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
  • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
  • A61K8/87—Polyurethanes
• • 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
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q3/00—Manicure or pedicure preparations
  • A61Q3/02—Nail coatings
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
  • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
  • C08G18/0828—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing sulfonate groups or groups forming them
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
  • C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
  • C08G18/3857—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur having nitrogen in addition to sulfur
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
  • C08G18/3878—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus
  • C08G18/3889—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus having nitrogen in addition to phosphorus
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/48—Polyethers
  • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
• • 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
  • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
  • A61K2800/54—Polymers characterized by specific structures/properties
  • A61K2800/542—Polymers characterized by specific structures/properties characterized by the charge
  • A61K2800/5424—Polymers characterized by specific structures/properties characterized by the charge anionic

Definitions

• the present invention relates to new anionic polyurethanes of elastic nature as well as their use in cosmetic compositions.
• T g glass transition temperatures
• the present invention therefore relates to anionic polyurethanes of elastic nature, essentially consisting
• anionic units derived from at least one monomer or polymer compound with a sulfonic and / or phosphonic acid function and having at least two reactive functions with labile hydrogen, optionally
• (b) of units derived from at least one diisocyanate it being understood that at least one type of units (al) and (a2) is derived from a polymer having a glass transition temperature (Tg), measured by enthalpy analysis differential, less than 10 ° C and that these Tg sequences less than 10 ° C represent from 20% to 90% of the total weight of the polyurethane.
• Tg glass transition temperature
• Another subject of the invention is the use of the anionic polyurethanes of elastic nature above in cosmetic compositions with a view to improving the viscoelastic properties of the deposits and cosmetic films obtained from these compositions.
• a subject of the invention is also cosmetic compositions containing the anionic polyurethanes of elastic nature above.
• anionic polyurethanes of elastic nature of the present invention makes it possible to improve the flexibility of the hairstyle, that is to say to obtain an elastic hold of the hair more natural than that obtained with usual fixing polymers.
• the anionic character of the new polyurethanes of the present invention also makes them very easy to remove by simple washing of the hair.
• These polyurethanes can be used to cover the nails with a shiny protective film resistant to mechanical attack.
• the above anionic polyurethanes can also be used to improve the hold of make-up compositions for the skin, the lips and the integuments.
• the deposits obtained follow the deformations of the keratinous substrates and do not pull the skin.
• anionic charges gives the polyurethanes of the present invention a fairly hydrophilic character independent of the pH of the medium containing them.
• the anionic polyurethanes of the present invention are therefore soluble, or at least dispersible, in polar solvents and in particular in water and lower alcohols, which greatly facilitates their formulation in cosmetic compositions.
• the anionic polyurethanes of elastic nature of the present invention consist essentially of three types of units which are
• sulfonic acid function and “phosphonic acid function” denote not only the protonated acid form of these functions but also the forms partially or totally neutralized by a base, that is to say ie the sulfonate (-SO 3 " ), phosphonate (-PO 3 H “ ) and diphosphonate (-PO 3 2 " ) groups.
• Reactive functions with labile hydrogen are understood to mean functions capable, after leaving a hydrogen atom, of forming covalent bonds with the isocyanate functions of the compounds forming the units (b). Mention may be made, by way of example of such functions, of the hydroxyl, primary amine (-NH 2 ) or secondary amine (-NHR) groups, or alternatively the thiol groups (-SH).
• the polycondensation of compounds carrying these reactive functions with labile hydrogen with diisocyanates gives, depending on the nature of the reactive functions carrying labile hydrogen (-OH, -NH 2 , -NHR or -SH), respectively polyurethanes in the strict sense. polyureas or polythio-urethanes. All these polymers are grouped together in the present application, for the sake of simplification, under the term polyurethanes.
• the compounds with a sulfonic and / or phosphonic acid function forming the units (a1) carry more than two functions containing labile hydrogen, the polyurethanes obtained have a branched structure, possibly even crosslinked.
• the compounds with a sulfonic and / or phosphonic acid function forming the anionic units (a1) have only two reactive functions with labile hydrogen and the polyurethanes obtained by polycondensation therefore have a structure essentially linear.
• the compounds with a sulfonic and / or phosphonic acid function forming the anionic units (a1) are preferably chosen from the compounds corresponding to one of the following formulas:
• Acid represents a sulfonic acid or phosphonic acid group, in protonated or salified form
• each R a independently represents a direct bond or a C 6 alkylene group, linear or branched, C 3 cycloalkylene. 6 or arylene, all of which may be substituted by one or more halogen atoms and contain one or more heteroatoms chosen from O, P and S
• R b represents a hydrogen atom or an alkyl group which may comprise one or more heteroatoms chosen from O, P and S
• Y represents a C 5 cyclic group.
• each X independently represents an oxygen or sulfur atom or an NH or NR C group , where R c represents an alkyl group in C 1.6 .
• the compounds with a sulfonic and / or phosphonic acid function forming the anionic units (a1) of the polyurethanes of the present invention can also be polymers.
• anionic polymers containing a sulphonic acid function and / or phosphonic acid can be obtained in one step, for j radical, anionic copolymerization, cationic, and in particular ring opening, or by polycondensation of nonionic monomers and anionic monomers bearing acid units sulfonic or phosphonic acid.
• anionic monomers which can be used for radical polymerization include sodium styrenesulfonate.
• the polymers can also be obtained in two stages, that is to say by polymerization or polycondensation of nonionic monomers, followed by grafting of units having a sulfonic or phosphonic acid function.
• the nonionic monomers which can be used are for example vinyl monomers, ethylene oxide or propylene oxide.
• the polymers obtained by polycondensation can be polyesters, polyamides or polyurethanes.
• the sulfonic acid or phosphonic acid functions can also be introduced by initiators carrying these functions.
• the labile hydrogen groups can be introduced by monomers, initiators or chain terminators carrying such groups. Mention may be made, for example, of a diol used as initiator in the polymerization of propylene oxide by ring opening.
• the weight-average molar mass of these polymers containing sulfonic and / or phosphonic acid functions is preferably between 200 and 10,000, and more preferably between 400 and
• polymers having a suitable sulfonic and / or phosphonic acid function examples include the polymers of formula
• n is between 2 and 100.
• the second type of units forming the polyurethanes of the present invention are monomeric or polymeric nonionic units, called units (a2), carrying reactive functions containing labile hydrogen at their ends.
• nonionic units (a2) are obligatory in the polyurethanes of the present invention, that of the nonionic units (a2) is optional.
• These nonionic units can be derived from monomers or polymers. Mention may be made, as examples of monomeric compounds capable of forming the nonionic units (a2), of neopentyl glycol, 1,6-hexanediol, 1,4-butanediol or aminoethanol.
• (a2) are chosen, for example, from polyethers, polyesters, polysiloxanes, copolymers of ethylene and butylene, polycarbonates, polyalkyl (meth) acrylates and fluorinated polymers.
• Polyethers are particularly preferred, and among these poly (tetramethylene oxide).
• the weight-average molar mass of these nonionic polymers is preferably between 400 and 10,000 and more particularly between 400 and 5000.
• the elasticity of the polyurethanes of the present invention is linked to the simultaneous presence, in the polymer, of a certain fraction of polymer blocks having a glass transition temperature below 10 ° C., and of a certain fraction of units forming sequences that have a glass transition temperature higher than room temperature.
• the blocks having a glass transition temperature below 10 ° C. are formed by the anionic polymers and / or the nonionic polymers described above.
• the viscoelastic properties of the anionic polyurethanes of the present invention are particularly advantageous when the units (al) or (a2) are derived from polymers having a glass transition temperature below 0 ° C and better still below
• Sequences with a Tg greater than 20 ° C. also called “rigid” sequences, are found, at room temperature, in the glassy state and thus form physical crosslinking nodes of the three-dimensional polymer network.
• the Applicant has found that the elasticity of the polyurethanes of the present invention is satisfactory when the fraction of polymeric units, anionic or nonionic, having a glass transition temperature below 10 ° C., represents from 20 to 90%, preferably from 20 to 80%, and in particular 20 to 70% of the total weight of the polyurethanes of the present invention.
• the diisocyanates forming the units (b) include aliphatic, alicyclic or aromatic diisocyanates.
• Preferred diisocyanates are chosen from methylenediphenyldiisocyanate, methylenecyclohexanediisocyanate, isophoronediisocyanate, toluenediisocyanate, naphthalene diisocyanate, butanediisocyanate and hexldiisocyanate. These diisocyanates can of course be used alone or in the form of a mixture of two or more diisocyanates.
• the elasticity of the anionic polyurethanes of the present invention is due to the fact that these polymers have at least two different glass transition temperatures (Tg), at least one of these Tg being less than 10 ° C and at least one other being higher or equal to 20 ° C.
• Tg glass transition temperatures
• the physical parameter characterizing the viscoelastic properties of the above anionic polyurethanes is their tensile recovery. This recovery is determined by tensile creep test consisting in rapidly stretching a test piece to a predetermined rate of elongation, then releasing the stress and measuring the length of the test piece.
• the creep test used for the characterization of anionic polyurethanes of elastic nature of the present invention is carried out as follows:
• This copolymer film is obtained by drying, at a temperature of
• each strip is fixed between two jaws, spaced 50 ⁇ 1 mm apart, and is stretched at a speed of 20 mm / minute (under the conditions of temperature and relative humidity above) until at an elongation of 50% ( ⁇ max ), that is to say up to 1.5 times its initial length.
• the stress is then relaxed by imposing a return speed equal to the traction speed, ie 20 mm / minute, and the elongation of the test piece (measured in% relative to the initial length) is measured immediately after return to load. null (£ i).
• the anionic polyurethanes of elastic nature of the present invention preferably have an instantaneous recovery (R;), measured under the conditions indicated above, of between 5% and
• the glass transition temperatures (Tg) of the polymers forming the units (a1) or (a2) and of the anionic polyurethanes of the present invention are measured by differential enthalpy analysis
• the fraction of units (a1) must be sufficient to give the polymers their negative charge responsible for their good ability to dissolve or to be dispersed in polar solvents such as water and alcohols.
• the anionic polyurethanes of the present invention preferably have an anionic charge rate of between 0.1 and 15 milliequivalents per gram (meq / g), more preferably between 0.1 and 10 meq / g, and very particularly between 0.1 and 5 meq / g.
• the units (a1) represent in particular from 1 to 90% and preferably from 5 to 60% by weight, and the units (a2) advantageously represent from 0 to 90% and preferably from 40 to 70 % by weight of the total polymer.
• the patterns (b) are present in an essentially stoichiometric amount relative to the sum of the patterns (al) and (a2).
• obtaining polyurethanes having large molar masses presupposes a number of isocyanate functions practically identical to the number of functions containing labile hydrogen.
• Those skilled in the art will know how to choose a possible molar excess of one or the other type of function to adjust the molar mass to the desired value.
• anionic polyurethanes of elastic nature can be incorporated into numerous cosmetic compositions, the cosmetic properties of which they improve.
• the quantity of polyurethane present in the various compositions depends of course on the type of composition and on the desired properties and can vary within a very wide range. broad, generally between 0.5 and 90% by weight, preferably between 1 and 50% by weight, based on the final cosmetic composition.
• anionic polyurethanes of elastic nature When the anionic polyurethanes of elastic nature are incorporated into hair sprays their concentration is generally between 0.5 and 15% by weight. In nail varnishes, they generally represent from 0.5 to 40% by weight of the composition, and makeup compositions for the skin, the lips and the integuments generally contain 0.5 to 20% by weight of the polyurethanes of the present invention.
• anionic polyurethanes of elastic nature of the present invention in pure form for example to form a protective film on the nails.
• the reaction mixture is allowed to cool to room temperature, then diluted with acetone until '' at a polymer concentration of about 40% by weight.
• the organic phase is then removed by vacuum distillation at a temperature of 40 ° C.
• R ⁇ (%) (( ⁇ m . ⁇ - ⁇ i ) / ⁇ max ) x 100

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• Health & Medical Sciences (AREA)
• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Polymers & Plastics (AREA)
• Public Health (AREA)
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• Animal Behavior & Ethology (AREA)
• Organic Chemistry (AREA)
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• Birds (AREA)
• Epidemiology (AREA)
• Engineering & Computer Science (AREA)
• Manufacturing & Machinery (AREA)
• Polyurethanes Or Polyureas (AREA)
• Cosmetics (AREA)

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• 2001
  • 2001-03-05 FR FR0102947A patent/FR2821621B1/fr not_active Expired - Fee Related
• 2002
  • 2002-02-27 JP JP2002570612A patent/JP2004529228A/ja active Pending
  • 2002-02-27 US US10/469,785 patent/US20040197293A1/en not_active Abandoned
  • 2002-02-27 WO PCT/FR2002/000703 patent/WO2002070577A1/fr active Application Filing
  • 2002-02-27 EP EP02708418A patent/EP1373346A1/de not_active Withdrawn

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