WO2011111054A1

WO2011111054A1 - Improved hair dye composition

Info

Publication number: WO2011111054A1
Application number: PCT/IN2010/000135
Authority: WO
Inventors: Kannan Tara; Radhakrishnan Sudarshanam Archana
Original assignee: Cavinkare Pvt. Ltd,
Priority date: 2010-03-09
Filing date: 2010-03-09
Publication date: 2011-09-15

Abstract

The invention relates to an improved auto oxidisable hair darkening preparation capable of coloring or darkening keratinous fibre when applied thereto and exposed to the atmosphere for a short span of time which comprises of a mixture of (i) at least one p- phenylene diamine compound or an acid addition salt thereof (ii) 2, 4-diaminophenoxy ethanol or its salts and (ϋi) Substituted benzenes

Description

IMPROVED HAIR DYE COMPOSITION

Field of the invention

The invention relates to an improved hair dye composition. The invention particularly relates to an improved hair dye composition which darkens the hair after 2 hours of exposure to air. More especially the composition does not employ any oxidizing agents.

Back ground of the invention The color of the hair, the skin and hair of human origin originates thainly from the melanin pigments secreted by the melanocytes.These pigments of natural origin, comprise , in particular, pigments known as eumelanins and pheomelamns.Their natural bio-synthesis takes place in several stages by polymerization of the oxidation products of an aminoacid, namely tyrosine, and one of these oxidation products is 5,6- dihydroxyindole, which, in turn, polymerizes to Eumelanin.

It has long been known that p-Phenylenediamine and p-toluenediamine are capable of coloring hair but the coloring process is very slow unless applied in combination with an oxidizing agent such as hydrogen peroxide which must be kept apart from these diamines until immediately prior to use and which often damages the hair.

The process of hair coloring with primary intermediates like p- Phenylenediamine or p- toluenediamine is by their auto oxidation capabilities .

p-Phenylenediamine p-Benzoquinonediirnine

(0 (III)

Bandrowski's Base

(VI)

The first step in the oxidation process is the oxidation of p-phenylene diamine (I) to the corresponding p-benzoquinonediimine (Π). The electrophilic attack by the conjugate acid (V) of p-benzoquinonediimine on the carbon ring of a molecule of p-phenylenediamine results in the production of triaminodiphenylamine. Triaminodtphenylamiue undergoes oxidation, followed by reaction with another molecule of the diamine to produce the trinuclear compound which is known as Bandrowski's base (VI). The coloring process by auto oxidation of primary intermediates like p- Phenylenediamine or p-toluenediamine is very slow and may take several hours for dyeing grey hair. This process is speeded up by using oxidizing agents like Hydrogen peroxide which releases perhydroxyl anion and the entire coloring process is completed within 30-45 minutes wherein the primary intermediates like p- Phenylenediamine or p- toluenediamine react with couplers like resorcinoL, m-aminophenol forming Indodyes. The use of peroxides on hair is know, to have damaging effects especially on the pore size and cuticle. This makes the hair look dull, weak and damaged (Reference : Harris cosmetology, 8^th Edition -Edited by Martin M. Rieger .Chapter 1 : The substrates-page Nos:66-68 ).

Color specialists have always been on the lookout for safer coloring without damaging the hair shaft. Prior art shows work done by using auto oxidisable dyes which colors the hair without the use of peroxides. But all these efforts have been at the risk of longer exposure of dyes to hair as will be explained in the prior art description.

Prior art :

US patent No. 4,529,404 discloses an auto oxidisable hair dye preparation capable of coloring or darkening hair when applied thereto and exposed to the atmosphere. The preparation comprises a mixture of (i) at least one p-phenylene diamine compounder an acid addition salt thereof (ii) at least one 1,2,4-benzenetriol compound, each compound optionally containing nuclearly substituted Ci-4 alkyL alkoxy, hydroxyalkyl or halogen.

The above preparation is preferably applied at multiple spaced intervals of time and exposed to the atmosphere until the desired degree of darkening or color build up is attained. The auto oxidisable hair color obtained is natural looking, drab and long wearing.

The drawbacks of the above preparation is the long drawn exposure of dyes on hair, as well as the multiple steps of coloring hair which is a very tedious task. The delivery of color on hair happens only after a long period of time.

US Patent No. 4,054,413 discloses a process for the preparation of the composition defined in the US patent No. 4,529,404.

US patent No. 3,920,384 describes an autoxidisable hair prepartion capable of coloring hair which comprises N,N- bis- ( 2 hydroxyethyl) p- Phenylene diamine or an acid addition salt thereof and a triol selected from the group consisting of 1,2,4 benzene triol and 1,4,5 trihydroxytoluene.

The above preparation is applied at multiple spaced intervals of time until the desired color build up is obtained.

Similar to the previous reference (US 4529404) this preparation also requires multiple exposure over a long period of time, which is not consumer friendly. US patent no 5,021,067 discloses a dyeing composition for keratinous fibres and especially for human keratinous fibres which comprises a cosmetically acceptable aqueous medium of:

(i) an Indole dye, and

(ii) a p-Phenylene diamine disubstituted on one of the amino-groups corresponding to the formula:

where

and R₂ may be identical or different, denote a Ci-C₄ lower alkyl group; C₂-C₄ lower hydroxyalkyl group; or a CrC₄ alkyl group substituted with an SO3H, or with a mesylamino group or with a carbamyl group substituted or otherwise with one or two C₁-C4 alkyl groups, or with a heterocyclic amine, R_\ and R₂ together with the nitrogen atom to which they are attached, form a 4-6- membered heterocycle ring, especially a piperidino group;

R3, in position 2- or 3,denotes hydrogen or a C₁-C4 alkyl, C₁-C₄ alkoxy or halogen group; as well as their commercially acceptable salts. The above composition is applied several times successively, and it is found that the tint obtained becomes increasingly dark, this also being known as "progressive dyeing". The application is followed after an exposure of 5-50 minutes, by a rinse, optional shampooing , a further rinse and air drying. After 4 successive applications of this composition on the permanent waved grey hair, the hair has a natural black coloration.

The drawback in this patent is also that of successive application to get desired level of hair darkening. This is again tedious, and a long process where the person has to spend a lot of time in getting hair colored.

In the modern day situation, where time is a premium commodity, everything is desired to be done at a faster rate. Though there are several faster coloring products in the market, they are all peroxide developers which are believed to be harsh and damaging to the hair. It has always been desirable to have safe hair coloring products but will also deliver results quickly and the consumer does not have to spend a lot of time in getting the hair colored.

Objectives of the present invention Therefore the main objective of the present invention is to provide an improved hair coloring / darkening composition capable of coloring or darkening hair when applied thereto and exposed to the atmosphere for a short span of time.

Another objective of the present invention is to provide an improved hair coloring/ darkening composition which does not contain any oxidizing agent.

Still another objective of the present invention is to provide an improved hair coloring darkening composition, the constituents of which are less harsh on the hair. Yet another objective of the present invention is to provide an improved hair coloring/ darkening composition which is economical.

Yet another objective of the present invention is to provide an improved hair darkening /coloring composition which is easy to apply where no special applicators are required.

The above objectives of the present invention are achieved by providing a composition which is a combination of primary intermediates like p-Phenylenediamine or an acid addition salt thereof and couplers like resorcinol, m-aminophenol without using oxidizing agents which provides color to keratinous fibres within a short span of time. The composition ensures that there is no damage to the hair due to exposure to peroxides and also the retention time of dyes in hair is minimized.

Summary of the invention

Accordingly, the present invention provides an improved auto oxidisable hair preparation capable of coloring or darkening hair when applied thereto and exposed to the atmosphere for a short span of time which comprises of a mixture of

(i) at least one p-phenylene diamine compound or an acid addition salt thereof corresponding to the formula I

Formula I

where i and R_ may be identical or different and may independently be H; a C1-C4 lower alkyl group; C2-C₄ lower hydroxyalkyl group; a C1-C₄ alkyl group substituted with an SO3H group ,or with a mesylamino or acetylamino group ; a C1-C4 alkoxy group.a carbamyl group substituted; with one or two C1-C₄ alkyl groups ; Ri and R₂ may also be covalently linked to form a 4-6 membered heterocyclic and preferably a Piperidino group;

R₃₎ in position 2- or 3,denotes hydrogen or a Ci-C₄ alkyl, Ci-C₄ alkoxy or halogen group; as well as their commercially acceptable salts.

(ii)2,4-diaminophenoxy ethanol of the formula (II) or its salts

NH2

Formula-Π and (iii) Substituted benzenes corresponding to the formula (ΙΠ )

Formula-HI

Where R4, R₅ can independently be OH, NH₂ or NH(CH₂ )_2-4 OH Re and R₇ independently be H or electron donating groups such as halides, alkyls, alkoxyls, etc.

Especially preferred compounds corresponding to the formula (I) are those in which Ri and R₂ which may be identical or different, denote a hydrogen or methyl or ethyl or hydroxylethyl group; an ethyl group substituted with an SO3H, mesylamino group, acetylamino group or methoxy radical, or with a heterocyclic amine such as piperidine, or a methyl group substituted with a carbamyl group or diethylcarbamyl group, and R₃, preferably denotes hydrogen or methyl or ethyl, and their salts. The salts are preferably chosen from hydrochlorides, sulphates, tartrates, etc.

Preferred compounds are chosen, in particular, from p-phenylenediamine, N-ethyl-N- (2- hydroxyethyl)-para-phenylenediarnine, the sulphate arid hydrochloride,N,N-bis(2- hydroxyethyl)-paraphenylenediamine and its salts, N-ethyl-N-(2-piperidinoethyl)-para- phenylenediamine and its trihydrochloride, N-ethyl-N- (carbamylmethyl)para- phenylenediamine, N-ethyl-N-[2-(mesylarnmo)ethyl -paraphenylenediarnineand its sulphates, and 2-methyl-N,N-dimethyl-para-phenylenediamine and its salts, such as the dihydrochloride. The most especially preferred compounds of formula (Γ) are chosen from p- phenylenediamine, N,N-bis(2-hydroxyethyl)-para-phenylenediamine and its addition salts such as, for example, the sulphate, hydrochloride and tartrate. p-phenylene diamine compound or an acid addition salt thereof or para- phenylenediamines disubstituted on one of the nitrogen atoms, corresponding to the formula-I are preferably used in the composition according to the invention in proportions of between 0.05 and 8% by weight, especially between 0.1 and 5% by weight, relative to the total weight of the composition. 2 ,4-diaminophenoxy ethanol corresponding to the formula Π is preferably used in the composition according to the invention in proportions of between 0.01%-10%, preferably between 0.05-8% and more preferably between 0.1-5% by weight , relative to the total weight of the composition. Disubstituted benzenes like Resorcinol and m-aminophenol, corresponding to the formula-ΠΙ are preferably used in the composition according to the invention in proportions of between 0.01 and 10% by weight, especially between 0.05 and 8 % and more preferably between 0.1-5% by weight , relative to the total weight of the composition. A preferred embodiment of the invention comprises of a composition containing ,in a cosmetically acceptable medium like a thickened lotion, unthickened lotion, a gel, an aerosol foam, oil, pomades, brilliantines, hair tonics, serum and other hair grooming products, suitable for darkening or colouring, a mixture of p-phenylene diamine compound of the formula I or an acid addition salt thereof para-phenylenediamines . disubstituted on one of the nitrogen atoms, 2,4-diaminophenoxy ethanol and substituted benzenes like resorcinol or meta-aminophenol in sufficient proportions,

The compositions according to the invention described above suitable for darkening /coloring has a pH which can vary between 4 and 11, and preferably between 6 and 9.

The compositions according to the invention described above for darkening/coloring can contain, in addition cosmetically acceptable solvents in proportions by weight which can range upto 20% relative to the total weight of the composition ,and which are chosen more especially from alcohols such as ethyl alcohol, propyl alcohol , Isopropyl alcohol , tert-butyl alcohol or lauryl alcohol, cetostearyl alcohol; glycols such as ethylene glycol, propylene glycol. Especially preferred solvents consist of Lauryl alcohol and propylene glycol.

The composition of the invention can be in the form of thickened or unthickened lotions, gel or an aerosol foam and can contain adjuncts which are well known in hair dyeing for this type of application, such as plasticizing agents, antioxidant agents, thickening agents, conditioning agents such as cationic polymers and cationic surfactant agents; they may also contain anionic, nonionic or amphoteric surfactant agents as well as silicones, in particular volatile silicones. The thickening agents when used may be chosen, more especially, from sodium alginate, gum arabis, guar of carob gum. xanthum gum, cellulose derivatives such as methyl cellulose, hydroxyethyl cellulose, hydroxymethyl cellulose, hydroxypropyl cellulose and carboxymethylcellulose and various polymers having thickening functions such as acrylic acid derivatives. It is also possible to use in organic thickeners such as bentonite.

These thickening agents are preferably present in proportions between 0.1 and 5% by weight, and especially between 0.5 and 3% by weight, relative to the total weight of the composition.

In view of the sensitivity of the composition of the invention to oxidation, the composition of invention should preferably be prepared, packaged and stored under anaerobic condition. When packaged as an aerosol under pressure, the hydrocarbon or haolohydrocarbon propellants such as butane, propane, LPG, CFC free freons, Liquid- Nitrogen, Liquid Carbon di-oxide therein effectively provide such anaerobic conditions. - For other product formats like cream, lotion, gels, oil packaged in Non aerosol - packagings, premature oxidation of the composition of invention may be further reduced- or eliminated by including in such preparations antioxidant agents or nitrogen gas or inert gas. Antioxidant agents in sufficient proportions preferably between 0.03% and 1% by weight may be used for protection against oxidation. They are chosen in particular, from sulphites, hydrosulphites and ascorbic acid.

The composition of the present invention are generally fluid or liquid, in the form of a solution, dispersion, suspension, cream, lotion, gel or aerosol or the like and optionally in combination with hair grooming or hair conditioning agents whereby the hair, whether it be live as on the head ,or dead as in a swatch, wig or hairpiece, is simultaneously colored and groomed or conditioned.

The process of dyeing kerationous fibres and especially human hair, consists in applying on the said fibres the composition of the present invention, for a minimum span of time for developing a coloration in the air. The application is followed, after an exposure period of a minimum span of time, by a rinse, optional shampooing a further rinse and drying.

The details of the invention are given in the Examples which follow which are designed to illustrate the invention only and therefore should not be construed to limit the scope of the invention

The composition of the present invention is generally prepared the process described below .

Cetostearyl and lauryl alcohol are heated to a temperature of 75 deg C.

Sodium lauryl ether and water are added to the mixture and agitated for 5 minutes. Cooled to 55 deg C, added the cationic polymer Polyquaternium 10 and^' agitated for a further period of 5 minutes. Cooled to 45 deg C,added Sodium s rf mt¾f ίό it and agitated . again- for 5 minutes. The dye intermediates p-PDA, N,N-bis l^L¾ytlrbxyethyl)-p- phenylenediamine , Meta-aminophenol, Resorcinol, 2,4-diaminoph6noxy ethanol dihydrochloride dissolved in propylene glycol are then added and agitated for 10 minutes and cooled to 30 deg C .

Example 1:

Cetostearyl alcohol 3.0g

Lauryl alcohol 0.5g

p-PDA 3.0g

N,N-bis(2-hydroxyethyl)- 0.3g

para-phenylenediamine

2,4-Diaminophenoxy ethanol 0.90g

dihydrochloride

Resorcinol 0.3g

Sodium sulphite O. lg

Propylene glycol 3.0g

Polyquaternium 10 O.lg

Sodium lauryl ether sulphate 2.0g

Water qs lOO.Og Example 2:

Cetostearyl alcohol 3.0g

Lauryl alcohol 0.5g p-PDA 3.0g

N,N-bis(2-hydroxyethyl)- 0.3g para-phenylenediamine

2,4-Diaminophenoxy ethanol 0.90g dihydrochloride

Meta-aminophenol 0.25g

Sodium sulphite O. lg

Propylene glycol 3.0g

Polyquaternium 10 O. lg

Sodium lauryl ether sulphate 2.0g

Water qs lOO.Og

Example 3:

Cetostearyl alcohol 3.0g

Lauryl alcohol 0.5g p-PDA 3.0g

N,N-bis(2-hydroxyethyl)- 0.3g para-phenylenediamine

2,4-Diaminophenoxy ethanol 0.90g dihydrochloride

Meta-aminophenol 0.25g

Resorcinol 0.30g

Sodium sulphite O. lg

Propylene glycol 3.0g

Polyquaternium 10 O.lg

Sodium lauryl ether sulphate 2.0g

Water qs 100.0 For comparative purposes compositions as shown in Examples 4 & 5 with only one ingredient of the formula 1 is prepared .

Example 4:

Cetostearyl alcohol 3.0g

Lauryl alcohol 0.5g

p-PDA 3.0g

Sodium sulphite O.lg

Propylene glycol 3.0g

Poluquaternium 10 O.lg

Sodium lauryl ether sulphate 2.0g

Water qs lOO.Og

The above composition is prepared as follows

Cetostearyl and lauryl alcohol are heated to a temperature of 75 deg C.

Sodium lauryl ether and water are added to the mixture and agitated for 5 minutes. Cooled to 55 deg C,add the cationic polymer Polyquatemium 10 and agitated for a further period of 5 minutes. Cooled to 45 deg C,added Sodium sulphite to it and agitated again for 5 minutes. The dye intermediates p-PDA, dissolved in propylene glycol are then added and agitated for 10 minutes and cooled to 30 Jeg C .

Example 5:

Cetostearyl alcohol . 3 :0g

Lauryl alcohol

N,N-bis(2-hydroxyetliyl)- para henylenediamme 3?0g

Sodiunj sulphite O.lg

Propylene glycol 3.Og Polyquaternium 10 O. lg

Sodium lauryl ether sulphate 2.0g

Water qs lOO.Og

The above composition is prepared as follows

Cetostearyl and lauryl alcohol are heated to a temperature of 75 deg C.

Sodium lauryl ether and water are added to the mixture and agitated for 5 minutes.

Cooled to 55 deg C,add the cationic polymer Polyquaternium 10 and agitated for a further period of 5 minutes. Cooled to 45 deg C,added Sodium sulphite to it and agitated again for 5 minutes. The dye intermediates p-PDA, dissolved in propylene glycol are then added and agitated for 10 minutes and cooled to 30 deg C .

To compare the relative merits of autoxidation dyeing properties of the compositions of the present invention on hair samples as to depth, shade and the lasting qualities of coloring, the experiments below were carried out. This was evaluated with for dye uptake (hair darkening as a measure) over a period of time. eratinous fibres particularly non black hair swatches were impregnated with the composition of invention described in the Examples 1 to 3 at room temperature for a minimum period of 2 hours, then shampooed ,rinsed and blow dried. For comparative purposes Keratinous fibres particularly non black hair swatches were also impregnated as described above with compositions described in examples 4 and 5.

The color readings L, a, b were obtained with Gretag Macbeth™ Color eye Reflectometer 2180UV immediately and again after exposure of the swatches to the atmosphere for 120 hours.

The color readings L, a, b were measured by diffuse reflectance spectroscopy for the swatch before dyeing and after dyeing. The color units L stands for lightness(0=black,100=white), +a is red, -a is green, +b is yellow, -b is blue. The difference DL is the difference in L values for the swatch before and after dyeing. Greater the DL values, greater is the level of darkening.

The abbreviations in the table given above for the dye intermediates listed as compounds have the following significance :

1 and 2: para-phenylenediamine

3 and 4: N,N-bis-(2-hydroxyethyl)-p-phenylenediamine

5: para-phenylenediamine + N,N-bis-(2-hydroxyethyl)-p-phenylenediamine +Meta- aminophenol + 2,4-diaminophenoxy ethanol dihydrochloride.

6: para-phenylenediamine + N,N-bis-(2-hydroxyethyl)-p-phenylenediamine +Resorcinol + 2,4-diaminophenoxy ethanol dihydrochloride.

7: para-phenylenediamine + N,N-bis-(2-hydroxyethyl)-p-phenylenediamine +Meta- aminophenol + 2,4-diaminophenoxy ethanol dihydrochloride +Resorcinol.

The following inferences can be drawn from the table:

1. The darkening produced by the primary intermediate p-phenylene diamine even after 120 hours is almost 1.5 times lower than the darkness produced by the composition of the present invention. 2. The darkening produced by the primary intermediate N,N-bis-(2-hydroxyethyl)-p- phenylenediamine even after 120 hours is almost 6 times lower than the darkness produced by the composition of the present invention.

3. The composition of the present invention described in Examples 1, 2 and 3 delivers significant darkening in 2 hours on a keratinous fibre such as non black hair swatch.

This property of the composition of invention to darken hair after exposure to air for a short span of time is not reported in the prior art review.

The composition of the present invention is most conveniently applied in the form of a hair grooming composition which will simultaneously groom and color the hair. The autoxidizable compounds are usually contained in solution in the composition of

. invention. In a typical application, enough composition is applied on dry hair followed by

¾simpiy¾0mbing^;into the de¾ired style.

The composition of^'the present invention may be used in various vehicles such as not limited to aerosols, foams, gels, oils, pomades, brilliantines, hair tonics, serums and other hair grooming products which can conveniently be used.

Advantages of the invention

1. The hair darkening using the composition of invention occurs after a minimal period of exposure to air .

2. The composition of invention does not use oxidising agents. Hence the damaging effects of peroxides are avoided. Therefore it is less harsher on the hair.

3. The composition is economically cost beneficial.

4. The composition of invention is easy to apply where no special applicators are required.

Claims

We Claim

1. An improved auto oxidisable hair darkening preparation capable of coloring or darkening keratinous fibre when applied thereto and exposed to the atmosphere for a short span of time which comprises of a mixture of

Formula !

where Rj and R₂ may be identical or different and may independently be H; a C1-C4 lower alkyl group; C₂-C4 lower hydroxyalkyl group; a C₁-C4 alkyl group substituted with an S0₃H group, or with a mesylamino or acetylamino group; a C1-C4 alkoxy group;a carbamyl group substituted; with one or two C₁-C4 alkyl groups; Rj and R₂ may also be covalently linked to form a 4-6 membered heterocyclic and preferably a Piperidino group; R3, in position 2- or - 3, denotes hydrogen or a C1-C4 alkyl, C1-C4 alkoxy or halogen' roup; as well as their commercially acceptable salts.

(ii) 2, 4-diaminophenoxy ethanol of the formula (Π) or its salts

Formula Π and (iii) Substituted benzenes corresponding to the formulaQH)

Formula ΙΠ

Where R4, R₅ can independently be OH, NH₂ or NH(CH₂ )_2-4 OH R5 and R? independently be H or electron donating groups such as halides, alkyls, alkoxyls, etc.

2. The composition as claimed in claim 1 wherein the said para-phenylenediamine is selected from the group consisting of p-phenylenediamine, N-ethyl-N- (2-hydroxyethyl)- para-phenylenediamine.and its salts ,N,N-bis(2-hydroxyethyl)-parapphenylenediamine and its salts,N-ethyl-N-(2-piperidinoethyl)-para-phenylenediamine and its salts ,N-ethyl- N-(carbamylmethyl)para-phenylenediamine,N-ethyl-N-[2-(mesyIamino)ethyl]- paraphenylenediamine and its salts, and 2-methyl-N,N-dimethyl-para-phenylenediamine and its salts.

3. The composition as claimed in claims 1 & 2 wherein the said para-phenylenediamine is preferably used in an amount in the range of 0.05 to 8% by weight, especially in the range of 0.1 to 5% by weight, relative to the total weight of the composition. 4. The composition as claimed in claims 1 to 3 wherein said 2,

4-diaminophenoxy ethanol corresponding to the formula Π is preferably used in an amount in the range of 0.01%- to 10%,preferably in the range of 0.05 to 8% and more preferably in the range of 0.1 to5% by weight, relative to the total weight of the composition.

5. The composition as claimed in claims 1 to 4 wherein the disubstituted benzenes of the formula ΙΠ used is selected from Resorcinol and m-aminophenol .

6. The composition as claimed in claims 1 to 5 wherein the said substituted benzenes is used in an amount in the range of 0.01% to 10%, preferably in the range of 0.05 to 8% and more preferably in the range of 0.1 to 5% in the composition.

7. The Composition as claimed in claims 1 to 6 wherein it also contains adjuncts which are well known in hair dyeing for this type of application, such as plasticizing agents, antioxidant agents, tliickening agents, conditioning agents such as cationic polymers and cationic surfactant agents; anionic, nonionic or amphoteric surfactant agents as well as silicones, in particular volatile silicones.

8. The composition as claimed in claim6 wherein the adjuncts are preferably present in an amount in the range of 0.1 to 5% by weight, and especially in the range of 0.5 to 3% by weight .relative to the total weight of the composition.

9.The composition as claimed in claims 1 to 5 wherein it is in the form of a thickened lotion, an unthickened lotion, a gel , an aerosol foam , oil, pomades, brilliantines , hair tonics, serum and other hair grooming products and having a pH in the range of 4 to 11.