(19)
(11)EP 3 558 463 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
05.05.2021 Bulletin 2021/18

(21)Application number: 17836022.8

(22)Date of filing:  20.12.2017
(51)International Patent Classification (IPC): 
A61Q 5/06(2006.01)
C08F 8/28(2006.01)
C08F 116/06(2006.01)
A61K 8/81(2006.01)
C09D 129/14(2006.01)
C08F 8/48(2006.01)
C08F 216/06(2006.01)
C08F 16/06(2006.01)
C08F 8/30(2006.01)
(86)International application number:
PCT/EP2017/083799
(87)International publication number:
WO 2018/115113 (28.06.2018 Gazette  2018/26)

(54)

PROCESS FOR TREATING KERATIN FIBRES WITH A PHOTOCROSSLINKABLE POLYVINYL ALCOHOL

VERFAHREN ZUR BEHANDLUNG VON KERATINFASERN MIT EINEM PHOTOVERNETZBAREN POLYVINYLALKOHOL

PROCÉDÉ DE TRAITEMENT DE FIBRES DE KÉRATINE AU MOYEN D'UN ALCOOL POLYVINYLIQUE PHOTORÉTICULABLE


(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

(30)Priority: 21.12.2016 FR 1663052

(43)Date of publication of application:
30.10.2019 Bulletin 2019/44

(73)Proprietor: L'Oréal
75008 Paris (FR)

(72)Inventor:
  • JEGOU, Gwenaëlle
    93601 Aulnay-sous-Bois (FR)

(74)Representative: L'Oreal 
Service D.I.P.I. 9, rue Pierre Dreyfus
92110 Clichy
92110 Clichy (FR)


(56)References cited: : 
WO-A1-2016/174041
US-A- 5 206 113
US-A1- 2006 239 946
US-A- 4 777 114
US-A1- 2003 022 104
US-A1- 2013 167 859
  
      
    Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


    Description


    [0001] The present invention relates to a process for the cosmetic treatment of keratin fibres using a polyvinyl alcohol polymer bearing photocrosslinkable and hydrophobic groups, and also to novel polymers.

    [0002] Hair products generally contain film-forming polymers to give the hair good hairstyle hold. However, the quality of the hair hold may be impaired on contact with water, for example with rain or when showering: this impairment may be due to the fact that the deposit of the film-forming polymer on the hair has poor resistance to contact with water and is removed over time.

    [0003] The aim of the present invention is to provide a process for the cosmetic treatment of the hair which can produce a film-forming deposit that has good resistance to water and that is suitable for application to the hair to obtain good cosmetic properties in terms of a soft feel and disentangling, which properties are persistent after shampoo washing one or more times (for example 5 times).

    [0004] In the field of electronics and recording equipment, photosensitive resins comprising photodimerizable units and hydrophobic units have been developed (US 4 777 114, US 5 206 113 and US 2003/0022104).

    [0005] Other photodimerizable polymers have been used in cosmetics (US2006/0239946, WO 2016/174041, US 2013/0167859 and US 2013/0167859).

    [0006] However, the feel, disentangling and persistence especially on shampooing is not always satisfactory.

    [0007] The inventors have discovered that a particular vinyl alcohol polymer applied to the hair gives the hair good cosmetic properties which show good persistence on shampooing.

    [0008] More precisely, one subject of the present invention is a process, especially a cosmetic process, for treating keratin fibres, comprising:
    1. (i) a step of applying, to the keratin fibres, a cosmetic composition comprising a polyvinyl alcohol polymer as defined below;
    2. (ii) a step of irradiating the composition on the keratin fibres to crosslink said polymer;


    [0009] steps (i) and (ii) being performed at the same time or separately, in the order (i) and then (ii).

    [0010] The polyvinyl alcohol polymer used according to the invention comprises:
    • at least one alcohol unit of formula (I)
    • optionally at least one acetate unit of formula (II)
    • at least one photocrosslinkable unit of formula (P) and
    • at least one hydrophobic unit of formula (H1) below:





      in which:
      A denotes a monovalent aromatic group of formula (A1) chosen from 1-5, 8, 9, 13-14, 18, 20 and 29 as defined later.
      Q denotes a styrylpyridinium (stilbazolium, also known as SbQ) group of formula (Q1) or (Q2) below:

      in which:

      R1 and R3, which may be identical or different, represent a halogen atom or a (C1-C6)alkyl group; or alternatively two contiguous groups R1 or R3 form, together with the carbon atoms that bear them, a benzo group;

      R2 represents a hydrogen atom, a (C1-C6)alkyl group optionally substituted with one or more halogen atoms such as chlorine, or hydroxyl; preferably, R2 represents a (C1-C6)alkyl group such as methyl, ethyl or propyl;

      q and r represent an integer between 0 and 4 inclusive; and

      X- represents an anionic counterion preferably chosen from halide ions such as chlorides, bromides or iodides, perchlorates, tetrafluoroborates, methylsulfate, phosphates, sulfates, methanesulfonates or p-toluenesulfonate;

      * represents the bond that connects the part of the monovalent radical to the rest of the polymer, it being understood that the side group Q2 may be connected to the rest of the polymer via R2;

      preferably the bond* is on the phenyl in the para position relative to the styryl group on A1 or connected to the rest of the polymer via R2 on Q2; preferentially, the styryl group of Q1 and Q2 is para to the pyridinium group.


    [0011] Preferably, the group Q represents a group bearing a stilbazolium function of formula (Ia):

    in which:

    R represents a hydrogen atom or a C1-C4 alkyl or C1-C4 hydroxyalkyl group;

    R' represents a hydrogen atom or a C1-C4 alkyl group, and

    X- denotes an anionic counterion preferably chosen from halide ions such as chlorides, bromides and iodides, perchlorates, tetrafluoroborates, methylsulfate, phosphates, sulfates, methanesulfonates, p-toluenesulfonate; preferably, the styryl group is para to the pyridinium group and/or para to the connecting bond -----*



    [0012] Preferentially, Q represents the group:

    X- being as defined previously, and preferably the methylsulfate or chloride anion.

    [0013] In the chemical structures drawn, the * represents the bond connecting the part of the radical to the rest of the polymer.

    [0014] Advantageously, the units of formula (II) may be present in the polyvinyl alcohol in a proportion ranging from 0.1 mol% to 40 mol% relative to the polymer, preferably ranging from 5 mol% to 20 mol%.

    [0015] Advantageously, the polymer used according to the invention comprises a content of photocrosslinkable unit (P) ranging from 0.2 mol% to 10 mol%, preferably ranging from 0.5 mol% to 15 mol% and preferentially ranging from 0.5 mol% to 10 mol% relative to the polymer.

    [0016] Advantageously, the polymer used according to the invention comprises a content of hydrophobic unit (H1) ranging from 0.2 mol% to 50 mol%, preferably ranging from 0.5 mol% to 40 mol%, preferentially ranging from 0.5 mol% to 30 mol%, more preferentially ranging from 3 mol% to 25 mol% and better still ranging from 10 mol% to 25 mol% relative to the polymer.

    [0017] The following scheme shows the crosslinking reaction which takes place between the photocrosslinkable groups such as the stilbazolium groups, under the effect of light, as illustrated below:



    [0018] These materials are particularly appreciated since they do not require a photoinitiator and react with visible light or with radiation that may comprise both UV light and visible light, in particular a low dose of UV.

    [0019] Preferably, the polymer used according to the invention has a weight-average molecular weight ranging from 10 000 to 200 000 g/mol.

    [0020] The polymer used according to the invention may be prepared by reacting a polyvinyl alcohol with an aldehyde of formula A-CHO or a dialdehyde of formula OHC-D-CHO and an aldehyde of formula Q-CHO, the groups A, D and Q being as defined previously. The reaction may be performed in acidic aqueous medium (water or mixture of water and water-miscible solvents such as ethanol, isopropanol or butanol), especially at a temperature of between 25°C and 85°C, especially for 1 to 12 hours.

    [0021] The hydrophobic monovalent aromatic groups (A1) are :















    [0022] Preferably, (A1) is chosen from groups
    1 to 5, 8, 9 and 18, and more preferentially from groups 1 and 4.

    [0023] A subject of the invention is also a composition comprising, in a physiologically acceptable medium, a novel polymer as described previously.

    [0024] The polymer used according to the invention may be used in a composition comprising a physiologically acceptable medium, in particular in a cosmetic composition.

    [0025] The term "physiologically acceptable medium" means a medium that is compatible with human keratin fibres, in particular with the hair.

    [0026] The term "cosmetic composition" means a composition that is compatible with keratin fibres, which has a pleasant colour, odour and feel and which does not cause any unacceptable discomfort (stinging, tautness or redness) liable to discourage the consumer from using it.

    [0027] The polymer as defined previously may be present in the composition used according to the invention in a content ranging from 0.1% to 40% by weight, relative to the total weight of the composition derived from the extemporaneous mixing, preferably from 0.5% to 30% by weight, preferentially ranging from 1% to 20% by weight and more preferentially ranging from 1% to 10% by weight.

    [0028] The process of the invention comprises a step ii) of irradiating the composition on the keratin fibres to crosslink the polymer.

    [0029] This irradiation may consist of illumination, with ambient light or with a source of artificial light, of the composition applied to the keratin fibres.

    [0030] The ambient or artificial light may emit radiation in the visible and/or UV range. Preferably, it emits at least a proportion of radiation in the UV range, for example a UV proportion of at least 2% of the total illuminating energy of the ambient light.

    [0031] According to a particular embodiment, the exposure comprises, or even consists of, illumination with ambient light of the treated hair, in particular for a time of at least 1 minute.

    [0032] The exposure time to the ambient light may range more particularly from 10 seconds to 30 minutes and especially from 2 to 15 minutes.

    [0033] According to another particular embodiment, the exposure comprises, or even consists of, illumination with a source of artificial light of the surface of said coat.

    [0034] The exposure time to said artificial light may range from 1 second to 20 minutes and in particular from 1 second to 1 minute.

    [0035] The crosslinking may take place with natural or artificial light, for example using lighting with a lamp, a flash, a laser or LEDs, for example in the form of an LED array.

    [0036] The artificial light source may emit radiation in the visible range and/or radiation in the UV range.

    [0037] The light emitted may or may not be monochromatic. The wavelength of the emitted light is preferably centred on 365 nm, in particular between 100 nm and 500 nm and better still between 200 nm and 420 nm.

    [0038] Advantageously, the crosslinking is initiated by simple illumination without the need for a photoinitiator.

    [0039] Preferably, it will be a source of artificial light emitting energy between 0.5 and 5 W/cm2, the exposure times being adapted in consequence.

    [0040] The crosslinking may occur with reduced light intensity, the lighting system may produce this light intensity for example between 500 mJ/cm2 and 10 J/cm2.

    [0041] The twofold characteristic of the absence of a photoinitiator and the relatively low light intensity is particularly advantageous since it makes it possible to limit the harmful effects of aggressive initiators or of prolonged exposure to intense light, in particular in the UV wavelengths.

    [0042] A person skilled in the art will be capable of adapting the illumination characteristics, especially in terms of exposure time and of radiation wavelengths, with regard to the nature of the photocrosslinkable polymer(s) (A) used.

    [0043] According to a preferred embodiment, the composition is applied to keratin fibres such as the hair.

    [0044] According to this embodiment, the composition may be applied to wet or dry, clean or unclean keratin fibres. Preferably, the keratin fibres are dried after applying the composition and before irradiation.

    [0045] It is also possible to include in the process, before or after the irradiation step ii), a pause at room temperature, or at elevated temperature, or under red light.

    [0046] The process according to the invention may also comprise an additional step of drying the keratin fibres, after step (i) of applying the composition containing the polymer and before or after step (ii) of irradiating the keratin fibres. The drying step may be performed using a hairdryer or a drying hood or by drying naturally. The drying step is advantageously performed at a temperature ranging from 20 to 70°C.

    [0047] After the irradiation step, the keratin fibres may be optionally rinsed with water or washed with a shampoo. The keratin fibres are then optionally dried using a hairdryer or a drying hood or dried naturally.

    [0048] According to one embodiment, the process according to the invention is performed on natural or damaged or sensitized keratin fibres, which have optionally been dyed and/or have optionally undergone a prior long-lasting or temporary hair shaping treatment.

    [0049] Damaged fibres are, for example, dry or coarse or brittle or split or soft fibres.

    [0050] Sensitized fibres are, for example, bleached, relaxed or permanent-waved fibres.

    [0051] The process according to the invention is preferably performed on dry keratin fibres, i.e. fibres that are not wet, especially dry hair.

    [0052] After step (i) of applying to the keratin fibres the composition containing the polymer, and before performing step (ii) of irradiating the keratin fibres, the composition containing the applied polymer may be left on the fibres for a time ranging from 1 to 60 minutes, preferably ranging from 2 to 50 minutes and preferentially ranging from 5 to 45 minutes. The leave-on time may take place at a temperature ranging from 15°C to 45°C, preferably at room temperature (25°C).

    [0053] The composition described previously is advantageously applied to the keratin fibres in an amount ranging from 0.1 to 10 grams and preferably from 0.2 to 5 grams of composition per gram of keratin fibres.

    [0054] After application of the composition to the keratin fibres, they may be wrung out to remove the excess composition.

    [0055] The treatment process according to the invention may be performed during and/or after, preferably after, an additional process of cosmetic treatment of the keratin fibres, such as a process for temporary hair shaping (hair shaping with curlers, a curling iron or a straightening iron) or a process for durable hair shaping (permanent-waving or relaxing) or a process for dyeing or bleaching the keratin fibres.

    [0056] The treatment process according to the invention may also be performed as a post-treatment to a cosmetic treatment process.

    [0057] In particular, the treatment process is performed as a post-treatment to a dyeing, bleaching, relaxing or straightening process and/or a permanent-waving process.

    [0058] The composition used according to the invention is generally suitable for topical application to keratin fibres, and thus generally comprises a physiologically acceptable medium, i.e. a medium that is compatible with the skin and/or its integuments. It is preferably a cosmetically acceptable medium, i.e. a medium which has a pleasant colour, odour and feel and which does not cause any unacceptable discomfort (stinging, tautness or redness).

    [0059] The cosmetic composition used according to the invention contains a physiologically acceptable medium, i.e. a medium that is compatible with human keratin materials such as the skin (of the body, face, eye contour or the scalp), the hair, the eyelashes, the eyebrows, bodily hair, the nails or the lips.

    [0060] According to one embodiment of the invention, the cosmetic composition used according to the invention may comprise a physiologically acceptable aqueous medium. It may be constituted, for example, of water or of a mixture of water and of at least one cosmetically acceptable organic solvent. Examples of organic solvents that may be mentioned include C2-C4 lower alcohols, such as ethanol and isopropanol ; polyols, especially those containing from 2 to 6 carbon atoms, for instance glycerol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, dipropylene glycol or diethylene glycol; short esters such as ethyl acetate or butyl acetate; and mixtures thereof.

    [0061] According to another embodiment of the invention, the cosmetic composition used according to the invention comprises a physiologically acceptable non-aqueous medium. It may be constituted, for example, of one or more cosmetically acceptable organic solvents, such as those described previously, or alternatively one or more common cosmetic oils.

    [0062] The non-aqueous medium preferably comprises a volatile oil.

    [0063] The term "volatile oil" means an oil (or non-aqueous medium) that is capable of evaporating on contact with the skin in less than one hour, at room temperature and at atmospheric pressure. The volatile oil is a volatile cosmetic oil, which is liquid at room temperature, especially having a non-zero vapour pressure, at room temperature and at atmospheric pressure, in particular having a vapour pressure ranging from 0.13 Pa to 40 000 Pa (10-3 to 300 mmHg), preferably ranging from 1.3 Pa to 13 000 Pa (0.01 to 100 mmHg) and preferentially ranging from 1.3 Pa to 1300 Pa (0.01 to 10 mmHg).

    [0064] These volatile oils may be hydrocarbon-based oils or silicone oils, or mixtures thereof. The term "hydrocarbon-based oil" means an oil mainly containing hydrogen and carbon atoms and possibly oxygen, nitrogen, sulfur and/or phosphorus atoms.

    [0065] The volatile hydrocarbon-based oils may be chosen from hydrocarbon-based oils containing from 8 to 16 carbon atoms, and especially branched C8-C16 alkanes such as C8-C16 isoalkanes of petroleum origin (also known as isoparaffins), for instance isododecane (also known as 2,2,4,4,6-pentamethylheptane), isodecane, isohexadecane and, for example, the oils sold under the trade names Isopar® or Permethyl®.

    [0066] Volatile silicone oils that may be mentioned include volatile linear or cyclic silicone oils, especially those with a viscosity ≤ 8 centistokes (cSt) (8 × 10-6 m2/s), and especially containing from 2 to 10 silicon atoms and in particular from 2 to 7 silicon atoms, these silicones optionally comprising alkyl or alkoxy groups containing from 1 to 10 carbon atoms. As volatile silicone oils that may be used in the invention, mention may be made in particular of dimethicones with viscosities of 5 and 6 cSt (5 x 10-6m2/s and 6 x 10-6m2/s) octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane and dodecamethylpentasiloxane, and mixtures thereof.

    [0067] The compositions used according to the invention may also contain one or more cosmetic additives chosen from surfactants, sunscreens, fillers, colorants, nacreous agents, opacifiers, sequestrants, film-forming polymers, plasticizers, thickeners, oils, waxes, fragrances and preserving agents.

    [0068] The compositions used according to the invention may be in any presentation form conventionally used and especially in the form of aqueous solutions, aqueous-alcoholic solutions, oil-in-water (O/W), water-in-oil (W/O) or multiple (triple: W/O/W or O/W/O) emulsions, aqueous gels or aqueous-alcoholic gels. These compositions are prepared according to the usual methods.

    [0069] According to an advantageous embodiment of the invention the cosmetic composition used according to the invention comprises a mixture of water and protic polar solvent such as alcohols, especially C2-C4 lower alcohols, such as ethanol and isopropanol, preferably in equivalent amount such as 50/50, vol/vol.

    [0070] The invention will now be described with reference to the examples that follow.

    Example 1: Polyvinyl alcohol polymer functionalized with SbQ and vanillin groups (P1)



    [0071] 

    20 g of polyvinyl alcohol (Selvol® 540 from Sekisui) and 200 ml of a solvent mixture (50/50 weight/weight water/isopropanol) were placed in a reactor. The mixture was heated at 80°C until dissolution of the polyvinyl alcohol was complete. 5 ml of 1M HCl and 1 g of vanillin and 1 g of N-methyl-4-(p-formylstyryl)pyridinium methyl sulfate (CA No. 74401-04-0) were then added. The reaction medium was maintained at 80°C for 8 hours. The product was purified three times by precipitation from 600 ml of acetone. The purified product was placed in water/isopropanol aqueous-alcoholic solution (50/50 weight/weight) at 10% by weight of polymer (solution S1). The polymer obtained comprises 20% by weight of group derived from vanillin and 15% by weight of SbQ group derived from N-methyl-4-(p-formylstyryl)pyridinium methyl sulfate.

    Example 2: Polyvinyl alcohol polymer functionalized with SbQ and 3,4-dihydroxybenzaldehyde groups (P2)



    [0072] 



    [0073] The polymer was prepared according to the procedure described in Example 1, using:

    20 g of polyvinyl alcohol (Selvol 540 from Sekisui)

    1 g of 3,4-dihydroxybenzaldehyde

    1 g of N-methyl-4-(p-formylstyryl)pyridinium methyl sulfate

    Solvent: water/isopropanol (40/60 weight/weight): 200 ml



    [0074] The polymer obtained comprises 18% by weight of group derived from 3,4-dihydroxybenzaldehyde and 15% by weight of SbQ group derived from N-methyl-4-(p-formylstyryl)pyridinium methyl sulfate. After purification, the polymer was dissolved at 10% by weight in a water/isopropanol mixture (50/50 weight/weight).

    [0075] A solution S2 of polymer 2 was thus obtained.

    Example 3 (outside the invention) : Polyvinyl alcohol polymer functionalized with SbQ and terephthaldehyde groups (P3)



    [0076] 



    [0077] The polymer was prepared according to the procedure described in Example 1, using:

    20 g of polyvinyl alcohol (Selvol 540 from Sekisui)

    1 g of 3,4-dihydroxybenzaldehyde

    1 g of N-methyl-4-(p-formylstyryl)pyridinium methyl sulfate

    0.5 g of terephthaldehyde

    Solvent: water/isopropanol (200/50): 250 ml



    [0078] by first adding HCI and the SbQ, and maintaining the reaction mixture at 80°C for 6 hours, followed by adding the terephthaldehyde. The formation of a hydrogel is observed.

    [0079] The polymer obtained comprises 2.5% by weight (i.e. 0.8 mol%) of group derived from terephthaldehyde and 1% by weight (i.e. 0.98 mol%) of SbQ group derived from N-methyl-4-(p-formylstyryl)pyridinium methyl sulfate.

    Example 4 (outside the invention): Polyvinyl alcohol polymer functionalized with SbQ groups (P4)



    [0080] 



    [0081] The polymer was prepared according to the procedure described in Example 1, using:

    20 g of polyvinyl alcohol (Selvol 540 from Sekisui)

    1 g of N-methyl-4-(p-formylstyryl)pyridinium methyl sulfate

    Solvent: 200 ml of water



    [0082] The polymer obtained comprises 15% by weight of SbQ group derived from N-methyl-4-(p-formylstyryl)pyridinium methyl sulfate.

    Example 5 (outside the invention): polyvinyl alcohol polymer functionalized with SbQ groups (P5)



    [0083] 

    sold by the company Polysciences, Inc. under the catalogue reference 22570-75 with a degree of grafting with SbQ groups derived from N-methyl-4-(p-formylstyryl)pyridinium methyl sulfate of 4.1 mol%; molecular weight: -45 000.

    Comparative Examples 6 to 10: Evaluation of the cosmetic properties of the polymers applied to the hair



    [0084] The five compositions described below were prepared (weight percentages).
     Ex. 6Ex. 7Ex. 8*Ex. 9*Ex. 10*
    Polymer 1 10        
    Polymer 2   10      
    Polymer 4     10    
    Polymer 5       10  
    PVA         10
    Water     qs 100 qs 100 qs 100
    50/50 water/isopropanol (weight/weight) qs 100 qs 100      

    * examples outside the invention



    [0085] A mixture of 40% by weight of bleaching powder sold under the name Platifiz® Precision by L'Oreal and 60% of aqueous hydrogen peroxide solution at 0.6% by weight was applied to locks of hair of curly type IV, in a bath ratio equal to 4, and the treated locks were then heated on a hotplate at 33°C for 30 minutes. The locks were then rinsed with tap water and left to dry in a ventilated oven at 70°C for one hour. This protocol was repeated a second time.

    [0086] The polymer composition to be evaluated was applied to the locks thus bleached, using a brush, with a bath ratio equal to 1, on each side of the lock of hair. The lock was then exposed under a Sina UV Lamp & Dryer - 56 W UV lamp for 6 minutes and was then dried on a hotplate at 50°C for 15 minutes. The treated locks were then left at room temperature for 24 hours.

    [0087] 1 g of DOP camomile shampoo sold by La Scad was then applied per 2.8 g of locks, and the locks were massaged for 10 seconds, left to stand for three minutes and then rinsed with water at 37°C, 10 passes. The locks were then dried in a ventilated oven at 70°C for 1 hour. Shampoo was applied five times in total.

    [0088] The following cosmetic properties were then evaluated:
    Feel: the feel by finger of the treated locks was evaluated by three people trained in sensory evaluation on hair, on softness tactile criteria.

    [0089] Disentangling: disentangling using a comb was performed after immersing the lock for 10 seconds in water, with 5 passes of a small-toothed plastic comb (7 teeth/cm, tooth diameter of about 800 µm).

    [0090] The evaluation was made in the following manner:

    ++: cosmetic property evaluated as effective

    +: cosmetic property evaluated as moderately effective

    0: cosmetic property evaluated as ineffective



    [0091] The following results were obtained:
     Before shampooingAfter 5 shampoo washes
    ExamplesFeel wet (softness)Disentang lingFeel dry (softness)Feel wet (softness)Disentang lingFeel dry (softness)
    6 (P1) Invention ++ + ++ ++ ++ ++
    7 (P2) Invention ++ + ++ ++ + ++
    8* (P4) Comparative + 0 + 0 0 0
    9* (P5) Comparative + 0 + 0 0 0
    10* (PVA) Comparative 0 0 0 0 0 0


    [0092] It is seen from the results of the table that polymers P1 and P2 of the invention make it possible to improve the feel and the disentangling, before and even after five shampoo washes, versus PVA alone, or polymers P4 and P5 outside the invention which do not comprise hydrophobic chains.

    [0093] The results obtained show that the polymers according to the invention give improved feel and disentangling properties.

    Example 11 (outside the invention)



    [0094] The following composition is prepared (weight percentage):
    Polymer 3 (Example 3) 6%    
    Water/isopropanol (50/50)   qs 100%


    [0095] The composition is applied to the hair and left to dry for 15 minutes at room temperature, and the hair is then exposed to light under a Sina UV Lamp & Dryer - 56 W UV lamp for 6 minutes.

    [0096] The hair thus treated has a soft feel and good disentangling, including after shampooing.


    Claims

    1. Cosmetic process for treating keratin fibres, comprising:

    (i) a step of applying to the keratin fibres a cosmetic composition comprising a polyvinyl alcohol polymer;

    (ii) a step of irradiating the composition on the keratin fibres to crosslink said polymer; steps (i) and (ii) being performed at the same time or separately, in the order (i) and then (ii);

    the polyvinyl alcohol polymer comprising:

    - at least one alcohol unit of formula (I)

    - optionally at least one acetate unit of formula (II)

    - at least one photocrosslinkable unit of formula (P) and

    - at least one hydrophobic unit of formula (H1) below:





    in which:
    A denotes a monovalent aromatic group of formula (A1) chosen from:







    preferably, (A1) is chosen from groups 1 to 5, 8, 9 and 18, and more preferentially from groups 1 and 4;
    Q denotes a styrylpyridinium (stilbazolium, also known as SbQ) group of formula (Q1) or (Q2) below:

    in which:

    R1 and R3, which may be identical or different, represent a halogen atom or a (C1-C6)alkyl group; or alternatively two contiguous groups R1 or R3 form, together with the carbon atoms that bear them, a benzo group;

    R2 represents a hydrogen atom, a (C1-C6)alkyl group optionally substituted with one or more halogen atoms such as chlorine, or hydroxyl; preferably, R2 represents a (C1-C6)alkyl group such as methyl, ethyl or propyl;

    q and r represent an integer between 0 and 4 inclusive; and

    X- represents an anionic counterion preferably chosen from halide ions such as chlorides, bromides or iodides, perchlorates, tetrafluoroborates, methylsulfate, phosphates, sulfates, methanesulfonates or p-toluenesulfonate;

    * represents the bond that connects the part of the radical to the rest of the polymer.


     
    2. Process according to the preceding claim, characterized in that the group Q of the unit (P) represents a group bearing a stilbazolium function of formula (Ia):

    in which:

    R represents a hydrogen atom or a C1-C4 alkyl or C1-C4 hydroxyalkyl group;

    R' represents a hydrogen atom or a C1-C4 alkyl group, and

    X- denotes an anionic counterion preferably chosen from halide ions, perchlorates, tetrafluoroborates, methylsulfate, phosphate, sulfate, methanesulfonates, p-toluenesulfonate; preferably, the styryl group is para to the pyridinium group and/or para to the connecting bond -----*.


     
    3. Process according to one of the preceding claims, characterized in that the group Q of the unit (P) represents the group:

    in which X- denotes an anionic counterion preferably chosen from halide ions, perchlorates, tetrafluoroborates, methylsulfate, phosphate, sulfate, methanesulfonates and p-toluenesulfonate; and preferably the methylsulfate or chloride anion.
     
    4. Process according to one of the preceding claims, characterized in that the polymer comprises at least one unit of formula (II) preferably present in the polyvinyl alcohol in a proportion ranging from 0.1 mol% to 40 mol% relative to the polymer, preferably ranging from 5 mol% to 20 mol%.
     
    5. Process according to one of the preceding claims, characterized in that the polymer comprises a content of photocrosslinkable unit (P) ranging from 0.2 mol% to 10 mol%, preferably ranging from 0.5 mol% to 15 mol% and preferentially ranging from 0.5 mol% to 10 mol% relative to the polymer.
     
    6. Process according to one of the preceding claims, characterized in that the polymer comprises a content of hydrophobic unit (H1) ranging from 0.2 mol% to 50 mol%, preferably ranging from 0.5 mol% to 40 mol%, preferentially ranging from 0.5 mol% to 30 mol%, more preferentially ranging from 3 mol% to 25 mol% and better still ranging from 10 mol% to 25 mol% relative to the polymer.
     
    7. Process according to one of the preceding claims, characterized in that said polymer has a weight-average molecular weight ranging from 10 000 to 200 000 g/mol.
     
    8. Process according to one of the preceding claims, characterized in that the polymer is present in the cosmetic composition in a content ranging from 0.1% to 40% by weight, relative to the total weight of the composition derived from the extemporaneous mixture, preferably from 0.5% to 30% by weight, preferentially ranging from 1% to 20% by weight and more preferentially ranging from 1% to 10% by weight.
     
    9. Process according to one of the preceding claims, characterized in that the irradiation is irradiation with radiation in the UVA or the visible domain, and preferably radiation in the UVA.
     
    10. Polyvinyl alcohol polymer comprising:

    - at least one alcohol unit of formula (I)

    - optionally at least one acetate unit of formula (II)

    - at least one photocrosslinkable unit of formula (P) and

    - at least one hydrophobic unit of formula (H1) below:





    in which:

    A denotes a monovalent aromatic group of formula (A1) chosen from:







    preferably, (A1) is chosen from groups 1 to 5, 8, 9 and 18, and more preferentially from groups 1 and 4;

    Q denotes a styrylpyridinium (stilbazolium, also known as SbQ) group of formula (Q1) or (Q2) below:

    in which:

    R1 and R3, which may be identical or different, represent a halogen atom or a (C1-C6)alkyl group; or alternatively two contiguous groups R1 or R3 form, together with the carbon atoms that bear them, a benzo group;

    R2 represents a hydrogen atom, a (C1-C6)alkyl group optionally substituted with one or more halogen atoms such as chlorine, or hydroxyl; preferably, R2 represents a (C1-C6)alkyl group such as methyl, ethyl or propyl;

    q and r represent an integer between 0 and 4 inclusive; and

    X- represents an anionic counterion preferably chosen from halide ions such as chlorides, bromides or iodides, perchlorates, tetrafluoroborates, methylsulfate, phosphates, sulfates, methanesulfonates or p-toluenesulfonate;

    * represents the bond that connects the part of the radical to the rest of the polymer.


     
    11. Polymer according to Claim 10, characterized in that the group Q of the unit (P) represents a group bearing a stilbazolium function of formula (Ia):

    in which:

    R represents a hydrogen atom or a C1-C4 alkyl or C1-C4 hydroxyalkyl group;

    R' represents a hydrogen atom or a C1-C4 alkyl group, and

    X- denotes an anionic counterion preferably chosen from halide ions, perchlorates, tetrafluoroborates, methylsulfate, phosphate, sulfate, methanesulfonates, p-toluenesulfonate; preferably, the styryl group is para to the pyridinium group and/or para to the connecting bond -----*.


     
    12. Polymer according to one of Claims 10 or 11, characterized in that the group Q of the unit (P) represents the group:

    in which X- denotes an anionic counterion preferably chosen from halide ions, perchlorates, tetrafluoroborates, methylsulfate, phosphate, sulfate, methanesulfonates and p-toluenesulfonate; and preferably the methylsulfate or chloride anion.
     
    13. Polymer according to one of Claims 10 to 12, characterized in that it comprises at least one unit of formula (II) preferably present in the polyvinyl alcohol in a proportion ranging from 0.1 mol% to 40 mol% relative to the polymer, preferably ranging from 5 mol% to 20 mol%.
     
    14. Polymer according to one of Claims 10 to 13, characterized in that it comprises a content of photocrosslinkable unit (P) ranging from 0.2 mol% to 10 mol%, preferably ranging from 0.5 mol% to 15 mol% and preferentially ranging from 0.5 mol% to 10 mol% relative to the polymer.
     
    15. Polymer according to one of Claims 10 to 14, characterized in that it comprises a content of hydrophobic unit (H1) ranging from 0.2 mol% to 50 mol%, preferably ranging from 0.5 mol% to 40 mol%, preferentially ranging from 0.5 mol% to 30 mol%, more preferentially ranging from 3 mol% to 25 mol% and better still ranging from 10 mol% to 25 mol% relative to the polymer.
     
    16. Polymer according to one of Claims 10 to 15, characterized in that said polymer has a weight-average molecular weight ranging from 10 000 to 200 000 g/mol.
     
    17. Composition comprising, in a physiologically acceptable medium, a polymer according to any one of the preceding claims.
     


    Ansprüche

    1. Kosmetisches Verfahren zur Behandlung von Keratinfasern, umfassend:

    (i) einen Schritt des Aufbringens einer kosmetischen Zusammensetzung, die ein Polyvinylalkohol-Polymer umfasst, auf die Keratinfasern;

    (ii) einen Schritt des Bestrahlens der Zusammensetzung auf den Keratinfasern zum Vernetzen des Polymers;

    wobei die Schritte (i) und (ii) gleichzeitig oder separat in der Reihenfolge (i) und dann (ii) durchgeführt werden;
    wobei das Polyvinylalkohol-Polymer Folgendes umfasst:

    - mindestens eine Alkoholeinheit der Formel (I),

    - gegebenenfalls mindestens eine Acetateinheit der Formel (II),

    - mindestens eine photovernetzbare Einheit der Formel (P) und

    - mindestens eine hydrophobe Einheit der nachstehenden Formel (H1):





    wobei:

    A für eine einwertige aromatische Gruppe der Formel (A1) steht, die aus







    ausgewählt ist, vorzugsweise (A1) aus den Gruppen 1 bis 5, 8, 9 und 18 und weiter bevorzugt aus den Gruppen 1 und 4 ausgewählt ist;

    Q für eine Styrylpyridiniumgruppe (Stilbazoliumgruppe, auch bekannt als SbQ-Gruppe) der nachstehenden Formel (Q1) oder (Q2) steht:

    wobei:

    R1 und R3, die gleich oder verschieden sein können, für ein Halogenatom oder eine (C1-C6)-Alkylgruppe stehen; oder alternativ dazu zwei benachbarte Gruppen R1 oder R3 zusammen mit den Kohlenstoffatomen, die sie tragen, eine Benzogruppe bilden;

    R2 für ein Wasserstoffatom, eine (C1-C6)-Alkylgruppe, die gegebenenfalls durch ein oder mehrere Halogenatome wie Chlor oder Hydroxyl substituiert ist; vorzugsweise R2 für eine (C1-C6)-Alkylgruppe wie Methyl, Ethyl oder Propyl steht;

    q und r für eine ganze Zahl zwischen 0 und 4 inklusive stehen und

    X- für ein anionisches Gegenion steht, das vorzugsweise aus Halogenidionen wie Chloriden, Bromiden oder Iodiden, Perchloraten, Tetrafluoroboraten, Methylsulfat, Phosphaten, Sulfaten, Methansulfonaten oder p-Toluolsulfonat ausgewählt ist;

    * für die Bindung steht, die den Teil des Rests mit dem Rest des Polymers verbindet.


     
    2. Verfahren nach dem vorhergehenden Anspruch, dadurch gekennzeichnet, dass die Gruppe Q der Einheit (P) für eine Gruppe mit einer Stilbazoniumfunktion der Formel (Ia) steht:

    wobei:

    R für ein Wasserstoffatom oder eine C1-C4-Alkyl- oder C1-C4-Hydroxyalkylgruppe steht;

    R' für ein Wasserstoffatom oder eine C1-C4-Alkylgruppe steht und

    X- für ein anionisches Gegenion steht, das vorzugsweise aus Halogenidionen, Perchloraten, Tetrafluoroboraten, Methylsulfat, Phosphat, Sulfat, Methansulfonaten und p-Toluolsulfonat ausgewählt ist; vorzugsweise die Styrylgruppe in para-Position zur Pyridiniumgruppe und/oder in para-Position zur verknüpfenden Bindung -----* steht.


     
    3. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Gruppe Q der Einheit (P) für die Gruppe:

    steht, wobei X- für ein anionisches Gegenion steht, das vorzugsweise aus Halogenidionen, Perchloraten, Tetrafluoroboraten, Methylsulfat, Phosphat, Sulfat, Methansulfonaten und p-Toluolsulfonat und vorzugsweise aus dem Methylsulfat- oder Chlorid-Anion ausgewählt ist.
     
    4. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Polymer mindestens eine Einheit der Formel (II) umfasst, die vorzugsweise in dem Polyvinylalkohol in einem Anteil im Bereich von 0,1 Mol-% bis 40 Mol-%, bezogen auf das Polymer, vorzugsweise im Bereich von 5 Mol-% bis 20 Mol-%, vorliegt.
     
    5. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Polymer einen Gehalt an photovernetzbarer Einheit (P) im Bereich von 0,2 Mol-% bis 10 Mol-%, vorzugsweise im Bereich von 0,5 Mol-% bis 15 Mol-% und bevorzugt im Bereich von 0,5 Mol-% bis 10 Mol-%, bezogen auf das Polymer, umfasst.
     
    6. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Polymer einen Gehalt an hydrophober Einheit (H1) im Bereich von 0,2 Mol-% bis 50 Mol-%, vorzugsweise im Bereich von 0,5 Mol-% bis 40 Mol-%, bevorzugt im Bereich von 0,5 Mol-% bis 30 Mol-%, weiter bevorzugt im Bereich von 3 Mol-% bis 25 Mol-% und noch besser im Bereich von 10 Mol-% bis 25 Mol-%, bezogen auf das Polymer, aufweist.
     
    7. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Polymer ein gewichtsmittleres Molekulargewicht im Bereich von 10.000 bis 200.000 g/mol aufweist.
     
    8. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Polymer in der kosmetischen Zusammensetzung in einem Gehalt im Bereich von 0,1 bis 40 Gew.-%, bezogen auf das Gesamtgewicht der aus der extemporalen Mischung erhaltenen Zusammensetzung, vorzugsweise 0,5 bis 30 Gew.-%, bevorzugt im Bereich von 1 bis 20 Gew.-% und weiter bevorzugt im Bereich von 1 bis 10 Gew.-%, vorliegt.
     
    9. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass es sich bei der Bestrahlung um Bestrahlung mit Strahlung im UVA oder im sichtbaren Bereich und vorzugsweise Strahlung im UVA handelt.
     
    10. Polyvinylalkohol-Polymer, umfassend:

    - mindestens eine Alkoholeinheit der Formel (I),

    - gegebenenfalls mindestens eine Acetateinheit der Formel (II),

    - mindestens eine photovernetzbare Einheit der Formel (P) und

    - mindestens eine hydrophobe Einheit der nachstehenden Formel (H1):





    wobei:

    A für eine einwertige aromatische Gruppe der Formel (A1) steht, die aus







    ausgewählt ist, vorzugsweise (A1) aus den Gruppen 1 bis 5, 8, 9 und 18 und weiter bevorzugt aus den Gruppen 1 und 4 ausgewählt ist;

    Q für eine Styrylpyridiniumgruppe (Stilbazoliumgruppe, auch bekannt als SbQ-Gruppe) der nachstehenden Formel (Q1) oder (Q2) steht:

    wobei:

    R1 und R3, die gleich oder verschieden sein können, für ein Halogenatom oder eine (C1-C6)-Alkylgruppe stehen; oder alternativ dazu zwei benachbarte Gruppen R1 oder R3 zusammen mit den Kohlenstoffatomen, die sie tragen, eine Benzogruppe bilden;

    R2 für ein Wasserstoffatom, eine (C1-C6)-Alkylgruppe, die gegebenenfalls durch ein oder mehrere Halogenatome wie Chlor oder Hydroxyl substituiert ist; vorzugsweise R2 für eine (C1-C6)-Alkylgruppe wie Methyl, Ethyl oder Propyl steht;

    q und r für eine ganze Zahl zwischen 0 und 4 inklusive stehen und

    X- für ein anionisches Gegenion steht, das vorzugsweise aus Halogenidionen wie Chloriden,

    Bromiden oder Iodiden, Perchloraten, Tetrafluoroboraten, Methylsulfat, Phosphaten, Sulfaten, Methansulfonaten oder p-Toluolsulfonat ausgewählt ist;

    * für die Bindung steht, die den Teil des Rests mit dem Rest des Polymers verbindet.


     
    11. Polymer nach Anspruch 10, dadurch gekennzeichnet, dass die Gruppe Q der Einheit (P) für eine Gruppe mit einer Stilbazoniumfunktion der Formel (Ia) steht:

    wobei:

    R für ein Wasserstoffatom oder eine C1-C4-Alkyl- oder C1-C4-Hydroxyalkylgruppe steht;

    R' für ein Wasserstoffatom oder eine C1-C4-Alkylgruppe steht und

    X- für ein anionisches Gegenion steht, das vorzugsweise aus Halogenidionen, Perchloraten, Tetrafluoroboraten, Methylsulfat, Phosphat, Sulfat, Methansulfonaten und p-Toluolsulfonat ausgewählt ist; vorzugsweise die Styrylgruppe in para-Position zur Pyridiniumgruppe und/oder in para-Position zur verknüpfenden Bindung -----* steht.


     
    12. Polymer nach einem der Ansprüche 10 oder 11, dadurch gekennzeichnet, dass die Gruppe Q der Einheit (P) für die Gruppe:

    steht, wobei X- für ein anionisches Gegenion steht, das vorzugsweise aus Halogenidionen, Perchloraten, Tetrafluoroboraten, Methylsulfat, Phosphat, Sulfat, Methansulfonaten und p-Toluolsulfonat und vorzugsweise dem Methylsulfat- oder Chlorid-Anion ausgewählt ist.
     
    13. Polymer nach einem der Ansprüche 10 bis 12, dadurch gekennzeichnet, dass es mindestens eine Einheit der Formel (II) umfasst, die vorzugsweise in dem Polyvinylalkohol in einem Anteil im Bereich von 0,1 Mol-% bis 40 Mol-%, bezogen auf das Polymer, vorzugsweise im Bereich von 5 Mol-% bis 20 Mol-%, vorliegt.
     
    14. Polymer nach einem der Ansprüche 10 bis 13, dadurch gekennzeichnet, dass es einen Gehalt an photovernetzbarer Einheit (P) im Bereich von 0,2 Mol-% bis 10 Mol-%, vorzugsweise im Bereich von 0,5 Mol-% bis 15 Mol-% und bevorzugt im Bereich von 0,5 Mol-% bis 10 Mol-%, bezogen auf das Polymer, umfasst.
     
    15. Polymer nach einem der Ansprüche 10 bis 14, dadurch gekennzeichnet, dass es einen Gehalt an hydrophober Einheit (H1) im Bereich von 0,2 Mol-% bis 50 Mol-%, vorzugsweise im Bereich von 0,5 Mol-% bis 40 Mol-%, bevorzugt im Bereich von 0,5 Mol-% bis 30 Mol-%, weiter bevorzugt im Bereich von 3 Mol-% bis 25 Mol-% und noch besser im Bereich von 10 Mol-% bis 25 Mol-%, bezogen auf das Polymer, umfasst.
     
    16. Polymer nach einem der Ansprüche 10 bis 15, dadurch gekennzeichnet, dass das Polymer ein gewichtsmittleres Molekulargewicht im Bereich von 10.000 bis 200.000 g/mol aufweist.
     
    17. Zusammensetzung, die in einem physiologisch unbedenklichen Medium ein Polymer nach einem der vorhergehenden Ansprüche umfasst.
     


    Revendications

    1. Procédé cosmétique de traitement des fibres kératiniques comprenant :

    (i) une étape d'application sur les fibres kératiniques d'une composition cosmétique comprenant un polymère de type poly(alcool vinylique) ;

    (ii) une étape d'irradiation de la composition sur les fibres kératiniques pour réticuler ledit polymère ;

    les étapes (i) et (ii) étant réalisées en même temps ou séparément dans l'ordre (i) puis (ii) ;
    le polymère de type poly(alcool vinylique) comprenant :

    - au moins une unité alcool de formule (I)

    - éventuellement au moins une unité acétate de formule (II)

    - au moins une unité photoréticulable de formule (P) et

    - au moins une unité hydrophobe de formule (H1) ci-dessous :





    dans lesquelles :

    A désigne un groupe aromatique monovalent de formule (A1) choisi parmi :







    préférablement, (A1) est choisi parmi les groupes 1 à 5, 8, 9 et 18, et plus préférentiellement parmi les groupes 1 et 4 ;

    Q désigne un groupe styrylpyridinium (stilbazolium, aussi connu comme SbQ) de formule (Q1) ou (Q2) ci-dessous :

    dans lesquelles :

    R1 et R3, qui peuvent être identiques ou différents, représentent un atome d'halogène ou un groupe (C1-C6)alkyle ; ou en variante deux groupes R1 ou R3 contigus forment, conjointement avec les atomes de carbone qui les portent, un groupe benzo ;

    R2 représente un atome d'hydrogène, un groupe (C1-C6)alkyle éventuellement substitué par un ou plusieurs atomes d'halogène tels que le chlore, ou par hydroxy ; préférablement, R2 représente un groupe (C1-C6)alkyle tel que méthyle, éthyle ou propyle ;

    q et r, représentent un entier compris entre 0 et 4 inclus ; et

    X- représente un contre-ion anionique préférablement choisi parmi des ions halogénure tels que des chlorures, des bromures ou des iodures, des perchlorates, des tétrafluoroborates, méthylsulfate, des phosphates, des sulfates, des méthanesulfonates ou un p-toluènesulfonate ;

    * représente la liaison qui relie la partie du radical au reste du polymère.


     
    2. Procédé selon la revendication précédente, caractérisé en ce que le groupe Q de l'unité (P) représente un groupe portant une fonction stilbazolium de formule (Ia) :

    dans laquelle :

    R représente un atome d'hydrogène ou un groupe C1-C4 alkyle ou C1-C4 hydroxyalkyle ;

    R' représente un atome d'hydrogène ou un groupe C1-C4 alkyle, et

    X- désigne un contre-ion anionique préférablement choisi parmi des ions halogénure, des perchlorates, des tétrafluoroborates, méthylsulfate, phosphate, sulfate, des méthanesulfonates, p-toluènesulfonate ;

    préférablement, le groupe styryle est en para du groupe pyridinium et/ou en para à la liaison de connexion ------*.


     
    3. Procédé selon l'une des revendications précédentes, caractérisé en ce que le groupe Q de l'unité (P) représente le groupe :

    dans lequel X- désigne un contre-ion anionique préférablement choisi parmi des ions halogénure, des perchlorates, des tétrafluoroborates, méthylsulfate, phosphate, sulfate, des méthanesulfonates, et p-toluènesulfonate ; et préférablement l'anion méthylsulfate ou chlorure.
     
    4. Procédé selon l'une des revendications précédentes, caractérisé en ce que le polymère comprend au moins une unité de formule (II), préférablement présente dans le poly(alcool vinylique) en une proportion dans la plage de 0,1 % en moles à 40 % en moles par rapport au polymère, préférablement dans la plage de 5 % en moles à 20 % en moles.
     
    5. Procédé selon l'une des revendications précédentes, caractérisé en ce que le polymère comprend une teneur en unité photoréticulable (P) dans la plage de 0,2 % en moles à 10 % en moles, préférablement dans la plage de 0,5 % en moles à 15 % en moles, et préférentiellement dans la plage de 0,5 % en moles à 10 % en moles, par rapport au polymère.
     
    6. Procédé selon l'une des revendications précédentes, caractérisé en ce que le polymère comprend une teneur en unité hydrophobe (H1) dans la plage de 0,2 % en moles à 50 % en moles, préférablement dans la plage de 0,5 % en moles à 40 % en moles, préférentiellement dans la plage de 0,5 % en moles à 30 % en moles, plus préférentiellement dans la plage de 3 % en moles à 25 % en moles, et encore mieux dans la plage de 10 % en moles à 25 % en moles, par rapport au polymère.
     
    7. Procédé selon l'une des revendications précédentes, caractérisé en ce que ledit polymère possède un poids moléculaire moyen en poids dans la plage de 10 000 à 200 000 g/mole.
     
    8. Procédé selon l'une des revendications précédentes, caractérisé en ce que le polymère est présent dans la composition cosmétique en une teneur dans la plage de 0,1 % à 40 % en poids, par rapport au poids total de la composition issue du mélange extemporané, préférablement de 0,5 à 30 % en poids, préférentiellement dans la plage de 1 % à 20 % en poids et plus préférentiellement dans la plage de 1 % à 10 % en poids.
     
    9. Procédé selon l'une des revendications précédentes, caractérisé en ce que l'irradiation est une irradiation avec un rayonnement dans l'UVA ou dans le domaine visible, et préférablement un rayonnement dans l'UVA.
     
    10. Polymère de type poly(alcool vinylique) comprenant :

    - au moins une unité alcool de formule (I)

    - éventuellement au moins une unité acétate de formule (II)

    - au moins une unité photoréticulable de formule (P) et

    - au moins une unité hydrophobe de formule (H1) ci-dessous :





    dans lesquelles :

    A désigne un groupe aromatique monovalent de formule (A1) choisi parmi :







    préférablement, (A1) est choisi parmi les groupes 1 à 5, 8, 9 et 18, et plus préférentiellement parmi les groupes 1 et 4 ;

    Q désigne un groupe styrylpyridinium (stilbazolium, aussi connu comme SbQ) de formule (Q1) ou (Q2) ci-dessous :

    dans lesquelles :

    R1 et R3, qui peuvent être identiques ou différents, représentent un atome d'halogène ou un groupe (C1-C6)alkyle ; ou en variante deux groupes R1 ou R3 contigus forment, conjointement avec les atomes de carbone qui les portent, un groupe benzo ;

    R2 représente un atome d'hydrogène, un groupe (C1-C6)alkyle éventuellement substitué par un ou plusieurs atomes d'halogène tels que le chlore, ou par hydroxy ;

    préférablement, R2 représente un groupe (C1-C6) alkyle tel que méthyle, éthyle ou propyle ;

    q et r, représentent un entier compris entre 0 et 4 inclus ; et

    X- représente un contre-ion anionique préférablement choisi parmi des ions halogénure tels que des chlorures, des bromures ou des iodures, des perchlorates, des tétrafluoroborates, méthylsulfate, des phosphates, des sulfates, des méthanesulfonates ou un p-toluènesulfonate ;

    * représente la liaison qui relie la partie du radical au reste du polymère.


     
    11. Polymère selon la revendication 10, caractérisé en ce que le groupe Q de l'unité (P) représente un groupe portant une fonction stilbazolium de formule (Ia) :

    dans laquelle :

    R représente un atome d'hydrogène ou un groupe C1-C4 alkyle ou C1-C4 hydroxyalkyle ;

    R' représente un atome d'hydrogène ou un groupe C1-C4 alkyle, et

    X- désigne un contre-ion anionique préférablement choisi parmi des ions halogénure, des perchlorates, des tétrafluoroborates, méthylsulfate, phosphate, sulfate, des méthanesulfonates, p-toluènesulfonate ;

    préférablement, le groupe styryle étant en para du groupe pyridinium et/ou en para à la liaison de connexion -----*.


     
    12. Polymère selon l'une des revendications 10 et 11, caractérisé en ce que le groupe Q de l'unité (P) représente le groupe :

    dans lequel X- désigne un contre-ion anionique préférablement choisi parmi des ions halogénure, des perchlorates, des tétrafluoroborates, méthylsulfate, phosphate, sulfate, des méthanesulfonates, p-toluènesulfonate ; et préférablement l'anion méthylsulfate ou chlorure.
     
    13. Polymère selon l'une des revendications 10 à 12, caractérisé en ce qu'il comprend au moins une unité de formule (II), préférablement présente dans le poly(alcool vinylique) en une proportion dans la plage de 0,1 % en moles à 40 % en moles par rapport au polymère, préférablement dans la plage de 5 % en moles à 20 % en moles.
     
    14. Polymère selon l'une des revendications 10 à 13, caractérisé en ce qu'il comprend une teneur en unité photoréticulable (P) dans la plage de 0,2 % en moles à 10 % en moles, préférablement dans la plage de 0,5 % en moles à 15 % en moles, et préférentiellement dans la plage de 0,5 % en moles à 10 % en moles, par rapport au polymère.
     
    15. Polymère selon l'une des revendications 10 à 14, caractérisé en ce qu'il comprend une teneur en unité hydrophobe (H1) dans la plage de 0,2 % en moles à 50 % en moles, préférablement dans la plage de 0,5 % en moles à 40 % en moles, préférentiellement dans la plage de 0,5 % en moles à 30 % en moles, plus préférentiellement dans la plage de 3 % en moles à 25 % en moles, et encore mieux dans la plage de 10 % en moles à 25 % en moles, par rapport au polymère.
     
    16. Polymère selon l'une des revendications 10 à 15, caractérisé en ce que ledit polymère possède un poids moléculaire moyen en poids dans la plage de 10 000 à 200 000 g/mole.
     
    17. Composition comprenant, dans un milieu physiologiquement acceptable, un polymère selon l'une quelconque des revendications précédentes.
     






    Cited references

    REFERENCES CITED IN THE DESCRIPTION



    This list of references cited by the applicant is for the reader's convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.

    Patent documents cited in the description