 15O 0 C and the pressure at about 50 to 350 bar.
• the hydroformylated polyisobutenes obtained in step iv) are subjected to further functionalization of a reaction with hydrogen and ammonia or a primary or secondary amine in the presence of an amination catalyst to give a polyisobutene functionalized at least in part with amine groups.
• Suitable amination catalysts are the hydrogenation catalysts described above in step ⁇ ), preferably copper, cobalt or nickel, which can be used in the form of the Raney metals or on a support. Also suitable are platinum catalysts. Amination with ammonia yields aminated polyisobutenes with primary amino functions.
• Suitable for amination primary and secondary amines are compounds of the general formulas R-NH2 and RR'NH, wherein R and R 'independently of one another, for example, Ci-Cio-alkyl, C 6 -C 2 O-ArVl, C 7 -C 2 O. -ArVIa I ky I, C 7 -C 20 - alkylaryl or cycloalkyl.
• the polyisobutene functionalized with amino groups is reacted with alkylene oxides in a further step by means of graft polymerization.
• alkylene oxides which alkylene oxides are preferably used is described in the section "Hydrophilic units B".
• the derivatized polyisobutene is subjected to a subsequent reaction which is selected from: ⁇ ) graft polymerization with at least one alkylene oxide to give a polyisobutene functionalized with phosphonic ester groups, ⁇ ) hydrolysis to give a polyisobutene functionalized with phosphonic acid groups; Phosphonic acid groups as under a) are reacted with alkylene oxides by graft polymerization, ⁇ ) reaction with at least one amine to give a polyisobutene functionalized at least partially with phosphonamide groups, which is reacted in a further reaction with alkylene oxides by graft polymerization, ⁇ ) reaction with at least an alcohol to give a polyisobutene functionalized with phosphonic ester groups, which is reacted in a further reaction with alkylene oxides by means of graft polymerization, ⁇ ) reaction with at least one polyethylenimine to obtain a least s) reaction with
• mino group has, to obtain a polyisobutene functionalized at least partially with phosphonamide groups, ⁇ ) reaction with at least one polyalkylene oxide having at least one thio group to give a polyisobutene functionalized at least in part with phosphonothio groups, if after the implementation of the phosphonic acid halide group still free acid or halide groups are present, they can also be converted into salts.
• Suitable cations in salts are, in particular, alkali metal cations, ammonium ions and alkylammonium ions.
• Suitable polar reactants are preferably alcohols ROH or primary amines RNH 2 or secondary amines RR 1 NH, where R is a linear or branched saturated hydrocarbon radical containing at least two substituents selected from the group OH, SH, NH 2 or NH 3 + and optionally one or more CH (O) groups and optionally not adjacent -O- and / or -NH- and / or tertiary -N groups, and R 1 is independently of R den- same meaning.
• both phosphonic acid groups can come to implementation or even one, while the other phosphonic acid group is present as a free acid group or as a salt.
• the free substituents (substituents not reacted with the phosphonic acid halide group) are modified by alkoxylation to give the described block copolymers a).
• the phosphonic acid halide groups can be reacted with polyethyleneimines in a polymer-analogous manner, one or more polyisobutene chains being linked per polyethyleneimine chain, depending on the reaction procedure. Binding occurs via phosphonamide groups.
• the polyethylenimines represent preformed hydrophilic units B.
• the succinic anhydride groups are reacted with polyalkylene oxides in a polymer-analogous manner.
• the polyalkylene oxides used must have at least one group selected from OH, SH, NH 2 or NH.
• the polyethylene oxides are preformed hydrophilic units B.
• the phosphonic acid halide groups are reacted with polyalkylene oxides in a polymer-analogous manner.
• the polyalkylene oxides used must have at least one group selected from OH, SH, NH 2 or NH.
• the polyethylene oxides are preformed hydrophilic units B.
• Suitable hydroboration reagents are, for example, diborane, which is generally generated in situ by reacting sodium borohydride with BF 3 etherate, diisamylborane (bis [3-methylbut-2-yl] borane), 1,1,2-trimethylpropylborane, 9-borbicyclo [3.3.1] nonane, diisocampheylborane, by
• Hydroboration of the corresponding alkenes with diborane are available, chloroborane dimethyl sulfide, alkyldichloroboranes or H3B-N (C2Hs) 2.
• a solvent for hydroboration are, for example, acyclic ethers, such as diethyl ether, methyl tert-butyl ether, dimethoxyethane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, cyclic ethers, such as tetrahydrofuran or dioxane, and hydrocarbons, such as hexane or toluene, or mixtures thereof.
• the reaction temperature is generally determined by the reactivity of the hydroboration and is typically between the melting and boiling point of the reaction mixture, preferably in the range of from 0 ° C to 6O 0 C.
• the hydroborating agent is used in excess with respect to the alkene.
• the boron atom preferably adds to the less substituted and thus less sterically hindered carbon atom.
• the alkyl boranes formed are not isolated, but converted by subsequent reaction directly into the desired products.
• a very important reaction of the alkyl boranes is the reaction with alkaline hydrogen peroxide to give an alcohol which preferably corresponds formally to the anti-Markovnikov hydroxylation of the alkene.
• the polyisobutene functionalized with hydroxyl groups is reacted with alkylene oxides by means of graft polymerization.
• alkylene oxides which alkylene oxides are preferably used is described in the section "Hydrophilic units B".
• the reactive polyisobutene may further be reacted with an SCv source to form a polyisobutene having terminal sulfonic acid groups.
• the sulfonic acid functionalized polyisobutenes can be prepared by reacting the reactive polyisobutenes with a SO 3 source.
• Suitable SCv sources are a mixture of sulfur trioxide and air, sulfur trioxide hydrates, sulfur trioxide amine complexes, sulfur trioxide ether complexes, sulfur trioxide phosphate complexes, oleum, acetyl sulfate, a mixture of sulfur trioxide and acetic anhydride, sulfamic acid, alkyl sulfates or chlorosulfonic acids.
• the reaction can be either neat or in any inert anhydrous solvent. Suitable reaction temperatures are in the range of -30 0 C to +200 0 C and are dependent on the sulfonating reagent used.
• sulfonation with acetyl sulfate is carried out at low temperatures and elevated temperatures should be avoided, as otherwise decomposition of the product may occur.
• the sulfonating reagent is generally used in a molar ratio to polyisobutene of 1: 1 to 2: 1.
• Acetyl sulfate or a mixture of sulfuric acid and acetic anhydride, wherein acetyl sulfate is formed in situ is preferably used, wherein directly formed with sulfonic acid functionalized polyisobutene is formed.
• the polyisobutenes functionalized with sulfonic acid groups can also be reacted with alkylene oxides, polyalkylene oxides or polyethyleneimines to form the block copolymers a).
• alkylene oxides or polyalkylene oxides are preferably used is described in the section "Hydrophilic units B".
• the reactive polyisobutene can be reacted with nitrogen oxides, polyisobutenes having terminal amino groups being obtained after subsequent hydrogenation.
• Suitable nitrogen oxides are, for. As NO, NO2, N2O3, N2O4, mixtures of these nitrogen oxides with each other and mixtures of these nitrogen oxides with oxygen. Particularly preferred are mixtures of NO or NO 2 with oxygen.
• the nitrogen oxides may additionally inert gases, for. As nitrogen, included.
• the reaction of the polyisobutenes with the nitrogen oxides is generally carried out at a temperature of -30 to +150 0 C in an inert organic solvent.
• the products obtained are then hydrogenated, preferably by catalytic hydrogenation with hydrogen in the presence of hydrogenation catalysts.
• the hydrogenation is generally carried out in a temperature range of 20 to 250 0 C, onssystem depending on the used reductive.
• the hydrogenation pressure in the catalytic hydrogenation is generally 1 bar to 300 bar.
• a process for the preparation of amino-terminated polymers is z. As disclosed in WO 97/03946.
• the polyisobutene functionalized with amino groups is reacted with alkylene oxides by means of graft polymerization in a further step.
• alkylene oxides which alkylene oxides are preferably used is described in the section "Hydrophilic units B".
• the reactive polyisobutene can be subjected to a reaction with hydrogen sulfide or thiols, such as alkyl- or arylthiols, hydroxymercaptans, aminomethane captans, thiocarboxylic acids or silanethiols, to give a thio-functionalized polyisobutene.
• hydrogen sulfide or thiols such as alkyl- or arylthiols, hydroxymercaptans, aminomethane captans, thiocarboxylic acids or silanethiols.
• Suitable hydro-alkylthio additions are described in J. March, Advanced Organic Chemistry, 4th Edition, John Wiley & Sons, pp. 766-767, incorporated herein by reference.
• the reaction can generally be carried out both in the absence and in the presence of initiators and in the presence of electromagnetic radiation.
• Suitable initiators of the hydro-alkylthio addition are, for example, protic and Lewis acids, such as concentrated sulfuric acid or AICI3. Suitable initiators are furthermore those which are capable of forming free radicals. Hydro-alkylthio addition in the presence of these initiators usually gives the anti-Markovnikov addition products.
• the reaction can furthermore be carried out in the presence of electromagnetic radiation having a wavelength of 10 to 400 nm, preferably 200 to 300 nm.
• the polyisobutene functionalized with thiol groups is reacted with alkylene oxides by means of graft polymerization in a further step.
• alkylene oxides which alkylene oxides are preferably used is described in the section "Hydrophilic units B".
• the amphiphilic polymers a) consist of one or more hydrophobic units A and one or more hydrophilic units B.
• the hydrophobic units A consist of reactive polyisobutenes modified with terminal, polar groups. These functionalizations of the reactive polyisobutenes are described above.
• the functionalized polyisobutenes (units A) are reacted either with alkylene oxides by graft polymerization or in polymer-analogous reactions with polyalkylene oxides or polyethyleneimines, depending on the nature of their polar group (s). The mode of introduction of the hydrophilic units has been described above.
• Amphiphilic block copolymers a) can be obtained by reacting the functionalized polyisobutene with alkylene oxide or by polymer-analogous reaction with polyalkylene oxide. Which way to choose depends on the type of functionalization of the reactive polyisobutene.
• Preferred alkylene oxides for reaction with functionalized polyisobutene are ethylene oxide or ethylene oxide / propylene oxide mixtures, preferably with a proportion of 0 to 50% by weight of propylene oxide, particularly preferably with a fraction of 0 to 20% by weight of propylene oxide, very particularly preferably ethylene oxide.
• the forming alkylene oxide block may be a random copolymer, a gradient copolymer, an alternating or a block copolymer of ethylene oxide block. oxide and propylene oxide act.
• Al kylenoxide or mixtures can be used: 1, 2-butene oxide 2,3-butene oxide, 2-methyl-1, 2-propene oxide (isobutene), 1-pentenoxide, 2,3-pentenoxide, 2 - Methyl-1, 2-butene oxide, 3-methyl-1, 2-butene oxide, 2,3-hexene oxide, 3,4-hexene oxide, 2-methyl-1, 2-pentenoxide, 2-ethyl-1, 2-butene oxide , 3-methyl-1, 2-pentenoxide, decene oxide, 4-methyl-1, 2-pentenoxide, styrene oxide, or may be formed from a mixture of oxides of technically available raffinate streams.
• both polyalkylene oxides and polyethyleneimines can be used. Preference is given to polyalkylene oxides based on ethylene oxide, propylene oxide, butylene oxide or else further alkylene oxides. Further alkylene oxides which can be used are the following pure alkylene oxides or else mixtures: 1-butene oxide, 2,3-butene oxide, 2-methyl-1,2-propene oxide (isobutene oxide), 1-pentenoxide, 2,3-pentenoxide, 2-methyl-1, 2-butene oxide, 3-methyl-1,2-butene oxide, 2,3-hexene oxide, 3,4-hexene oxide, 2-methyl-1,2-pentene oxide, 2-ethyl-1,2-butene oxide, 3-methylene 1, 2-pentenoxide, decene oxide, 4-methyl-1, 2-pentenoxide, styrene oxide or mixture of oxides formed from technically available raffinate streams.
• polyglycerol and polyTHF can also be used.
• polyalkylene oxides contain the following structural units:
• the structural units may be homopolymers as well as random copolymers, gradient copolymers, alternating or block copolymers.
• alkyl radicals for R 6 and R 11 and R 12 are branched or unbranched Ci-C 24 -
• Alkyl chains preferably methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1, 1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1, 1-dimethylpropyl, 1, 2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-
• Preferred representatives of the abovementioned alkyl radicals are branched or unbranched C 1 -C 12 -, particularly preferably C 1 -C 6 -alkyl chains.
• polyalkylene oxides which are composed of repeating alkylene oxide units, such as of ethylene oxide or ethylene oxide / propylene oxide units, preferably with a proportion of 0 to 50% propylene oxide, particularly preferably with a proportion of 0 to 20% propylene oxide units.
• This may be a random copolymer, a gradient copolymer, an alternating copolymer or a block copolymer of ethylene oxide and propylene oxide.
• Very particularly preferred as the polyalkylene oxide is polyethylene oxide.
• the number average molecular weight of the polyalkylene oxides ranges from 150 to 50,000, preferably from 200 to 50,000, more preferably from 500 to 30,000, most preferably from 800 to 15,000.
• alkyl is for example methyl, ethyl, Ci 2 -, C 8 -, etc.
• Suitable polyethylene oxides are, for example Pluriol commercially available ® E brands (BASF)
• suitable polypropylene oxides are, for example Pluriol commercially available ® P brands (BASF)
• suitable mixed copolymers of ethylene oxide and propylene oxide are, for example, those available commercially Pluriol® ® PE or Pluriol® ® RPE grades (BASF)
• suitable Monoalkylpolyethylenoxide include the commercially available Lutensol ® - brands (BASF).
• branched homopolymers or copolymers can also be used as the hydrophilic unit B.
• Branched polymers can be prepared by, for example, polyalcohol radicals, for example pentaerythritol, glycerol, trimethylolpropane or sugar alcohols such as sucrose, D-sorbitol and D-mannitol, but also polysaccharides such as cellulose and starch, ethylene oxide and, if appropriate, propylene oxide and / or or butylene oxide attaches.
• polyalcohol radicals for example pentaerythritol, glycerol, trimethylolpropane or sugar alcohols such as sucrose, D-sorbitol and D-mannitol, but also polysaccharides such as cellulose and starch, ethylene oxide and, if appropriate, propylene oxide and / or or butylene oxide attaches.
• the alkylene oxide blocks may be randomly distributed, in gradient distribution, alternating or sequential.
• polyesters of polyalkylene oxides and aliphatic or aromatic dicarboxylic acids e.g. Oxalic acid, succinic acid, adipic acid and terephthalic acid having molecular weights of from 1500 to 25,000, such as e.g. described in EP-A-0 743 962 to use as the polyether-containing compound.
• polycarbonates can also be prepared by reacting polyalkylene oxides with phosgene or carbonates, such as, for example, Diphenyl carbonate, and polyurethanes by reaction of polyalkylene oxides with aliphatic and aromatic diisocyanates are used.
• polyalkylene oxides homopolymers and copolymers of polyalkylene oxide-containing ethylenically unsaturated monomers
• polyalkylene oxide (meth) acrylates polyalkylene oxide vinyl ethers
• polyalkylene oxide (meth) acrylamides polyalkylene oxidally amines or polyalkylene oxide vinylamines.
• copolymers of such monomers with other ethylenically unsaturated monomers include the Pluriol® ® AR brands (BASF).
• reaction products of polyethyleneimines with alkylene oxides can also be used as hydrophilic unit B.
• alkylene oxides ethylene oxide, propylene oxide, butylene oxide and mixtures thereof, particularly preferably ethylene oxide, are preferably used in this case.
• polyethyleneimines polymers with number average molecular weights of 300 to 20,000, preferably 500 to 10,000, most preferably 500 to 5000, are used.
• the weight ratio between alkylene oxide and polyethyleneimine used is in the range from 100: 1 to 0.1: 1, preferably in the range from 50: 1 to 0.5: 1, very particularly preferably in the range from 20: 1 to 0.5: 1.
• alkoxylation catalysts are used to prepare the hydrophilic polyalkylene oxide units B.
• Alkoxylation bases can be used, for example, alkali metal hydroxides or alkali metal alcoholates, but also Lewis acids, such as BF 3, SbCl 5, SnCl 4 x 2H 2 O, BF 3 x H 3 BO 4, or BF3 dietherate.
• Particularly suitable alkoxylation catalysts are double hydroxide clays such as hydrotalcite, which may be modified in particular with additives, as described in DE-A 43 25 237.
• alkoxylation catalyst Depending on the choice of the alkoxylation catalyst, specific properties of the alkoxylates result, in particular with regard to the distribution of the degree of alkoxylation.
• alkoxylation products having a narrow molecular weight distribution or homolog distribution are obtained which are suitable for use in the invention Block copolymers are particularly suitable.
• DMC double metal cyanide
• amphiphilic block copolymers a) used for the preparations according to the invention consist of at least one hydrophilic unit A, formed from reactive polyisobutenes, and at least one hydrophilic unit B, formed from a polyalkylene oxide or a polyethyleneimine.
• the hydrophobic units A contain at least one polar functional group as anchor group.
• the functionalized polyisobutenes are reacted either with alkylene oxides in a graft polymerization or in a polymer-analogous reaction with polyalkylene oxides or polyethyleneimines.
• the linking of the hydrophobic units A and the hydrophilic units B preferably takes place in a polymer-analogous reaction.
• one or more functionalized polyisobutenes are reacted with polyalkylene oxides or polyethyleneimines.
• preformed blocks A and B are therefore used.
• Particularly preferred as preformed blocks B polyalkylene oxides are used.
• This can be a statistical Copolymer, a gradient copolymer, an alternating or a block copolymer of ethylene oxide and propylene oxide.
• Very particularly preferred as the polyalkylene oxide is polyethylene oxide.
• the molecular weight of the polyalkylene oxides ranges from 150 to 50,000 (by number average), preferably from 200 to 50,000, more preferably from 500 to 30,000, most preferably from 800 to 15,000.
• polyalkylene oxides such as polyethylene oxide, polypropylene oxide, mixed copolymers of EO and PO.
• the mixed copolymers of EO and PO may be a random copolymer, a gradient copolymer, an alternating or a block copolymer of ethylene oxide and propylene oxide.
• Suitable polyethylene oxides are for example the Pluriol® ® e grades from BASF AG
• suitable polypropylene oxides are, for example Pluriol ® P brands from BASF AG
• suitable mixed copolymers of ethylene oxide and propylene oxide are, for example Pluriol ® PE or PLURIOL ® RPE grades from BASF AG
• suitable Monoalkylpolyethylenoxide for example, the Lutensol ® - grades from BASF AG ,
• Hydrophobic units A formed from reactive polyisobutenes, which have at least one polar functional group which is capable of polymer-analogous reactions with hydrophilic blocks B are preferably used for the preparations according to the invention.
• Preferred hydrophobic units A are selected from phosphated polyisobutenephenols described in i), phosphated hydrogenated polyisobutenephenols, phosphated polyisobutenephenols previously subjected to Mannich reaction, sulfated polyisobutenephenols, sulfated hydrogenated polyisobutene phenols, sulfated polyisobutene phenols previously subjected to a Mannich reaction, functionalized as described under iii) Polyisobutene, which are prepared by En-reaction.
• Suitable enophiles are fumaric acid, fumaric acid, maleic acid, maleic anhydride and maleic acid, preferably maleic anhydride and maleic acid, more particularly maleic anhydride, polyisobutenes functionalized with carboxy groups under iv), polyisobutenes functionalized with phosphonic acid groups under v), sulfonic acids described under vii) Groups functionalized polyisobutenes.
• Particularly preferred hydrophobic units A are selected from phosphonic acid, sulfonic acid and maleic anhydride groups functionalized polyisobutenes.
• particularly suitable hydrophobic units A are succinic anhydride groups functionalized polyisobutenes (PIBSA).
• PIBSA succinic anhydride groups functionalized polyisobutenes
• the polyisobutene block has an average molecular weight of M n of 150 to
• amphiphilic block copolymers a) used according to the invention their hydrophobic units A consist of polyisobutene succinic anhydrides (PIBSA) and their hydrophilic units B of polyalkylene oxides.
• PIBSA polyisobutene succinic anhydrides
• polyalkylene oxides are polyethylene oxide, polypropylene oxide, mixed copolymers of EO and PO, monoalkylpolyethylene oxides and monoalkylpolypropylene oxides.
• amphiphilic block copolymers A composed of polyethylene oxides or monoalkylpolyethylene oxides and PIBSA.
• Named reaction products form linear AB and ABA structures when a polyisobutene succinic anhydride is used as a polyisobutene functionalized only at one chain end with a succinanydride group. If z.
• linear BAB and (AB) n structures can also be formed.
• the hydrophilic units B of the block copolymers preferably have a number average molecular weight M n in the range from 150 to 50,000, preferably from 500 to 30,000 and in particular from 800 to 15,000, g / mol.
• the amphiphilic polymer a) preferably has structures of the empirical formula A p B q , in which p and q independently of one another are from 1 to 8.
• the amphiphilic polymer a) has a triblock structure ABA.
• branched or comb-like polyalkylene oxides can be used as hydrophilic units B.
• Branched or comb-like polyalkylene oxides are formed by alkoxylation of polyhydric alcohols.
• Polyalcohols are, for example, glycerol, trimethylolpropane, pentaerythritol, glucose, sucrose, in general carbohydrates, starch and starch hydrolysates or polyvinyl alcohols.
• Possible hydrophilic units are, for example, the reaction products of polyhydric alcohols, for example glycerol with alkylene oxide, for example ethylene oxide. This results in comb-like molecules, with the glycerol structure forming the "stem” and the polyethylene oxide chains the "teeth" of the comb. About the free OH Groups of the polyalkylene oxide chain ends can then be linked to the hydrophobic units A.
• Particularly preferred structures are diblock copolymers AB and triblock copolymers ABA synthesized from PIBSA as hydrophobic block A and from polyethylene oxide and monoalkylpolyethylene oxide as hydrophilic block B.
• PIBSA polyisobutene succinic anhydride
• Succinic anhydride acts as a linker linking blocks A and B together.
• PIBSA is converted to the half-esters in a polymer-analogous reaction with polyethylene oxides. The reaction of PIBSA with polyalkylene glycols thus consists in an esterification.
• hydrophobic PIB block Depending on the application, a certain ratio between hydrophobic PIB block and hydrophilic polyalkylene oxide block is chosen. Another way to control the desired effect is to use diblock or triblock copolymers or other block structures. In some cases, a mixture of the copolymers described herein is advantageous. Mixture variants can be variable hydrophobic block, variable hydrophilic block, variable structure (AB or ABA or A p B q with p and q independently of each other from 3 to 8 or comb structures).
• the cosmetic preparations contain, in addition to the amphiphilic block copolymers a), which may still contain residues of starting materials, further polyalkylene oxides, in particular polyethylene oxides, monoalkylpolyethylene oxides or branched polyalkylene oxides and / or free, preferably non-functionalized PIB.
• free PIB is meant such PIB, which has not been covalently linked with alkylene oxide, polyalkylene oxide or polyethyleneimine.
• this free PIB is not functionalized with a polar group.
• the weight ratio of amphiphilic block copolymer a) to free PIB is preferably from 100: 1 to 0.1: 1, particularly preferably 50: 1 to 0.2: 1, completely particularly preferably 20: 1 to 0.2: 1.
• the weight ratio of amphiphilic block copolymer a) to free polyethylene oxide, monoalkyl polyethylene oxide and / or branched polyalkylene oxide is in the range from 100: 1 to 0, 1: 1, preferably in the range 50: 1 to 0.2: 1, most preferably in the range 20: 1 to 0.2: 1.
• block copolymers contained in the preparations according to the invention are block copolymers composed of at least one hydrophobic block A consisting of polyisobutene and at least one hydrophilic block B consisting of polyalkylene oxide.
• the structure of the block copolymers can be described generally with A p B q (with p and q independently of one another from 1 to 8).
• block copolymers having a comb structure wherein A stands for a polyisobutene block with an average molecular weight M n of 150 to 50,000, and B stands for a polyalkylene oxide block with an average molecular weight M n of 150 or 200 to 50,000.
• the block copolymers a) for the preparations according to the invention can be provided beforehand in water.
• aqueous preparations which comprise block copolymers of polyisobutene (PIBSA) functionalized with succinic anhydride groups as hydrophobic
• Block A polyethylene oxide or monoalkylpolyethylene oxide as the hydrophilic block
• B contain the structure ABA or AB, where
• A represents a polyisobutene block having an average molecular weight M n of 450 to 5000
• B represents a polyalkylene oxide block having an average molecular weight M n of 800 to 15,000.
• a preferred embodiment of the invention are cosmetic preparations according to the invention, wherein the hydrophobic unit A and the hydrophilic unit B have a number-average molar mass M n of 150 to 50,000 g / mol.
• Another preferred embodiment of the invention are cosmetic preparations according to the invention, wherein M n of the hydrophobic unit A in the range of 200 to 20,000 g / mol and M n of the hydrophilic unit B in the range of 500 to 30,000 g / mol.
• Another preferred embodiment are cosmetic preparations according to the invention, wherein M n of the hydrophobic unit A in the range of 450 to 5000 g / mol and M n of the hydrophilic unit B in the range of 800 to 15000 g / mol.
• hydrophobic units having M n of at least 150 g / mol, more preferably of at least 200 g / mol and in particular of at least 450 g / mol and of not more than 50 000 g / mol, more preferably not more than 20 000 g / mol and in particular not more than 5000 g / mol.
• hydrophilic units having M n of at least 150 g / mol, particularly preferably of at least 200 g / mol, in particular of at least 500 g / mol and most preferably of at least 800 g / mol and of at most 50 000 g / mol, particularly preferred of at most 30,000 g / mol and in particular of at most 15,000 g / mol.
• Amphiphilic block copolymers a) which are obtained by linking hydrophilic units of any desired aforementioned molecular weight M n with hydrophobic units of any desired molecular weight can be used in the preparations according to the invention.
• any mixtures of different amphiphilic block copolymers a) having different respective stoichiometry A p B q and / or structure (block, comb etc.) and / or different respective molecular weights of the hydrophobic and hydrophilic units A and B can be used in the preparations according to the invention.
• Unreacted polyalkylene oxides, polyisobutene, reactive polyisobutene and functionalized polyisobutene may also be present in the formulations according to the invention.
• Polyalkylene oxides, monoalkylpolyethylene oxides, branched polyalkyleneoxides, polyisobutene, reactive polyisobutene and functionalized polyisobutene can also be added to the formulations in a targeted manner.
• amphiphilic block copolymer can be used in substance, dissolved or dispersed in the preparations.
• Suitable solvents or dispersants are all cosmetically acceptable solvents, in particular water and mixtures of water and alcohols.
• Emulsions based on the amphiphilic block copolymers a) produce a very pleasant feeling on the treated with them surfaces such as Skin and have in comparison to the prior art very high salt stability, ie stability even at high electrolyte concentrations on.
• Emulsions according to the invention can have particles with diameters of less than one ⁇ m and form multiphase emulsions (MPE), which leads to an increased transparency which is advantageous over the prior art preparations.
• MPE multiphase emulsions
• Another special feature of the emulsions according to the invention is that they can be provided with a multimodal, preferably bimodal particle size distribution.
• a further advantage is that the amphiphilic block copolymers a) in cosmetic preparations can also take on the role of a thickening agent, in particular in preparations with increased salt and / or pigment concentration. Thus, if necessary, the number of necessary ingredients of a preparation can be reduced or the addition of rheology modifiers made superfluous.
• Boosting effect Another advantage of the preparations according to the invention is the enhancement of the action of other ingredients of the preparations, in particular the active ingredients contained.
• the formulations have such boosting effects, for example, in the presence of UV sunscreen filters such as TiO 2, i. the sun protection factor (SPF) is increased over the presence of TiO 2 in the absence of the amphiphilic block copolymers a).
• SPDF sun protection factor
• This boosting effect also occurs in the coexistence of amphiphilic block copolymer a) and other cosmetic and dermatological agents.
• a further advantage of the preparations according to the invention is that the active ingredients, such as, for example, vitamins or pigments, are present in a very uniform and finely divided manner, while the amphiphilic block copolymers a) being present.
• the cosmetic preparations according to the invention comprise the amphiphilic block copolymer a) in an amount in the range from 0.01 to 15% by weight, preferably at least 0.1 and at most 10, more preferably at most 5 and most preferably a concentration of 0, 2 to at most 3.5 wt .-%, based on the weight of the cosmetic preparation.
• the cosmetic preparations according to the invention can be used as O / W emulsions, hydrodispersion formulations, solid-stabilized formulations, stick formulations, PIT formulations in the form of creams, foams, sprays (pump spray or aerosol), gels, gel sprays, lotions, oils, oil gels or mousses be present and accordingly formulated with conventional further excipients.
• Preferred cosmetic preparations for the purposes of the present invention are gel creams, hydroformulations, stick formulations, cosmetic oils and oil gels, mascara, self-tanner, facial care, personal care products, after-sun preparations, hair shaping compositions, hair setting agents, hair gels and decorative cosmetics.
• An object of the invention are finely divided emulsions containing the components a) to d) according to claim 1.
• Such finely divided emulsions can be PIT emulsions and are characterized by high storage stability, ie even at elevated temperature finds neither agglomeration of the droplets nor segregation of Preparation instead.
• cosmetic preparations according to the invention are skin cosmetic preparations, in particular those for the care of the skin. These are in particular as O / W skin creams, day and night creams, eye creams, face creams, anti-wrinkle creams, facial expressions creams, moisturizing creams, bleaching creams, vitamin creams, skin lotions, body lotions and moisturizing lotions.
• cosmetic preparations such as toners, face masks, deodorants and other cosmetic lotions and for use in decorative cosmetics, for example as concealer, theatrical paint, in mascara and eye shadow, lipsticks, kohl pencils, eyeliners, make-up, primers, rouges and powders and eyebrow pencils, preparations for washing, showering and bathing.
• the preparations according to the invention can be used in nose strips for pore cleansing, in anti-acne agents, repellents, shaving agents, hair removal agents, personal hygiene products, foot care agents and in baby care.
• the skin-cosmetic preparations according to the invention may contain other active ingredients and auxiliaries customary in skin cosmetics, as described below.
• These preferably include b) various emulsifiers, preservatives, perfume oils, cosmetic active ingredients such as phytantriol, vitamins A, E and C, retinol, bisabolol, panthenol, natural and synthetic light stabilizers, bleaching agents, colorants, tinting agents, suntanning agents, collagen, protein hydrolysates, Stabilizers, pH regulators, dyes, salts, thickeners, gelling agents, bodying agents, silicones, humectants, conditioners, moisturizers and other conventional additives.
• various emulsifiers such as phytantriol, vitamins A, E and C, retinol, bisabolol, panthenol, natural and synthetic light stabilizers, bleaching agents, colorants, tinting agents, suntanning agents, collagen, protein hydrolysates, Stabilizers, pH regulators, dyes, salts, thickeners, gelling agents, bodying agents, silicones, humectants, conditioners, moisturizer
• Cosmetically acceptable polymers can also be added to the preparations according to the invention if special properties are to be set. To improve certain properties such. B of the feeling of touch, the spreading behavior, the water resistance and / or the binding of active and auxiliary substances such as pigments, the preparations can also conditioning substances based on Silicone compounds included. Suitable silicone compounds are, for example, polyalkylsiloxanes, polyarylsiloxanes, polyarylalkylsiloxanes, polyethersiloxanes or silicone resins.
• the preparations according to the invention contain no further conditioning polymers, since already the common presence of components a) to d) leads to a good conditioning effect. Further possible ingredients of the preparations according to the invention are described below.
• Hair cosmetic preparations according to the invention are leveling agents for perms, curl relaxers, styling wrap lotions, hair fixatives, hair gels, hair lotions, hair foams, hair mousses, shampoos, hair shaping compositions and hair colorants.
• a preferred embodiment are preparations which are in the form of sprays or hair foams.
• a water-containing standard hair spray formulation for hair setting comprises, in addition to the components a) to d), for example, 2 to 10 wt .-% of a Festigerpolymer, ethanol, water and propellant gas (e) dimethyl ether and / or propane / n-butane and / or propane / iso-butane on.
• Component suitable as emulsifier with an HLB value in the range from 8 to 20 Components b) suitable for use in the preparations according to the invention are emulsifiers having an HLB value of from 8 to 20, preferably from 8 to 17 and particularly preferably from 10 to 17 ,
• Component b) is present in the preparations according to the invention, based on the total preparation, in an amount of 0.01 to 10, preferably 0.1 to 5 and in particular 0.5 to 2.5 wt .-%.
• HLB hydrophilic-lipophilic balance
• Component c) is present in the preparations according to the invention in an amount of at least% by weight, preferably at least, more preferably at least and at most, preferably at most and most preferably at most.
• preparations according to the invention contain an oil and / or fat phase c).
• this term means all cosmetically acceptable oils, fats and waxes.
• a particular advantage of the present invention is that when using amphiphilic polymer a) and emulsifier b) the required amount of further
• Oils, fats or waxes c) can be significantly lower than in conventional preparations, wherein the application properties are at least as good or even better.
• Ingredients of the oil and / or fat phase of the preparation according to the invention are advantageously selected from the group of lecithins and fatty acid triglycerides, namely the triglycerol esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids having a chain length of 8 to 24, in particular 12 to 18 C. -atoms.
• the fatty acid triglycerides may be advantageously selected from the group of synthetic, semi-synthetic and natural oils such as olive oil, sunflower oil, soybean oil, peanut oil, rapeseed oil, almond oil, palm oil, coconut oil, castor oil, wheat germ oil, grapeseed oil, thistle oil, evening primrose oil, macadamia nut oil and the like .
• Other polar oil components can be 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 unsaturated, branched and / or unbranched alcohols having a chain length of 3 to 30 carbon atoms and 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 chosen 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-octyl dodecyl palmitate, oleyl oleate, oleyl erucate, erucyl oleate, erucyl lerucat dicaprylyl carbonate (Cetiol CC) and cocoglycerides (Myritol 331), butylene glycol dicaprylate / dicaprate and
• one or more olefin components can advantageously be selected from the group of branched and unbranched hydrocarbons and waxes, the SiI-konöle, the dialkyl ethers, the group of saturated or unsaturated, branched or unbranched alcohols.
• any mixtures of such oil and wax components are also advantageous to use in the context of the present invention. It may also be advantageous to use waxes, for example cetyl palmitate, as the sole lipid component of the oil phase.
• the olefin component is advantageously selected from the group consisting of 2-ethylhexyl isostearate, octyldodecanol, isotridecyl isononanoate, isoeicosane, 2-ethylhexyl cocoate, C 12-15 -alkyl benzoate, caprylic-capric triglyceride, dicaprylyl ether.
• mixtures of C 12-18 -alkyl benzoate and 2- are advantageous.
• Ethylhexylisostearat mixtures of Ci 2 -i5-Alkylbenzoat and Isotridecylisononanoat and mixtures of Ci 2 -i5-Alkylbenzoat, 2-Ethylhexylisostearat and Isotridecylisononanoat.
• fatty acids triglycerides in particular soybean oil and / or almond oil, as oils having a polarity of from 5 to 50 mN / m.
• paraffin oil cycloparaffin, squalane, squalene, polydecene and in particular (optionally hydrogenated) polyisobutenes in the context of the present invention.
• hydrogenated polyisobutenes are described, for example, in unpublished German patent application with the file reference DE 102005022021.5, which is incorporated herein by reference.
• the preparations according to the invention comprise polyisobutene and / or reactive polyisobutene which, as described above, is used for preparing the amphiphilic block copolymers a), the polyisobutene used being partially unreactive and / or the reactive polyisobutene not being as described above one of the steps i) to xi) is implemented, ie the reactive double bond remains unchanged.
• the oil phase can advantageously be chosen from the group of Guerbet alcohols.
• Guerbet alcohols are named after Marcel Guerbet, who first described their production. They arise according to the reaction equation
• Guerbet alcohols are fluid even at low temperatures and cause virtually no skin irritation.
• They can be used as greasing, overfatting and also moisturizing ingredients in cosmetic preparations.
• the use of Guerbet alcohols in cosmetics is known per se.
• Such spe- cies are usually characterized by the structure
• Ri and R 2 are generally unbranched alkyl radicals.
• the Guerbet alcohol or alcohols are selected from the group, where
• Ri propyl, butyl, pentyl, hexyl, heptyl or octyl and
• R 2 hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl or tetradecyl.
• preferred Guerbet alcohols are 2-butyl (for example, 12 (Condea) commercially available as Isofol) and 2-hexyl decanol (for example commercially available as Isofol ® 16 (Condea)).
• mixtures of Guerbet alcohols are according to the invention may advantageously be used such as mixtures of 2-butyloctanol and 2-hexyl decanol (for example as Isofol ® 14 (Condea) commercially available). Any mixtures of such oil and wax components are also advantageous to use in the context of the present invention.
• the oil component may further comprise a content of cyclic or linear silicone oils or consist entirely of such oils, although it is preferred, in addition to silicone oil, an additional content of other ⁇ lphasenkom- components to use.
• Low molecular weight silicones or silicone oils are generally defined by the following general formula
• silicon atoms may be substituted by identical or different alkyl radicals and / or aryl radicals, which are here generalized by radicals R 1 to R 4 .
• radicals R 1 to R 4 the number of different radicals is not necessarily limited to 4, m can assume values of 2 to 200,000.
• silicon atoms can be substituted with identical or different alkyl radicals and / or aryl radicals, which are here generalized by the radicals Ri to R 4 .
• the number of different radicals is not necessarily limited to 4, n may assume values of 3/2 to 20. Broken values for n take into account that odd numbers of siloxyl groups may be present in the cycle.
• phenyltrimethicone is chosen as the silicone oil.
• Other silicone oils for example dimethicone, hexamethylcyclotrisiloxane, phenyldimethicone, cyclomethicone (eg decamethylcyclopentasiloxane), hexamethylcyclotrisiloxane, polydimethylsiloxane, poly (methylphenylsiloxane), cetyldimethicone, behenoxydimethicone, are to be used advantageously in the context of the present invention. Also advantageous are mixtures from cyclomethicone and isotridecyl isononanoate, as well as those from cyclomethicone and 2-ethylhexyl isostearate.
• silicone oils of similar constitution to the compounds described above, whose organic side chains are derivatized, for example polyethoxylated and / or polypropoxylated.
• organic side chains are derivatized, for example polyethoxylated and / or polypropoxylated.
• silicone oils include, for example, polysiloxane-polyalkyl-polyether copolymers such as e.g. Cetyl dimethicone copolyol.
• cyclomethicone octamethylcyclotetrasiloxane
• Fat and / or wax components which can advantageously be used according to the invention can be selected from the group of vegetable waxes, animal waxes, mineral waxes and petrochemical waxes.
• Candelilla wax, carnauba wax, Japan wax, Esparto grass wax, cork wax, guaruma wax, rice germ oil wax, sugarcane wax, berry wax, ouricury wax, montan wax, jojoba wax, shea butter, beeswax, shellac wax, spermaceti, lanolin (wool wax), crepe fat, ceresin, ozokerite are advantageous, for example (Ground wax), paraffin waxes and micro waxes.
• fat and / or wax components are chemically modified waxes and synthetic waxes, such as Syncrowax ® (glyceryl tribehenate), and Syncrowax ® AW 1 C (C 8 - 3 6 fatty acid) as well as Montanesterwachse, sasol waxes, hydrogenated, jojoba, synthetic or modified beeswaxes (z. B. dimethicone copolyol beeswax and / or C 3 o-5o alkyl beeswax), cetyl ricinoleates leate such as Tegosoft ® CR, polyalkylene waxes, polyethylene glycol waxes, but also chemically modified fats such.
• Syncrowax ® glycol waxes
• Syncrowax ® AW 1 C C 8 - 3 6 fatty acid
• Montanesterwachse sasol waxes
• sasol waxes hydrogenated, jojoba
• triglycerides such as hydrogenated soy glyceride, trihydroxystearin, fatty acids, fatty acid esters and glycol kolesteres such as C2o-4o-alkyl stearate, C2o-4o-Alkylhydroxystearoylstearat and / or glycol montanate
• Other advantageous compounds are certain organosilicon compounds which have similar physical properties to the abovementioned fatty and / or wax components, for example stearoxytrimethylsilane.
• the fat and / or wax components can be used both individually and as a mixture in the preparations.
• the oil phase is selected from the group 2-ethylhexyl isostearate, octyldodanol, isotridecyl isononanoate, butylene glycol dicaprylate / dicaprate, 2-ethylhexyl isostearate,
• Particularly advantageous are mixtures of octyldodecanol, caprylic-capric triglyceride, dicaprylyl ether, dicaprylyl carbonate, cocoglycerides or mixtures of Ci2-15 benzoate and 2-ethylhexyl isostearate, mixtures of Ci2-i5-alkyl benzoate and butylene glycol dicaprylate / dicaprate and mixtures of Ci2-15 benzoate, 2-ethylhexyl isostearate and isotridecyl isononanoate.
• the oil component is also advantageously selected from the group of phospholipids.
• the phospholipids are phosphoric acid esters of acylated glycerols.
• the lecithins which are distinguished by the general structure
• R 1 and R are typically unbranched aliphatic radicals having 15 or 17 carbon atoms and up to 4 cis double bonds.
• advantageous paraffin oil may according to the invention Mercury Weissoel Pharma 40 from Merkur Vaseline, Shell Ondina ® 917, Shell Ondina ® 927, Shell Oil 4222, Shell Ondina ® 933 from Shell & DEA OiI, Pioneer ® 6301 S, Pioneer ® 2071 (Hansen & Rosenthal ) are used.
• the content of the oils and / or fat phase c) is at most 50, preferably at most 30, more preferably at most 20% by weight, based on the total weight of the preparation.
• the preparations according to the invention preferably contain, in addition to the abovementioned substances, further additives customary in cosmetics or dermatology.
• Such further additives include, for example, UV light stabilizers, antioxidants, moisturizers, superfatting agents, antiperspirants, perfume, dyes, antimicrobials, replenishing agents, complexing and sequestering agents, pearlescing agents, plant extracts, vitamins, agents, conditioners, preservatives, bactericides, pigments containing a have coloring, thickening, softening, wetting and / or moisturizing substances, alcohols, polyols, polymers, organic acids, foam stabilizers, electrolytes, organic solvents or silicone derivatives.
• further ingredients known to the person skilled in the art for the preparations, reference is made to "Cosmetics and hygiene from head to toe", ed. W. Limbach, 3rd edition, Wiley-VCH, 2004, pp.123-128 Full reference is made.
• Antiperspirants reduce the formation of sweat by influencing the activity of eccrine sweat glands and thus counteract underarm wetness and body odor.
• Aqueous or anhydrous formulations of antiperspirants typically contain the following ingredients: astringent agents,
• non-aqueous solvents such as ethanol, propylene glycol and / or glycerol.
• Salts of aluminum, zirconium or zinc are especially suitable as astringent antiperspirant active ingredients.
• suitable antiperspirant active ingredients are e.g. Aluminum chloride, aluminum chlorohydrate, aluminum dichlorohydrate, aluminum sesquichlorohydrate and their complex compounds, eg. With propylene glycol-I, 2.
• antiperspirants may contain customary oil-soluble and water-soluble adjuvants in smaller amounts. Such oil-soluble adjuvants may be e.g. be:
• Typical water-soluble additives are, for example, preservatives, water-soluble fragrances, pH adjusters, for example buffer mixtures, water-soluble thickeners, for example water-soluble natural or synthetic polymers such as xanthan gum, hydroxyethyl cellulose, polyvinyl pyrrolidone or high molecular weight polyethylene oxides.
• pH adjusters for example buffer mixtures
• water-soluble thickeners for example water-soluble natural or synthetic polymers such as xanthan gum, hydroxyethyl cellulose, polyvinyl pyrrolidone or high molecular weight polyethylene oxides.
• Antidandruff agents may ® Octopirox (1-hydroxy-4-methyl-6- (2,4,4-trimythylpentyl) -2- (1H) -pyridone monoethanolamine salt), Baypival ®, piroctone olamine, ketoconazole ®, 4- ( Acetyl-1 - (- 4- [2- (2,4-dichlorophenyl) -2- (1 H -imidazol-1-ylmethyl) -1,3-dioxylan-c-4-ylmethoxyphenyl) piperazine, selenium disulfide, sulfur colloidal, sulfur po Lyethylenglykolsorbitanmonooleat, Schwefelrizinolpolyethoxylat, Schwefelelteer distillates, salicylic acid (eg in combination with hexachlorophene), undeylenic acid monoethanolamide sulfosuccinate Na-SaIz, Lamepon ® UD (protein undecylenic acid conden
• ethoxylated oils selected from the group of ethoxylated glycerol fatty acid esters, more preferably PEG-10 olive oil glycerides, PEG-11 avocado oil glycerides, PEG-11 cocoa butter glycerides, PEG-13 sunflower oil glycerides, PEG-15 Glyceryl Isostearate, PEG-9 Coconut Fatty Acid Glycerides, PEG-54 Hydrogenated Castor Oil, PEG-7 Hydrogenated Castor Oil, PEG-60 Hydrogenated Castor Oil, Jojoba Oil Ethoxylate (PEG-26 Jojoba Grease Acids, PEG-26 Jojoba Alcohol), Glycereth-5 Cocoate, PEG 9 Coconut fatty acid glycerides, PEG-7 glyceryl cocoate, PEG-45 palm oil glycerides, PEG-35 castor oil, olive oil PEG-7 ester, PEG-6 caprylic acid / capric acid glycerides, PEG-6 caprylic acid / capric acid
• Preferred ethoxylated oils are PEG-7 glyceryl cocoate, PEG-9 coconut glycerides, PEG-40 hydrogenated castor oil, PEG-200 hydrogenated glyceryl palmat.
• Ethoxylated glycerol fatty acid esters are used in aqueous cosmetic preparations for various purposes.
• Low-ethoxylated glycerol fatty acid esters (3-12 ethylene oxide units) are usually used as a moisturizer to improve the skin feel after drying, glycerol fatty acid ester with a degree of ethoxylation of about 30-50 serve as solubilizers for non-polar substances such as perfume oils.
• Highly ethoxylated glycerol fatty acid esters are used as thickeners. All these substances have in common that they produce on the skin when used in dilution with water, a special skin feel.
• conditioners 3-12 ethylene oxide units
• the preparations also contain conditioning agents.
• Conditioning agents which are preferred according to the invention are, for example, all compounds disclosed in section 4 of the International Cosmetic Ingredient Dictionary and Handbook (Volume 4, published by: RC Pepe, JA Wenninger, GN McEwen, The Cosmetic, Toiletry, and Fragrance Association, 9th Edition, 2002) the terms Hair Conditioning Agents, Humectants, Skin Conditioning Agents, Skin Conditioning Agents Emollient, Skin Conditioning Agents Humectant, Skin- Conditioning Agents-Miscellaneous, Skin Conditioning Agents-Occlusive, and Skin Protects are listed all compounds listed in EP-A 934 956 (p.11-13) under "water-soluble conditioning agent” and "oil-soluble conditioning agent.”
• Further advantageous conditioning agents are, for example, the compounds designated as polyquaternium according to INCI (in particular Polyquaternium 1 to Polyquaternium-56). Suitable conditioning agents include, for example, polymeric qua - Ternary ammonium compounds, cationic cellulose derivatives,
• Conditioning agents which are advantageous according to the invention can be chosen from the compounds shown in Table 1 below.
• guar hydroxypropylammonium eg Jaguar Excel ®, Jaguar C 162 ® (Rhodia), CAS 65497-29-2, CAS 39421-75-5.
• non-ionic poly N-vinylpyrrolidone / polyvinyl acetate copolymers eg Lu viskol ® VA 64 (BASF)
• anionic acrylate copolymers eg Luviflex soft ® (BASF)
• amphoteric amide / acrylate / methacrylate copolymers for example, Amphomer ® (National Starch)
• Other possible conditioning agents are quaternized silicones.
• the cosmetic preparations contain antioxidants.
• all antioxidants which are suitable or customary for cosmetic and / or dermatological applications can be used as antioxidants.
• the antioxidants are selected from the group consisting of amino acids (eg glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles (eg urocanic acid) and their derivatives, peptides such as D, L-camosine, D-camosine, L-carnosine and their derivatives (eg anserine), carotenoids, carotenes (eg .alpha.-carotene, .beta.-carotene, .gamma.-lycopene) and their derivatives, chlorogenic acid and its derivatives, lipoic acid and derivatives thereof (eg dihydrolipoic acid), aurothioglucose, propylthiouracil and other thiols (eg Thioredoxin, glutathione, cysteine, cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl
• the amount of the aforementioned antioxidants (one or more compounds) in the preparations is preferably 0.001 to 30 wt .-%, particularly preferably 0.05 to 20 wt .-%, in particular 0.1 to 10 wt .-%, based on the Total weight of the preparation.
• vitamin E and / or its derivatives are the antioxidant (s), it is advantageous to provide them in concentrations of from 0.001 to 10% by weight, based on the total weight of the preparation.
• vitamin A, or vitamin A derivatives, or carotenes or derivatives thereof are the antioxidant or antioxidants, it is advantageous to provide them in concentrations of from 0.001 to 10% by weight, based on the total weight of the preparation.
• the preparations according to the invention may also contain other (co) emulsifiers different from b).
• Nonionic surfactants from at least one of the following groups, for example, are suitable as such:
• Polysiloxane-polyalkyl-polyether copolymers or corresponding derivatives Polyalkylene glycols and glycerol carbonate.
• the addition products of ethylene oxide and / or of propylene oxide to fatty alcohols, fatty acids, alkylphenols or castor oil are known, commercially available products. These are mixtures of homologues whose average alkoxylation degree is the ratio of the molar amounts of ethylene oxide and / or propylene oxide and Substrate, with which the addition reaction is carried out corresponds.
• C12 / 18 fatty acid mono- and diesters of addition products of ethylene oxide with glycerol are known from DE 2024051 PS as refatting agents for cosmetic preparations.
• Suitable partial glycerides are Hydroxystearin Textremonoglyce- chloride, hydroxystearic acid diglyceride, isostearic acid, Isostearinklaredigly- cerid, oleic acid monoglyceride, oleic acid diglyceride, Ricinolklaremoglycerid, Rici nolklaredig lycerid, Linolklaremonoglycerid, Linolklarediglycerid, LinolenTalkremonoglycerid, Linolenchurediglycerid, Erucaklaklamonoglycerid, Erucaklakladiglycerid, Weinklarer- nonoglycerid, Weinklarediglycerid, Citronenklamonoglycerid, Citronendiglycerid Malic acid monoglyceride, malic acid diglyceride and their technical mixtures, which may contain subordinated from the manufacturing process still small amounts of triglyceride.
• sorbitan sorbitan, sorbitan sesquiisostearate, sorbitan come tandiisostearat, sorbitan triisostearate, sorbitan monooleate, sorbitan tandioleat, trioleate, Sorbitanmonoerucat, Sorbitansesquierucat, Sorbitandieru- cat, Sorbitantrierucat, Sorbitanmonoricinoleat, Sorbitansesquiricinoleat, Sorbitandirici- noleat, Sorbitantriricinoleat, Sorbitanmonohydroxystearat, Sorbitansesquihydroxystea- advice, Sorbitandihydroxystearat , Sorbitan trihydroxystearate, sorbitan monotartrate, sorbitan sesquitartrate, sorbitan ditartrate, sorbitan
• polyglycerol esters are Polyglyceryl-2 Dipolyhydroxystearate (Dehymuls ® PGPH), Polyglycerin-3-Diisostearate (Lameform ® TGI), Polyglyceryl-4 Isostearate (Isolan ® GI 34), Polyglyceryl-3 Oleate, Diisostearoyl Polyglyceryl-3 Diisostearate ( lsolan B PDI), Polyglyceryl-3 methylglucose Distearate (Tego Care ® 450), Polyglyceryl-3 Beeswax (Cera Bellina ®), Polyglyceryl-4 Caprate (polyglycerol Caprate T2010 / 90), Polyglyceryl-3 Cetyl ether (Chimexane ® NL), Polyglyceryl-3 Distearate (Cremophor ® GS 32) and Polyglyceryl polyricinoleates (Admul ® WOL 1403) polyg
• polystyrene resin examples include the mono-, di- and triesters of trimethylolpropane or pentaerythritol reacted with 1 to 30 mol of ethylene oxide with lauric acid, coconut fatty acid, tallow fatty acid, palmitic acid, stearic acid, oleic acid, behenic acid and the like.
• zwitterionic surfactants can be used as emulsifiers.
• Zwitterionic surfactants are those surface-active compounds which carry at least one quaternary ammonium group and at least one carboxylate and one sulfonate group in the molecule.
• Particularly suitable zwitterionic surfactants are the so-called betaines, such as N-alkyl-N, N-dimethylammonium glycinates, for example cocoalkyldimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinates, for example cocoacylaminopropyldimethylammonium glycinate, and 2-alkyl-3-carboxylmethyl-3 hydroxyethyl imidazolines having in each case 8 to 18 C atoms in the alkyl or acyl group, and the cocoacylaminoethylhydroxyethyl carboxymethylglycinate.
• betaines such as N-alkyl-N, N-dimethylammonium glycinates, for example cocoalkyldimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinates, for example
• fatty acid amide derivative known by the CTFA name Cocamidopropyl Betaine.
• ampholytic surfactants are understood as meaning those surface-active compounds which, apart from a C ⁇ / 18-alkyl or acyl group in the molecule, contain at least one free amino group and at least one -COOH or -SOsH group and for the formation of internal salts are capable.
• ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each having about 8 to 18 C atoms in the alkyl group.
• Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C12 / 18 acylsarcosine.
• cationic surfactants are also suitable as emulsifiers, those of the esterquat type, preferably methyl-quaternized difatty acid triethanolamine salts, being particularly preferred.
• the preparations according to the invention need not contain any further (co) emulsifiers.
• the preparations according to the invention comprise oil-soluble and / or water-soluble UVA and / or UVB filters.
• the preparations contain substances which absorb UV radiation in the UVB range and substances which absorb UV radiation in the UVA range, the total amount of filter substances being e.g. From 0.1 to 30% by weight, preferably from 0.5 to 20% by weight, in particular from 1 to 15% by weight, based on the total weight of the preparations, in order to provide cosmetic preparations which contain Protect skin from the entire area of ultraviolet radiation.
• the majority of sunscreens in cosmetic or dermatological preparations used to protect the human epidermis consist of compounds that absorb UV light in the UV-B range.
• the proportion of the UV-A absorbers to be used according to the invention is 10 to 90% by weight, preferably 20 to 50% by weight, based on the total amount of UV-B and UV-A absorbing substances.
• the UVB filters may be oil-soluble or water-soluble.
• Advantageous UVB filter substances are, for example: benzimidazole sulfonic acid derivatives, e.g. 2-phenylbenzimidazole-5-sulfonic acid and its salts
• Benzotriazole derivatives such as e.g. 2,2'-methylenebis (6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) -phenol)
• 4-aminobenzoic acid derivatives preferably (2- ethylhexyl) 4- (dimethylamino) benzoate, 4- (dimethylamino) benzoic acid amyl ester;
• Esters of benzalmalonic acid preferably di (2-ethylhexyl) 4-methoxybenzalmalonate;
• Esters of cinnamic acid preferably 4-Methoxyzi mtklare (2-ethylhexyl) ester, 4-Methoxzimt yarnreisopentylester;
• benzophenone preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy- 1- methoxy-1'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone;
• Methylidene camphor derivatives preferably 4-methylbenzylidene camphor, benzylidene camphor;
• Triazine derivatives preferably 4,4 ', 4 "- (1,3,5-triazine-2,4,6-triylimino) tris-benzoic acid tris (2-ethylhexyl ester) [INCI: diethylhexyl butamido triazines, UVA sorb ® HEB (Sigma 3V)] and 2,4,6-tris [anilino (p-carbo-2 l -ethyl-1 l -hexyloxy)] - l, 3,5-triazine [INCI: Octyl Triazzone , UVINUL ® T 150 (BASF)].
• water-soluble UVB filter substances to be used are e.g. Sulfonic acid derivatives of the 3-benzylidene camphor, such as e.g. 4- (2-0xo-3-bornylidenemethyl) benzenesulfonic acid, 2-methyl-5- (2-oxo-3-bomylidenemethyl) sulfonic acid and its salts.
• Sulfonic acid derivatives of the 3-benzylidene camphor such as e.g. 4- (2-0xo-3-bornylidenemethyl) benzenesulfonic acid, 2-methyl-5- (2-oxo-3-bomylidenemethyl) sulfonic acid and its salts.
• UVA filters are, for example:
• 1,4-phenylenedimethine camphorsulfonic acid derivatives e.g. 3,3 '- (1,4-phenylenedimethine) bis- (7,7-dimethyl-2-oxobicyclo [2.2.1] heptane-1-meth) sulfonic acid and its salts
• Dibenzoylmethane derivatives preferably 4-isopropyldibenzoylmethane, 4- (tert-butyl) -4'-methoxydibenzoylmethane
• Benzoxazole derivatives for example the 2,4-bis [4- [5- (1, 1-dimethyl-propyl) benzoxazol-2-yl] phenylimino] -6 - [(2-ethyl-phenyl) imino] -1,3 , 5- triazine (CAS no. 288254-1 6-0, Uvasorb K2A ® (3V Sigma))
• Hydroxybenzophenones for example the 2- (4'-diethylamino-2 1 -hydoxybenzoyl) - benzoate (also: aminobenzophenone) (Uvinul A Plus ® (BASF))
• preparations with further UVA and / or UVB filters for example certain salicylic acid derivatives such as 4-isopropylbenzyl salicylate, 2-ethylhexyl salicylate, octyl salicylate, homo-menthyl salicylate.
• the total amount of salicylic acid derivatives in the cosmetic or dermatological preparations is advantageously selected from the range of 0.1-15.0, preferably 0.3-10.0,% by weight, based on the total weight of the preparations.
• a facedr according to the invention to be used advantageously sunscreen is ethylhexyl 2-cyano- 3,3-diphenylacrylate (octocrylene, Uvinul ® N 539 (BASF)).
• UV protection filters are:
• Polymeric or polymer-bound filter substances can also be used according to the invention.
• Metal oxides such as titanium dioxide or zinc oxide are widely used in sunscreens. Their effect is based essentially on reflection, scattering and absorption of harmful UV radiation and depends essentially on the primary particle size of the metal oxides.
• the cosmetic or dermatological preparations according to the invention may also advantageously comprise inorganic pigments based on metal oxides and / or other sparingly soluble or insoluble metal compounds selected from the group of the oxides of zinc (ZnO), iron (e.g.
• Suitable sunscreen agents for use in the preparations according to the invention are the compounds mentioned in EP-A 1 084 696 in paragraphs [0036] to [0053]. fertilize, to which reference is made at this point.
• Suitable for use according to the invention are all UV photoprotective filters, which are mentioned in Appendix 7 (to ⁇ 3b) of the German Cosmetics Regulation under "Ultraviolet filters for cosmetic products”.
• UV light protection filters which can be used in the preparations according to the invention is not exhaustive.
• the active ingredients can be advantageously selected from the group consisting of acetylsalicylic acid, atropine, azulene, hydrocortisone and its derivatives, for.
• B. hydrocortisone 17-valerate vitamins of the B and D series, in particular vitamin Bi, vitamin B12, vitamin D, vitamin A or its derivatives such as retinyl palmitate, vitamin E or its derivatives such.
• Tocopheryl acetate, vitamin C and its derivatives such as e.g.
• vitamin F unsaturated fatty acids
• ceramides and ceramide-like compounds frankincense extract, green tea extract, water extract, licorice extract, witch hazel, antidandruff active ingredients (eg, selenium disulfide, zinc pyrithione, piroctone, olamine, climbazole, octopirox, polydocanol and their combinatines) complexing agents such as those from ⁇ -oryzanol and calcium salts such as calcium panthotenate, calcium chloride, calcium acetate.
• antidandruff active ingredients eg, selenium disulfide, zinc pyrithione, piroctone, olamine, climbazole, octopirox, polydocanol and their combinatines
• complexing agents such as those from ⁇ -oryzanol and calcium salts such as calcium panthotenate, calcium chloride, calcium acetate.
• the active ingredients from the group of emollients advantageous, for example PurCellin, Eucerit ® and Neocerit® ®.
• the active ingredient (s) are furthermore advantageously selected from the group of NO synthase inhibitors, in particular when the preparations according to the invention are used for the treatment and prophylaxis of the symptoms of intrinsic and / or extrinsic skin aging and for the treatment and prophylaxis of the harmful effects of ultraviolet radiation on the skin and the hair should serve.
• Preferred NO synthase inhibitor is nitroarginine.
• the active ingredient (s) are selected from the group comprising catechins and bile acid esters of catechins and aqueous or organic extracts from plants or plant parts which have a content of catechins or bile acid esters of catechins, such as the leaves of the plant family Theaceae, in particular of the species Camellia sinensis (green tea).
• catechins and bile acid esters of catechins are selected from the group comprising catechins and bile acid esters of catechins and aqueous or organic extracts from plants or plant parts which have a content of catechins or bile acid esters of catechins, such as the leaves of the plant family Theaceae, in particular of the species Camellia sinensis (green tea).
• Particularly advantageous are their typical ingredients (e.g., polyphenols or catechins, caffeine, vitamins, sugars, minerals, amino acids, lipids).
• Catechins represent a group of compounds which are to be regarded as hydrogenated flavones or anthocyanidins and derivatives of "catechins" (catechol, 3,3 ', 4', 5 ''). Flavanpentaol, 2- (3,4-dihydroxyphenyl) chroman-3,5,7-triol). Epicate-chin ((2R, 3R) -3,3 1 , 4 1 , 5, 7-flavanpentaol) is also an advantageous active ingredient in the context of the present invention.
• herbal extracts containing catechins in particular extracts of green tea, such as. B. extracts from leaves of the plants of the species Camellia spec, especially the teas Camellia sinenis, C. assamica, C. taliensis and C. inawadiensis and crosses of these with, for example, Camellia japonica.
• Further preferred active substances are polyphenols or catechins from the group (-) - catechin, (+) - catechin, (-) - catechin gallate, (-) - gallocatechin gallate, (+) - epicatechin, (-) - epicatechin, (-) Epicatechin gallate, (-) - epigallocatechin, (-) - epigallocatechin gallate.
• flavone and its derivatives are advantageous active ingredients in the sense of the present invention and are characterized by the following basic structure (substitution positions indicated):
• flavones usually occur in glycosidated form.
• the flavonoids are preferably selected from the group of substances of the general formula
• Zi to Z 7 independently of one another, are selected from the group consisting of H, OH, alkoxy and hydroxyalkoxy, where the alkoxy or hydroxyalkoxy groups can be branched and unbranched and can have 1 to 18 C atoms, and where GIy is selected is selected from the group of mono- and oligoglycoside radicals.
• the flavonoids can also be chosen advantageously from the group of substances of the general formula
• Z 1 to Z 6 are independently selected from the group consisting of H, OH, alkoxy and hydroxyalkoxy, where the alkoxy or hydroxyalkoxy groups can be branched and unbranched and have 1 to 18 C atoms, and where GIy is selected from the group of mono- and Oligoglycosidreste.
• such structures can be selected from the group of substances of the general formula
• GIy 2 and GIy 3 independently represent monoglycoside or oligoglycoside.
• GIy 2 or GIy 3 can also individually or together represent saturations by hydrogen atoms.
• Glyi, Gly 2 and Gly 3 are preferably selected independently of one another from the group of the hexosyl radicals, in particular the rhamnosyl radicals and glucosyl radicals.
• hexosyl radicals for example allosyl, altrosyl, galactosyl, gulosyl, idosyl, mannosyl and talosyl, may also be advantageous to use.
• pentosyl radicals may also be advantageous according to the invention to use pentosyl radicals.
• Zi to Z 5 are independently selected from the group H, OH, methoxy, ethoxy and 2-hydroxyethoxy, and the flavone glycosides correspond to the general structural formula
• the flavone glycosides are selected from the group represented by the following structure.
• Gly 1 , Gly 2 and Gly 3 independently represent monoglycoside residues or oligoglycoside residues.
• GIy 2 or GIy 3 can also individually or jointly represent saturations by hydrogen atoms.
• Gly 1 , Gly 2 and Gly 3 are preferably selected independently of one another from the group of the hexosyl radicals, in particular the rhamnosyl radicals and glucosyl radicals.
• hexosyl radicals for example allosyl, altrosyl, galactosyl, gulosyl, idosyl, mannosyl and talosyl, may also be advantageous to use.
• pentosyl radicals it may also be advantageous according to the invention to use pentosyl radicals.
• the flavone glycoside (s) from the group ⁇ -glucosylrutin, ⁇ -glucosylmyricetin, ⁇ -glucosylisoquercitrin, ⁇ -glucosylisoquercetin and ⁇ -glucosylquercitrin.
• active substances are sericoside, pyridoxol, vitamin K, biotin and aroma substances.
• the active ingredients can also be chosen very advantageously from the group of hydrophilic active ingredients, in particular from the following group: ⁇ -hydroxy acids such as lactic acid or salicylic acid or salts thereof, such as. Na-lactate, Ca-lactate, TEA-lactate, urea, allantoin, serine, sorbitol, glycerine, milk proteins, panthenol, chitosan.
• ⁇ -hydroxy acids such as lactic acid or salicylic acid or salts thereof, such as. Na-lactate, Ca-lactate, TEA-lactate, urea, allantoin, serine, sorbitol, glycerine, milk proteins, panthenol, chitosan.
• the list of active substances or combinations of active substances which can be used in the preparations according to the invention should of course not be limiting.
• the active substances can be used individually
• the amount of such active ingredients (one or more compounds) in the preparations according to the invention is preferably 0.001 to 30 wt .-%, particularly preferably 0.05 to 20 wt .-%, in particular 1 to 10 wt .-%, based on the Total weight of the preparation.
• Suitable pearlescing waxes for use in the preparations according to the invention are, for example: alkylene glycol esters, special ethylene glycol disterate; Fatty acid alkanolamides, especially coconut fatty acid diethanoamide; Partial glycerides, especially stearic acid monoglyceride; Esters of polybasic, optionally hydroxysubstituted carboxylic acids with fatty alcohols having 6 to 22 carbon atoms, especially long-chain esters of tartaric acid; Fatty substances, such as, for example, fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates, which have a total of at least 24 carbon atoms, especially lauron and D isearyl ether; Fatty acids such as stearic acid, hydroxystearic acid or behenic acid, ring-opening products of olefin epoxides having 12 to 22 carbon atoms with fatty alcohols having 12 to 22 carbon atoms
• the preparations according to the invention may furthermore contain glitter substances and / or other effect substances (eg color streaks).
• enzyme inhibitors e.g color streaks.
• esterase inhibitors are suitable as enzyme inhibitors. These are preferably trialkyl such as trimethyl citrate, tripropyl, triisopropyl citrate, tributyl citrate and especially triethyl citrate (Hydagen® ® CAT).
• the substances inhibit the enzyme activity and thereby reduce the formation of odors.
• esterase inhibitors include sterol sulfates or phosphates, such as, for example, lanosterol, cholesterol, campesterol, stigmasterol and sitosterol sulfate or phosphate, dicarboxylic acids and their esters, for example glutaric acid, glutaric acid monoethyl ester, Glutaric acid diethyl ester, adipic acid, adipic acid monoethyl ester, diethyl adipate, malonic acid and diethyl malonate, hydroxycarboxylic acids and their esters such as citric acid, malic acid, tartaric acid or diethyl tartrate, and zinc glycinate.
• sterol sulfates or phosphates such as, for example, lanosterol, cholesterol, campesterol, stigmasterol and sitosterol sulfate or phosphate
• dicarboxylic acids and their esters for example glutaric acid, glutaric acid monoethy
• Dyes which may be used are those which are suitable and approved for cosmetic, dermatological or pharmaceutical purposes, as compiled, for example, in the publication "Kosmetician Anlagenrbesch" of the Dye Commission of the Irish Anlagenstician, Verlag Chemie, Weinheim, 1984, pp. 81-106. These dyes are usually used in concentrations of 0.001 to 0.1 wt .-%, based on the total mixture.
• Typical film formers are, for example, chitosan, microcrystalline chitosan, quaternized chitosan, polyvinylpyrrolidone, vinylpyrrolidone / vinyl acetate copolymers, polymers of the acrylic acid series, quaternary cellulose derivatives, collagen, hyaluronic acid or salts thereof and similar compounds.
• gel formers all gel formers customary in cosmetics can be used. These include slightly crosslinked polyacrylic acid, for example carbomer (INCI), cellulosic derivatives, for example hydroxypropylcellulose, hydroxyethylcellulose, cationically modified celluloses, polysaccharides, for example xanthum gum, caprylic / capric triglycerides, sodium acrylate copolymer, polyquaternium-32 (and) paraffin liquid (INCI), Sodium Acrylates Copolymer (and) Paraffin Liquidum (and) PPG-1 Trideceth-6, Acrylamidopropyl Trimonium Chloride / Acrylamide Copolymer, Steareth-1 O Allyl Ether Acrylates Copolymer, Polyquatemium-37 (and) Paraffin Liquidum (and) PPG-1 trideceth-6, polyquaternium 37 (and) propylene glycols dicaprate dicaprylate (and) PPG-1 tri- deceth
• Suitable consistency factors are primarily fatty alcohols or hydroxy fatty alcohols having 12 to 22 and preferably 16 to 18 carbon atoms and, in addition, partial glycerides, fatty acids or hydroxyfatty acids. Preference is given to a combination of these substances with alkyl oligoglucosides and / or fatty acid N-methylglucamides of the same chain length and / or polyglycerol poly-12-hydroxystearates.
• Suitable thickeners are, for example, polysaccharides, in particular xanthan gum, guar-guar, agar-agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl cellulose, also relatively high molecular weight polyethylene glycol mono- and diesters of fatty acids, polyacrylates (for example Carbopol ® of Goodrich or Synthalen ® from Sigma), polyacrylamides, polyvinyl alcohol and polyvinylpyrrolidone, surfactants such as ethoxylated fatty acid reglycerides, esters of fatty acids with polyols such as pentaerythritol or trimethylolpropane, fatty alcohol ethoxylates with restricted homolog distribution or alkyl oligoglucosides and electrolytes such as sodium chloride and ammonium chloride.
• polysaccharides in particular xanthan gum, guar-guar, agar-agar, alginates and
• the cosmetic preparations according to the invention may also contain thickening agents.
• suitable thickeners for the preparations according to the invention are crosslinked polyacrylic acids and their derivatives, polysaccharides such as xanthan gum, guar-guar, agar-agar, alginates or tyloses, cellulose derivatives, eg. As carboxymethylcellulose or hydroxycarboxymethylcellulose, also higher molecular weight polyethylene glycol mono- and diesters of fatty acids, fatty alcohols, monoglycerides and fatty acids, polyvinyl alcohol and polyvinylpyrrolidone.
• Suitable thickeners are also polyacrylates such as Carbopol ® (Noveon), Ultrez ® (Noveon), Luvigel EM ® (BASF), Capigel ® 98 (Seppic), Synthalens ® (Sigma), the Aculyn ® -. Trademarks of Rohm and Haas as Aculyn ® 22 (copolymer of acrylates and methacrylic acid with stearyl (20 EO units)) and Aculyn ® 28 (copolymer of acrylates and methacrylic acid with behenyl (25 EO units)).
• thickeners are, for example, Aerosil types (hydrophilic silicic acids), polyacrylamides, polyvinyl alcohol and polyvinylpyrrolidone, surfactants such as ethoxylated fatty acid glycerides, esters of fatty acids with polyols such as pentaerythritol or trimethylolpropane, fatty alcohol ethoxylates with narrow hornloid distribution or alkyl oligoglucosides and electrolytes such as sodium chloride and ammonium chloride.
• Aerosil types hydrophilic silicic acids
• polyacrylamides polyacrylamides
• polyvinyl alcohol and polyvinylpyrrolidone surfactants
• surfactants such as ethoxylated fatty acid glycerides
• esters of fatty acids with polyols such as pentaerythritol or trimethylolpropane
• Suitable odor absorbers are substances that absorb and largely retain odor-forming compounds. They reduce the partial pressure of the individual components and thus also reduce their propagation speed. Important is, that perfumes must remain unimpaired. Odor absorbers have no activity against bacteria. They contain, for example, as a main component of a complex zinc salt of ricinoleic acid or special, largely odorless fragrances, which are known in the art as "fixatives", such. For example, extracts of Labdanum or Styrax or certain Abietinklarivate.
• Odor maskers are fragrances or perfume oils which, in addition to their function as odor maskers, give the deodorants their respective scent.
• perfume oils are mixtures of natural and synthetic fragrances. Natural fragrances are extracts of flowers, stems and leaves, fruits, fruit peel, roots, woods, herbs and grasses, needles and twigs, as well as resins and balsams. Furthermore, animal raw materials come into question, such as civet and Castoreum.
• Typical synthetic fragrance compounds are ester type products, ethers, aldehydes, ketones, alcohols and hydrocarbons. Fragrance compounds of the ester type are known e.g.
• ethers include, for example, benzyl ethyl ether, to the aldehydes e.g.
• the linear alkanals having ⁇ to 18 carbon atoms citrate, citronellal, citronellyloxyacetaldehyde, cyclamaldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones e.g. the alcohols include anethole, citronellol, eugenol, isoeugenol, geraniol, linalool, phenylethyl alcohol and terpineol; the hydrocarbons mainly include the terpenes and balsams.
• fragrance oils which are mostly used as aroma components, are suitable as perfume oils, eg sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon oil, linden blossom oil, juniper berry oil, vetiver oil, oliban oil, galbanumol, labdanum oil and lavandin oil.
• Hydrotropes such as, for example, ethanol, isopropyl alcohol, or polyols can also be used to improve the flow behavior.
• Polyols which are considered here preferably have 2 to 15 carbon atoms and at least two hydroxyl groups.
• Typical examples are glycerol; Alkylene glycols such as ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, hexylene glycol, and polyethylene glycols having an average molecular weight of 100 to 1000 g / mol; technical oligoglycerine blends having an inherent degree of condensation of from 1.5 to 10, such as technical grade diglycerin blends having a diglycerol content of from 40 to 50% by weight; Methylol compounds, in particular trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol and dipentaerythritol;
• Niedrigalkylglucoside in particular those having 1 to 8 carbons in the alkyl radical, such as methyl and Butylglucosid;
• Sugar alcohols having 5 to 12 carbon atoms such as sorbitol or mannitol
• Sugars having 5 to 12 carbon atoms such as glucose or sucrose
• Amino sugars, such as glucamine such as glucamine
• Insect repellents are N, N-diethyl-m-toluamide, 1, 2-pentanediol or ethyl Butylacetylaminopropionate in question, suitable as a self-tanner dihydroxyacetone.
• Tyrosinhinbitoren that prevent the formation of melanin and find application in de-pigmentation, for example, arbutin, kojic acid, coumaric acid and ascorbic acid (vitamin C) come into question.
• germ-inhibiting agents are basically all effective against Gram-positive bacteria substances such.
• B 4-hydroxybenzoic acid and its salts and esters, N- (4-chlorophenyl) -N 1 - (3,4-dichlorophenyl) urea, 2,4,4 1 -trichloro-2 1 -hydroxydiphenyl ether (triclosan), 4- chloro-3,5-dimethyl-phenol, 2,2 1-methylene-bis (G-bromo-4-chlorophenol), 3-methyl-4- (1-methylethyl) phenol, 2-benzyl-4-chlorophenol, 3 - (4-chlorophenoxy) -1, 2-propanediol, 3-iodo-2-propynyl butylcarbamate, chlorhexidine, 3,4,4'-trichlorocarbanilide (TTC), antibacterial fragrances, thymol, thyme oil, eugenol, clove oil, menthol, mint oil, Famesol,
• the antibacterial substances are usually used in concentrations of about 0.1 to 0.3 wt .-%. preservative
• the cosmetic preparations according to the invention may also contain preservatives in one embodiment of the invention. Preparations with high water contents must be reliably protected against contamination.
• the most important preservatives used for this purpose are urea condensates, p-
• Hydroxybenzoic acid ester the combination of phenoxyethanol with methyldibromoglutaronitrile and acid preservation with benzoic acid, salicylic acid and sorbic acid.
• Preparations with high levels of surfactants or polyols and low water content can also be formulated preservative-free.
• the preparations according to the invention may advantageously contain one or more preservatives.
• Advantageous preservatives for the purposes of the present invention are, for example, formaldehyde donors (such as, for example, DMDM hydantoin, which, for example, under the trade name Glydant ® (Lonza) commercially ER- biblich is), iodopropyl butylcarbamates (for example Glycacil-L ®, Glycacil-S ® (Lonza ), deca- ben ® LMB (Jan Dekker)), parabens (p-hydroxybenzoic acid alkyl ester such as methyl, ethyl, propyl and / or butyl paraben), Dehydroacetic Acid (Euxyl® K 702 (Schül- ke & Mayr), phenoxyethanol, Ethanol, benzoic acid
• preservative aids such as octoxyglycerol
• Preservatives or preservatives which are common in cosmetics are also advantageous, such as dibromodicyanobutane (2-bromo-2-bromomethylglutarodinitrile), phenoxyethanol, 3-iodo-2-propynyl butyl carbamate, 2-bromo-2-nitropropane-1,3-diol, imidazolidinyl urea, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-chloroacetamide, benzalkonium chloride, benzyl alcohol, salicylic acid and salicylates.
• dibromodicyanobutane (2-bromo-2-bromomethylglutarodinitrile)
• phenoxyethanol 3-iodo-2-propynyl butyl carbamate
• 2-bromo-2-nitropropane-1,3-diol imidazolidinyl urea
• preservatives are generally the other classes of substances listed in Appendix 6, Part A and B of the Cosmetics Regulation. According to the invention, preservatives are contained in a total concentration of at most 2, preferably at most 1, 5 and particularly preferably at most 1% by weight, based on the total weight of the preparation.
• complexing agents Since the raw materials and also the preparations themselves are predominantly produced in steel equipment, the end products may contain trace amounts of iron (ions). In order to prevent these contaminants from adversely affecting product quality via reactions with dyes and perfume oil ingredients, complexing agents such as salts of ethylenediaminetetraacetic acid, nitrilotriacetic acid, iminodibemic acid or phosphates are added.
• the preparations according to the invention contain at least one pigment.
• the pigments are present in undissolved form in the product composition and may be present in an amount of from 0.01 to 25% by weight, particularly preferably from 5 to 15% by weight.
• the preferred particle size is 1 to 200 .mu.m, in particular 3 to 150 .mu.m, particularly preferably 10 to 100 .mu.m.
• the pigments are practically insoluble colorants in the application medium and may be inorganic or organic. Also inorganic-organic mixed pigments are possible. Preference is given to inorganic pigments.
• the advantage of inorganic pigments is their excellent light, weather and temperature resistance.
• the inorganic pigments may be of natural origin, for example made of chalk, ocher, umber, green soil, terraced terraza or graphite.
• the pigments may be white pigments such as titanium dioxide or zinc oxide, black pigments such as iron oxide black, colored pigments such as ultramarine or iron oxide red, luster pigments, metallic effect pigments, pearlescent pigments and fluorescent or phosphorescent pigments where at least one pigment is preferably a colored, non-white pigment.
• Suitable are metal oxides, hydroxides and oxide hydrates, mixed phase pigments, sulfur-containing silicates, metal sulfides, complex metal cyanides, metal sulfates, chromates and molybdates and the metals themselves (bronze pigments).
• Titanium dioxide (Cl 77891), black iron oxide (Cl 77499), yellow iron oxide (Cl 77492), red and brown iron oxide (Cl 77491), manganese violet (Cl 77742), ultramarines (sodium aluminum sulfosilicates, Cl 77007, Pigment Blue 29 ), Chromium oxide hydrate (C 177289), iron blue (Ferric Ferro-Cyanide, CI 7751 0), Carmine (Cochineal).
• pearlescent and color pigments based on mica or mica which are coated with a metal oxide or a metal oxychloride, such as titanium dioxide or bismuth chloride, and optionally other coloring substances, such as iron oxides, iron blue, ultramarines, carmines, etc., and the color can be modified by varying Layer thickness can be determined.
• a metal oxide or a metal oxychloride such as titanium dioxide or bismuth chloride
• other coloring substances such as iron oxides, iron blue, ultramarines, carmines, etc.
• Such pigments are marketed under the trade names Rona ®, Colorona® ®, ® and Dichrona® Timiron ® from Merck, Germany.
• Organic pigments include, for example, the natural pigments sepia, cambogia, bone charcoal, Kasseler brown, indigo, chlorophyll and other plant pigments.
• Synthetic organic pigments include azo pigments, anthraquinoids, indigoids, dioxazine, quinacridone, phthalocyanine, isoindolinone, perylene and perinone, metal complex, alkali blue and diketopyrrolopyrrole pigments.
• the preparation according to the invention contains from 0.01 to 10, particularly preferably from 0.05 to 5,% by weight of at least one particulate substance.
• Suitable substances are e.g. Substances which are solid at room temperature (25 ° C) and in the form of particles. Suitable examples are silica, silicates, aluminates, clays, mica, salts, in particular inorganic metal salts, metal oxides, e.g. Titanium dioxide, minerals and polymer particles.
• the particles are present in the preparation in undissolved, preferably stably dispersed form and can be deposited in solid form after application to the surface of the application and evaporation of the solvent.
• Preferred particulates are silica (silica gel, silica) and metal salts, especially inorganic metal salts, with silica being particularly preferred.
• Metal salts are e.g. Alkali or alkaline earth halides such as sodium chloride or potassium chloride; Alkali or alkaline earth sulfates such as sodium sulfate or magnesium sulfate.
• the cosmetic preparations according to the invention may furthermore contain additional polymers to achieve certain advantageous effects or effects.
• Suitable polymers are, for example, cationic polymers with the name Polyquater- nium according to INCI, for example, copolymers of vinylpyrrolidone / N-vinylimidazolium salts (Luviquat ® FC, Luviquat ® HM, Luviquat ® MS, Luviquat ® Care, Luviquat ® Ultra Care, Luviquat ® Supreme) , copolymers of N-vinylpyrrolidone / dimethylaminoethyl methacrylate, quaternized with diethyl sulfate (Luviquat ® PQ 11), copolymers of N-
• Vinylcaprolactam / N-vinylpyrrolidone / N-vinylimidazolium salts (Luviquat Hold ®); cationic cellulose derivatives (polyquaternium-4 and -10), acrylamidocopolymers (polyquaternium-7) and chitosan.
• Suitable cationic (quaternized) polymers are also Merquat ® (polymer based on dimethyldiallylammonium chloride), Gafquat ® (quaternized ary polymers which are formed by reaction of polyvinylpyrrolidone with quaternary ammonium compounds), Polymer JR (hydroxyethylcellulose with cationic groups) and cationic polymers plant Base, for example guar polymers, such as the Jaguar ® brands from the company Rhodia.
• polystyrene resins are also neutral polymers, such as polyvinylpyrrolidones, copolymers of N-vinylpyrrolidone and vinyl acetate and / or vinylpropionate and / or stearyl (meth) acrylate, polysiloxanes, polyvinylcaprolactam and other copolymers with N-vinylpyrrolidone, polyethyleneimines and their salts, polyvinylamines and their Salts, cellulose derivatives, polyaspartic acid salts and derivatives.
• Luviflex® ® Swing partially hydrolyzed copolymer of vinyl acetate and Po Iy Polyethylengly- kol, Messrs. BASF
• Kollicoat ® IR Kollicoat ® IR.
• Suitable polymers are also those described in WO 03/092640, in particular those described as Examples 1 to 50 (Table 1, page 40 et seq.) And Examples 51 to 65 (Table 2, page 43) described (meth) Acryl Acidmidcopolymere, to the this site is fully incorporated by reference.
• Suitable polymers are also nonionic, water-soluble or wasserdispergierba- re polymers or oligomers, such as polyvinylcaprolactam, including Luviskol Plus ® (BASF), or polyvinyl pyrrolidone and their copolymers, in particular vinyl esters such as vinyl acetate, for example, Luviskol ® VA 37 (BASF); Polyamides, for example based on itaconic acid and aliphatic diamines, as described, for example, in DE-A-43 33 238.
• polyvinylcaprolactam including Luviskol Plus ® (BASF)
• BASF Luviskol Plus ®
• polyvinyl pyrrolidone and their copolymers in particular vinyl esters such as vinyl acetate, for example, Luviskol ® VA 37 (BASF);
• Polyamides for example based on itaconic acid and aliphatic diamines, as described, for example, in DE-A-43 33 238.
• Suitable polymers are also amphoteric or zwitterionic polymers, such as those available under the names Amphomer ® (National Starch) Octylacryla- mid / methyl methacrylate / tert-Butylaminoethylmethacryla ⁇ -hydroxypropylmethacrylat- copolymers and zwitterionic polymers, as described for example in German patent applications DE 39 29 973, DE 21 50 557, DE 28 17 369 and DE 37 08 451 are disclosed.
• Methacrylic acid copolymers and their alkali metal and ammonium salts are preferred zwitterionic polymers.
• Further suitable zwitterionic polymers are methacroylethylbetaine / methacrylate copolymers, which are available under the name Amersette® ® (AMERCHOL), and copolymers of hydroxyethyl lat, methyl methacrylate, N, N-Dimethylaminoethylnnethacrylat and acrylic acid (Jordanian pon ®).
• Suitable polymers are also nonionic, siloxane-containing, water soluble or dispersible polymers, for example, polyether siloxanes, such as Tegopren ® (Fa. Goldschmidt) or Belsil ® (Fa. Wacker).
• polyether siloxanes such as Tegopren ® (Fa. Goldschmidt) or Belsil ® (Fa. Wacker).
• biopolymers i. Polymers derived from naturally renewable raw materials and composed of natural monomer building blocks, e.g. Cellulose derivatives, chitin, chitosan, DNA, hyaluronic acid and RNA derivatives.
• Further preparations according to the invention comprise at least one further water-soluble polymer, in particular chitosans (poly (D-glucosamine)) of different molecular weight and / or chitosan derivatives.
• Suitable polymers for the preparations according to the invention are carboxylic acid group-containing copolymers. These are polyelectrolytes with a larger number of anionically dissociable groups in the main chain and / or a side chain. They are capable of forming polyelectrolyte complexes (symplexes) with the copolymers A).
• the polyelectrolyte complexes used in the agents according to the invention have an excess of anionogenic / anionic groups.
• the polyelectrolyte complexes also comprise at least one acid group-containing polymer.
• the polyelectrolyte complexes preferably comprise copolymer (e) A) and acid group-containing polymers in a weight ratio of from about 50: 1 to 1:20, particularly preferably from 20: 1 to 1: 5.
• Suitable carboxylic acid group-containing polymers are e.g. obtainable by free-radical polymerization of ⁇ , ⁇ -ethylenically unsaturated monomers.
• Monomers m1) which contain at least one free-radically polymerizable, ⁇ , ⁇ -ethylenically unsaturated double bond and at least one anionogenic and / or anionic group per molecule are used.
• Suitable polymers containing carboxylic acid groups are also polyurethanes containing carboxylic acid groups.
• the monomers are selected from monoethylenically unsaturated carboxylic acids, sulfonic acids, phosphonic acids and mixtures thereof.
• the monomers m1) include monoethylenically unsaturated mono- and dicarboxylic acids having 3 to 25, preferably 3 to 6, carbon atoms, which are also present in the form of their salts or Anhydrides can be used. Examples thereof are acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid and fumaric acid.
• the monomers also include the half-esters of monoethylenically unsaturated dicarboxylic acids having 4 to 10, preferably 4 to 6, carbon atoms, for example maleic acid, such as monomethyl maleate.
• the monomers also include monoethylenically unsaturated sulfonic acids and phosphonic acids, for example vinylsulfonic acid, allylsulfonic acid, sulfoethyl acrylate, sulfoethyl methacrylate, sulfopropyl acrylate, sulfopropyl methacrylate, 2-hydroxy-3-acryloxypropylsulfonic acid, 2-hydroxy-3-methacryloxypropylsulfonic acid, styrenesulfonic acid,
• the monomers also include the salts of the abovementioned acids, in particular the sodium, potassium and ammonium salts and the salts with the abovementioned amines.
• the monomers can be used as such or as mixtures with one another. The stated proportions by weight are all based on the acid form.
• the monomer m1) is selected from acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, crotonic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid and mixtures thereof, more preferably acrylic acid, methacrylic acid and mixtures thereof.
• the abovementioned monomers m1) can each be used individually or in the form of any desired mixtures.
• the comonomers used for the preparation of the carboxylic acid group-containing polymers are the compounds a) to d) previously mentioned as components of the copolymer A), with the proviso that the molar proportion of anionogenic and anionic groups which contains the polymer containing carboxylic acid groups in a larger proportion increases is the mole fraction of cationogenic and cationic groups.
• the carboxylic acid group-containing polymers contain at least one monomer in copolymerized form, which is selected from the abovementioned crosslinkers d). Suitable and preferred crosslinkers d) are referred to.
• polymers containing carboxylic acid groups preferably contain in copolymerized form at least one monomer m2) which is selected from compounds of the general formula (VI)
• R 1 is hydrogen or C 1 -C 8 -alkyl
• Y 1 is O, NH or NR 3 , and
• R 2 and R 3 independently of one another are C 1 -C 30 -alkyl or C 5 -C 8 -cycloalkyl, where the alkyl groups are substituted by up to four nonadjacent heteroatoms or heteroatom-containing groups selected from O, S and NH can be interrupted.
• R 1 in the formula VI is preferably hydrogen or C 1 -C 4 -alkyl, in particular hydrogen, methyl or ethyl.
• R 2 in the formula VI is C 1 -C 8 alkyl, preferably methyl, ethyl, n-butyl, isobutyl, tert-butyl or a group of the formula - CH 2 -CH 2 -NH-C (CH 3 ).
• R 3 is alkyl, then preferably C 1 -C 4 -alkyl, such as methyl, ethyl, n-propyl, n-butyl, isobutyl and tert-butyl.
• Suitable monomers m2) are methyl (meth) acrylate, methyl methacrylate, ethyl (meth) acrylate, ethyl ethacrylate, tert-butyl (meth) acrylate, tert-butyl ethacrylate, n-octyl (meth) acrylate, 1, 1,3,3 Tetramethylbutyl (meth) acrylate, ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, n-decyl (meth) acrylate, n-undecyl (meth) acrylate, tridecyl (meth) acrylate, myristyl (meth) acrylate , Pentadecyl (meth) acrylate, palmityl (meth) acrylate, heptadecyl (meth) acrylate, nonadecyl (meth)
• Suitable monomers m2) are furthermore acrylic acid amide, methacrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N- (n-butyl) (meth) acrylamide, N- (tert Butyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide piperidinyl (meth) acrylamide and morpholinyl (meth) acrylamide, N- (n-octyl) (meth) acrylamide, N- (1,1,3,3-tetramethylbutyl) (meth) acrylamide, N-ethylhexyl (meth) acrylamide, N- (n-nonyl) (meth) acrylamide, N- (n-decyl) (meth) acrylamide, N- (n-undecy
• H 2 C CCY 2 (CH 2 CH 2 O) (CH 2 CH (CH 3 ) O) 1 R 4
• the sequence of the alkylene oxide units is arbitrary, k and I independently of one another are an integer from 0 to 1000, the sum of k and I being at least 5,
• R 4 represents hydrogen, Ci-C 3 -alkyl or C 5 -C 8 -cycloalkyl
• R 5 is hydrogen or C 8 alkyl-C
• Y 2 is O or NR 6 , wherein R 6 is hydrogen, Ci-C 3 o-alkyl or C 5 -C 8 - cycloalkyl.
• k is preferably an integer from 1 to 500, in particular from 3 to 250.
• I is an integer from 0 to 100.
• R 5 is preferably hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl or n-hexyl, in particular for hydrogen, methyl or ethyl.
• R 4 is preferably hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, n-pentyl, n-hexyl, octyl, 2-ethylhexyl, decyl, lauryl, palmityl or stearyl ,
• Y 2 in formula VII is O or NH.
• Suitable polyether acrylates VII) are, for example, the polycondensation products of the abovementioned ⁇ , ⁇ -ethylenically unsaturated mono- and / or dicarboxylic acids and their acid chlorides, amides and anhydrides with polyetherols.
• Suitable polyetherols can easily be prepared by reacting ethylene oxide, 1,2-propylene oxide and / or epichlorohydrin with a starter molecule, such as water or a short-chain alcohol R 4 -OH.
• the alkylene oxides can be used individually, alternately in succession or as a mixture.
• the polyether acrylates VII) can be used alone or in mixtures for the preparation of the polymers used according to the invention.
• Suitable polyether acrylates II) are also urethane (meth) acrylates with alkylene oxide groups. Such compounds are described in DE 198 38 851 (component e2)), to which reference is made in its entirety.
• anionic polymers which are preferred as carboxylic acid-containing polymers are, for example, homo- and copolymers of acrylic acid and methacrylic acid and salts thereof.
• These also include crosslinked polymers of acrylic acid, such as those available under the INCI name Carbomer.
• crosslinked homopolymers of acrylic acid are available commercially for example under the name Carbopol ® by the company Noveon.
• hydrophobically modified crosslinked polyacrylate polymers such as Carbopol ® Ultrez 21 are preferably from Noveon.
• suitable anionic polymers are copolymers of acrylic acid and acrylamide and their salts; Sodium salts of polyhydroxycarboxylic acids, water-soluble or water-dispersible polyesters, polyurethanes and polyureas.
• Particularly suitable polymers are copolymers of (meth) acrylic acid and polyether acrylates, wherein the polyether chain is terminated with a C 1 -C 30 -alkyl radical.
• These include, for example, acrylate / Beheneth ⁇ ⁇ -methacrylate copolymers, which are available under the name Aculyn ® from Rohm and Haas.
• Particularly suitable polymers are also copolymers of t-butyl acrylate, ethyl acrylate, methacrylic acid (for example, Luvimer ® 100P, Luvimer ® Pro55), copolymers of ethyl acrylate and methacrylic acid (eg Luviu- mer MAE ®), copolymers of N-tert-butylacrylamide, ethyl acrylate, acrylic acid (Ultrahold ® 8, Ultrahold ® Strong), copolymers of vinyl acetate, crotonic acid and optionally further Vinylester (eg Luviset ® brands), maleic anhydride copolymers, optionally reacted with alcohol, anionic polysiloxanes, for example carboxy, t- butyl acrylate, methacrylic acid (such as Luviskol VBM ®), copolymers of acrylic acid and methacrylic acid with hydrophobic monomers, such as C4-C3o-alkyl est
• anionic polymers are also vinyl acetate / crotonic acid copolymers, as are, for example, under the names Resyn ® (National Starch) and Gafset ® (GAF), and vinyl pyrrolidone / vinyl acrylate copolymers, obtainable for example under the trade name Luviflex ® (BASF) ,
• Other suitable polymers are the commercially available under the name Luviflex VBM-35 ® (BASF) vinylpyrrolidone / acrylate terpolymer and sodium sulfonate or sodium sulfonate containing polyamides containing polyesters.
• the group of suitable anionic polymers comprises Balance CR ® (National Starch; Acrylate Copolymer), balance 0/55 ® (National Starch; Acrylate Copolymer), Balance ® 47 (National Starch; octylacrylamide / - acrylates / butylaminoethyl methacrylate copolymer ) Aquaflex ® FX 64 (ISP; isobutylene Ien / ethylmaleimide / hydroxyethylmaleimide copolymer) Aquaflex ® SF-40 (ISP / National Starch; VP / vinyl caprolactam / D MAPA acrylate copolymer), Alliance ® LT-120 (ISP / Rohm &Haas; acrylates / C1-2 succinate / hydroxyacrylate copolymer), Aquarez ® HS (Eastman, polyester-1), and ® Diaformer Z-400 (Clariant; methacryloyleth
• Suitable polymers containing carboxylic acid groups are also the terpolymers of vinylpyrrolidone, C 1 -C 10 -alkylcycloalkyl and aryl (meth) acrylates and acrylic acid described in US Pat. No. 3,405,084. Suitable polymers containing carboxylic acid groups are furthermore the terpolymers of vinylpyrrolidone, tert-butyl (meth) acrylate and (meth) acrylic acid described in EP-AO 257 444 and EP-AO 480 280.
• Suitable polymers containing carboxylic acid groups are furthermore the copolymers described in DE-A-42 23 066, which comprise at least one (meth) acrylic ester, (meth) acrylic acid and also N-vinylpyrrolidone and / or N-vinylcaprolactam in copolymerized form.
• the disclosure of these documents is hereby incorporated by reference.
• the preparation of the abovementioned carboxylic acid group-containing polymers is carried out by known processes, for example the solution, precipitation, suspension or emulsion polymerization, as described above for the copolymers A).
• Suitable carboxylic acid group-containing polymers are also polyurethanes containing carboxylic acid groups.
• EP-A-636361 discloses suitable block copolymers having polysiloxane blocks and polyurethane / polyurea blocks having carboxylic acid and / or sulfonic acid groups.
• Suitable silicone-containing polyurethanes are also described in WO 97/25021 and EP-A-751 162.
• Suitable polyurethanes are also described in DE-A-42 25 045, which is incorporated herein by reference in its entirety.
• the acid groups of the carboxylic acid group-containing polymers may be partially or completely neutralized. Then at least a part of the acid groups is present in deprotonated form, the counterions are preferably selected from alkali metal ions, such as Na + , K + , ammonium ions and their organic derivatives, etc. propellant
• propellants are the customary propellants, such as n-propane, isopropane, n-butane, isobutane, 2,2-dimethylbutane, n-pentane, isopentane, dimethyl ether, difluoroethane, fluorotrichloromethane, dichlorodifluoromethane or dichlorotetrafluoroethane, HFC 152 A or mixtures thereof.
• propellants are the customary propellants, such as n-propane, isopropane, n-butane, isobutane, 2,2-dimethylbutane, n-pentane, isopentane, dimethyl ether, difluoroethane, fluorotrichloromethane, dichlorodifluoromethane or dichlorotetrafluoroethane, HFC 152 A or mixtures thereof.
• hydrocarbons in particular propane, n-butane, n-pentane and mixtures thereof, as well as dimethyl ether and difluoroethane are used. If appropriate, one or more of the stated chlorinated hydrocarbons are used in blowing agent mixtures, but only in small amounts, for example up to 20% by weight, based on the blowing agent mixture.
• the hair cosmetic preparations according to the invention are also suitable for pump spray formulations without the addition of propellants or else for aerosol sprays with customary compressed gases such as nitrogen, compressed air or carbon dioxide as propellant.
• Suitable swelling agents for aqueous phases are montmorillonites, clay minerals, and alkyl-modified Carbopol PEMT len ® grades (Goodrich). Further suitable polymers or swelling agents can be found in the review by R. Lochhead in Cosm.Toil.108, 95 (1993).
• metal salts of fatty acids such as z.6.
• Magnesium, aluminum and / or zinc stearate or ricinoleate can be used as stabilizers metal salts of fatty acids.
• the preparations according to the invention may also contain surfactants.
• surfactants anionic, cationic, nonionic and / or amphoteric surfactants can be used.
• acylamino acids and their salts such as
• Acylglutamates in particular sodium acylglutamate sarcosinates, for example myristoyl sarcosine, TEA-lauroyl sarcosinate, sodium lauroyl sarcosinate and sodium cocoyl sarcosinate,
• Acyl isethionates for example sodium or ammonium cocoyl isethionate Sulfosuccinates, for example dioctyl sodium sulphosuccinate, disodium laureth sulphosuccinate, disodium lauryl sulphosuccinate and disodium undecylenamido MEA sulphosuccinate, disodium PEG-5 lauryl citrate sulphosuccinate and derivatives, and sulfuric acid esters such as alkyl ether sulphate, for example sodium, ammonium, magnesium, MIPA, TIPA laureth sulphate, sodium myreth sulfate and sodium C12-13 pareth sulfate,
• Sulfosuccinates for example dioctyl sodium sulphosuccinate, disodium laureth sulphosuccinate, disodium lauryl sulphosuccinate and disodium undecylenamido MEA s
• Alkyl sulfates for example sodium, ammonium and TEA lauryl sulfate. Further advantageous anionic surfactants are
• Taurates for example sodium lauroyl taurate and sodium methyl cocoyl taurate, ether carboxylic acids, for example sodium laureth-13 carboxylate and sodium PEG-6 cocamide carboxylate, sodium PEG-7 olive oil carboxylate
• Phosphoric acid esters and salts such as, for example, DEA-oleth-10-phosphate and dilaureth-4-phosphate,
• Alkyl sulfonates for example sodium coconut monoglyceride sulfate, sodium C 12-14 olefin sulfonate, sodium lauryl sulfoacetate and magnesium PEG-3 cocamide sulfate,
• Acylglutamates such as di-TEA-palmitoylaspartate and sodium caprylic / capric glutamate,
• Acyl peptides for example palmitoyl hydrolyzed milk protein, sodium cocoyl-hydrolyzed soy protein and sodium / potassium cocoyl-hydrolyzed collagen, and carboxylic acids and derivatives such as lauric acid, aluminum stearate, magnesium alkoxide and zinc undecylenate, ester carboxylic acids, for example calcium stearoyl lactylate, laureth-6 citrate and sodium PEG-4 Lauramidcarboxylate
• Advantageous cationic surfactants for the purposes of the present invention are quaternary surfactants.
• Quaternary surfactants contain at least one N atom covalently linked to 4 alkyl or aryl groups.
• alkylbetaine, alkylamidopropylbetaine and alkylamidopropylhydroxysultaine are advantageous.
• cationic surfactants for the purposes of the present invention are furthermore - alkylamines
• amphoteric surfactants for the purposes of the present invention are acyl / dialkylethylenediamines, for example sodium acylamphoacetate, disodium acylamphorodipropionate, disodium alkylamphodiacetate, sodium acylamphohydroxypropylsulfonate, disodium acylamphodiacetate, sodium acylamphopropionate, and N-coconut fatty acid amidoethyl-N-hydroxyethylglycinate sodium salts.
• acyl / dialkylethylenediamines for example sodium acylamphoacetate, disodium acylamphorodipropionate, disodium alkylamphodiacetate, sodium acylamphohydroxypropylsulfonate, disodium acylamphodiacetate, sodium acylamphopropionate, and N-coconut fatty acid amidoethyl-N-hydroxyethylglycinate sodium salts.
• amphoteric surfactants are N-alkylamino acids, for example aminopropylalkylglutamide, alkylaminopropionic acid, sodium alkylimidodipropionate and lauroamphocarboxyglycinate.
• compositions for the purposes of the present invention are alkanolamides, such as cocamide MEA / DEA / MIPA,
• ethers for example ethoxylated alcohols, ethoxylated lanolin, ethoxylated polysilane Loxane, propoxylated POE ethers, alkyl polyglycosides, such as lauryl glucoside, decyl glycoside and cocoglycoside, glycosides with an HLB value of at least 20 (for example, BEI sil ® SPG 128V (Wacker)).
• nonionic surfactants are alcohols and amine oxides, such as cocoamidopropylamine oxide.
• alkyl ether sulfates sodium alkyl ether sulfates based on di- or tri-ethoxylated lauryl and myristyl alcohol are particularly preferred. They clearly outperform the alkyl sulfates with regard to their resistance to water hardness, colourability, low solubility and, in particular, skin and mucous membrane compatibility. Lauryl ether sulfate has better foam properties than myristyl ether sulfate, but this is inferior in mildness. Medium and especially higher alkyl ether carboxylates are among the mildest surfactants ever but exhibit poor foam and viscosity performance. They are often used in combination with alkyl ether sulfates and amphoteric surfactants.
• Sulfosuccinic acid esters are mild and, because of their poor thickenability, preference is given to using surfactants which are preferred only in neutral or well-buffered products only together with other anionic and amphoteric surfactants and, owing to their low hydrolytic stability.
• Amidopropylbetains have excellent skin and eye mucous membrane compatibility. In combination with anionic surfactants their mildness could be improved synergistically. Preferred is the use of cocamidopropyl betaine.
• Amphoacetate / Arnphodiacetate as amphoteric surfactants have a very good skin and mucous membrane compatibility and can have a conditioning effect or the Nursing Increase kung of additives. They are similar to the betaines used to optimize alkyl ether sulfate formulations. Most preferred are sodium cocoamphoacetate and disodium cocoamphodiacetate.
• Alkyl polyglycosides are mild, have good universal properties, but foam weakly. For this reason, they are preferably used in combination with anionic surfactants.
• Buffer buffers ensure the pH stability of aqueous compositions of the invention. Citrate, lactate and phosphate buffers are preferably used.
• Solubilizers are used to bring nourishing oils or perfume oils into solution and to keep them clear even in the cold.
• the most common solubilizers are ethoxylated nonionic surfactants, eg. B. hydrogenated and ethoxylated ricin oils.
• Superfatting agents which can be used are substances such as lanolin and lecithin, as well as polyethoxylated or acylated lanolin and lecithin derivatives, polyol fatty acid esters, monoglycerides and fatty acid alkanolamides, the latter also serving as foam stabilizers.
• a further object of the present invention was thus to provide self-tanning products which do not have the aforementioned disadvantages.
• preparations according to the invention which contain one or more self-tanning substances.
• Another object of the invention are therefore also kosme- table preparations, which also contain one or more self-tanning substances and optionally other cosmetic and / or dermatological active ingredients, auxiliaries and additives.
• the preparations according to the invention can be present and used in various forms. So they can z.
• Emulsifier-free formulations such as hydrodispersions, hydrogels or a Pickering emulsion are advantageous embodiments.
• the consistency of the formulations can range from pasty formulations via free-flowing formulations to low-viscosity, sprayable products. Accordingly, creams, lotions or sprays can be formulated.
• the cosmetic preparations according to the invention are applied to the skin in a sufficient amount in the manner customary for cosmetics and dermatological agents.
• Glycerol aldehyde, hydroxymethylglyoxal, ⁇ -dialdehyde, erythrulose, 5-hydroxy-1,4-naphthoquinone (Jug Ion) and 2-hydroxy-1,4-naphthoquinone occurring in the henna leaves are advantageously used as self-tanning agents according to the invention .
• DHA 1,3-dihydroxyacetone
• troxerutin a trivalent sugar occurring in the human body or the combination of dihydroxyacetone and troxerutin marketed by Merck under the name DHA Rapid® .
• 6-aldo-D-fructose and ninhydrin can also be used as self-tanning agents according to the invention.
• a self-tanner in the context of the invention are also substances to understand that cause a deviating from Braunton skin color.
• these preparations contain a plurality of self-tanning substances in a concentration of 0.1 to 10 wt .-% and particularly preferably from 0.5 to 6 wt .-%, each based on the total weight of the composition.
• these preparations contain as self-tanning substance 1, 3-dihydroxyacetone. More preferably, these preparations contain organic and / or inorganic sunscreen filters. The preparations may also contain inorganic and / or organic and / or modified inorganic pigments.
• An object of the invention is also the use of such preparations for coloring the skin of multicellular organisms, in particular the skin of humans and animals, in particular also for color matching of differently pigmented skin sites.
• PIBSA succinic anhydride end-functionalized polyisobutene.
• Example 1 Preparation of a linear triblock copolymer ABA:
• Example 8 Preparation of a diblock copolymer AB:
• Pluriol P 900 ® polypropylene oxide, M n ⁇ 900
• Pluriol P ® presented 900th
• heating to 80 0 C was evacuated 3 times and aerated with N 2.
• the reaction mixture was then heated to 130 ° C and held at this temperature for 3 h. Thereafter, the product was allowed to cool to room temperature.
• Example 12 Preparation of a linear triblock copolymer ABA:
• Pluronic ® PE 6400 block copolymer of polypropylene oxide (PPO) and polyethylene oxide (PEO) with PEO-PPO-PEO structure, M n ⁇ 2900, 60 wt % PPO and 40% by weight PEO
• the quantities are in wt .-%, unless otherwise noted.
• the preparations mentioned below are preferably provided in the customary devices known to the person skilled in the art; for example, in bottles, tubes, squeeze bottles, cans, spray cans, pots, in soaked wipes, spray bottles, pump spray bottles, bottles, etc.
• hydrodispersions formulations (amounts in% by weight)
• phase A homogeneously and stir phase B into phase A and then stir in phase C slowly.
• the analogous formulation is also prepared analogously with the copolymers from Preparation Examples 1 and 3-18.
• Application Example 42 to Application Example 58 Repeat Application Example 41, but instead of the polymer from Example 1, the copolymers from Preparation Examples 2-18 are used.
• the analogous formulation is also prepared analogously with the copolymers from Preparation Examples 2-18.
• the analogous formulation is also prepared analogously with the copolymers from Preparation Examples 2-18.
• the analogous formulation is also prepared analogously with the copolymers from Preparation Examples 2-18.
• the analogous formulation is also prepared analogously with the copolymers from Preparation Examples 2-18.
• the analogous formulation is also prepared analogously with the copolymers from Preparation Examples 2-18.
• the analogous formulation is also prepared analogously with the copolymers from Preparation Examples 2-18.
• the analogous formulation is also prepared analogously with the copolymers from Preparation Examples 2-18.
• the analogous formulation is also prepared analogously with the copolymers from Preparation Examples 2-18.
• the analogous formulation is also prepared analogously with the copolymers from Preparation Examples 2-18.
• the analogous formulation is also prepared analogously with the copolymers from Preparation Examples 2-18.
• the analogous formulation is also prepared analogously with the copolymers from Preparation Examples 2-18.
• Citric acid 0,10 0,10 0,10 0,10 0,10
• the analogous formulation is also prepared analogously with the copolymers from Preparation Examples 2-18.
• the analogous formulation is also prepared analogously with the copolymers from Preparation Examples 2-18.
• phase A is allowed to swell; then dissolve phase B and phase C separately.
• the solutions of phases B and C are stirred into phase A.
• the analogous formulation is also prepared analogously with the copolymers from Preparation Examples 2-18.
• the analogous formulation is also prepared analogously with the copolymers from Preparation Examples 2-18.
• the analogous formulation is also prepared analogously with the copolymers from Preparation Examples 2-18.
• the analogous formulation is also prepared analogously with the copolymers from Preparation Examples 2-18.
• the analogous formulation is also prepared analogously with the copolymers from Preparation Examples 2-18.
• the analogous formulation is also prepared analogously with the copolymers from Preparation Examples 2-18.
• the analogous formulation is also prepared analogously with the copolymers from Preparation Examples 2-18.
• Stepanhold R-1 poly (vinyl pyrrolidone / ethyl methacrylate / methacrylic acid)
• Phase A and Phase B are heated separately to 80 0 C.
• phase B is mixed in phase A with a stirrer. It is allowed to cool to 40 0 C and thereafter Phase C and Phase D to. Homogenize several times.
• the application example is repeated, but instead of the polymer from Example 1, copolymers from Preparation Examples 2-18 are used.
• phase A and B are heated separately to about 80 0 C. Thereafter, the phase B is stirred in phase A with homogenization; After brief Nachhomogen I is allowed to cool to about 40 0 C, the phase C is added and homogenized again.
• phase A and B are heated separately to about 80 ° C. Thereafter, phase B is stirred into phase A and homogenized. It is allowed to cool to about 40 0 C, phase C is added and homogenized briefly again. Subsequently, the mixture is stirred under phase D.
• Poloxamer 407 5.00 dist. Water 52.00
• phase A The components of phase A are mixed. Thereafter, phase B is stirred with homogenization in phase A and homogenized shortly after. With phase C neutralized and homogenized again.
• phase A Dissolve phase A. Thereafter, phase B is dispersed in phase A and dissolved. Phase C is added and allowed to stand under reduced pressure at room temperature for about 45 minutes.
• Phase A is solved clearly. Add phase B and homogenize. The components of phase C are added and the mixture is melted at 80 ° C. Phase D is heated to 80 ° C. Phase D is added to the mixture of phases A, B and C and homogenized. It is allowed to cool to about 40 0 C, the phase E and phase F and homogenized again.
• Phase A Leave phase A to swell; Thereafter, the phases B and C are separately dissolved separately. Phase A and B are stirred in phase C.
• phase A The components of phase A are mixed.
• the components of phase B are added one after the other, so that a clear solution is formed.

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