WO2013064597A2

WO2013064597A2 - Hair styling composition

Info

Publication number: WO2013064597A2
Application number: PCT/EP2012/071660
Authority: WO
Inventors: Ezat Khoshdel; Prem Kumar Cheyalazhagan Paul; Li RAN; Qiqing Zhang
Original assignee: Unilever Plc; Unilever N.V.; Hindustan Unilever Limited; Conopco, Inc., D/B/A Unilever
Priority date: 2011-11-04
Filing date: 2012-11-01
Publication date: 2013-05-10
Also published as: WO2013064597A3

Abstract

A hair treatment composition comprising: a) from 0.6 to 10 wt% of an aluminium salt, titanium salt and mixtures thereof and b) an emulsion comprising: i) hydrophobically modified particles selected from the group consisting of silica, metal oxide and mixtures thereof; ii) amino functionalised silicone; and iii) water.

Description

HAIR STYLING COMPOSITION

The present invention relates hair styling compositions, especially those designed to straighten hair.

Hair can be styled in many ways. One manner of styling hair is to decrease its volume enhancing the hair's straight appearance. Decreasing the volume is seen as a way of mitigating the frizzy appearance of the hair. US4960588 discloses hair styling compositions comprising amino silicones and aluminium chloride.

Hair styling compositions comprising titanium citrate are disclosed in

WO2010/121924.

However formulations containing metal salts are often unstable on storage.

Instability can occur in several ways such as thinning of a product or phase separation. The present invention relates to improved straightening compositions comprising metals that are stable on storage.

Summary of the Invention

Accordingly the present invention relates to a hair treatment composition comprising:

a) from 0.6 to 10 wt% of a metal salt selected from aluminium, titanium and mixtures thereof and

b) an emulsion comprising:

i) hydrophobically modified particles selected from the group

consisting of silica, metal oxide and mixtures thereof;

ii) amino functionalised silicone; and iii) water.

In a second aspect the invention relates to a hair treatment composition

comprising:

a) a metal salt selected from aluminium chloride, titanium citrate, titanium

tartrate, titanium oxalate, the metal alkali salt of these and mixtures thereof and

b) an emulsion comprising:

i) hydrophobically modified particles selected from the group consisting of silica, metal oxide and mixtures thereof;

ii) amino functionalised silicone; and

iii) water.

The invention further relates to a method of treating hair comprising the steps of applying to the hair a composition comprising:

a) an aluminium salt, titanium salt or mixtures thereof and

b) an emulsion comprising:

amino functionalised silicone; and

iii) water.

Description of the Invention Compositions of the invention may be water in oil or oil in water based emulsions. Preferably they are oil in water based emulsions.

Unless stated otherwise the viscosity of materials can be measured by means of a glass capillary viscometer as set out further in Dow Corning Corporate Test Method CTM004, July 20 1970 a temperature of 25°C. Hydrophobically modified particles

The compositions of the invention comprise hydrophobically modified particles of silica, metal oxide or mixtures thereof. Preferably the hydrophobically particles comprise silica or titanium oxide, more preferably hydrophobically modified silica (silicone dioxide).

It is particularly preferred if the hydrophobically modified silica comprises the hydrophobic group of formula:

in which R is a C₄ to Cie alkyl group. Particularly preferred is the hydrophobically modified silicone dioxide comprising:

Preferred silica particles are described in US 7 282 236 and made commercially available from suppliers like Evonik Degussa GmbH under the names Aerosil R812, R202, and R805. Silica having a C4 to C15 alkyl group attached to the silane are preferred. Particularly preferred is octylsilane comprising the group represented by formula above (sold under the name Aerosil R805). The hydrophobically modified silica preferably has a primary particle size (in its dry state) from 1 nm to 100 nm, more preferably from 5 to 70nm.

Primary particles sizes can be derived from Transmission Electron Microscopy according to the method described by S. Gu et al in Journal of Colloid and Interface Science 289 (2005) 419-426.

Composition of the invention preferably comprise from 0.05 to 15 wt% of the total composition of hydrophobically modified silica, more preferably from 0.1 to 10 wt%, and most preferably from 0.2 to 5 wt%.

Amino Functionalised Silicone

Compositions according to the invention comprise an amino functional silicone. By "amino functionalised silicone" is meant a silicone containing at least one primary, secondary or tertiary amine group, or a quaternary ammonium group.

The primary, secondary, tertiary and/or quaternary amine groups may either form part of the main polymer chain or more preferably be carried by a side or pendant group carried by the polymeric backbone.

Suitable amino functionalised silicone polymers for use with the invention are described in US 4 185 087.

Amino functionalised silicones suitable for use in 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 and therefore conditioning performance.

In a preferred embodiment, the functionalized polymers are of the

amodimethicone having the general formula:

where each R is independently H, or a Ci_-4 alkyl, preferably H;

each R¹ is independently OR or a Ci_-4 alkyl; and

each x is independently an integer from 1 to 4 and each y is greater than zero and independently an integer to yield a polymer having a molecular weight from 500 to 1 million, and preferably, from 750 to 25,000, and most preferably from 1 ,000 to 15,000. Particularly preferred are silicones comprising an amino glycol copolymer. Especially preferred is Bis (C13-C15 alkoxy) PG amodimethicone such as DC 8500 by Dow Corning. It is also within the scope of this invention for the functionalized polymer to comprise trimethylsilylamodimethicone. Preferably the level of amino functionalised silicone polymers make up from 0.05 to 15 wt% of the total composition, preferably from 0.1 to 10%, and most preferably from 0.2 to 5 wt%. Preferably the weight ratio of hydrophobically modified particle to amino functionalised silicone is from 3: 1 to 1 :50, more preferably from 1 : 1 to 1 : 10.

When a high ratio (greater than 1 : 1 ) of hydrophobically modified particle to amino silicone is used it is preferred if the a non-amino functional silicone is present, preferably at a weight ratio of greater than 1 : 1 non-amino functional silicone to amino functional silicone, more preferably at a ratio of greater than 2: 1.

Suitable non-amino functional silicones are disclosed below. Metal Salts

Compositions of the invention comprise metal salts selected from aluminium salt, titanium salts or mixtures thereof. In the context of the present invention metal oxides are not considered metal salts.

In one aspect of the invention the level of metal salt is preferably from 0.1 wt% to 20 wt% of the total composition, more preferably from 0.2 to 15 wt%, most preferably from 0.6 to 10 wt%. In one aspect of the invention the salt is a titanium salt.

Preferred titanium salts are selected from the group consisting of citrate, oxalate and tartrate or the metal alkali salt of these. It is advantageous if the titanium salt is titanium citrate or its metal alkali salt, particularly advantageous is sodium titanium salt, especially the sodium salt of titanium citrate (sodium titanium citrate). It is also preferable if the titanium salt is such that all the co-ordination bonds form cyclic structures with the ligands.

The level of titanium salt in the total composition is preferably from 0.01 to 10 wt% of the total composition, more preferably from 0.1 to 5 wt%.

In a second or additional aspect of the invention compositions of the invention comprise a salt of aluminium.

It is particularly preferred if the metal salt is aluminium chloride.

The level of aluminium salt in the total composition is preferably from 0.1 to 10 wt%, more preferably from 0.1 to 8 wt%, most preferably from 0.6 to 10 wt%.

Styling Polymers

Compositions of the invention may comprise styling polymers.

Hair styling polymers are well known articles of commerce and many such polymers are available commercially which contain moieties which render the polymers cationic, anionic, amphoteric or nonionic in nature. The polymers may be synthetic or naturally derived.

The amount of the hair styling polymer may range from 0.1 to 12%, preferably 0.5 to 10 %, more preferably 0.75 to 8% by weight based on total weight of the composition. Further ingredients

The formulation may include conditioning materials such as surfactants, cationic conditioners suitable for hair, non amino functionalised silicones and their emulsions.

Preferably the composition does not contain anionic or nonionic surfactants.

Suitable non amino functionalised silicones include polydiorganosiloxanes, in particular polydimethylsiloxanes which have the CTFA designation dimethicone. Also suitable for use compositions of the invention (particularly shampoos 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 example in WO 96/31 188.

The viscosity of the emulsified silicone itself (not the emulsion or the final hair conditioning composition) is typically at least 10,000 est. The viscosity of the silicone itself is preferably at least 60,000 est, most preferably at least 500,000 est, ideally at least 1 ,000,000 est. Preferably the viscosity does not exceed 10⁹ est for ease of formulation.

Emulsified silicones for use 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. 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 micron. Silicone emulsions having an average silicone particle size of < 0.15 microns are generally termed microemulsions. Silicone particle size may be measured by means of a laser light scattering technique, using a 2600D Particle Sizer from Malvern Instruments.

Suitable silicone emulsions for use in the invention are also commercially available in a pre-emulsified form.

Examples of suitable pre-formed emulsions include emulsions DC 1784, DC 1785, DC 2-1865 available from Dow Corning. 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.

Other oils can also be included in the composition such as ester emolliants, polyhydric alcohol esters, wax esters and sugar ester of fatty acids.

If present particularly preferred are natural ester emollients principally are based upon mono-, di- and tri- glycerides. Representative glycerides include sunflower seed oil, cottonseed oil, borage oil, borage seed oil, primrose oil, castor and hydrogenated castor oils, rice bran oil, soybean oil, olive oil, safflower oil, shea butter, jojoba oil and combinations thereof. Animal derived emollients are represented by lanolin oil and lanolin derivatives. Amounts of the natural esters may optionally range from about 0.1 to about 20% by weight of the end use compositions.

Creams according to the invention may contain a structurant or thickener, typically in an amount of from 0.01 % to 15% by weight. Examples of suitable structurants or thickeners are polymeric thickeners such as carboxyvinyl polymers. Particularly preferred thickeners are cationic thickening agents, more preferred are acrylamide/methacrylate based copolymers, especially preferred are polymers of dimethylacrylamide and methacrylate in particular dimethylacrylamide/ethyltrimonium chloride methacrylate copolymer such as Tinovis CD ex BASF.

Other materials that can also be used as structurants or thickeners include those that can impart a gel-like viscosity to the composition, such as water soluble or colloidally water soluble polymers like cellulose ethers (e.g. methylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose and carboxymethylcellulose), guar gum, sodium alginate, gum arabic, xanthan gum, polyvinyl alcohol, polyvinyl pyrrolidone, hydroxypropyl guar gum, starch and starch derivatives, and other thickeners, viscosity modifiers, gelling agents, etc. It is also possible to use inorganic thickeners such as bentonite or laponite clays.

Such styling products frequently include a carrier and further additional

components. The carriers and additional components required to formulate such products vary with product type and can be routinely chosen by one skilled in the art. The following is a description of some of these carriers and additional components.

The pH of the formulation is preferably from 4.5 to 8 at 25°C. More preferably from 5 to 7.

Hair care compositions of the present invention can comprise a carrier, or a mixture of such carriers, which are suitable for application to the hair. The carriers are present at from about 0.5% to about 99.5%, preferably from about 5.0% to about 99.5%, more preferably from about 10.0% to about 98.0%, of the

composition. As used herein, the phrase "suitable for application to hair" means that the carrier does not damage or negatively affect the aesthetics of hair or cause irritation to the underlying skin.

Compositions according to the invention comprise a buffer or pH adjuster.

Preferred buffers or pH adjusters include weak acids and bases such

glycine/sodium hydroxide, citric acid, lactic acid, succinic acid, acetic salt and salts thereof. Frequently a mixture of buffering system is used such as sodium citrate and citric acid. Compositions of the invention comprise water as a solvent. Further solvents may be present. Suitable solvents include the C1 -C6 alcohols, lower alkyl acetate and mixtures thereof being preferred. The solvents can also contain a wide variety of additional materials such volatile silicones such as cyclomethicone.

The compositions of the present invention may also contain adjuncts suitable for hair care. Generally such ingredients are included individually at a level of up to 2 wt&, preferably up to 1 wt% of the total composition. Suitable hair care adjuncts, include amino acids, sugars and ceramides, sun-screening agents, carboxylic acid polymer thickeners. Compositions of the present invention are formulated into hair care compositions with hair styling claims. The compositions are preferably used to non-permanently style human hair and, more preferably, they are packaged and labeled as such. The term non-permanently mean that during the styling process the inter cystine- disulphide bonds are not broken. This means that there are preferably no reductive agents in the hair care composition.

It is preferred if the products are left on hair after application and not immediately washed off (within 10 minutes of application). Such products are known as leave in compositions. Leave in styling compositions are particularly preferred. Process

A preferred process comprises forming a pre-emulsion comprising hydrophobic particles (preferably silica) dispersed in the silicone oils (aminosilicone).

Preferably this phase is free of nonionic and anionic surfactants.

Especially preferred is a process for producing the composition comprising the following steps: i) forming a first phase by dispersing hydrophobe particles (preferably silica) in silicone oils (aminosilicone) ; followed by addition to water to form an emulsion.

ii) forming a second aqueous phase.

iii) combined the two phases to form a uniform structure.

Preferably the aluminium/titanium salt is added to the first emulsion phase.

The following non-limiting Examples further illustrate the preferred embodiments of the invention. Examples of the invention are illustrated by a number, comparative examples are illustrated by a letter. All percentages referred to in the examples and throughout this specification are by weight based on total weight

Examples Table 1

Formulation process:

To form compositions of the invention the silica particles are dispersed in the silicone oils (aminosilicone oil DC8500/DC 200 fluid 50 est). Aluminium chloride, and some of the water are added to the oil phase by stirring to form an emulsion. The remainder of the cream is made in the conventional manner by mixing the ingredients, the emulsion is added to the cream. The process takes place under ambient temperature.

Examples A and B are made in the conventional manner.

After storage at 20°C for 24 hours the viscosity of the product was measured by DV-I+ PRO Digital Viscometer (from Brookfield Ltd) at a consistent shear rate of 20 rmp. The values measured after 1 minute at a temperature of 25°C.

The results are shown in Table 2 Table 2

Formulation of the invention (Example 1 ) mitigate the shear thinning effect and are thus more stable compared with the comparative compositions (Examples A and B).

Table 3

Formulations of were made as for Example 1 and Example B with replacement of the aluminium chloride with titanium citrate. After storage for 24 hours 20°C Example 2 did not phase separate, Example C had phased separated. Thus Example 2 is more stable than Example C on storage.

Claims

1 . A hair treatment composition comprising:

a) from 0.6 to 10 wt% of an aluminium salt, titanium salt and mixtures thereof and

b) an emulsion comprising:

ii) amino functionalised silicone; and

iii) water.

2. A hair treatment composition comprising:

a) a metal salt selected from aluminium chloride, titanium citrate

titanium tartrate, titanium oxalate, the metal alkali salt of these and mixtures thereof and

b) an emulsion comprising:

ii) amino functionalised silicone; and

iii) water.

3. A composition according to claim 1 or claim 2 in which the hydrophobically particles comprise silica or titanium oxide.

4. A composition according to any preceding claim in which the

hydrophobically particles comprise silica.

5. A composition according to claim 4 in which the hydrophobically modified silica comprise:

in which R is a C₄ to Cie alkyl group.

A composition according to claim 5 in which the hydrophobically modified silica comprises the group:

A composition according to any preceding claim in which the

hydrophobically modified particle has a primary particle size from 1 nm to 100 nm.

A composition according to any preceding claim in which the amino functionalized silicone comprises an amino glycol copolymer.

A composition according to any preceding claim in which the weight ratio of hydrophobically modified particle to amino functionalised silicone is from 3: 1 to 1 :50.

10. A composition according to any one of the preceding claims wherein the emulsion further comprises at least one non amino functionalised silicone.

1 1 . A composition according to any preceding claim in which the level of

hydrophobically modified silica particles is from 0.1 to 10 wt% of the total composition.

12. A process for manufacturing a composition as described in any of the above claims comprising the step of forming a pre-emulsion comprising hydrophobic particles dispersed in the silicone oil (aminosilicone).

13. A method of treating hair comprising the steps of applying to the hair a composition comprising:

a) an aluminium salt, titanium salt or mixtures thereof and

b) an emulsion comprising:

ii) amino functionalised silicone; and

iii) water.