(19) TZZ ¥Z__T

(11) EP 2 435 016 B1

(12) EUROPEAN PATENT SPECIFICATION

(45) Date of publication and mention (51) Int Cl.: of the grant of the patent: A61K 8/34 (2006.01) A61K 8/31 (2006.01) 18.04.2018 Bulletin 2018/16 A61Q 5/12 (2006.01) A61K 8/41 (2006.01) A61K 8/04 (2006.01) (21) Application number: 10717614.1 (86) International application number: (22) Date of filing: 27.04.2010 PCT/EP2010/055590

(87) International publication number: WO 2010/136285 (02.12.2010 Gazette 2010/48)

(54) CONDITIONER HAARPFLEGEMITTEL Après-shampooing

(84) Designated Contracting States: • RICHARDS, Claire Louise AT BE BG CH CY CZ DE DK EE ES FI FR GB GR Wirral Merseyside CH63 3JW (GB) HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR (74) Representative: Chisem, Janet et al Unilever Patent Group (30) Priority: 28.05.2009 EP 09161386 Colworth House Sharnbrook (43) Date of publication of application: Bedford MK44 1LQ (GB) 04.04.2012 Bulletin 2012/14 (56) References cited: (73) Proprietors: EP-A- 0 407 040 EP-A- 1 258 236 • Unilever PLC WO-A-01/17502 WO-A-01/85108 London EC4Y 0DY (GB) WO-A-97/14396 WO-A-2005/025525 Designated Contracting States: WO-A-2005/039517 US-A- 4 886 660 CY GB IE MT US-A- 5 714 136 • Unilever N.V. 3013 AL Rotterdam (NL) Remarks: Designated Contracting States: Thefile contains technical information submitted after AT BE BG CH CZ DE DK EE ES FI FR GR HR HU the application was filed and not included in this IS IT LI LT LU LV MC MK NL NO PL PT RO SE SI specification SK SM TR

(72) Inventors: • MURRAY, Andrew Malcolm Wirral Merseyside CH63 3JW (GB)

Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent Bulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with the Implementing Regulations. Notice of opposition shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention). EP 2 435 016 B1

Printed by Jouve, 75001 PARIS (FR) EP 2 435 016 B1

Description

[0001] The present invention relates to an improved conditioning composition. [0002] Despite the prior art there remains a need for improved conditioning compositions. 5 [0003] Accordingly, there is provided a hair conditioner as defined in claim 1 [0004] Surprisingly, the conditioner according to the invention is capable of delivering to the hair surface and thereby produce a desirable conditioning benefit. The is a light mineral oil. Preferably, the light mineral oil has a density of from 0.7 to 0.85 g/ml. [0005] Preferably, the composition as a whole comprises less than 2% wt. anionic . 10 [0006] Preferably, the composition as a whole comprises substantially no anionic surfactant. [0007] Such a conditioning gel phase is common in the art and means an arrangement of cationic surfactant and fatty materials which are capable of conditioning hair. are also be present in the formulation but are typically not part of the conditioning gel phase such as in WO01/17502. The conditioning are cosmetically acceptable and suitable for topical application to the hair. 15 [0008] Suitable conditioning surfactants are selected from cationic surfactants, used singly or in admixture. Examples include quaternary ammonium hydroxides or salts thereof, e.g. chlorides. [0009] Suitable cationic surfactants for use in hair conditioners of the invention include cetyltrimethylammonium chlo- ride,behenyltrimethylammonium chloride, cetylpyridinium chloride,tetramethylammonium chloride, tetraethylammonium chloride, octyltrimethylammonium chloride, dodecyltrimethylammonium chloride, hexadecyltrimethylammonium chlo- 20 ride, octyldimethylbenzylammonium chloride, decyldimethylbenzylammonium chloride, stearyldimethylbenzylammoni- um chloride, didodecyldimethylammonium chloride, dioctadecyldimethylammonium chloride, tallowtrimethylammonium chloride, cocotrimethylammonium chloride, and the corresponding hydroxides thereof. Further suitable cationic sur- factants include those materials having the CTFA designations Quaternium-5, Quaternium-31 and Quaternium-18. Mix- tures of any of the foregoing materials may also be suitable. A particularly useful cationic surfactant for use in hair 25 conditioners of the invention is cetyltrimethylammonium chloride, available commercially, for example as DEHYQUART, ex Henkel. [0010] In conditioners of the invention, the level of cationic surfactant is preferably from 0.01 to 10%, more preferably 0.05 to 5%, most preferably 0.1 to 2% by weight of the composition. [0011] The conditioning gel phase of the invention advantageously incorporates a material. The combined 30 use of fatty alcohol materials and cationic surfactants in conditioning compositions is believed to be especially advan- tageous, because this leads to the formation of a lamellar phase, in which the cationic surfactant is dispersed. [0012] Representative fatty alcohols comprise from 8 to 22 carbon atoms, more preferably 16 to 20. Examples of suitable fatty alcohols include cetyl alcohol, and mixtures thereof. The use of these materials is also advantageous in that they contribute to the overall conditioning properties of compositions of the invention. 35 [0013] The level of fatty alcohol material in conditioners of the invention is conveniently from 0.01 to 10%, preferably from 0.1 to 5% by weight of the composition. The weight ratio of cationic surfactant to fatty alcohol is suitably from 10:1 to 1:10, preferably from 4:1 to 1:8, optimally from 1:1 to 1:4. [0014] The resulting formulation comprising a conditioning gel phase also comprises a silicone. [0015] The silicone is insoluble in the aqueous matrix of the composition and so is present in an emulsified form, with 40 the silicone present as dispersed particles. [0016] Suitable silicones include polydiorganosiloxanes, in particular which have the CTFA designation dimethicone. Also suitable for use compositions of the invention (particularly and conditioners) are polydimethyl siloxanes having hydroxyl end groups, which have the CTFA designation dimethiconol. Also suitable for use in compositions of the invention are silicone gums having a slight degree of cross-linking, as are described for 45 example in WO 96/31188. These materials can impart body, volume and stylability to hair, as well as good wet and dry conditioning. [0017] The viscosity of the emulsified silicone itself (not the emulsion or the final hair conditioning composition) is typically at least 10,000 cst. In general we have found that conditioning performance increases with increased viscosity. Accordingly, the viscosity of the silicone itself is preferably at least 60,000 cst, most preferably at least 500,000 cst, 50 ideally at least 1,000,000 cst. Preferably the viscosity does not exceed 10 9 cst for ease of formulation. [0018] Emulsified silicones for use in hair shampoos and conditioners of the invention will typically have an average silicone particle size in the composition of less than 30, preferably less than 20, more preferably less than 10 microns. We have found that reducing the particle size generally improves conditioning performance. Most preferably the average silicone particle size of the emulsified silicone in the composition is less than 2 microns, ideally it ranges from 0.01 to 1 55 micron. Silicone emulsions having an average silicone particle size of ≤ 0.15 microns are generally termed microemul- sions. [0019] Particle size may be measured by means of a laser light scattering technique, using a 2600D Particle Sizer from Malvern Instruments.

2 EP 2 435 016 B1

[0020] Suitable silicone emulsions for use in the invention are also commercially available in a pre-emulsified form. [0021] Examples of suitable pre-formed emulsions include emulsions DC2-1766, DC2-1784, and microemulsions DC2-1865 and DC2-1870, all available from Dow Corning. These are all 5 emulsions/microemulsions of dimethiconol. Cross-linked silic one gums are also available in a pre-emulsified form, which is advantageous for ease of formulation. A preferred example is the material available from Dow Corning as DC X2-1787, which is an emulsion of cross-linked dimethiconol gum. A further preferred example is the material available from Dow Corning as DC X2-1391, which is a microemulsion of cross-linked dimethiconol gum. [0022] A further preferred class of silicones for inclusion in shampoos and conditioners of the invention are amino 10 functional silicones. By "amino functional silicone" is meant a silicone containing at least one primary, secondary or tertiary amine group, or a quaternary ammonium group. [0023] Examples of suitable amino functional silicones include:

(i) polysiloxanes having the CTFA designation "amodimethicone", and the general formula: 15

HO-[Si(CH3)2-O-]x-[Si(OH)(CH2CH2CH2-NH-CH2CH2NH2)-O-]y-H

in which x and y are numbers depending on the molecular weight of the , generally such that the molecular weight is between about 5,000 and 500,000. 20 (ii) polysiloxanes having the general formula:

R’aG3-a-Si(OSiG2)n-(OSiGbR’2-b)m-O-SiG3-a-R’a

25 in which:

G is selected from H, phenyl, OH or C1-8 alkyl, e.g. methyl; a is 0 or an integer from 1 to 3, preferably 0; b is 0 or 1, preferably 1; 30 m and n are numbers such that (m + n) can range from 1 to 2000, preferably from 50 to 150; m is a number from 1 to 2000, preferably from 1 to 10; n is a number from 0 to 1999, preferably from 49 to 149, and R’ is a monovalent radical of formula -CqH2qL in which q is a number from 2 to 8 and L is an aminofunctional group selected from the following: 35

- NR"-CH2-CH2-N(R")2 - N(R")2 + - - N (R")3A + - - N H(R")2A 40 + - - N H2(R")A + - - N(R")-CH2-CH2-N H2(R")A

in which R" is selected from H, phenyl, benzyl, or a saturated monovalent hydrocarbon radical, e.g. C 1-20 alkyl, and; 45 A is a halide ion, e.g. chloride or bromide.

Suitable amino functional silicones corresponding to the above formula include those polysiloxanes termed "trimeth- ylsilylamodimethicone" as depictedbelow, and whichare sufficiently water insoluble so as to be usefulin compositions 50 of the invention:

Si(CH3)3-O-[Si(CH3)2-O-]x-[Si(CH3)(R-NH-CH2CH2NH2)-O-]y-Si(CH3)3

wherein x + y is a number from about 50 to about 500, and wherein R is an alkylene group having from 2 to 5 carbon 55 atoms. Preferably, the number x + y is in the range of from about 100 to about 300.

(iii) quaternary silicone having the general formula:

3 EP 2 435 016 B1

1 2 3 + 4 5 6 7 {(R )(R )(R )N CH2CH(OH)CH2O(CH2)3[Si(R )(R )-O-]n-Si(R )(R )-(CH2)3-O- + 8 9 10 - CH2CH(OH)CH2N (R )(R )(R )} (X )2

wherein R1 and R10 may be the same or different and may be independently selected from H, saturated or 5 unsaturated long or short chain alk(en)yl, branched chain alk(en)yl and C 5-C8 cyclic ring systems;

R2 thru’ R9 may be the same or different and may be independently selected from H, straight or branched chain lower alk(en)yl, and C5-C8 cyclic ring systems;

10 n is a number within the range of about 60 to about 120, preferably about 80, and

X- is preferably acetate, but may instead be for example halide, organic carboxylate, organic sulphonate or the like.

15 [0024] Suitable quaternary silicone polymers of this class are described in EP-A-0 530 974. [0025] Amino functional silicones suitable for use in shampoos and conditioners of the invention will typically have a mole % amine functionality in the range of from about 0.1 to about 8.0 mole %, preferably from about 0.1 to about 5.0 mole %, most preferably from about 0.1 to about 2.0 mole %. In general the amine concentration should not exceed about 8.0 mole % since we have found that too high an amine concentration can be detrimental to total silicone deposition 20 and therefore conditioning performance. [0026] The viscosity of the amino functional silicone is not particularly critical and can suitably range from about 100 to about 500,000 cst. [0027] Specific examples of amino functional silicones suitable for use in the invention are the aminosilicone DC2-8220, DC2-8166, DC2-8466, and DC2-8950-114 (all ex Dow Corning), and GE 1149-75, (ex General Electric 25 Silicones). [0028] Also suitable are emulsions of amino functional silicone oils with non ionic and/or cationic surfactant. [0029] Suitably such pre-formed emulsions will have an average amino functional silicone particle size in the composition of less than 30, preferably less than 20, more preferably less than 10 microns. Again, we have found that reducing the particle size generally improves conditioning performance. Most preferably the average amino functional 30 silicone particle size in the composition is less than 2 microns, ideally it ranges from 0.01 to 1 micron. Silicone emulsions having an average silicone particle size of ≤ 0.15 microns are generally termed microemulsions. [0030] Pre-formed emulsions of amino functional silicone are also available from suppliers of silicone oils such as Dow Corning and General Electric. Specific examples include DC929 Cationic Emulsion, DC939 Cationic Emulsion, and the non-ionic emulsions DC2-7224, DC2-8467, DC2-8177 and DC2-8154 (all ex Dow Corning). 35 [0031] An example of a quaternary silicone polymer useful in the present invention is the material K3474, ex Gold- schmidt. [0032] The total amount of silicone incorporated into compositions of the invention depends on the level of conditioning desired and the material used. A preferred amount is from 0.01 to about 10% by weight of the total composition although these limits are not absolute. The lower limit is determined by the minimum level to achieve conditioning and the upper 40 limit by the maximum level to avoid making the hair and/or skin unacceptably greasy. [0033] We have found that a total amount of silicone of from 0.3 to 5%, preferably 0.5 to 3%, by weight of the total composition is a suitable level. [0034] Density of the mineral oil is also known as specific gravity and is measured according to ASTM D 4052 at 15.6C.

45 EXAMPLE 1

[0035] A composition according to an embodiment of the invention.

% w/w Trade Name 50 1.25 Stearamidopropyl dimethylamine 86.59 WATER, CHLORINATED DEMINERALISED 1 Mineral oil

55 0.1 DISODIUM EDTA 1.25 Behenyl trimethyl ammonium chloride

4 EP 2 435 016 B1

(continued)

% w/w Trade Name 5 Cetearyl alcohol 5 0.1 SODIUM CHLORIDE 0.06 CIT/MIT 0.5 Parfum 10 0.2 Methyl Paraben 0.38 Lactic 3.57 DC 5-7134 9:1 600K/8566 CTAC 70%

15 EXAMPLE 2

[0036] A process for making a composition according to the invention.

1. Add mineral oil to side pot and heat to 50°C. Add cetearyl alcohol and melt out keeping T at 75°C. 20 2. Add water to mixer and start heating to 85°C. 3. Mix with Silverson. 4. Add methyl paraben and disperse then lactic acid and disperse. 5. At 60C add stearamidopropyl dimethylamone over top and disperse. At 80°C add behenyl trimethyl ammonium chloride and disperse. 25 6. At 85°C with mixing inject molten cetearyl alcohol and mineral oil mixture into loop. Mix for 30mins. 7. Start jacket cooling to 30°C without mixing. 8. Add quench water then other ingredients such as perfumes, etc.

EXAMPLE 3 30 [0037] Evidence illustrating how the composition of the invention delivers more silicone than a comparative composition comprising heavy mineral oil.

ABC 35 Silicone deposition (ppm) 2157.89 2197.47 1294.59 A: Control, no oil B: Test sample, light mineral oil C: Comparative, heavy mineral oil 40

[0038] Table shows that compositions according to the invention deliver more silicone than compositions comprising heavy mineral oil.

45 Claims

1. Hair conditioner comprising silicone and a conditioning gel phase, said conditioning gel phase obtainable by heating a fatty alcohol and a light mineral oil having a density of from 0.7 to 0.85 g/ml. measured according to ASTM D 4052 50 at 15.6°C until they are molten, separately heating a cationic surfactant in water until it is dissolved/suspended, then adding the molten fatty alcohol and oil mix to the cationic surfactant before adding any remaining ingredients of the conditioning gel phase, wherein the silicone is present in the hair conditioner in emulsified form, with the silicone present as dispersed particles.

55 2. Composition according to claim 1 wherein the composition as a whole comprises less than 2% wt. anionic surfactant.

5 EP 2 435 016 B1

Patentansprüche

1. Haarkonditioniermittel, das Silikon und eine konditionierende Gelphase umfasst, wobei die konditionierende Gel- phase erhältlich ist durch Erhitzen eines Fettalkohols und eines leichten Mineralöls einer Dichte von 0,7 bis 0,85 5 g/ml, gemessen gemäß ASTM D 4052 bei 15,6°C, bis sie geschmolzen sind, gesondertes Erhitzen eines kationischen Tensids in Wasser, bis es aufgelöst/suspendiert ist, dann Zugeben der geschmolzenen Mischung des Fettalkohols und Öls zu dem kationischen Tensid, bevor irgendwelche restlichen Bestandteile der konditionierenden Gelphase zugegeben werden, wobei das Silikon in dem Haarkonditioniermittel in emulgierter Form vorliegt, wobei das Silikon als dispergierte Partikel vorliegt. 10 2. Zusammensetzung nach Anspruch 1, wobei die Zusammensetzung als Ganzes weniger als 2 Gew.-% anionisches Tensid umfasst.

15 Revendications

1. Après-shampoing comprenant du silicone et une phase de gel de conditionnement, ladite phase de gel de condi- tionnement pouvant être obtenue en chauffant un alcool gras et une huile minérale légère ayant une densité de 0,7 à 0,85 g/ml, mesurée selon ASTM D 4052 à 15,6°C jusqu’à ce qu’ils soient fondus, en chauffant séparément un 20 tensioactif anionique dans de l’eau jusqu’à ce qu’il soit dissous/mis en suspension, en ajoutant ensuite le mélange d’alcool gras et d’huile fondu au tensioactif cationique avant l’addition des ingrédients restants de la phase de gel de conditionnement, où le silicone est présent dans l’après-shampoing dans une forme émulsionnée, avec le silicone présent comme particules dispersées.

25 2. Composition selon la revendication 1, où la composition dans sa totalité comprend moins de 2 % en masse de tensioactif anionique.

30

35

40

45

50

55

6 EP 2 435 016 B1

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

• WO 0117502 A [0007] • EP 0530974 A [0024] • WO 9631188 A [0016]

7