AU727223B2 - Use of selected benzotriazole and triazine derivatives for protecting human hair from the harmful effects of UV radiation - Google Patents

Abstract

The use of benzotriazole or triazine compounds of formula (I) or (II) is claimed to protect human hair against damage caused by UV radiation. R = H or Cl; R1 = 1-12C alkyl or phenyl-(1-3C)-alkyl; R2 = 1-4C alkyl or SO3M; A = phenyl (optionally mono- to tri- substituted by 1-12C alkyl, 1-18C alkoxy, halo, OH or E) or 1-(1-18C alkyl)-pyrrol-1-yl; E = O(CH2)mN(R15)(R16)(R14)nX; R3 = Ar; R4 = halogen or Ar'; Ar, Ar' = phenyl (optionally mono- to tri- substituted, by OH, 1-8C alkyl, 1-8C alkoxy, phenyl-(1-3C)-alkyl, 5-7C cyclohexyl or SO3M; R14-R16 = 1-5C alkyl; or when n = 0, then NR15R16 = 6-membered heteroaryl; M = H, Na or K; X = halo; m = 1-5; and n = 0-1. Also claimed is a hair cosmetic formulation containing at least 0.25-5 wt.% UV absorber of formula (I) and/or (II), and at least one skin and hair compatible auxiliary agent.

Description

S F Ref: 388811

AUSTRALIA

PATENTS ACT 1990 COMPLETE SPECIFICATION FOR A STANDARD PATENT

ORIGINAL

Name and Address of Applicant: Actual Inventor(s): Address for Service: Invention Title: Ciba Specialty Chemicals Holding Inc.

Klybeckstrasse 141 4057 Basel

SWITZERLAND

Helmut Luther, Rene Baudin, Albert Stehlin and Jurg Haase Spruson Ferguson, Patent Attorneys Level 33 St Martins Tower, 31 Market Street Sydney, New South Wales, 2000, Australia Use of Selected Benzotriazole and Triazine Derivatives for Protecting Human Hair from the Harmful Effects of UV Radiation The following statement is a full description of this invention, including the best method of performing it known to me/us:- 5845 Use of selected benzotriazole and triazine derivatives for protecting human hair from the harmful effects of UV radiation The present invention relates to the use of selected benzotriazole and triazine derivatives for protecting human hair from the harmful effects of UV radiation.

If human hair is exposed to sunlight over a prolonged period of time it may be damaged in different ways. Under the influence of sunlight, dyed hair can change its colour and shade. Blond hair turns yellowish. The hair surface becomes rougher and at the same time drier. Furthermore, the hair gradually loses its sheen.

The use of UV absorbers can effectively protect natural and dyed hair from harmful I sun radiation. Unfortunately, the UV absorbers employed so far have an insufficient fibre affinity on human hair, i.e. they can easily be washed out and therefore have only a shortterm effect.

Surprisingly, it has now been found that specific benzotriazole and triazine derivatives have.excellent substantivity for human hair while at the same time providing.

i5 effective UV protection for hair.

Accordingly, this invention relates to the use of selected benzotriazole and triazine derivatives for protecting human hair from the harmful effects of UV radiation.

According to one embodiment of this invention there is provided a method for protecting human hair from the harmful effects of UV radiation which method comprises 20o applying to said hair an effective amount of at least one compound of the formula N HO

R

N

R

1

RN

SR2 \wherein R is hydrogen or chloro, R C-Cl 2 alkyl or phenyl-Ci-C 3 alkyl;

R

2 is Ci-C 4 alkyl; or SO 3 M; and M is hydrogen; sodium; or potassium.

According to another embodiment of this invention there is provided a cosmetic formulation for hair, comprising at least 0.25 to 5% by weight, based on the total weight of the composition, of a UV absorber of formula

I

;C

JR'4 0 6.docaak n 2

HO

-NN0

R

whierein R is hydrogeni or chioro,

RI

1 IS Ci-C] 2 alkyl or plienyl-CI-C 3 alkyI; R, I iC -C 4 alkyI; Or SO 3 M; and N/l is hydrogen; sodium; or potassium.

and at least one assistant compatible with skin and hair.

According to a further embodiment of this invention there is provided a cosmetic formu11-lation for hair, comprising at least 0.25 to 5% by weight, based on the total weight I of the composition of a UV absorber which is a benizotriazole compound of formula HO

R

N\

N

N'

.*S0 3

M

wherein RI IS CI-C 1 2 alkyl; and M is hydrogen; sodium; or potassium, triethylene glycol butyl ether and tributyl 15 citrate.

The selected benzotriazole compounds are 3- H-benizotriazol- hydroxybenzenie-sulfonic acids which conform to formula

HO

R

N

NR

In formulae (1) R is hydrogen or chloro, RI I S C I -C 12 alkyl or phenyl-C I-C 3 alkyl; R~ IS Cr-C 4 alkyl; or SO 3 M; and NM is hydrogen; sodium; or potassium.

The CI-Cl 2 alkyl radicals may be the groups miethyl, ethyl, propyl, isopropyl, butyl, isobutN'1, sec-butyl, tert-butyl, pentyl, hexyl, octyl, decyl or dodecyl.

1R:\Li1lNN 1O 23 ')6.doc:aaL Ci-CisAlkoxy is straight-chain or branched radicals, suIch as methoxy., ethoxy, propx. btoxy penty loxy, hexyloxy. heptyloxy. octyloxy. I sooctylox. nonyloxy, Llndecv loxy, dodecyloxy. tetradecyloxy or pentadecyl oxy, hexadecyloxy. heptadecy lox)' or octadecyloxy.

The phienyl-CI-C 3 alkyI radical is typically the benzyL, phenethyl or 2.2climethylbenzyl radical.

H-alogen IS filoro. bromo or, preferably, chioro.

Si-table benzotriazole derivatives are preferably compounds Ot* 60ormul-1a \.Vlereinl R is hydrogen, and

R

1 I IS C 1 -Cp~alkvl.

Particularly preferred benzotriazoles are those of Formul1-1a *0 0 a 4.

0 a *40* *0 0 0* .4 0 40 9 0

R

S0 3

M

\vherein a 5 R, R 1 and M have the meanings stated above.

4000 0 9 0*9@ *004 0 *0*0 0**0 04

S.

*000 0 0 0000 00 00 00 0 a 0 000000 4 ci' 0' Very particularly preferred compounds are those of formula

HO

N N

SO

3

M

wherein

R

1 is C 1

-C

1 2 alkyl; and M is hydrogen; sodium; or potassium.

If Rs, R 6 or R 7 is a radical of formula then this radical preferably corresponds to formula

CH

3 -O-(CH 2 MN-C H 5 C1

CH

-0O-(C N wherein mi is as defined above.

Preferred hydroxyphenyl-s-triazines conform to formula R6

R

OH

Ra N N R 11 R6' R,12 Rio

R

1 3 wherein

R

5 is hydrogen; or SO 3

M;

R

6 is hydrogen; hydroxy; C 1 -Csalkoxy; or a radical of formula (2e);

R

8

R

9

R

1 l and R 12 are each independently of one another hydrogen or hydroxy; and Rio and R 1 3 are each independently of the other hydrogen; or sulfo.

Particularly interesting compounds are those of formula which contain at least one sulfo group or a radical of formula (2e).

Very particularly interesting compounds are hydroxyphenyl-s-triazines of formula wherein

R

s Rs, Rg, Rio, R 11

R

12 and R 1 3 are hydrogen; and

R

6 is a radical of formula (2e).

Likewise preferred are triazine compounds of formula wherein

R

5 is hydrogen; or SOsM;

R

6 is hydroxy or CI-Csalkoxy;

R

8

R

9

R

11 and R 1 2 are hydroxy; Rio and R 13 SOaM; and M is hydrogen; sodium; or potassium.

The following compounds are illustrative of the triazine derivatives which may be used Saccording to this invention:

HOS

OH

OH

OH N N HO OH N N HO HO OH HO

OH

SO

3 H SO 3 H SO 3 H SO 3

H

a -6- 0f (8) (9)

C.

According to this invention it is also possible to use mixtures of UV absorbers of formulae and and also The benzotriazole derivatives of formulae and are known compounds. Sodium salts of 3-[2'H-benzotriazol-(2')-yl]-4-hydroxybenzenesulfonic acids are known, inter alia, from EP-A-0 112 120. They are prepared by sulfonating the corresponding 2-[2'H-benzotriazol-(2')-yl]phenols with chlorosulfonic acid, these starting materials being prepared in accordance with the process of J. Rosevear and J.F.K: Wilshire, Aust. J. Chem. 1985, 38, 1163-1176.

The triazine derivatives of formulae and to are also known from the literature and can be prepared in a manner known per se, e.g. by heating an amidine and an o-hydroxybenzenecarboxylate, preferably at about molar amounts in the ratio of 2:1, in boiling organic solvents [cf. US-A-3,896,125 and Helv.Chim. Acta 55 (1972), 1566-1595].

The 3-[2'H-benzotriazol-(2')-yl]-4-hydroxybezenesulfonic acids of formulae and (4) and the 2-(2'-hydroxyphenyl)-s-triazines of formulae and which are used according to this invention, are known as UV absorbers for technical applications, e.g. for plastic materials, paints systems and films, natural or synthetic resins, waxy materials, rubber or also as light stabilisers in cosmetic formulations for the skin.

The benzotriazole and triazine derivatives used according to this invention are distinguished by having a high substantivity for human hair and guaranteeing high UV protection for hair.

Another object of this invention is the provision of a cosmetic formulation for hair, which comprises at least 0.25 to 5 by weight, based on the total weight of the composition, of a UV absorber of formula and/or and at least one auxiliary compatible with skin and hair.

The cosmetic formulation for hair can be prepared by physical mixing of the UV absorber or UV absorbers with the auxiliary or auxiliaries by customary methods, e.g. by simply stirring the individual components together.

Unless they are soluble in water, the novel UV absorbers used for cosmetic applications for hair usually have an average particle size in the range from 0.02 to 2, preferably from 0.05 to 1.5 and, very particularly preferably, from 0.1 to 1.0 gi. The insoluble novel UV absorbers can be reduced to the desired particle size by customary methods, such as grinding in a nozzle mill, ball mill, vibratory mill or hammer mill. Grinding is preferably carried out in the presence of 0.1 to 30 by weight, more preferably of 0.5 to 15 by weight, based on the UV absorber, of a grinding auxiliary, such as an alkylated vinyl pyrrolidone polymer, a vinyl pyrrolidone/vinyl acetate copolymer, an acyl glutamate or, preferably, a phospholipid.

99 To prepare the novel cosmetic formulations for hair it is possible to use any conventionally usable emulsifier, typically one or several ethoxylated esters of natural derivatives, such as polyethoxylated ester of hydrogenated castor oil; or a silicone oil emulsifier, such as silicone -8polyol; a free or ethoxylated fatty acid soap; an ethoxylated fatty alcohol; a free or ethoxylated sorbitan ester; an ethoxylated fatty acid; or an ethoxylated glyceride.

In this case, the cosmetic formulation for hair may be used in the form of a shampoo, lotion, gel, or of an emulsion for rinsing, before or after shampooing, before or after dyeing or removing dye, before or after a perming or straightening process, in the form of a lotion, foam or gel for setting or treating hair, in the form of a lotion or a gel for brushing or waving hair, in the form of a hair lacquer, in the form of a composition for perming or straightening hair, for dyeing or removing dye.

It is possible to use, for example, the following cosmetic formulations for hair: spontaneously emulsifying stock formulations, consisting of the UV absorber, PEG-6 Clooxoalcohol and sorbitan esquioleate, which is charged with water and any quaternary ammonium compound, such as 4% minkamidopropyldimethyl-2-hydroxyethyl ammonium chloride or Quaternium a 2 spontaneously emulsifying stock formulation, consisting of the UV absorber, tributyl i citrate and PEG-20 sorbitan monooleate, which is charged with water and any quaternary ammonium compound, such as 4% minkamidopropyldimethyl-2-hydroxyethyl ammonium chloride or Quaternium b) quat-doped solutions of the UV absorber in butyl triglycol and tributyl citrate; c) dispersions of micronised UV absorbers obtained by known methods (precipitation from solutions or mixtures of solutions, grinding), having an average diameter of 0.05 1.0 lam in APG Plantaren), and a quat minkamidopropyldimethyl-2hydroxyethyl ammonium chloride) in an aqueous formulation; d) mixtures or solutions of the UV absorber with n-alkylpyrrolidone.

It is preferred to use cosmetic formulations for hair comprising, as UV absorber, a benzotriazole compound of formula triethylene glycol butyl ether and tributyl citrate.

Of these formulations, those are very particularly preferred wherein the UV absorber is a benzotriazole compound of formula -9- These last-mentioned formulations preferably comprise to 50 parts of the benzotriazole compound of formula preferably of formula to 80 parts of triethylene glycol butyl ether, and to 5 parts of tributyl citrate.

In addition to the novel UV absorbers, the cosmetic formulation for hair can also contain one or more than one further UV protective of the following substance classes: 1. p-aminobenzoic acid derivatives, typically 2-ethylhexyl-4-dimethylaminobenzoate; 2. salicylic acid derivatives, typically 2-ethylhexyl salicylate; 3. benzophenone derivatives, typically 2-hydroxy-4-methoxybenzophenone and its nic acid derivative; 4. dibenzoylmethane derivatives, typically 1-(4-tert-butylphenyl)-3-(4-methoxyphenyl)propane-i ,3-dione; 5. diphenylacrylates, typically 2-ethylhexyl-2-cyano-3,3-diphenylacrylate and 3-(benzofuranyl)-2-cyanoacrylate; 6. 3-imidazol-4-yl-acrylic acid and 3-imidazol-4-yl-acrylate; 7. benzofuran derivatives, preferably 2-(p-aminophenyl)benzofuran derivatives, disclosed in EP-A-582 189, US-A-5 338 539, US-A-5 518 713 and EP-A-613 893; 8. polymeric UV absorbers, such as the benzylidenemalonate derivatives described, inter *alia, in EPA-709 080; 9. cinnamic acid derivatives, typically the 2-ethylhexyl-4-methoxycinnamate or isoamylate or cinnamic acid derivatives disclosed, inter alia, in US-A-5 601 811 and WO 97/00851; camphor derivatives, typically 3-(4'-methyl)benzylidenebornan-2-one, 3-benzylidenebornan-2-one, N-[2(and 4)-2-oxyborn-3-ylidenemethyl)benzyl]acrylamide polymer, trimethylammonium)benzylidenebornan-2-one methylsulfate, 3,3'-(1,4-phenylenedimethine)-bis(7,7-dimethyl-2-oxobicyclo-[2..1 ]heptane-1 -methanesulfonic acid) and the salts thereof, 3-(4'-sulfo)benzylidenebornan-2-one and the salts thereof; 11. trianilino-s-triazine derivatives, typically 2,4,6-trianiline-(p-carbo-2'-ethyl-1 '-oxi)-1,3,5triazines as well as the UV absorbers disclosed in US-A-5 332 568, EP-A-517 104, EP-A-507 691, WO 93/17002 and EP-A-570 838; 12.2-hydroxyphenylbenzotriazole derivatives; 13.2-phenylbenzimidazole-5-sulfonic acids and the salts thereof; 14. menthyl-o-aminobenzoate, TiO 2 (coated differently), ZnO and mica.

The UV absorbers described in "Sunscreens", Eds. N.J. Lowe, N.A.Shaath, Marcel Dekker, Inc., New York and Basel, or in Cosmetics Toiletries (107), 50ff (1992), can also be used as additional UV protectives in the inventive formulations for hair.

The cosmetic formulations for hair can also be used together with known antioxidants, such as vitamin E, carotinoids or HALS compounds.

The novel compositions can also comprise other useful auxiliaries, typically surfactants, thickeners, polymers, preservatives, fragrances, foam stabilisers, electrolytes, organic solvents, oils, waxes, degreasants, dyes and/or pigments, which serve to provide the cosmetic composition for hair with the same shade as that of the hair to be treated, as well as other auxiliaries conventionally used in hair cosmetics.

This invention also relates to a method of treating human hair to protect it from the harmful effects of UV radiation. This method comprises treating hair with a shampoo, lotion or gel, or with an emulsion for rinsing, before or after shampooing, before or after dyeing or removing dye, before or after a perming or straightening process; with a lotion, foam or gel for setting; with a lotion, foam or gel for brushing or waving; with a hair lacquer; with a composition for perming or straightening hair, for dyeing or removing dye, which shampoo, lotion, gel, emulsion, foam, hair lacquer or composition for perming, straightening, dyeing or ":"removing dye comprises at least one UV absorber of formula or SoThe following non-limitative Examples illustrate the invention in more detail. .l .o• -11 Example 1: Determining the affinity of UV absorbers on hair by determinino the denree nf exhaustion from formulations or solutions ml of a 10 mmolar UV absorber solution and 1g of a lock of hair are defined in a glass vessel and shaken in reproducible manner. The decrease in UV absorber concentration in the test formulation or test solution is determined after 30 and 60 minutes using a spectrophotometer (see Table The degree of exhaustion determined in this manner is a measure of the substantivity of the UV absorber or of the formulation in which it is present.

Table 1: Determination of the degree of exhaustion 0 V .0.

0 0.

0..0 00*0 0 0 UV absorber used degree of exhaustion [%1 after after minutes 60 minutes

O-CH

3 27.0 39.0

OH

(101)

N

N N CH, 15.0 19.0 HO CH-CHs (102)

N

N Ia SONa 12- Table 1: Determination of the degree of exhaustion (continuation) UV absorber used degree of exhaustion [%1 after after minutes 60 minutes OH 55.0 61.0 H0 3

S

OH

(103) OH NNN N HO

N

HO

OH

S0 3 H so 3

H

OCH

3 27.0 27.0 1

OH

(104) OH N~ N HO HOJ

OH

so 3 H S0 3

H

S

-13- Table 1: Determination of the degree of Degree of exhaustion f%1o exhaustion (continuation) UV absorber used after after minutes 60 minutes C-25.0 25.0 0fN (105)

OH

We N N 21.0 24.0

N-OH

3 (16) HO N N OH HO OH S0 3 H S0 3

H

Example 2: Preparation of a hair rinse: Composition[g UV absorber of formula (102)1 mixture of cetyistearyl alcohol and the polyadduct of 1 mol of 2 cetylstearyl alcohol and 33 mol of ethylene oxide monoethanol amide xanthan gum 0.8 water 95.7 -14- The individual components are mixed, charged with preservatives and perfume oil and then adjusted to pH 6.5 with dilute HCI.

This gives a ready-to-use hair rinse which provides good and long-lasting UV protection for human hair.

o

Claims (10)

1. A method for protecting human hair from the harmful effects of UV radiation which method comprises applying to said hair an effective amount of at least one compound of the formula HO R N 1 R2 w\herein R is hydrogen or chloro, RI CI-C 2alkyl or phenyl-Ci-C 3 alkyl; R-2 is CI-C 4 alkyl; or SO 3 M; and M is hydrogen; sodium; or potassium.

2. Method according to claim 1, wherein in the compounds of formula (1) R is hydrogen; RI is Ci-Ci2alkyl. .o 3 Method according to either claim 1 or claim 2, wherein the compounds conform to formula HO N R 1 3 R N SO 3 M wherein RI and M have the meaning claimed in claim 1.

4. Method according to any one of claims 1 to 3, which comprises using compounds of formula HO R, N N N- SO 3 M wherein RI is Ci-Cl2alkyl; and M is hydrogen; sodium; or potassium. 16 A cosmetic formulation for hair, comprising at least 0.25 to 5% by weight, based on the total weight of the composition, of a UV absorber of formula HO R N R2. wherein R is hydrogen or chloro, RI is Ci-Ci 2 alkyl or phenyl-Ci-C 3 alkyl; IR2 is Ci-C 4 alkyl; or SO 3 M; and M is hydrogen; sodium; or potassium. and at least one assistant compatible with skin and hair. In 6. A formulation according to claim 5, wherein the UV absorber is a benzotriazole compound of formula triethylene glycol butyl ether and tributyl citrate.

7. A cosmetic formulation for hair, comprising at least 0.25 to 5% by weight, based on the total weight of the composition of a UV absorber which is a benzotriazole compound of formula HO R1 N N *SO 3 M wherein R: RI is Ci-Cl 2 alkyl; and M is hydrogen; sodium; or potassium, triethylene glycol butyl ether and tributyl citrate.

8. A formulation according to claim 6, which comprises to 50 parts of the benzotriazole compound of formula to 80 parts of triethylene glycol butyl ether, and to 5 parts of tributyl citrate.

9. A formulation according to claim 7 which comprises 25 to 50 parts of the benzotriazole compound of formula to 80 parts of triethylene glycol butyl ether, and to 5 parts of tributyl citrate. SR:\LIII XJX 1239'6.doc:aak 17 A formulation according to any one of claims 5 to 9. which comprises as additional UV protectives p-aminobenzoic acid derivaties. salicyclic acid derivaties, henzophenone derivatives. dibenzoylmethane derivatives. diphenylacrylates benzofiran Jerivatives- cinnamic acid derivatives, camp)hor derivaties. trianilino-s-triazine derivatives. 2 -hydroxyplhenylbenzotriazole derivatives, 2 -phenylbenzimidazole-5-sul fonic acids and the salts thereof menthyl-o-ainobenzoate, TiO (coated differently) ZnO and 1111C. II A formulation according to any one of claims 5 to 10. w\vhich additionally comprises antioxidants.

12. Use of the cosmetic formulation for hair according to any one of claims 5 to I I for protecting natural and dyed human hair from ultraviolet radiation, which is used in the 1form of a shampoo, lotion or gel. or emulsion for rinsing, before or after shampooing, before or ater dyeing or removing dye, before or after a perming or straightening process, in the form of a lotion, foam or gel for setting or treating hair. in the form of a lotion, foam or gel for brushing or waving, in the form of a hair lacquer, in the form of a composition for perming or straightening hair, for dyeing or removing dye. I3. A method of treating natural or dyed human hair bfor protecting it from the lharmfull effects of UV radiation, which comprises treating hair with a shampoo, lotion or gel. or with an emulsion for rinsing, before or after shampooing, before or after dyeing or removing dye, before or after a perming or straightening process, with a lotion, foam or gel for setting, with a lotion, foam or gel for brushing or waving, with a hair lacquer, with *a composition for perming or straightening hair, for dyeing or removing dye, which shampoo, lotion, gel, emulsion, foam, hair lacquer or composition for perming, straightening, dyeing or removing dye comprises at least one UV absorber of formula HO N *1 /R R N' R2 \wherein R is hydrogen or chloro, RI Cl-Cl2alkyl or phenyl-CI-C 3 alkyl; Z2 is Ci-C 4 alkyl; or SO 3 M; and M is hydrogen; sodium; or potassium. I R:\ITHXX l 2 39(6.d-caAk 18

14. A cosmetic formulation for hair as defined in any one of claims 5-11 and substantially as herein described with reference to the Examples. A process of preparing a cosmetic formulation for hair as defined in any one of claims 5-11 which process is substantially as herein described with reference to the SExamples.

16. A cosmetic formulation prepared by the process of claim 14.

17. Use of a compound of formula HO P N 1 R2 wherein I, R is hydrogen or chloro, Rli Ci-Ci2alkyl or phenyl-Ci-C 3 alkyl; 2 is Ci-C 4 alkyl; or SO 3 M; and Ml is hydrogen; sodium; or potassium lor the preparation of a cosmetic formulation for hair. 15 18. A method according to claim 13 wherein the composition is the formulation of claim 14 or 16. Dated 11 September, 2000 Ciba Specialty Chemicals HoldingInc. ooIc *0 Patent Attorneys for the Applicant/Nominated Person 2" SPRUSON FERGUSON I R:\IAII X X)0231)6.dIoc:aak