EA040336B1 - COMPOSITIONS FOR THE TREATMENT OF DAMAGED HAIR - Google Patents

Description

Technical field

The present invention relates to a method for protecting hair, preferably the intrinsic protein of the hair, from damage by applying a hair treatment composition containing a lactone, a disaccharide, an inorganic salt, and an organic acid or salt thereof, before ultraviolet damage to the hair; and to the use of such hair treatment compositions to protect hair from damage caused by ultraviolet light.

State of the art

Consumers routinely subject their hair to intensive treatments, care and styling to make it easier to achieve the desired look. Actions taken by consumers introduce changes in the hair protein keratin chemistry, resulting in micro- and macrostructural changes, which in turn change the physical properties of the fiber: the consequences of these changes are usually perceived by the consumer as damage.

Daily exposure to environmental elements exacerbates this problem. UV radiation is a particularly harmful element of the environment and is a particular problem in countries with a high UV index.

Damaged hair has an internal protein with a lower denaturation temperature than untreated hair. The decrease in denaturation temperature is associated with photochemical degradation of the proteins of the inner cortex of the hair. Amino acids in proteins absorb UV-A and UV-B radiation, resulting in the formation of free radicals and destruction of bonds, reducing the overall structural integrity of the proteins of the inner cortex.

Various organic molecules and combinations thereof have been proposed for use in treating damaged hair.

WO 2004054526 describes hair treatment compositions for the care and repair of damaged hair and for improving hair manageability, and said compositions contain a disaccharide (in particular trehalose).

WO 2004054525 describes hair treatment compositions for the care and repair of damaged hair and for improving hair manageability, and said compositions contain a disaccharide (particularly trehalose) and a diol (particularly 3-methyl-1,3-butanediol).

WO 2009040240 discloses hair treatment compositions containing lactone and a disaccharide for the treatment of dry, damaged and/or unruly hair.

Applicants' yet unpublished European Patent Application EP 15169037.7 discloses the use of a hair treatment composition, wherein said composition contains a lactone, a disaccharide, an inorganic salt and an organic acid or salt thereof and has a pH in the range of 3 to 6.5, when treated hair to increase the denaturation temperature of the hair's internal protein.

Various low molecular weight compounds have also been used to protect hair from the damaging effects of chemical treatments.

Protein hydrolysates have been used to protect hair from chemical treatments. For example, Roddick-Lanzilotta et al have used protein hydrolyzate pretreatment to reduce oxidative damage caused by oxidative treatments (permanent dyes and bleaches). The inventors claim that these proteins act as victim molecules, removing oxidative damage from hair proteins (Roddick-Lanzilotta et al., J. Cosmet. Sci. 58 (July/August), 405-411 (2007)).

Antioxidants are also used to protect hair from free radical damage. For example, Meinert et al. have investigated the effect of commercially available antioxidants on the sun protection properties of hair care products (Meinert et al., J Cosmet Sci. 55 Suppl: S105-12 (2004)).

Despite the prior art, there remains a need for better UV protection of the hair. Protection differs from recovery in that it helps prevent damage. Restoration is required for hair that is already damaged, and restoration procedures are generally applied to hair after the hair has been damaged, such as exposure to a damaging agent or action. On the contrary, protection is required before the hair is damaged, thus reducing or preventing damage to the hair. Accordingly, the impact of injury, such as exposure to a damaging agent or action, is reduced.

The changes in hair that occur when the hair is damaged differ depending on the type of damage. Heat damage caused by hair dryers and heated appliances such as curling irons and straighteners is limited mainly to the hair cuticle. Similarly, scratching and other mechanical damage mainly affects the cuticle with minimal effect on internal proteins. Chemical treatments, such as bleach and dyes, involve the application of liquid actives to the hair, while photochemical sources, such as ultraviolet light, expose the hair to radiation. Both chemical and photochemical damage can reach the internal structure of the hair shaft.

The specific action of ultraviolet light on hair has been studied. For example, coll. Antro

- 1 040336 pol. 32 (2008) Suppl. 2:163-165 Review; UV Damage of the Hair; K Sebetic et al report that photochemical damage to hair includes degradation and loss of hair proteins, as well as degradation of hair pigment. UV-B radiation is responsible for hair protein loss, while UV-A radiation is responsible for color change. Absorption of radiation by photosensitive amino acids of the hair and their photochemical degradation leads to the formation of free radicals, which have an adverse effect on hair proteins, especially keratin. The amino acids cystine, methionine, tryptophan, tyrosine, and histidine are the most susceptible to photochemical degradation. It is also disclosed that protecting the cuticle is very important in maintaining the integrity of the hair shaft, and this can be achieved by avoiding harmful exposures or using hair care products with UV filters. Physical and chemical filters provide protection against UV-A and UV-B radiation.

From Robbins C.R. (2012) Chemical and Physical Behavior of Human Hair it is known that carbonyl groups are formed by oxidation on the carbon of the peptide backbone during exposure to ultraviolet radiation. These carbonyl groups react with the amino groups of the protein, primarily with lysine.

Photochemical destruction of disulfide bridges occurs in the exocuticle and cortical matrix.

Amino acid oxidation due to bleaching damage was studied by Dyer JM, Bell F, Koehn H, Vernon JA, Cornellison CD, Clerens S et al. in Redox proteomic evaluation of bleaching and alkali damage in human hair. Int J Cosm Sci. 2013;35(6):555-61. Epub 22 July 2013. Amino acids such as serine, cysteine, and phenylalanine have also been shown to undergo a series of structural changes and become rich in hydroxy, nitro, and sulfo groups when discoloration damage is reduced.

The present inventors have also found that different types of damage affect different amino acids in the hair.

When comparing bleaching damage and UV damage, the present inventors have found that methionine is significantly more susceptible to UV damage than bleach damage. On the other hand, bleaching leads to a much higher excretion of aspartic acid than UV radiation.

Due to the differences in the amino acids involved, different methods of targeting each type of damage are required.

The present inventors have found that hair can be protected from damage by ultraviolet light by using a hair treatment composition containing a lactone, a disaccharide, an inorganic salt, and an organic acid or salt thereof, wherein said composition has a pH in the range of 3 to 6.5 to exposure to ultraviolet radiation on the hair.

Benefits are shown for hair that has been previously damaged as well as undamaged hair.

Brief description of the invention

In a first aspect, a method is provided for protecting hair from damage caused by exposure to ultraviolet radiation, comprising the step of applying to the hair a hair treatment composition containing a lactone, a disaccharide, an inorganic salt, and an organic acid or salt thereof and having a pH in the range of 3 to 6, 5, before exposure to ultraviolet radiation on the hair.

In a second aspect of the present invention, there is provided the use of a hair treatment composition containing a lactone, a disaccharide, an inorganic salt and an organic acid or salt thereof, and having a pH in the range of 3 to 6.5, in treating hair to protect against damage caused by ultraviolet radiation.

Hair damage can be defined in many different ways. The present invention aims to protect the structural integrity of hair cortex proteins, which can be determined using differential scanning calorimetry, single-fiber mechanical testing, and a variety of other methods. The protection in the first and second aspects relates to the hair protein, preferably the inner cortex protein of the hair. The composition for use in the present invention is preferably applied to the hair several times to provide a gradual increase in protein protection.

In the method according to the present invention, the step of applying to the hair a hair treatment composition containing a lactone, a disaccharide, an inorganic salt and an organic acid or salt thereof having a pH in the range of 3 to 6.5 is performed several times, preferably 2 to 50 times, more preferably 5 to 30 times.

Hair

The hair may be intact or damaged.

The damage is caused by exposure of the hair to ultraviolet radiation, preferably the hair is exposed to ultraviolet radiation several times.

Detailed description of the invention

lactones

The composition for use in the present invention contains a lactone. Examples of suitable

- 2 040336 lactones include the following.

(a) Aldonic acid lactones.

Aldonic acids are polyhydroxy acids obtained by the oxidation of the aldehyde group of an aldose to a carboxylic acid group, and this acid can be represented by the following general formula:

R(CHOH) _n CH(OH)COOH, where R is H or an alkyl group (typically H) and n is an integer from 1 to 6.

Aldonic acids form intramolecular lactones by removing 1 mol of water between the carboxyl group and one hydroxyl group.

Examples of aldonic acid lactones are as follows:

2,3-dihydroxypropanoic acid lactones (glyceric acid lactones);

2,3,4-trihydroxybutanoic acid lactones (stereoisomers: erythronolactone, threonolactone);

2,3,4,5-tetrahydroxypentanoic acid lactones (stereoisomers: ribonolactone, arabinolactone, xylonolactone, lixonolactone);

lactones of 2,3,4,5,6-pentahydroxyhexanoic acid (stereoisomers: allonolactone, altronolactone, gluconolactone, mannolactone, gulonolactone, idonolactone, galactonolactone, talonolactone), lactones of 2,3,4,5,6,7-hexahydroxyheptanoic acid (stereoisomers : alloheptonolactone, altrogeptonolactone, glucoheptonolactone, mannoheptonolactone, gulogeptonolactone, idoheptonolactone, galactoheptonolactone, thalogeptonolactone).

(b) Aldaric acid lactones.

Aldaric acids are polyhydroxydicarboxylic acids derived from aldose by oxidation of both terminal carbons to carboxyl groups, and this acid can be represented by the following general formula:

HOOC(CHOH)pCH(OH)COOH, where n is an integer from 1 to 4.

Aldaric acids form intramolecular lactones when one mole of water is removed between one carboxyl group and one hydroxyl group.

Examples of aldaric acid lactones are as follows:

2,3-dihydroxybutane-1,4-dioic acid lactones;

2,3,4-trihydroxypentane-1,5-dioic acid lactones (stereoisomers: ribarolactone, arabarolactone, xylarolactone, lixarolactone);

2,3,4,5-tetrahydroxyhexane-1,6-dioic acid lactones (allarolactone, altrarolactone, glucarolactone, mannarolactone, gular acid and gularolactone, idarolactone, galactarolactone, talarolactone);

2,3,4,5,6-pentahydroxyheptane-1,7-dioic acid lactones (stereoisomers: alloheptarolactone, altrogeptarolactone, glucoheptarolactone, mannoheptarolactone, gulogeptarolactone, idoheptarolactone, galactoheptarolactone, taltoheptarolactone).

(c) Alduronic acids.

Alduronic acids are polyhydroxy acids resulting from the oxidation of the alcohol group of an aldose to a carboxylic acid and can be represented by the following general formula:

HOOC(CHOH)pCH(OH)CHO, where n is an integer from 1 to 4.

Many alduronic acids form intramolecular lactones when 1 mole of water is removed between the carboxyl group and one hydroxyl group.

The following are typical alduronic acid lactones:

riburonolactone; araburonolactone; xyluronolactone; lixuronolactone; alluronolactone; altruronolactone; glucuronolactone; mannuronolactone; guluronolactone; iduronolactone; galacturonolactone; taluronolactone;

allohepturonolactone; altrogepturonolactone; glucohepturonolactone;

mannohepturonolactone; gulogepturonolactone; idogepturonolactone;

galactohepturonolactone and talohepturonolactone.

(d) Aldobionic acids.

Aldobionic acids are also known as bionic acids and typically include a single monosaccharide chemically ester-linked to an aldonic acid. Aldobionic acids can also be described as the oxidized form of a disaccharide or dimeric carbohydrate such as lactobionic acid from lactose.

In most aldobionic acids, the carbon at position one of the monosaccharide is chemically bonded to the hydroxyl group at the other position of the aldonic acid. Therefore, two identical monosaccharides and aldonic acids can form different aldobionic acids or stereoisomers, respectively.

- 3 040336

With respect to the above acids (a) to (c), aldobionic acids contain a plurality of hydroxyl groups attached to carbon chains.

Aldobionic acids can be represented by the following general formula:

H(CHOH) _m (CHOR)(CHOH) _n COOH, where m and n are integers independently selected from 0-7 and R is a monosaccharide.

Aldobionic acids can form intramolecular lactones by removing one mole of water between the carboxyl group and one hydroxyl group.

The following compounds are examples of aldobionic acid lactones:

lactobionolactone and isolactobionolactone; maltobionolactone; isomaltobionolactone isomaltobionic acid; cellobionolactone; gentiobionolactone; cogibionolactone; laminaribionolactone; belibionolactone; nigerobionolactone; rutinobionolactone and sophorobionolactone.

Preferably the lactone is a delta lactone. More preferably the lactone is selected from gluconolactone, galactonolactone, glucuronolactone, galacturonolactone, gulonolactone, ribonolactone, sugar lactone, pantoyllactone, glucoheptonolactone, mannonolactone and galactoheptonolactone, most preferably the lactone is gluconolactone.

Mixtures of any of the carbohydrate-derived acids described above may also be used in compositions for use in the present invention.

The total amount of lactone in hair treatment compositions for use in the present invention is generally 0.02 to 20%, preferably 0.05 to 2%, more preferably 0.05 to 0.8%, of the total weight of lactone from calculation for the total weight of the composition.

Preferably the total content of gluconolactone, trehalose and sodium sulfate is from 0.005 to 5 wt.%, more preferably from 0.2 to 5 wt.% of the total weight of the composition. When the composition for use in the present invention is a shampoo, the content is preferably 0.005 to 4% by weight, more preferably 0.6 to 4% by weight, based on the total weight of the shampoo. If the composition is a conditioner, the content is preferably 0.005 to 3% by weight, more preferably 0.2 to 3% by weight, based on the total weight of the conditioner.

organic acid

The composition for use in the present invention contains an organic acid or a salt thereof. Preferably the acid is a hydroxy acid, most preferably an alpha hydroxy acid. Suitable examples include glycolic acid, lactic acid, citric acid, mandelic acid, and mixtures thereof. Suitable beta-hydroxy acids include propanoic acid, beta-hydroxypropionic acid, beta-hydroxybutyric acid, salicylic acid, carnitine, and mixtures thereof. Sodium benzoate is also suitable. Preferably the acid is used in an amount of 0.01 to 1% by weight, more preferably 0.1 to 0.75% by weight.

disaccharide

The present invention includes a disaccharide, preferably the disaccharide contains a pentose or hexose sugar, most preferably the disaccharide contains two hexose units.

Disaccharides may be reducing or non-reducing sugars. Non-reducing sugars are preferred. The D(+) form of the disaccharides is preferred. Especially preferred are trehalose and cellobiose or mixtures thereof. Trehalose is the most preferred disaccharide.

The level of disaccharides present in the total composition is from 0.001 to 8 wt.% of the total weight of the composition, preferably from 0.005 to 5 wt.%, more preferably from 0.01 to 3 wt.%, most preferably from 0.05 to 2 wt.%.

inorganic salt

Preferably the composition according to the present invention contains an inorganic salt.

Examples of suitable inorganic salts include sodium sulfate, potassium fluoride, calcium chloride, sodium chloride and potassium phosphate.

In one preferred embodiment, the inorganic salt is an alkali metal salt, preferably the alkali metal salt is sulfate, more preferably sodium sulfate.

The alkali metal salt is present in an amount of from 0.001% by weight of the total composition, preferably from 0.05% by weight, most preferably from 0.1% by weight. The maximum salt content is less than 10% by weight, preferably less than 7% by weight, more preferably less than 5% by weight.

In a second alternative preferred embodiment, the inorganic salt is an ammonium ion source, preferably ammonium carbonate.

This second preferred inorganic salt is preferably present at a content of from 0.01% by weight based on the total weight of the composition, more preferably from 0.05% by weight. The maximum content of ammonium carbonate is preferably less than 10 wt.%, more preferably less than 5 wt.%, most preferably less than 1 wt.%. Also preferably, if the content of ammonium carbonate is from 0.01 to 2.0 wt.% of the total weight of the composition.

- 4 040336

Composition for hair treatment

The hair treatment compositions of the present invention may suitably take the form of shampoos, conditioners, sprays, mousses, gels, waxes or lotions.

Preferably, the hair treatment composition is a rinse-off hair treatment composition, preferably selected from shampoo, conditioner and mask. More preferably, the shampoo or conditioner is applied one after the other, and most preferably they are applied several times after several washes or treatments.

Shampoos

Shampoo compositions for use in the present invention are typically aqueous, that is, they contain water, or an aqueous solution, or a lyotropic liquid crystalline phase as their main component.

Suitably, the shampoo composition will contain 50 to 98%, preferably 60 to 90% water by weight based on the total weight of the composition.

Shampoo compositions of the present invention will generally contain one or more anionic cleansing surfactants that are cosmetically acceptable and suitable for topical application to the hair.

Examples of suitable anionic cleansing surfactants are alkyl sulfates, alkyl ether sulfates, alkaryl sulfonates, alkanoyl isethionates, alkyl succinates, alkyl sulfosuccinates, alkyl ether sulfosuccinates, N-alkyl sarcosinates, alkyl phosphates, alkyl ether phosphates and alkyl ether carboxylic acids and their salts, in particular their sodium, magnesium, ammonium and mono-, di- and triethanolamine. Alkyl and acyl groups usually contain from 8 to 18, preferably from 10 to 16 carbon atoms, and may be unsaturated. Alkyl ether sulfates, alkyl ether sulfosuccinates, alkyl ether phosphates and alkyl ether carboxylic acids and their salts may contain from 1 to 20 units of ethylene oxide or propylene oxide per molecule.

Типичные анионные очищающие поверхностно-активные вещества для применения в композициях шампуней для применения в настоящем изобретении включают олеилсукцинат натрия, лаурилсульфосукцинат аммония, лаурилсульфат натрия, лаурилэфирсульфат натрия, лаурилэфирсульфатосукцинат натрия, лаурилсульфат аммония, лаурилэфирсульфат аммония, додецилбензолсульфонат натрия, триэтаноламиндодецилбензолсульфонат, кокоилизетионат натрия, лаурилизетионат натрия, lauryl ether carboxylic acid; and sodium N-lauryl sarcosinate.

Preferred anionic cleansing surfactants are sodium lauryl sulfate, sodium lauryl ether sulfate (n) EO, (where n is from 1 to 3), sodium lauryl ether sulfosuccinate (n) EO, (where n is from 1 to 3), ammonium lauryl sulfate, ammonium lauryl ether sulfate (p)EO (where n is from 1 to 3), sodium cocoyl isethionate and lauryl ethercarboxylic acid (p)EO (where n is from 10 to 20).

Mixtures of any of the above anionic cleansing surfactants may also be suitable.

The total amount of anionic cleansing surfactant in shampoo compositions for use in the present invention is typically 0.5 to 45%, preferably 1.5 to 35%, more preferably 5 to 20%, of the total weight of the anionic cleansing surfactant. -active substance based on the total weight of the composition.

Optionally, a shampoo composition for use in the present invention may contain additional ingredients, as described below, to improve performance and/or consumer acceptability.

The composition may include co-surfactants to help impart aesthetic, physical, or cleansing properties to the composition.

An example of a co-surfactant is a non-ionic surfactant, which may be included in an amount of 0.5 to 8%, preferably 2 to 5% by weight based on the total weight of the composition.

For example, typical nonionic surfactants that can be included in shampoo compositions for use in the present invention include the condensation products of aliphatic (C8-C18) primary or secondary straight or branched chain alcohols or phenols with alkylene oxides, typically ethylene oxide, and usually containing from 6 to 30 ethylene oxide groups.

Other exemplary nonionic surfactants include mono- or dialkylalkanolamides. Examples include cocomono- or diethanolamide and cocomonoisopropanolamide.

Other nonionic surfactants that may be included in shampoo compositions for use in the present invention are alkyl polyglycosides (APGs). Typically, APG is a group that contains an alkyl group linked (optionally via a bridging group) to a block of one or more glycosyl groups. Preferred APGs are determined by the following formula:

RO - (G)n,

- 5 040336 where R represents a branched or linear alkyl group, which may be saturated or unsaturated and G represents a saccharide group.

R may be an alkyl chain of medium length: from about C5 to about C ₂₀ . Preferably R is an alkyl chain of medium length: from about C ₈ to about C ₁₂ . Most preferably, the R value is in the range of about 9.5 to about 10.5. G may be selected from C ₅ or C ₆ monosaccharide residues and is preferably a glucoside. G may be selected from the group consisting of glucose, xylose, lactose, fructose, mannose and derivatives thereof. Preferably G is glucose.

The degree of polymerization n may be from about 1 to about 10 or more. Preferably, n is from about 1.1 to about 2. Most preferably, n is from about 1.3 to about 1.5.

Suitable alkyl polyglycosides for use in the present invention are commercially available and include, for example, materials under the following names: Oramix NS10 from Seppic; Plantaren 1200 and Plantaren 2000 from Henkel.

Other nonionic sugar-derived surfactants that may be included in compositions for use in the present invention include C ₁₀ -C ₁₈ N-alkyl-(C1-C ₆ ) polyhydroxy fatty acid amides, such as C ₁₂ -C ₁₈ N-methylglucamides as described, for example, in WO 9206154 and US 5194639, and N-alkoxypolyhydroxy fatty acid amides such as C ₁₀ -C ₁₈ N-(3-methoxypropyl)glucamide.

A preferred example of a co-surfactant is an amphoteric or zwitterionic surfactant, which may be included in an amount in the range of 0.5 to about 8%, preferably 1 to 4% by weight based on the total weight of the composition.

Examples of amphoteric or zwitterionic surfactants include alkylamine oxides, alkyl betaines, alkylamidopropyl betaines, alkylsulfobetaines (sultaines), alkyl glycinates, alkylcarboxyglycinates, alkylamphoacetates, alkylamphopropionates, alkylamphoglycinates, alkylamidoylhydroxysultaines, acyl taurates, and acyl glutamates, wherein the 19 alkyl groups contain alkyl and acyl groups from 8 to acyl atoms. . Typical amphoteric and zwitterionic surfactants for use in shampoos for use in the present invention include laurylamine oxide, cocodimethylsulfopropyl betaine, lauryl betaine, cocamidopropyl betaine, and sodium cocoamphoacetate.

A particularly preferred amphoteric or zwitterionic surfactant is cocoamidopropyl betaine.

Mixtures of any of the above amphoteric or zwitterionic surfactants may also be suitable. Preferred mixtures are mixtures of cocamidopropyl betaine with other amphoteric or zwitterionic surfactants as described above. A preferred additional amphoteric or zwitterionic surfactant is sodium cocoamphoacetate.

The total amount of surfactant (including any additional surfactant and/or any emulsifier) in a shampoo composition for use in the present invention is typically 1 to 50%, preferably 2 to 40%, more preferably 10 to 25%. total weight of surfactant based on the total weight of the composition.

Cationic polymers are preferred ingredients in shampoo compositions for use in the present invention to improve conditioning performance.

Suitable cationic polymers may be homopolymers that are cationically substituted or may be formed from two or more types of monomers. The weight average (M _w ) molecular weight of polymers typically ranges from 100,000 to 2 million daltons. The polymers will have cationic nitrogen-containing groups such as quaternary ammonium or protonated amino groups, or mixtures thereof. If the molecular weight of the polymer is too low, then the conditioning effect will be poor. If it is too high, high tensile viscosity problems can occur, resulting in the composition becoming viscous when poured.

The cationic nitrogen-containing group will typically be present as a substituent in the fraction of all monomeric units of the cationic polymer. Thus, when the polymer is not a homopolymer, it may contain spacer non-cationic monomer units. Such polymers are described in the CTFA Cosmetic Ingredient Directory, 3rd edition. The ratio of cationic to non-cationic monomer units is chosen so as to obtain polymers having a cationic charge density in the desired range, which is usually from 0.2 to 3.0 meq/g. The cationic charge density of the polymer is suitably determined by the Kjeldahl method, as described in the USP, in nitrogen chemical tests. Suitable cationic polymers include, for example, copolymers of cationic amine or quaternary ammonium-functional vinyl monomers with water-soluble spacer monomers such as (meth)acrylamide, alkyl and dialkyl (meth)acrylamides, alkyl (meth)acrylate, vinylcaprolactone, and vinylpyrrolidine. Alkyl and dialkyl substituted monomers

- 6 040336 preferably contain C1-C7 alkyl groups, more preferably C1-3 alkyl groups.

Other suitable spacers include vinyl ethers, vinyl alcohol, maleic anhydride, propylene glycol and ethylene glycol.

Cationic amines may be primary, secondary or tertiary amines, depending on the specific species and pH of the composition. Generally, secondary and tertiary amines, especially tertiary ones, are preferred.

Amino-substituted vinyl monomers and amines can be polymerized in the form of an amine and then converted to ammonium by quaternization.

The cationic polymers may contain mixtures of monomer units derived from an amine and/or quaternary ammonium monomer and/or compatible spacer monomers.

Suitable cationic polymers include, for example:

cationic diallyl-quaternary ammonium-containing polymers, including, for example, dimethyldiallylammonium chloride homopolymer and copolymers of acrylamide and dimethyldiallylammonium chloride, referred to in the industry (CTFA) as Polyquaternium 6 and Polyquaternium 7, respectively;

salts of mineral acids formed with aminoalkyl esters of homo - and copolymers of unsaturated carboxylic acids containing from 3 to 5 carbon atoms (as described in US patent 4009256);

cationic polyacrylamides (described in WO 95/22311).

Other cationic polymers that may be used include cationic polysaccharide polymers such as cationic cellulose derivatives, cationic starch derivatives, and cationic guar gum derivatives.

Suitable cationic polysaccharide polymers for use in compositions for use in the present invention include monomers of the formula:

AO-[RN ⁺ (R ¹ )(R ² )(R ³ )X'], where A is a residual anhydroglucose group, such as an anhydroglucose residue of starch or cellulose; R represents an alkylene, oxyalkylene, polyoxyalkylene or hydroxyalkylene group or a combination thereof; R ¹ , R ² and R ³ are independently alkyl, aryl, alkylaryl, arylalkyl or alkoxyaryl groups each containing up to about 18 carbon atoms, the total number of carbon atoms of each cationic fragment (i.e. the sum of the carbon atoms in R ¹ , R ² and R ³ ) is preferably about 20 or less; and X is an anionic counterion.

Another type of cationic cellulose includes polymeric quaternary ammonium salts of hydroxyethyl cellulose reactive with lauryldimethylammonium epoxide, referred to in the industry (CTFA) as Polyquaternium 24. These materials are available from Amerchol Corporation, for example, under the tradename Polymer LM-200.

Other suitable cationic polysaccharide polymers include quaternary nitrogen-containing cellulose ethers (eg, described in US Pat. No. 3,926,418) and cellulose ester copolymers with starch (eg, described in US Pat. No. 3,958,581).

A particularly suitable type of cationic polysaccharide polymer that can be used is a cationic guar gum derivative such as guarhydroxypropyltrimethylammonium chloride (commercially available from Rhodia under their JAGUAR series of trade names). Examples of such materials are JAGUAR C13S, JAGUAR C14, JAGUAR C15 and JAGUAR C17.

Mixtures of any of the above cationic polymers may be used.

The cationic polymer will typically be present in a shampoo composition for use in the invention in an amount of from 0.01 to 5%, preferably from 0.05 to 1%, more than from 0.08 to 0.5% of the total weight of the cationic polymer, based on the total weight connections.

Preferably, the aqueous shampoo composition for use in the present invention further comprises a suspending agent. Suitable suspending agents are selected from polyacrylic acids, crosslinked polymers of acrylic acid, copolymers of acrylic acid with a hydrophobic monomer, copolymers of monomers containing carboxylic acid and acrylic acid esters, crosslinked copolymers of acrylic acid and esters of acrylates, heteropolysaccharide gums and crystalline long chain acyl derivatives. The long chain acyl derivative is preferably selected from ethylene glycol stearate, C16 to C22 fatty acid alkanolamides and mixtures thereof. Ethylene glycol distearate and polyethylene glycol 3-distearate are preferred long chain acyl derivatives because they impart a pearlescent effect to the composition. Polyacrylic acid is commercially available as Carbopol 420, Carbopol 488, or Carbopol 493. Acrylic acid polymers crosslinked with a polyfunctional agent may also be used; they are commercially available as Carbopol 910, Carbopol 934, Carbopol 941 and Carbopol 980. An example of a suitable carboxylic acid copolymer containing monomer and acrylic acid esters is Carbopol 1342. All Carbopol (trademark) materials are available from Goodrich.

Suitable cross-linked polymers of acrylic acid and acrylate esters

- 7 040336 are Pemulen TR1 or Pemulen TR2. A suitable heteropolysaccharide gum is xanthan gum, eg available as Kelzan mu.

Mixtures of any of the above suspending agents may be used. A mixture of a cross-linked acrylic acid polymer and a crystalline long chain acyl derivative is preferred.

The suspending agent will generally be present in a shampoo composition for use in the present invention at a content of 0.1 to 10%, preferably 0.5 to 6%, more preferably 0.9 to 4%, of the total weight of the suspending agent, based on to the total weight of the composition.

Air conditioners

Conditioning compositions will typically contain one or more cationic conditioning surfactants that are cosmetically acceptable and suitable for topical application to the hair.

Preferably cationic conditioning surfactants have the formula N ⁺ (R1)(R ² )(R ³ )(R ⁴ ) where R ¹ , R ² , R ³ and R ⁴ are independently (C ₁ -C ₃₀ )alkyl or benzyl.

Preferably one, two or three of R ¹ , R ² , R ³ and R ⁴ are independently (C ₄ -C ₃₀ )alkyl and the remaining group or groups of R ¹ , R ² , R ³ and R ⁴ are (C 1 -C6) alkyl or benzyl.

More preferably, one or two of R ¹ , R ² , R ³ and R ⁴ are independently (C6-C30) alkyl and the remaining R ¹ , R ² , R ³ and R ⁴ groups are (C 1 -C ₆ ) alkyl or benzyl groups. Optionally, alkyl groups may include one or more ester (-OCO- or -COO-) and/or ether (-O-) linkages with an alkyl chain. Alkyl groups may optionally be substituted with one or more hydroxyl groups. Alkyl groups may be straight or branched chain, and for alkyl groups containing 3 or more carbon atoms, cyclic. Alkyl groups may be saturated or may contain one or more carbon-carbon double bonds (an example is oleyl). The alkyl groups are optionally ethoxylated in the alkyl chain with one or more ethyleneoxy groups.

Подходящие катионные кондиционирующие поверхностно-активные вещества для применения в кондиционирующих композициях согласно настоящему изобретению включают цетилтриметиламмония хлорид, бегенилтриметиламмония хлорид, цетилпиридиния хлорид, тетраметиламмония хлорид, тетраэтиламмония хлорид, октилтриметиламмония хлорид, додецилтриметиламмония хлорид, гексадецилтриметиламмония хлорид, октилдиметилбензиламмония хлорид, децилдиметилбензиламмония хлорид, стеарилдиметилбензиламмония хлорид, дидодецилдиметиламмония chloride, dioctadecyldimethylammonium chloride, tallow trimethylammonium chloride, dihydrogenated tallow dimethylammonium chloride (eg Arquad 2HT/75 from Akzo Nobel), cocotrimethylammonium chloride, PEG-2-oleammonium chloride and their respective hydroxides. Other suitable cationic surfactants include materials designated by CTFA as Quaternium-5, Quaternium-31 and Quaternium-18. Mixtures of any of the above materials may also be suitable. A particularly suitable cationic surfactant for use in conditioners according to the invention is cetyltrimethylammonium chloride, commercially available, for example, as GENAMIN STAC, in Hoechst Celanese. Another particularly suitable cationic surfactant for use in the conditioners of the present invention is behenyltrimethylammonium chloride, commercially available, for example, as GENAMIN KDMP from Clariant.

Another example of a class of suitable cationic conditioning surfactants for use in the present invention, either alone or in admixture with one or more other cationic conditioning surfactants, is the combination of (i) and (ii) below:

(i) an amidoamine corresponding to the general formula (I):

/ ^R2

R ¹ CONH(CH ₂ ) _m N

R3 in which R ¹ is a hydrocarbon chain containing 10 or more carbon atoms, R ² and R ³ are independently selected from hydrocarbon chains from 1 to 10 carbon atoms, and m is an integer from 1 to about 10; and (ii) an acid.

In the present description, the term hydrocarbon chain means an alkyl or alkenyl chain.

Preferred amidoamine compounds are compounds according to formula (I) in which

R ¹ is a hydrocarbon residue containing from about 11 to about 24 carbon atoms, each of R ² and R ³ independently represents hydrocarbon residues, preferably alkyl groups containing from 1 to about 4 carbon atoms, and m is an integer

- 8 040336 from 1 to about 4.

Preferably R ² and R ³ are methyl or ethyl groups.

Preferably m is 2 or 3, i.e. an ethylene or propylene group.

Предпочтительные амидоамины, подходящие для применения в настоящем изобретении, включают стеарамидопропилдиметиламин, стеарамидопропилдиэтиламин, стеарамидоэтилдиэтиламин, стеарамидоэтилдиметиламин, пальмитамидопропилдиметиламин, пальмитамидопропилдиэтиламин, пальмитамидоэтилдиэтиламин, пальмитамидоэтилдиметиламин, бегенамидопропилдиметиламин, бегенамидопропилдиэтиламин, бегенамидоэтилдиэтиламин, бегенамидоэтилдиметиламин, арахидамидопропилдиметиламин, арахидамидопропилдиэтиламин, арахидамидоэтилдиэтиламин, арахидамидоэтилдиметиламин и их смеси.

Particularly preferred amidoamines suitable for use in the present invention are stearamidopropyldimethylamine, stearamidoethyldiethylamine and mixtures thereof.

Commercially available amidoamines suitable for use in the present invention include: stearamidopropyldimethylamine under the tradename LEXAMINE S13 available from Inolex (Philadelphia, PA, USA) and AMIDOAMINE MSP available from Nikko (Tokyo, Japan), stearamidoethyldiethylamine under the tradename AMIDOAMINE S available from Nikko, behenamidopropyl dimethylamine under the trade name INCROMINE BB available from Croda (North Humberside, England), and various amidoamines under the trade names of the SCHERCODINE series available from Scher (Clifton, New Jersey, USA).

The acid (ii) may be an organic or mineral acid capable of protonating the amidoamine in the hair treatment composition.

Suitable acids that can be used in the present invention include hydrochloric acid, acetic acid, tartaric acid, fumaric acid, lactic acid, malic acid, succinic acid, and mixtures thereof. Preferably the acid is selected from the group consisting of acetic acid, tartaric acid, hydrochloric acid, fumaric acid and mixtures thereof.

The main role of the acid is to protonate the amidoamine in the hair treatment composition, thereby producing a tertiary amine salt (STA) in situ in the hair treatment composition. The effect of CTA is that it is a non-permanent cationic surfactant based on quaternary ammonium or pseudo-quaternary ammonium.

The acid is suitably included in a sufficient amount to protonate all of the amidoamine present, ie at least equimolar to the amount of amidoamine present in the composition.

In conditioners for use in the present invention, the content of the cationic conditioning surfactant will generally be from 0.01 to 10%, more preferably from 0.05 to 7.5%, most preferably from 0.1 to 5 wt. % of the total weight of the cationic conditioning surfactant, based on the total weight of the composition.

Conditioners for use in the present invention will typically contain a fatty alcohol. The combined use of fatty alcohols and cationic surfactants in conditioning compositions is believed to be particularly advantageous because it results in the formation of a lamellar phase in which the cationic surfactant is dispersed.

Exemplary fatty alcohols contain from 8 to 22 carbon atoms, more preferably from 16 to 22. Fatty alcohols are generally compounds containing straight chain alkyl groups. Examples of suitable fatty alcohols include cetyl alcohol, stearyl alcohol, and mixtures thereof. The use of these substances is also preferred as they contribute to the overall conditioning properties of the compositions for use according to the present invention.

The fatty alcohol content of conditioners for use in the present invention will generally be 0.01 to 10%, preferably 0.1 to 8%, more preferably 0.2 to 7%, most preferably 0.3 to 6 wt.% by weight of the composition. The weight ratio of cationic surfactant to fatty alcohol is suitably 1:1 to 1:10, preferably 1:1.5 to 1:8, optimally 1:2 to 1:5. If the weight ratio of cationic surfactant to fatty alcohol is too high, this can result in the composition being irritating to the eyes. If it is too low, it can lead to a squeaky clean feeling in some users.

Composition form

Compositions for use in the present invention may suitably take the form of a hair oil for use before washing or after washing. Typically, hair oils predominantly contain water-insoluble oily conditioning agents such as triglycerides, mineral oils, and mixtures thereof.

Compositions for use in the present invention may also take the form of a lotion for

- 9 040336 hair, as a rule, for application between shampooing. Lotions are aqueous emulsions containing water-soluble oily conditioning materials. Suitable surfactants may also be included in lotions to improve the stability of the lotion with respect to phase separation.

Hair treatment compositions according to the present invention, in particular water-based shampoos and hair conditioners, will preferably also contain one or more silicone conditioning agents.

Particularly preferred silicone conditioning agents are silicone emulsions, for example those derived from silicones such as polydiorganosiloxanes, in particular polydimethylsiloxanes, which have the CTFA designation dimethicone, hydroxyl-terminated polydimethylsiloxanes, which have the CTFA designation dimethiconol, and amino-functionalized polydimethylsiloxanes, which have the designation according to CTFA amodimethicone.

The emulsion droplets typically have an average Sauter diameter (D ₃ .2) in the composition for use in the present invention of 0.01 to 20 µm, more preferably 0.2 to 10 µm.

A suitable method for measuring the average Sauter droplet diameter (D ₃ , ₂ ) is by laser light scattering using an instrument such as the Malvern Mastersizer.

Suitable silicone emulsions for use in compositions for use in the present invention are available from silicone suppliers such as Dow Corning and GE Silicones. The use of such preformed silicone emulsions is preferred for ease of handling and size control of the silicone particles. Such pre-emulsions will typically further contain a suitable emulsifier such as an anionic or non-ionic emulsifier, or a mixture thereof, and may be prepared by a chemical emulsification process such as emulsion polymerization or by mechanical emulsification using a high shear mixer. Preformed silicone emulsions having a mean Sauter droplet diameter (D ₃ , ₂ ) of less than 0.15 µm are generally referred to as microemulsions.

Examples of suitable preformed silicone emulsions include DC2-1766, DC2-1784, DC-1785, DC-1786, DC-1788 emulsions and DC2-1865 and DC2-1870 microemulsions, all available from Dow Corning. All of these emulsions are dimethiconol emulsions/microemulsions. Also suitable are amidodimethicone emulsions such as DC2-8177 and DC939 (from Dow Corning) and SME253 (from GE Silicones).

Also suitable are silicone emulsions in which several types of high molecular weight surfactant block copolymers are mixed with silicone emulsion droplets, as described for example in WO 03/094874. In such materials, the silicone emulsion droplets are preferably formed from polydiorganosiloxanes such as those described above. One preferred form of surface active block copolymer is as follows:

HO(CH2CH2O)x(CH(CH3)CH2O)y(CH2CH2O)xH, where the average x is 4 or more and the average y is 25 or more.

Another preferred form of surface-active block copolymer corresponds to the following formula:

(HO(CH2CH2O)a(CH(CH3)CH2O)b)2-N-CH2-CH2-N((OCH2CH(CH3))b(OCH2CH2)aOH)2 where the average value of a is 2 or more and the average value b is 6 or more. Mixtures of any of the silicone emulsions described above may be used.

The silicone emulsions described above will generally be present in a composition for use in the present invention at a content of 0.05 to 10%, preferably 0.05 to 5%, more preferably 0.5 to 2%, of the total weight of silicone based on the total weight of the composition.

Other Ingredients

The composition for use in the present invention may contain other ingredients to enhance performance and/or consumer acceptance. Such ingredients include perfume, colorants and pigments, pH adjusters, pearlescent agents or opacifiers, viscosity modifiers, and preservatives or antimicrobials. Each of said ingredients will be present in an amount effective to achieve their purpose. Typically, these optional ingredients are included individually in amounts up to 5% by weight, based on the total weight of the composition.

Hair treatment compositions for use in the present invention are generally intended for topical application to human hair and/or scalp, in rinse-off or leave-on formulations, for the treatment of dry, damaged and/or unruly hair.

The present invention will be further illustrated by the following non-limiting examples, in which all percentages are based on weight based on total weight, unless otherwise indicated.

Examples

In the following examples, hair was treated according to the present invention with shampoo and conditioner formulations containing a mixture of glucono-delta-lactone, sodium sulfate and trehalose and compared with control formulations that did not contain these active substances. Processing

- 10 040336 was carried out before exposure to ultraviolet radiation.

In the following examples, n=5.

Example 1 Shampoos 1 and A and conditioners 2 and B

The compositions of the shampoos used in these examples are given in table. 1 below.

Shampoo 1 contained glucono delta lactone, sodium sulfate and trehalose.

Shampoo A did not contain any of the indicated hair fiber actives.

Table 1. Compositions of shampoos 1 and A

starting material % activity Quantity in the product (wt.%, based on the total weight of the composition) 1 pH 4.4 A pH 5.8 Sodium laureth sulfate 70 17.14 17.14 Cocamidopropyl Betaine thirty 5.33 5.33 Guarhyde roxypropyltrimonium chloride 100 0.25 0.25 Dimethiconol 22 1.6 1.6 Glycerol 100 1 1 Disodium EDTA 100 0.05 0.05 Sodium hydroxide 50 0.02 0.02 Glucono delta lactone 100 0.4 0 Sodium sulfate powder 100 0.1 0 Trehalose 100 0.1 0 Lemon acid 50 1 1 Sodium chloride 100 1.3 1.3 Water and minor components (perfume, pigments, preservative) - Up to 100 Up to 100 pH 4.4 5.8

The compositions of air conditioners used in these examples are given below in table. 2.

Conditioner 2 contained glucono delta lactone, sodium sulfate and trehalose.

Conditioner B did not contain any of these hair fiber actives.

Table 2. Composition of conditioners 2 and B

starting material % activity Quantity in the product (wt.% of the total weight of the composition) 2 IN Stearamidopropyldimethylamine 100 0.75 0.75 Cetearyl alcohol 100 3 3 Dimethicone and Amodimethicone 100 1.429 1.429 Lactic acid 100 0.55 0.55 Sodium chloride 100 0.2 0.2 Trehalose 100 0.1 0 Sodium sulfate powder 100 0.01 0 Glucono-deltalactone 100 0.1 0 Begentrimonium chloride 100 0.75 0.75 Water and minor components (perfume, pigments, preservative) - Up to 100 4.0 Up to 100 5.0 pH

Example 2 Treatment of hair with shampoo formulations 1 and A and conditioner formulations 2 and B.

In these examples, dark brown European hair strands were used, the hair was 5 grams in weight and 10 inches (about 25 cm) long.

The hair strands were washed with a 14% SLES-1EO solution to remove any surface contaminants prior to any treatment. Each strand was treated with a solution of SLES-1EO in an amount of 0.1 ml g ¹ hair. Foamed the composition on the strands for 30 seconds and then rinsed with warm

-

Claims (14)

water for 30 s. This treatment was repeated, after which the hair was combed with a comb and air dried. Processing method For shampooing, 0.1 ml of shampoo product (compositions 1 and A) per gram of hair was applied to the strands. Foam the composition on the strands for 30 seconds and then rinse with warm water (35°C-40°C) for 30 seconds. This treatment was repeated, after which the hair was combed with a comb and air dried. In the case of conditioning treatment, the strands were treated with 0.2 g of conditioning product (compositions 2 and B) per 1 g of hair. The product was applied with massaging movements to towel-dried hair for 60 seconds and rinsed with warm water for 60 seconds. The treated strands were combed with a comb. The hair was left to air dry. Example 3 Damage to hair by exposure to ultraviolet radiation. Before applying each damage, the hair was treated 20 times. Samples were taken at two time points: (1) (after the initial main wash) before the introduction of any shampoos and conditioners, (2) after damage. The UV exposure protocols were as follows. An Atlas S3000 radiation resistance tester, settings: 0.35 W/m ² (340 nm), giving 385 W/m ² radiation in the range of 300-800 nm, was used to treat hair strands to provide UV damage in for 24 hours on each side, for a total of 48 hours of UV exposure. Example 4. Determination of the degree of damage using differential scanning calorimetry (DSC). To obtain hair samples for DSC, 2.54 cm of hair was cut from the end of each strand. The hair was cut into fragments of 1-2 mm. For measurements, a Mettler-Toledo DSC1 instrument (with an autosampler) was used. 7-10 mg samples of dry, finely chopped hair were placed in the smeared base sections of 0.7 mm stainless steel medium pressure DSC crucibles and weighed to 5 decimal places. Then, 50 μl of deionized water was added to each sample, after which the crucibles were closed with a lid (with a ground rubber gasket) and the lids on the crucibles were crimped to ensure tight closure. The crucibles were equilibrated for at least 24 hours before measurements to ensure complete wetting of the hair. The DSC instrument was programmed to first heat each sample to 100°C for 3 minutes, and then heat them further from 100 to 180°C at a constant rate of 5°C min ^-1 . The results are shown in table. 3 below. Table 3 Change in denaturation temperature (ΔT _pricem .) during bleaching or heat straightening of hair treated with shampoo and conditioner compositions 1 and 2, in accordance with the present invention, or compositions A and B as comparative examples Treatment Protection ATdenat. SO T-test (p-value) Shampoo and Conditioner Compositions 1 and 2 2.25 0.49 0.00090 Shampoo and Conditioner Compositions A and B 0.73 0.24 As can be seen from the results, the denaturation temperature associated with UV damage was significantly higher for the samples pre-treated with the shampoo and conditioner of the present invention. This confirms that the hair has been protected from protein damage. CLAIM 1. A method for protecting hair from damage caused by exposure to ultraviolet radiation, comprising the step of applying to the hair a hair treatment composition containing a lactone, a disaccharide, an inorganic salt, and an organic acid or salt thereof having a pH in the range of 3 to 6.5, before exposure to ultraviolet radiation on the hair. 2. The method of claim 1 wherein the intrinsic protein of the hair is protected. 3. The method according to claim 1 or 2, wherein the step of applying to the hair a hair treatment composition containing a lactone, a disaccharide, an inorganic salt, and an organic acid or salt thereof having a pH in the range of 3 to 6.5 is carried out several times, preferably 2 to 50 times. 4. The method according to any one of claims 1 to 3, wherein the damage is caused by exposing the hair to ultraviolet radiation several times. 5. The method according to any one of claims 1 to 4, wherein the hair treatment composition is - 12 040336 a rinse-off hair treatment composition, preferably selected from shampoo, conditioner and mask. 6. The method of claim 5, wherein shampoo and conditioner are applied sequentially or shampoo and mask are applied sequentially. 7. The method according to any one of claims 1 to 6, wherein the content of organic acid, preferably lactic acid, in the conditioner or mask is from 0.01 to 1 wt%. 8. The method according to any one of claims 1 to 7, wherein the lactone is a delta lactone selected from gluconolactone, galactonolactone, glucuronolactone, galacturonolactone, gulonolactone, ribonolactone, sugar lactone, pantoyl lactone, glucoheptonolactone, mannonolactone, galactoheptonolactone, and mixtures thereof. 9. The method of claim 8 wherein the lactone is gluconolactone. 10. The method according to any one of claims 1 to 9, wherein the disaccharide contains pentose or hexose sugars, more preferably the disaccharide contains two hexose units. 11. The method of claim 10 wherein the disaccharide is trehalose. 12. The method according to any one of claims 1 to 11, wherein the inorganic salt is sodium sulfate. 13. The method according to any one of claims 1 to 12, wherein said hair treatment composition contains gluconolactone, trehalose, sodium sulfate and an organic acid or a salt thereof, and the pH of the composition is from 3 to 6.5, preferably from 3 to 5, to protect the inner protein of the hair from damage. 14. Use of a hair treatment composition containing a lactone, a disaccharide, an inorganic salt and an organic acid or salt thereof having a pH of 3 to 6.5 in treating hair for protection against damage caused by ultraviolet radiation. Eurasian Patent Organization, EAPO Russia, 109012, Moscow, Maly Cherkassky per., 2 -