AU637596B2 - Creación de Inventos y Patentes con Inteligencia Artificial

AU637596B2 – Cosmetic use of benzalmalonate diorganopolysiloxanes and novel cosmetic compositions containing such compounds for the protection of skin and hair
– Google Patents

AU637596B2 – Cosmetic use of benzalmalonate diorganopolysiloxanes and novel cosmetic compositions containing such compounds for the protection of skin and hair
– Google Patents
Cosmetic use of benzalmalonate diorganopolysiloxanes and novel cosmetic compositions containing such compounds for the protection of skin and hair

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Publication number
AU637596B2

AU637596B2
AU49700/90A
AU4970090A
AU637596B2
AU 637596 B2
AU637596 B2
AU 637596B2
AU 49700/90 A
AU49700/90 A
AU 49700/90A
AU 4970090 A
AU4970090 A
AU 4970090A
AU 637596 B2
AU637596 B2
AU 637596B2
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AU
Australia
Prior art keywords
formula
benzalmalonate
radicals
inclusive
cosmetic
Prior art date
1989-02-15
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)

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AU49700/90A
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AU4970090A
(en

Inventor
Serge Forestier
Gerard Lang
Herve Richard
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)

LOreal SA

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LOreal SA
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1989-02-15
Filing date
1990-02-14
Publication date
1993-06-03

1990-02-14
Application filed by LOreal SA
filed
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LOreal SA

1990-08-23
Publication of AU4970090A
publication
Critical
patent/AU4970090A/en

1993-06-03
Application granted
granted
Critical

1993-06-03
Publication of AU637596B2
publication
Critical
patent/AU637596B2/en

2010-02-14
Anticipated expiration
legal-status
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Ceased
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Classifications

A—HUMAN NECESSITIES

A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE

A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS

A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings

A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations

A—HUMAN NECESSITIES

A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE

A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES

A61K8/00—Cosmetics or similar toiletry preparations

A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition

A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds

A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds

A61K8/89—Polysiloxanes

A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone

A61K8/893—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone modified by an alkoxy or aryloxy group, e.g. behenoxy dimethicone or stearoxy dimethicone

C—CHEMISTRY; METALLURGY

C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON

C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS

C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule

C08G77/04—Polysiloxanes

C08G77/38—Polysiloxanes modified by chemical after-treatment

A—HUMAN NECESSITIES

A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE

A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES

A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects

A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients

A61K2800/57—Compounds covalently linked to a(n inert) carrier molecule, e.g. conjugates, pro-fragrances

Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS

Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC

Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS

Y10S424/00—Drug, bio-affecting and body treating compositions

Y10S424/05—Stick

Abstract

Use in cosmetics, in particular as UV screening agents, of diorganopolysiloxanes with a benzalmalonate function, of formula: where R is C1-C10 alkyl, phenyl or 3,3,3-trifluoropropyl, B is R or A, r = 0-200 and s = 0-50, or of formula: where u = 1-20, t = 0-20 and t + u >/= 3, A and/or B denoting an optionally substituted alkylene- or alkyleneoxy-benzalmalonate group.

Description

37596 COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952-69 COMPLETE SPECIFICATION
(ORIGINAL)
Class In Application Number: Lodged: Form it. Class Complete Specification Lodged: Accepted: Co~o Priority:
S..
Related Art S.oo.
Published: Os.. Name of Applicant: :Address of Applicant: Actual Inventor Ad s f «Address for Service:
L’OREAL
14, rue Royale F-75008 Paris, France SERGE FORESTIER, GERARD LANG and HERVE RICHARD WATERMARK PATENT TRADEMARK ATTORNEYS, LOCKED BAG NO. 5, HAWTHORN, VICTORIA 3122, AUSTRALIA Complete Specification for the invention entitled: COSMETIC USE OF BENZAIMLONATE DIORGANOPOLYSILOXANES AND NOVEL COSMETIC COMPOSITIONS CONTAINING SUCH COMPOUNDS FOR THE PROTECTION OF SKIN AND
HAIR
The following statement is a full description of this invention, including the best method of performing it known to
COOS
S
55.5
OS@S
S
OSS
555.
S S S. S
S
Cosmetic rse of benzalmalonate diorganopolysiloxanes and novel cosmetic compositions containing such compounds for the protection of skin and hair The present invention, concerns the cosmetic use of benzalmalonate diorganopolysiloxanes, particularly as UV filters, as well as novel cosmetic compositions containing such compounds for the protection of skin and hair.
Light of wavelengths between 280 nm and 400 rm is known to cause browning of the human epidermis; radiation of wavelengths between 280 nim and 320 nm known as UV-B causes erythema and cutaneous burns which may hinder the development of a tan; UV-B radiation must therefore be filtered out.
15 It is further known that UV-A radiation, with wavelengths between 320 nm and 400 nm, promotes browning of the skin and is likely to damage it, particularly with sensitive skin or where the skin is continually exposed to the sun’s rays. In particular, UV-A radiation causes 20 loss of skin elasticity and the appearance of lines resulting in premature ageing. It promotes the erythmatic reaction or amplifies it in some cases and may even be the cause of phototoxic or photallergenic reactions.
25 It is desirable therefore to design UV absorbing compounds so that they absorb a wide band of UV radiation in order to filter out both UV-A and UV-B.
It is further known that constituents of cosmetic preparations do not always have sufficient light stability and degrade when exposed to light.
It is thus desirable to incorporate UV filtering compounds into such preparations. These filters must also be stable and have sufficient solubility in media normally used in cosmetics, in particular oils and fats.
With hair, it is also desirable to protect it
*SSO
S
SUeS 5 5 5S 0 *5 5 0 5 @5
S
55.5
S
5 5 o
C
g egg against photochemical degradation, particularly discolouring or change of shade.
Grafting molecules having a UV filtering effect onto polymer chains such as synthetic carbon polymers, natural polymers, protein hydrolysates or polyaminoamides is also known. Graft polymers as described, for example, in French patents numbers 2 197 023, 2 237 912, 2 531 960, 2 548 018, 2 549 069, 2 586 692 and 2 586 693 may be used to prepare cosmetic compositions for protection of human skin or as sun screens. However, graft polymers generally have low solubility in the usual cosmetic solvents, particularly in oily supports, and they form films having too rigid a structure.
The applicant has now discovered that, 15 surprisingly, certain benzalmalonate diorganopolysiloxanes have good cosmetic properties and good filtering properties over a wide range of wavelengths, from 280 nm to 360 nm. In particular they have excellent liposolubility and can thus be used in the fatty supports 20 used in cosmetics. Apart from their good filtering powers and good solubility in oily media and the usual cosmetic solvents, these benzalmalonate diorganopolysiloxanes also have excellent chemical and photochemical stability and soften the skin and hair, which tolerate them well.
An object of the present invention is, then, the cosmetic use of benzalmalonate diorganopolysiloxanes, particularly as UV filtering agents for radiation of wavelengths between 280 nm and 360 nm, selected from those having the formulas e V go
C
3 R R R R B-Si-O Si-O Si- Si-B (1) R R A R r S wherein: R may be the same for each occurrence or different and is selected from
C
1
-C
1 0 alkyl radicals, phenyl radicals and 3,3,3-trifluoropropyl radicals, at least 80% by number of the R radicals being methyl radicals.
B may be the same for each occurrence or different and is selected from radicals R and A, Sis a number between 0 and 200 inclusive, and may be an average calculated on the different value of r of the benzalmalonate diorganopoly- 10 siloxanes contained in the cosmetic composition, S is a number between 0 and 50 inclusive and if s is 0 at least one of the two B radicals is A; and from those having the formula: S-Si-O L. R
A
*is a number between 1 and 20 inclusive, and wherein in both formulae the symbol A denotes a radical having the Ifo t u wherein: R has the meaning defined for formula l is a number between 1 and 20 inclusive, t is a number between 0 and 20 inclusive, t uj is greater than or equal to 3; and wherein in both formulae the symbol A denotes a radical having the formula: c2 R 2R 6 26g
S
0 *5@ *0.
0 S. S
S
wherein: h. C R 1 and R 2 are selected from a hydrogen atom, a hyd~ey radical, a trimethylsiloxy radical, a C 1
-C
6 alkyl radical, a C 1
-C
6 alkoxy radical and a divalent group Y with the formula: -(0)n-(CH-M-CH2- 2 p 2 R wherein: 15 wherein: n is 0 or 1, e is a whole number between 1 and inclusive, preferably between 1 and 4, and R 4 is selected from a hydrogen atom and a CI-C 4 alkyl radical, one of the two radicals R 1 and R 2 necessarily representing group Y, 0 S* Q S0 S 6 *5 20
R
3 represents a hydrogen atom, a C 1
-C
6 alkyl radical or a C 1
-C
6 alkoxy radical, R5 and R 6 may be identical or different and represent a C1-C8 alkyl radical.
25 In the above formulae the alkyl and alkoxy radicals may be linear or branched. C The following linear or branched alkoxy radicals merit particular mention: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-amyloxy, isoamyloxy, neopentyloxy and n-hexyloxy. C The following linear or branchedk alkyl radicals merit particular mention: methyl, ethyl, n-propyl, isopropyl n-butyl, isobutyl, tert-butyl, n-amyl, isoamyl, neopentyl and n-hexyl, and the C 1
-C
8 alkyl radicals may be the foregoing radicals or the n-heptyl, n-octyl, and 2- +ylhe)ylI *-Bt4hexyl- radicals.
Preferred alkyl radicals R are methyl, ethyl, propyl, n-butyl, n-octyl and 2-ethylhexyl. Preferably at least 80% by number of the radicals are methyl.
Particularly preferred polymers are random or block polymers having the formula or with at least one of the following features: R is methyl, B is methyl, -0 R1 is H or Y, R2 is Y, methoxy or butoxy,
R
3 is H or methoxy, n 0 or 1, 0 0 0*SS
S
S*S
0000 1
S
0*O0 ,nS.
05 *5@6 0 p 1, 15 R 4 is H or methyl,
R
5 and R 6 are ethyl or 2-Ethylhexyl, r is between 5 and 20 inclusive, is between 2 and 15 inclusive, t u is between 3 and 10 inclusive.
20 Preparation of polymers with formula or may start from the corresponding polymer wherein all the A radicals are hydrogen.
This polymer is denoted by SiH; SiH groups may be present within the chain and/or at its extremities.
These SiH polymers are well known in the silicone industry and are generally commercially available.
They are described, fcir example, in American patents US-A-3 220 972, US-A-3 436 366, US-A-3 697 4/3 and US-A-4 340 709.
SiH polymers may thus be selected from those having the formula: R R i- B’ Si 0 Si 0 i i B I I I R R R r s (4) where R, r and s have the meanings given above for formula and radicals which may be the same for each occurrence or different, are selected from radicals R and a hydrogen atom; and from those having the formula: R R Si-0- I R 1 where P, t and u have the meanings given above for ,fee% formula SiH polymers having formula or are reacted by hydrosilylation in the presence of a catalytic quantity of a platinum catalyst or an organic doerivative selected from those having the formula: ROc1 2
R
(6) 20 R 3 2 R6 where R 1
R
2
R
3
R
5 and R 6 have the meanings given for formula above except that radical Y is the unsaturated homologue radical Y’ with the formula: n-(CH2)P-C CH 2 where n, p and R 4 have the meaning given for formula (3) above.
Certain derivatives with formula where n 1 have already been described in the chemical literature, especically J. Chem. Soc. PERKINS TRANS 1985, pp 1627-1635 and Chem. Ber. Vol 99 pp 1962-1965.
In general, derivatives with formula can be prepared using a KNOEVENAGEL reaction, viz. condensation of an aromatic aldehyde (II) with a malonic acid ester 7 (III) in toluene in the presence of a piperidinium acetate catalyst. Water is eliminated by azeotropy. The reaction scheme is as follows: 0- R5 OR6 piperidinium acetate toluene R CO 2
R
SCO 2R 6 0 0 0@S* Os 0.
0000 0S (II) (III) (6)
R
1
R
2
R
3
R
5 and R 6 having the meanings given above for formula The products are recrystallised, distilled or separated using column chromatography. Aldehydes (II), which are known compounds, may be obtained by one of the following methods: 15 First method Aldehyde with formula (II) where R 1 represents the moiety -(CH2)p-C(R4)=CH2 where p 1, R2 represents a hydroxyl moiety and R3 has the meaning defined above for formula may be obtained by the CLAISEN rearrangement 20 of an aldehyde with formula (IV) according to the following reaction scheme: Ca 2
=C(R
4
)-CH
2
C
2
-C(R
4
)=CH
2 R CRO R CRO 3 :0-
*OSO
S
0000 S S SO S S. 0
*S
*5 25 (IV)
(IIA)
This rearrangement can be carried out under the conditions described by TARBELL (Organic Reactions, Vol.
2, John WILEY, New York, 1944», page by heating the compound with formula (IV) to at least about 170 0 C, if necessary in the presence of a solvent.
Aldehyde with formula (IV) may be obtained by reaction of an alkenyl halide with formula with an aldehyde with formula (VI): C L 8 2CH=C(R4
C
R3 .C-HO X- C 2 C( R)=CH 2 R- 0 (VI) (IV) This reaction is carried out in the presence of a base in a. solve.nt, for example in the presence of an alkali metal carbonate in dimethylformaride, at a temperature between room temperature and the boiling point of the solvent. Aldehyde with formula (VI) may be sees prepared by known methods. In the compound with formula [e X represents a halogen atom, preferably chlorine or bromine.
Second method 15 Aldehyde with formula (IIB) corresponding to formula II where R 1 represents a -(CH 2 )p-C(R 4
)=CH
2 moiety where p 1, R 2 represents a CI-C 6 alkoxy moiety and R 3 has the meaning given above for formula may be obtained by one of the two following routes: 20 First route Formylation of a phenol ether with formula (VII) according to the following reaction scheme: 2 -C(R4) CZ C(R4)=C2
R
7 O R7 -0 1 R 0 (VII) (IIB) where R 7 represents a C -C 6 alkyl radical, R 3 having the meaning given above.
This reaction may, for example, be carried out by addition of the complexes formed by the action of phosphorus oxychloride on disubstituted formamides (see VILSMEIER and HAAK, Ber., 60, p 119, 1927) on compounds with formula (VII).
The phenol ether with formula (VII) can be prepared using known methods.
Second route Compound with formula (IIA) obtained from the first method can be transformed into compound with formula (IIB) by reaction with a C 1 alkyl halide or sulphate in the presence of a base, for example in the presence of an alkali metal carbonate, in a solvent such as dimethylformamide, or in the presence of an alkali metal hydride in 1,2-dimethoxyethane, according to the following reaction scheme: 2
C(R
4
)=CH
2
H
2 C(R )=CH 2 H R -0 0 7
-O
R 3 -CdO R 3 -CHO (IIA) (IIB) g
S.
*0 S S *0 S In the compound with formula (IIB), R, represents a
C
1
-C
6 alkyl moiety.
Third method Aldehyde with formula (II) where R, or R 2 represent a -(CH -C(R 4
)=CH
2 moiety and R 3 represents a hydrogen atom, a C.-C 6 alkyl moiety or a Ci-C 6 alkoxy moiety may also be obtained by reaction of ethyl orthoformate with phenylmagnesium bromide with formula (VIII) followed by hydrolysis of the resulting acetal: O0Sg
C
e g.
erg.
S
*0 S
S.
*e
C
R
3 MgBr
(VIII)
1) R C (OEt) 3 2) Hydrolysis
R
R
I
R CHO
(II)
20 This reaction may be carried out under the conditions described by QUELET Acad. Sci. vol. 182, p 1285 and Bull. Soc. Chim. Fr., vol. 45, p 267), for example in an inert solvent such as ethyl ether, dioxane or 1,2-dimethoxyethaneg at a temperature between room 0e**
*I
0@* 0 *0S* temperture and the boiling point of the solvent. In compounds with formula (II) and (VIII), one of the substituents R i or R 2 represents the radical
-(CH
2 )p-C(R 4
)=CH
2
R
4 and p having the meanings defined above, and the other represents hydrogen, a C 1
-C
6 alkyl radical or an alkoxy radical and R 3 represents hydrogen, a C, to C. alkyl radical or a C 1 to C 6 alkoxy radical.
Platinum catalysts used for hydrosilylation of polymers with formula or with the organic derivative with formula are amply described in the literature.
Complexes of platinum and an organic product merit particular mention. These are described in American patents U.S.-A-3,159,601, U.S.-A-3,159,602 and U.S.-A-3,220,972 and European patents EP-A-57 459, EP-A-188 978 and EP-A-190 530.
American patents U.S. A-3,419,593, U.S.-A-3,377,432 and U.S.-A-3,814,730 describe other complexes of platinum and a vinylated organopolysiloxane.
For the reaction of the SiH polymer with formula S or on the derivative with formula the amount of platinum catalyst used comprises between 5 and 600 ppm platinum, calculated by weight of platinum metal, preferably between 10 and 200 ppm based on the weight of SiH polymer with formula or The hydrosilylation reaction may take place in the dry state or using a volatile organic solvent such as toluene, heptane, xylene, tetrahydrofurane or tetrachloroethylene.
It is generally desirable to heat the reaction mixture to a temperature of 600 to 1200 for the time ’30 necessary to complete the reaction. The SiH polymer may be added dropwise to a solution of the derivative with formular in an organic solvent containing the catalyst. The SiH polymer and the derivative with formula may also be added simultaneously to a suspension of the catalyst in an 35 organic-solvent.
Reaction completeness is verified by titrating residual SiH against alcoholic potash. The solvent is 0050
S
S.
S
goe 0as.
4′
S
5
S.
*6 then eliminated, for example by distillation under reduced pressure.
The crude oil obtained can be purified, for example by passage over an absorbent silica column.
A further object of the invention is constituted by cosmetic compositions to protect the skin and hair against UV radiation, containing an effective quantity of a benzalmalonate diorganopolysiloxane having formula (1) or in a cosmetically acceptable medium.
A further object of the invention is a method of protecting skin and natural or sensitised hair against solar radiation, consisting in applying to the skin or hair an effective quantity of at least one compound having formula or in an acceptable cosmetic 15 support comprising at least one oily phase.
«Sensitised hair» means hair which has been permed, dyed or bleached.
A still further object of the invention is a tinted or untinted, light stable cosmetic composition comprising 20 an effective quantity of at least one benzalmalonate diorganopolysiloxane having formula or When used as a composition for protecting the human epidermis against ultraviolet radiation, the preparation may be in many of the diverse forms commonly used for 25 this type of cosmetic composition. In particular, oily, alcoholic or oleoalcoholic lotions may be used, also emulsions such as creams or milks, oleoalcoholic, alcoholic or hydroalcoholic gels, solid sticks or aerosols.
It may contain any cosmetic additives normally used in this type of composition, such as thickeners, softeners, moisturisers, surfactants, preservatives, anti-foaming agents, perfumes, oils, waxes, lanolin, propellants, dyes and/or pigments to colour the composition itself or the skin, or any other ingredient 5 Sb..
*5 *5 S *5 S 5*r normally used in cosmetics.
The compound with formula or is present in proportions of between 0.25 and 3% by weight with respect to the total weight of the protective cosmetic composition for the human epidermis.
As solubilising solvent, an oil may be used, or a wax or generally any oily body, a monoalcohol or a low polyol, or a C 12
-C
15 alcohol benzoate or a mixture thereof. Particularly preferred monoalcohols or polyols are ethanol, isopropanol, propyleneglycol, glycerine or sorbitol.
One embodiment of the invention is an emulsion in the form of a protective cream or milk comprising, as well as the compound with formula or fatty 15 alcohols, fatty acid esters in particular fatty acid triglycerides, fatty acids, lanolin, natural or synthetic oils or waxes and emulsifiers, in the presence of water.
A further embodiment is constituted by oily lotions with bases of natural or synthetic oils or waxes, lanolin 20 and fatty acid esters, in particular fatty acid triglycerides, or by oleoalcoholic lotions with a low 4 alcohol base such as ethanol or a glycol such as propyleneglycol and/or a polyol such as glycerine and oils, waxes and fatty acid esters such as fatty acid triglycerides.
The cosmetic composition of the invention may also be in the form of an alcoholic gel comprising one or more alcohols or low polyols such as propyleneglycol or glycerine and a thickener such as silica.
Oleoalcoholic gels further contain a natural or synthetic oil or wax.
Solid sticks are constituted by natural or synthetic waxes and oils, fatty alcohols, fatty acid esters, lanolin and other oily substances.
For aerosol type compositions, standard propellants such as alkanes, fluoroalkanes and chlorofluoroalkanes are used.
The scope of the present invention also covers sun screening cosmetic compositions containing at leasi one S compound with formula or and which may contain other UV-B and/or UV-A filters.
In this case the total quantity of filters present in the sun screen composition, i.e. the compound with formula or and other filters if any, lies between 0.3 and 15% by weight with respect to the total sun screen composition weight.
*u9J ,d The forms described above for the human skin protection compositions may also be used for these sun screen compositions.
15 When the inventive cosmetic composition is intended to protect natural or sensitised hair from UV radiation the composition may be in the form of a shampoo, lotion, gel or rinsing emulsion, for application before or after shampooing, before or after dyeing or bleaching, before 20 or after a perm, as a styling or treating gel, brushing or setting gel or lotion, hairspray or lacquer. As well
S
as the inventive compound the composition may contain any of the additives used in this type of composition such as surfactants, thickeners, polymers, softeners, preservatives, foam stabilisers, electrolytes, organic solvents, siliconised derivatives, oils, waxes, degreasing agents, dyes and/or pigments to colour the composition itself or the hair or any other ingredient which is normally used in hairdressing.
It contains 0.25% to 5% by weight of the compound with formula or The present invention further provides a cosmetic composition containing at least one compound with formula or as a protective agent against ultraviolet radiation constituted as a hairdressing composition such 14 as a hair lacquer, a setting lition, possibly for treating or untangling a setting lotion, a tinting shampoo, a hair dye composition, a cosmetic composition such as nail polish, a treatment cream or oil for the skin, a foundation, a lipstick, a skin care composition such as a bath oil or cream and any other cosmetic composition which, because of its ingredients may lack light stability during storage.
Such complsitions contain 0.25 to 3% by weight of compound with formula or The invention further envisages a method for protecting cosmetic compositions against ultraviolet radiation consisting in incorporating an effective quantity of at least one compound with formula or into these compositions.
The following examples illustrate the invention S without limiting its scope.
EXAMPLE 1 9 Preparation of a random polymer of formula: C CH C 3 3 3
SCH
3 Si Si 0 Si 0 Si CH 3
C
3
CH
3 A CH S 5 20 where A represents: COOCH 2 CCH3 C 0 C2 3 (H 2) 3 0 S..A solution in 55 ml toluene of 30 g diethyl 4-cllyloxy benzalmalonate and 16 g of the random polymer having the above formula where A is an atom of hydrogen was added dropwise over one hour 30 minutes to a suspension of 5% (166 mg) platinum on carbon in dry toluene (5 ml) at 90°-100 0 C under nitrogen and agitation.
The temperature was maintained throughout at 1000 to 105 C.
The mixture was stirred and refluxed until the SiH groups had disappeared (absence of 2 180 cm 1 infrared band), i.e. for ten hours. It was filtered over paper, the solvent eliminated and washed twice with 80% ethanol.
The oil obtained was taken up in chloroform, dried over sodium sulphate and filtered over celite to eliminate the remaining colloidal, platinum. After evaporation of the solvent a pale yellow oil was obtained (weight: 36 g, yield: ol UV spectrum (G ee) Xmax 311 nm 15 Nuclear magnetic resonsance analysis (1H and 9Si) indicated that the product had the desired structure.
EXAMPLE 2 Preparation of a random polymer with formula: C C2 CR CH H3 3 3 C
CH
3 Si Si 0- Si C j (1) CH CH A CH 20 where A represents: COOCaC /a OC CH 2
H
3
(CH
2 3 0 The method of example 1 was repeated using the random polymer having the above formula where A is an atom of hydrogen.
A light yellow oil was thus obtained.
UV spectrum (CHC1 3 Xmax 313 nm EXAMPLE 3 Preparation of a random polymer with f ormula: CH 3 Uri Si- 0 3 d @ee 0..0 0.4 where A represents:
COOMC
2
CH
3 /co CHI),CH 3 -q C 2 3 -0 CoC The method of example 1 was repeated starting from the random polymer with the above f ormula where A is a hydrogen atom.
A viscous yellow oil was obtained.
UiV spectrum (CHCl 3 Xmax 313 nm.
EXAMPLE 4 Preparation of a random polymer with f ormula: CR 3 i- ~1 CH i 0 .3 5a. 00 *0O 0 0 1 3 -Si CR 3 5 H 3 where A represents: CH 3 0 ‘o 2C 2 (C 2 3 0 The method of example 1 was repeated starting this time~~a’ wit 20gdety/~ IO)’ tim wih 2 g ietyl4-&;»-o-3-methoxybenzalmalonate and 9. 7 g of the random polymer with the above formula where A is a hydrogen atom.
22 g of a thick pale yellow oil was obtained (yield: 74%).
UV spectrum (CHC1 3 Xmax 330 nm Xmax 2 300 nm (shoulder) Nuclear magnetic resonance analysis (1H and 29Si) indicated that the product had the expected structure.
EXAMPLE Preparation of a random polymer with formula: 3 C3 C 3 3 e.CH Si 0 Si Si C 3 3 3 k CH C A 3 3 j L 3 7.3 9 where A represents: COOCH CC 33
H
2 cH 2l 0 00*0 CH, 3 22.7 g (0.071 mole) diethyl 4-methallyloxybenzalmalonate, 33 g toluene and 14.4p 1 of a solution in hexane by weight of platinum metal) of a platinum complex prepared from chloroplatinic acid and 1,3-divinyl 1,1,3,3-tetramethyldisiloxane as described in US patent US-A-3 814 730, were placed in a 3-necked flask equipped with a magnetic stirrer and a cooling column and maintained at 100°C in an oil bath.
10 g of a random polymer with the above formula where A is an atom of hydrogen, titrating 713 meq/100 g of SiH group (meq milliequivalent), was added over a period of one hour.
After 24 hours of reaction a transformation rate of 73% for the SiH groups was determined by titration of SiH groups against butanolic potassium.
A cloudy slightly yellow oil having an agreeable odour and very high viscosity was obtained following elimination of toluene by distillation at 100°C under a reduced pressure of 0.66 kPa.
Proton nuclear magnetic resonance analysis 1 H NMR) at 360 MH- in CDC13 was carried out on a sample of the oil obtained. This showed the existence of unreacted monomer, hydrogenosilane and the structure resulting from hydrosilylation of the unsaturated methallyloxy group of the monomer, viz: *ee f* *3 15 CH Si CH CH CH 0 0 2 00CHC23 :3 2 CH3 CH2CH3 Xmax 312 nm (CHC1 3 EXAMPLE 6 Example 6a Diethyl-3-allyl-4-methoxvbenzalmalonate Preparation of a compound having general formula where R 1 represents the radical -CH 2
-CH=CH
2
R
2 represents the radical -OCH 3
R
3 reprsents a hydrogen atom and R5 and R 6 represent the radical -C 2
H
5 Stage one Preparation of 3-allyl-4-methoxvbenzal- First method: 50 g (0.308 mole) 4-allyloxybenzaldehyde was heated at 220 0 C for four hours under nitrogen and with stirring.
The cooled reaction mixture was taken up in dichloromethane and extracted with 5N soda. The aqueous phase was acidified with 6N hydrochloric acid and extracted with dichloromethane. The organic phase was dried and the solvent evaporated off to leave a brown-black oil. After vacuum distillation the fraction boiling between 138 0 -140 0 C at 106 Pa was collected 15 g (yield 30%) 3-allyl-4-hydroxybenzaldehyde (white powder, melting point 66*C).
To this derivative (14.5 g, 0.089 mole) were successively added 30 ml N,N-dimethylformarqide, 13.6 g (0.098 mole) anhydrous potassium carbonate and 11 ml (0.178 mole) methyl iodide. This mixture was heated to 60′-70°C for three hours. The reaction mixture was poured onto iced water and extracted with diisopropyl ether. The organic phase was dried over sodium sulphate, filtered and the solvent evaporated off to obtain 3-allyl-4-methoxybenzaldehyde (pale yellow oil, 13.6 g, ‘o 15 yield 87%).
Second method 2-allylphenol (100 g, 0.75 mole), 2 litres dry N,Ndimethylformamide and anhydrous potassium carbonate (206 g, 1.49 mole) were successively introduced into a 5 litre reaction vessel. At room temperature methyl iodide (92 ml, 1.49 mole) was added dropwise. The vessel was left for four hours at 38″C. The reaction mixture was then poured onto iced water and extracted with dichloromethane.
The organic phase was washed with water and dried.
After evaporation of the solvent and vacuum distillation, the fraction distilling at 110 0 C at 5 000 Pa was collected: 2-allylanisole (colourless liquid, 46 g, yield N,N-dimethylformaide (75 ml, 0.98 mole) was placed in a 500 ml reactor. Added to this, whilst cooling to about 5°C, was phosphorus oxychloride (26 ml, 0.28 mole). The mixture was held at 10 0 C for one hour then the above derivative (41.5 g, 0.28 mole) added dropwise. The temperature was steadily raised to 100°C over a period of one hour and the reaction mixture maintained at this temperature for ten hours. The cooled mixture was poured onto iced water and extracted with diisopropyl ether. The organic phases were washed with water, dried over sodium sulphate, filtered and the solvent evaporated off to leave a crude product (31 g) which was purified by chromatography on silica (eluent: 50/50 toluene/hexane) to obtain a fraction g) of 3-allyl-4-methoxybenzaldehyde identical to that obtained by the first method.
Stage two Preparation of diethyl 3-ally.-4-methoxybenzalmalonate A Dean Stark apparatus was used to reflux under nitrogen a mixture of the above derivative (10 g, eo 0.057 mole), diethyl malonate, (9.09 g, 0.057 mole), 15 toluene (15 ml), acetic acid (0.36 ml) and piperidine roOS O. cr y I o-F O cF ec-4 wQs recovere A-Fre- (0.68 ml). After cooling, the toluene phase was washed with water, dried and the solvent distilled. An orange oil was obtained which crystallised. This was recrystallised from diisopropyl ether and animal black.
White crystals of diethyl 3-allyl-4-methoxybenzalmalonate (12.7 g, yield 70%) were obtained having t- following characteristics: melting point: 69°C H NMR spectrum (CDC1 3 agreed with expected structure
OSOO
0 UV spectrum (CHCl 3 Amax: 318 nm e: 24450 Elemental analysis: Calculated: C 67.91; H 6.97; O 25.13 Found C 68.04; H 6.89; O 25.23 Example 6b Preparation of a random polymer with formula: CHR3 CH 3 CH 3 3 3 3 3 CH3 Si 0 Si Si 0- Si C3 wherein A represents: 2)3 c oo0 CH 2 2 3 2 3 CH 0 *a 3 o A solution in toluene (20 ml) of diethyl 3-allyl-4metho;ybenzalmalonate (10 g, 31.4 meq) and a random 15 polymer having the above formula where A is a hydrogen atom (4.60 g, 31.4 meq of SiH) was added dropwise over a period of one hour 30 minutes to a stirred suspension of platinum on carbon (55 mg) in dry toluene (5 ml) at 0 -100°C under nitrogen. The temperature was maintained between 1000 and 105″C.
a* The mixture was stirred and refluxed until the SiH groups had disappeared (absence of 2 180 cm-1 band in the infrared), i.e. for eight hours. The mixture was filtered over paper, the solvent eliminated and then washed twice with 80% ethanol. The pale yellow oil obtained was taken up in dichloromethane, dried over sodium sulphate and passed over a bed of silica 0: Following evaporation of the solvent a viscous pale yellow oil was obtained (5.3 g, yield 36%).
IH NMR spectrum (CDC13) agreed with formula, 29 Si NMR spectrum (CDC13): agreed with formula, UV spectrum (CHC13) X max: 318 nm EXAMPLE 7 Example 7a Diethyl-3-allvl-4,5-dimethoxybenzalmalonate Preparation of a compound with general formula (6) as.
0:60 Q S
C
Sea So wherein R 1 represents the -CH2-CH=CH 2 radical, R 2 and R 3 represents the -OCH 3 radical and R5 and Rg represent the -C2H 5 radical.
Stage one: 4-allyloxy-3-methoxybenzaldehyde (62.5 g, 0.325 mole) was heated to 180″C and stirred for six hours minutes, then cooled. The brown solid was taken up in dicnloromethane and extracted with 5% soda. The aqueous phase was acidified with 3N hydrochloric acid. The solid obtained was filtered and recrystallised from a mixture of ethanol and water (40/60). 3-allyl-4-hydroxy-5methoxybenzaldehyde was obtained (light beige powder, 62.5 g, yield 71%, melting point 83 0 -84°C).
Stage two: 15 The above derivative (34 g, 0.18 mole) was introduced into a reactor followed successively by dimethylformo4n !d (500 ml), potassium carbonate (49 g, 0.35 mole) and methyl iodide (50 g, 0.35 mole). The temperature was maintained at 40 0 C for three hours. The reaction mixture was plunged into iced water and the oil formed extracted with dichloromethane. Following S washing, drying and evaporation of the solvent, a light brown oil was obtained which was passed over a bed of silica 60 to give a pale yellow oil, 3-allyl-4,5diathoxybenzaldehyde (34.3 g, yield 92%).
Stage three: Using a Dean Stark apparatus, the following were refluxed together for seven hours: the above derivative g, 0.073 mole), diethyl malonate (11.7 g, 0.073 mole), toluene (18 ml), acetic acid (0.46 ml) and piperidine (0.87 ml). After cooling, the toluene phase was washed with water, dried and the solvent distilled off. The pale orange oil .obtained (24.5 g, yield: 96%) was crystallised from a diisopropyl ether/hexane mixture (50/50) to produce white crystal of diethyl .585
C
*0 s.
S
to 6 saw#S 6000
SI
kAJT 56%) 3-allyl-4, 5-dimethoxybenzalmalonate having the following characteristics: Melting point: 43 0 -44 0
C,
IH NMR spectrum (CDC1 3 agrees with expected formula, UV spectrum (CHCI 3 X max 1 303 nm e 15700 X max 2 325 nm E 12830 (shoulder) Elemental analysis: Calculated: C 65.50; H 6.94; 0 27.55 Found C 65.33; H 6.91; 0 27.78 Example 7b Preparation of a random polymer with formula: C CR C CH 15 3 3 3 3 CH Si Si C3 3 3 se***es 3 3 -5 5 3 where A represents: -(CH 0 3C ee» a 2 3 2 3 C 0CoCH 2
CB
3 H3 3 A solution of diethyl 3-allyl-4,5-dimethoxybenzalmalonate (10 g, 28.7 meq) and the above random polymer where A is a hydrogen atom (4.55 g, 28 meq SiH) in toluene (30 ml) was added dropwise over one hour minutes to a stirred suspension of 5% platinum on carbon (106 mg) in dry toluene (5 ml) at 90 0 -100°C, under nitrogen. The temperature was maintained between 100° and 105 0 C The mixture was stirred and refluxed until the SiH groups had disappeared (absence of 2 180 cm-1 band in the infrared), viz. 12 hours. It was filtered over paper, the solvent eliminated and then wasdhed twice with ethanol 80%. The pale yellow oil thus obtained was taken up in dichloromethane, dried over sodium sulphate and passed over a bed of silica 60. Following evaporation of the solvent a viscous pale yellow oil was obtained (10.6 g, yield: 73%).
-H NMR spectrum (CDC1 3 agreed with formula, 29Si NMR spectrum (CDC1 3 agreed with formula, UV spectrum (CHCl 3 X max: 304 nm EXAMPLE 8 EXAMPLE 8a di-(2ethylhexyl)-3-allyl-4,5-dimethoxybenzalmalonate Preparation of a compound of general formula (6) where R i represents radical -CH 2
-CH=CH
2
R
2 and R 3 represent the radical -OCH 3 and R s and R 6 represent the radical
-CH
2
CH()C
2 H )C4H 9 A Dean Stark apparatus was used to reflux the .20 following mixture for five hours: 3-allyl-4,5,dimethoxybenzaldehyde (10.3 g, 0.05 mole) di-(2-ethylhexyl)malonate (16.4 g, 0.05 mole), toluene (20 ml), acetic acid (0.41. ml) and piperidine (0.77 After cooling, washing the toluene phase with water, drying and evaporation of the solvent, an orange oil was obtained which was purified by chromatography on a column of silica 60 (eluent: Heptane/ethyl acetate 90/10) to give di-2(ethylhexyl) 3-allyl-4,5-dimethoxybenzalmalonate (colourless oil, 15 g, yield 64%) with the following characteristics: *3 0 H NMR spectrum (CDC1 3 agreed with expected formula, UV spectrum (CHC1 3 Xmax, 303 nm e 15500 Xmax 2 320 nm e 13430 (shoulder) 0 4 LCG/JMW:EK(12.33) Elemental analysis: Calculated: C 72.06; H 9.36; 0 18.58 Found C 72.09; H 9.44; 0 18.69 Example 8b Preparation of a random polymer with formula:
S
S..
0O 0O0
S
CR
CH
3 Si 0 CH3 where A represents:
-(CH
2 3 C3 13 -Si _CH 3 KCH 3 Cd3 3 3 i-jSi Si C13 A j C3
WCOR
2 CH (C 2
H
5
)C
4 Hq
CH
3 0L 3 (j h e A solution in toluene (30 ml) of di-2-‘tho 20 3-allyl-4,5-dimethoxybenzalmalonate (10 g, 19.3 meq) and the random polymer with the above formula where A is an atom of hydrogen (2.86 g, 17.6 meq SiH) was added dropwise over a period of one hour 30 minutes to a stirred suspension of 5% platinum on carbon (80 mg) in dry toluene (5 ml) at 90″-100 0 C under nitrogen. The temperature was maintained throughout between 1000 and 105°C. The stirring and refluxing was maintained until the SiH groups had disappeared (absence of 2 180 cm 1 in infrared band), viz. 12 hours. Tt was filtered through paper, the solvent eliminated and then washed twice with ethanol. The pale yellow oil obtained was taken up in dichloromethane, dried over sodium sulphate and passed over a bed of silica 60. After evaporation of the solvent a viscous pale yellow oil was obtained (5.1 g, yield 43%).
S
0 0 0 C 000 0
OSSS
1 H NMR spectrum (CDC13): agreed with formula, 29 SiH NMR spectrum (CDC3l): agreed with formula, UV spectrum (CHC13): Xmax: 305 nm EXAMPLE 9 Example 9a diethyl-3-allyl-4-butox-5-methoxybenzalmalonate Preparation of a compound with general formula (6) where R 1 represents the radical -CH 2
CH=CH
2
R
2 represents the radical R3 represents the radical -OCH 3 and R 10 and R 6 represent the radical -C 2
H
5 Stage one: A mixture of 3-allyl-4-hydroxy-5-methoxybenzaldehyde. (10.25 g, 0.053 mole), dimethylfornamide (150 ml potassium carbonate (8.29 g, 0.06 mole) and 1- 15 bromobutane (8.22 g, 0.06 mole) was maintained at 0 C for three hours. The reaction mixture was plunged into iced water and the oil formed extracted with dichloromethane. After washing with water, drying and evaporation of the solvent, a brown oil was obtained 20 which was passed through a bed of silica 60 to give a pale yellow oil, 3-allyl-4-butoxy-5-methoxybenzaldehyde (13 g, yield 91%).
Stage two: A mixture of t1- following was refluxed in a Dean 25 Stark apparatus for seven hours: ;he above derivative (10.2 g, 0.041 mole), diethyl malonai.e (7 g, 0.041 mole), toluene (12 ml), acetic acid (0.26 ml) and piperidine (0.49 ml). Diethyl 3-allyl-4-butoxy-5-methoxybenzalmalonate (colourless oil, 10 g, yield 67%) was obtained using the same method as in example 8a. It had the following characteristics: H NMR spectrum (CDCl3)i agreed with expected formula, o S e g.
S
5* 0 S. C
SO
6.
~~LU
n> UV spectrum (CHCl 3 Xmax 1 305 nm e 15500 Xmax 2 325 rnm 13530 (shoulder) Elemental analysis: Calculated: C 67.67; H 7.74; 0 24.58 Found C 67.87; H 7.83; 0 24.44 Example 9b Preparation of a random polymer with formula:
SOO&
*00.
0000 G 0* *0 0SSO
LO
H
3
CH
3 Si 0- 3 CH 3 Si 0- L a3
C
3 Si 0
A
3 Si
C
3 CHl 5 3 wherein A represents: -(CR2) 3 COOCB CH3 3 CH 3 CH 3(C2) 3 3y OC3 Czom\) A solution in toluenekof diethyl 3-allyl-4-butoxy- (8.2 g, 21 meq) and a random polymer having -he above formula where A is an atom of 25 hydrogen (3.24 g, 19.9 meq SiH) was added dropwise over one hour 30 minutes to a stirred suspension of platinum on carbon (60 mg) in dry toluene (5 ml) at 100 0 C under nitrogen. The temperature was maintained throughout between 100″ and 105 0 C. The mixture was stirred and refluxed until the SiH groups had disappeared (absence of 2 180 cm 1 band in the infrared), viz. ten hours. It was filtered over paper, the solvent eliminated and washed twice with 80% ethanol. The pale yellow oil obtained was taken up in dichloromethane, dried over sodium sulphate and passed through a silica 0SSS
C
*O0 g
S
o..
Ogg0
*O
*0 *0SS 0 bed. After evaporation of the solvent a colourless viscous oil (4.7 g, yield 43%) was obtained.
1H NMR spectrum (CDCl 3 agreed with formula, 29Si, NMR spectrum (CDCl 3 agreed with formula, UV spectrum (CHC13): Xmax 1 306 nm Xmax 2 325 runm EXAMPLES OF USE Example A oil-in-water emulsion for the protection of human skin 10 Compound from example 4 2.0 g Oxyethylenated cetylstearyl acid, (C 16
/C
18 -35/65) (15 O.E.)(«MERGITAL CS15» from HENKEL) 3.0 g Glycerol monostearate 4.8 g Myristic alcohol 4.5 g 15 Benzoate of C12/C 15 alcohols («FINSOLV TN» from WITCO) 18.0 g Propylene glycol 6.0 g Preservative 0.2 g Perfume 0.6 g 20 Demineralised water qsp 100 g The oily substances and emulsifiers were heated to about 80°-85°C and the compound from example 4 added.
Alternatively the water containing the hydrosoluble compounds was heated to 80 0 -85 0 C and the oily phase added to the aqueous phase. After ten minutes brisk stirring the mixture was allowed to cool under moderate stirring, then the perfume and preservative added.
Example B oil-in-water sun screen emulsion This was similar to example A but contained 2.0 g of the compound from example 6 in place of the compound from example 4.
Example C oil-in-water sun screen emulsion Compound from example 3 2.0 g 2-hydroxy-4-methoxybenzophenone 1.0 g L^^’Liquid lanolin 7.0 g Triglycerides of myristic/palmitic/stearic acids («NESATOL» from VEVY) 5.0 g Oxyethylenated oleic triglycerides («LUBRAFIL M1969 CS» from GATTEFOSSE) 2.5 g Mixture of glycerol monostrearate and stearate of polyethylene glycol (100 OE) («ARLACEL 165» from SEPPIC) 5.0 g Stearyl alcohol 1.0 g Stearic acid 2.5 g Mixture of cetyl phosphate and the monocetyl phosphate of diethanolamine («AMPHISOL NP» from GIVAUDAN) 0.5 g Benzoates of C12/C15 alcohols («FINSOLV TN» from WITCO) 9.0 g *600
S
C
*3 0* @0
S
OS 0
S
C. S 0@ 0 0 0 @0 Triethanolamine 0.2 Preservative 0.4 Perfume 0.6 Demineralised water qsp 100 This emulsion was prepared as described g g g g for example A.
20 Example D oil-in-water sun screen emulsion Compound from example 1 3 Mixture of cetylstearyl alcohol and oxyethylenated (33 moles OE) cetylstearyl alcohol («SINNOWAX AO» from HENKEL) 7 25 Glycerol monostearate 2 Cetyl alcohol 1 .5 g we..
S C .0 .0 .3 Propylene glycol 10.0 Preservative 0.2 Perfume 0.6 Benzoates of C12/C15 alcohols («FINSOLV TN» from WITCO) 15.0 Demineralised water qsp 100 This emulsion was prepared as described example A.
g g g g g g g g for Example E sun screen stick Compound from example 4 5.0 g Hydrocarbonated mineral wax 20.0 g Beeswax 7.0 g Oleic alcohol 12.0 g Hydrogenated lanolin 8.0 g Liquid lanolin 8.0 g Carnauba wax 1.0 g Benzoate of alcohols C 12
/C
15 («FINSOLV TN» 10 from WITCO) 20.0 g Perfume 1.2 g Vaseline oil qsp 100 g Example F sun screen stick This was similar to example E but using 5.0 g of the compound from example 9 in place of the compound from
*.SS
0gS*
S
S. S 0 eeSO
SO
example 4.
Example G sun screen oil Compound from example 3 3.5 g Sweet almond oil 3.0 g Perfume 1.2 g Benzoate of alcohols C 12 15 («FINSOLV TN» from WITCO) qsp 100 g Example H ,un screen oil This was similar to example G but replacing the compound from example 3 with the compound from example 8.
Example I water-in-oil sun screen emulsion Compound from example 4 3.0 g Mixture of diorganopolysiloxane grafted with cetyl and polyethoxy-polypropoxy-propyloxy groups, polyglycerol oleate and hexyl laurate, denominated in the CTFA dictionary as cetyldimethicone copolyol/ cetyldimethicone/polyglycerol-3-oleate/hexyl laurate («ABIL WS 08» from GOLDSCHMIDT) 5.0 g Benzoate of alcohols C 12
/C
15 («FINSOLV TN» from WITCO) 12.0 g s ee 400.
S
0O@S 5 5.
0@0 Vaseline 2.0 g Beeswax 2.5 g Glycerine 2.0 g Sodium chloride 2.0 g Preservative 0.2 g Perfume 0.6 g Demineralised water 100 g This emulsion was prepared as described for example A except that the aqueous phase was added to the oily phase.
Example J oil-in-water sun screen emulsion Compound from example 5 1.7 g Compound from example 7 1.8 g Mixture of cetylstearyl alcohol and oxyethylenated (33 moles OE) cetylstearyl alcohol («SINNOWAX AO» from HENKEL) 7.0 g Glycerol monostearate 2.0 g Cetyl alcohol 1.3 g Propylene glycol 10.0 g 20 Benzoates of C12/C15 alcohols («FINSOLV TN» from WITCO) 1.5.0 g Preservative 0.2 g Demineralised water qsp 100 g This emulsion was prepared as described for 25 example A.
Example K oil-in-water sun screen emulsion Compound from example 2 5.0 g Mixture of cetylstearyl alcohol and oxyethylenated (33 moles OE) cetylstearyl alcohol («SINNOWAX AO» from HENKEL) 7.0 g Glycerol monostearate 2.0 g Propylene glycol 10.0 g Cetyl alcohol 1.3 g Benzoates of C12/C15 alcohols («FINSOLV TN» from WITCO) 15.0 g sees a go 0. 00 5 as** 55 055 0 S 0 6
V
Preservative Demineralised water 0.2 g 100 g qsp This emulsion was prepared as example A.
described in The compositions of examples A to K are intended for application to the skin to protect it from UV radiation.
Example L protective oil for the hair Compound from example 1 1.0 g Absolute ethanol 50 g 1,3,3,5-tetramethyl-l,1,5,5-trisiloxane («Huile 763» from RHONE POULENC) 65 g This product is in the form of a clear oil.
ell When applied to dry hair this oil makes it smooth 15 and shiny whilst simultaneously protecting it from ultraviolet radiation.
Go o 0,0 a C 0

Claims (20)

1. The cosmetic use as UV radiation filters for wavelengths between 280 nm and 360 nm of benzalmaL:,.ate diorganopolysiloxanes selected from those having the formula: R R R R B-Si-O Si-O Si-O Si-B (1) I I I I R R A R r s wherein: R may be the same for each occurrence or different and is selected from C-Clo alkyl radicals, phenyl radicals and 3,3,3-trifluoropropyl radicals, at least 80% by number of the R radicals being methyl radicals, B may be the same for each occurrence or different and is selected from radicals R and A, L is a number between 0 and 200 inclusive, as is a number between 0 and 50 inclusive and if s is 0 at least one of the two B radicals is A; and from those having the formula: R R Si- -Si-0- (2) R A 2) t u wherein: R has the meaning defined for formula u is a number between 1 and 20 inclusive, I is a number between 0 and 20 inclusive, S+ u is greater than or equal to 3; 3 and wherein in both formulae the symbol A denotes a radical having the formula: R 1 R 2 CO 2 R (3) R 3 CO2 R 6 wherein: R 1 and R 2 are selected from a hydrogen atom, a hydroxy radical, a trimethylsiloxy radical, a C1-Ce alkyl radical, a C1-C6 alkoxy radical and a divalent group Y with the formula: -(CH2)p-CHI- CH2- R4 wherein: n is 0 or 1, D. is a whole number between 1 and 10 inclusive, preferably between 1 and 4, and R 4 is selected from a hydrogen atom and a C1-C4 alkyl radical, one of the two radicals R 1 and R 2 necessarily representing group Y, R 3 represents a hydrogen atom, a C1-C6 alkyl radical or a C 1 -C 6 alkoxy e radical. Rs and R 6 may be identical or different and represent a C1-C8 alkyl radical.

2. The cosmetic use as UV radiation filters for wavelengths between 280 nm and 360 nm of random or block diorganopolysiloxanes having formula or according to claim 1, having at least one of the following characteristics: R is methyl, B is methyl, R 1 is H orY, R 2 is Y, methoxy or butoxy, R 3 is H or methoxy, n=Oor1, P=1, R 4 is H or methyl, Rs and R 6 are ethyl or 2-ethylhexyl, r is between 5 and 20 inclusive, is between 2 and 15 inclusive, U is between 3 and 10 inclusive.

3. The cosmetic use as a UV radiation filter for wavelengths between 280 nm and 360 nm of a benzalmalonate polydimethylsiloxane with formula (1) according to claim 1 wherein R and B represent methyl, r 5, s 5, R 1 is H, R 2 is Y with n 1, p 1 and R 4 is H, R 3 is H or rrethoxy and Rs and R 6 are ethyl.

4. The cosmetic use as UV radiation filters for wavelengths between 280 nm and 360 nm of a benzalmalonate polydimethysiloxane with formula (1) according to claim 1 wherein R and B represent methyl, r 20, s 5, Ri is H, R 2 is Y with n 1, p 1 and R4 is H, R 3 is H and R 5 and R 6 are ethyl. The cosmetic use as UV radiation filters for wavelengths between 280 nm and 360 nm of a benzalmalonate polydimetrryitiloxane with formula (1) according to claim 1 wherein R and B represent methyl, r s 40, R1 is H, R 2 is Y with n= 1, p 1 and R 4 is H, R 3 is H and R 5 and R 6 are ethyl.

6. The cosmetic use as UV radiation filters for wavelengths between 280 nm and 360 nm of a benzalmalonate polydimethylsiloxane with formula (1) according to claim 1 wherein R and B represent methyl, r 7.3, s 9, Ri is H, R 2 is Y with n 1, p 1 and R 4 is CH 3 R 3 is H and R 5 and Re are ethyl.

7. The cosmetic use as UV radiation filters for wavelengths between 280 nm and 360 nm of a benzalmalonate polydimethylsiloxane with formula (1) according to claim 1 wherein R and B represent methyl, r 5, s 5, Ri is Y with n 0, p 1 and R 4 is H, R2 is methoxy, R 3 is H or methoxy and R 5 and Re are ethyl.

8. The cosmetic use as UV radiation filters for wavelengths between 280 nm and 360 nm of a banzalmalonate polydimethylsiloxane with formula (1) according to claim 1 wherein R and B represent mr’hyl, r= 5, s 5, R 1 is Y with n 0, p 1 and R4 is H, R 2 is methoxy, Rs is methuxy and Rs and R 6 are 2- ethylhexy!.

9. The cosmetic use as UV radiation filters for wavelengths between 280 nm and 360 nm of a benzalmalonate polydimethylsiloxane with formula (1) according to claim 1 wherein R and B represent methy!, r= 5, s 5, Ri is Y with n 0, p 1 and R 4 is H, R 2 is butoxy, R 3 is methoxy and Rs and R 6 are ethyl. A cosmetic compc–tion characterized in that it comprises, as an UV- radiation filter for wavelength between 280 and 360 nm, in a cosmetically acceptable support, an effective quantity of at least one benzalmalonate Sdiorganopolysiloxane se’lcted from those having the formula: R R R R B-Si- i- Si- Si-B R R A R r s wherein: R may be the same for each occurrence or different and is selected from Ci-Cio alkyl radicals, phenyl radicals and 3,3,3-trifluoropropyl radicals, at least by number of the R radicals being methyl radicals, B may be the same for each occurrence or different and is selected from radicals R and A, I is a number between 0 and 200 inclusive, s is a number between 0 and 50 inclusive and if s is 0 at least one of the two B radicals is A; and from those having the formula: R R -0 I IA (2) R A t u wherein: S..R has the meaning defined for formula is a number between 1 and 20 inclusive, t is a number between 0 and 20 inclusive, t 1+ U is greater than or equal to 3; and wherein in both formulae the symbol A denotes a radical having the ‘formula: R R2 R *R3) R (3) 0 R3 CO 2 R 6 wherein: R 1 and R 2 are selected from a hydrogen atom, a hydroxy radical, a trimethylsiloxy radical, a Ci-C 6 alkyl radical, a C 1 -C 6 alkoxy radical and a divalent group Y with the formula: -(CH2)p -CH- H2 R4 39 n is 0 or 1, 1 is a whole number between 1 and 10 inclusive and, R 4 is selected from a hydrogen atom and a C1-C4 alkyl radical, one of the two radicals R 1 and R 2 necessarily representing group Y, Ra represents a hydrogen atom, a C1-C6 alkyl radical or a Ci-C6 alkoxy radical, Rs and R 6 may be identical or different and represent a CI-C8 alkyl radical, and cosmetic additives selected from thickeners, softeners, moisturisers, surfactants, preservatives, anti-foaming agents, perfumes, oils, waxes, lanolin, low monoalcohols and polyols, C12-Cis alcohol benzoates, propellants, dyes and pigments. 4 S.11. A cosmetic composition according to claim 10 characterized in that it comprises a random or block benzalmalonate diorganopoly.i loxane with formula or having at least one of the following characteristics: R is methyl, B is methyl, R is H orY, R 2 is Y, methoxy or butoxy, R 3 is H or methoxy, n=0or1, i p= 1, R 4 is H or methyl, Rs and Re are ethyl or 2-ethylhexyl, is between 5 and 20 inclusive, s is between 2 and 15 inclusive, 1+ u is between 3 and 10 inclusive.

12. A cosmetic composition according to claim 10 or claim 11 characterized in that it comprises a benzalmalonate polydimethylsiloxane with formula (1) according to claim 1 where R and B represent methyl, r 5, s 5, R1 is H, R2 is Y with n 1, p 1 and R 4 is H, R 3 is H or methoxy and Rs and R6 are ethyl.

13. A cosmetic composition according to claim 10 or claim 11 characterized in that it comprises a benzalmalonate polydimethylsiloxane with formula (1) according to claim 1 where R and B represent methyl, r 20, s 5, Ri is H, R2 is Y with n 1, p 1 and R4 is H, R 3 is H and Rs and Re are ethyl.

14. A cosmetic composition according to claim 10 or claim 11 characterized in that it comprises a benzalmalonate polydimethyisiloxane with formula (1) according to claim 1 where R and B represent methyl, r 0, s 40, R1 is H, R 2 is *i Y with n 1, p 1 and R4 is H, R 3 is H and Rs and R 6 are ethyl.

15. A cosmetic composition according to claim 10 or claim 11 characterized in that it comprises a benzalmalonate polydimethylsiloxane with formula (1) according to claim 1 wherein R and B represent methyl, r 7.3, s 9, R1 is H, R2 is Y with n 1, p 1 and R 4 is CH 3 R 3 is H and Rs and R6 are ethyl. S16. A cosmetic composition according to claim 10 or claim 11 characterized S’ in that it comprises a benzalmalonate polydimethylsiloxane with formula (1) according to claim 1 where R and B represent methyl, r= 5, s 5, R1 is Y with n 0, p 1 and R4 is H, R2 is methoxy, R 3 is H or methoxy and Rs and RF are ethyl.

17. A cosmetic composition according to claim 10 or claim 11 characterized in that it comprises a benzalmalonate polydimethylsiloxane with formula (1) according to claim 1 where R and B represent methyl, r 5, s 5, Ri is Y, with n 0, p 1 and R4 is H, R2 is methoxy, R3 is methoxy and Rs and Re are 2- ethylhexyl.

18. A cosmetic composition according to claim 10 or claim 11 characterized in that it comprises a benzalmalonate polydimethylsiloxane with formula (1) according to claim 1 where R and B represent methyl, r= 5, s 5, R 1 is Y, with n 0, p 1 and R 4 is H, R 2 is butoxy, R 3 is methoxy and R 5 and R 6 are ethyl.

19. A cosmetic composition according to any one of claims 10 through 18 characterized in that it is in the form of an oily, alcoholic or oleoalcoholic lotion, emulsion, oleoalcoholic, alcc)olic or hydroalcoholic gel, solid stick, spray or aerosol. A cosmetic composition according to any one of claims 10 through 19 characterized in that it constitutes a protective composition for the human skin and contains 0.25 to 5% by weight of diorganopolysiloxane with formula or

21. A cosmetic composition according to any one of claims 10 through 19 in the form of a sun screen composition, characterized in that it contains 0.5 to :15% by weight of diorganopolysiloxane with formula or and other filters, if any.

22. A sun screen cosmetic composition according to claim 21 characterized in that it further contains a UV-B and/or UV-A radiation filter agent.

23. A cosmetic composition according to any one of claims 10 through 18 for application to the hair characterized in that it is in the form of a shampoo, lotion, gel or rinsing emulsion, for application before or after shampooing, before or after dyeing or bleaching, before or after a perm, as a styling or treating gel, a brushing or setting lotion or gel, hair spray or hair lacquer and comprises 0.25 to 5% by weight of diorganopolysiloxane having formula or

24. A cosmetic composition according to any one of claims 10 through 18 in the form of a coloured or non-coloured cosmetic composition characterized in that it is constituted by a hairdressing composition, a cosmetic or a product for caring for or treating the skin, comprising 0.25 to 3% by weight of diorganopoly- siloxane having formula or A method for protecting skin and natural or sensitised hair against ultraviolet radiation characterized in that it consists in applying to the skin or hair an effective quantity of a cosmetic composition containing at least one benzotriazole diorganopolysiloxane having formula or as defined in any one of claims 1 through 9.

26. A method of protecting a cosmetic composition against ultraviolet radiation characterized in that it consists in incorporating into said composition an effective quantity of at least one benzalmalonate diorganopolysiloxane having formula or as defined in any one of claims 1 through 9. DATED this 12th day of November, 1992. L’OREAL WATERMARK PATENT TRADEMARK ATTORNEYS THE ATRIUM 290 BURWOOD ROAD HAWTHORN VICTORIA 3122 AUSTRALIA 4 ot .o C

AU49700/90A
1989-02-15
1990-02-14
Cosmetic use of benzalmalonate diorganopolysiloxanes and novel cosmetic compositions containing such compounds for the protection of skin and hair

Ceased

AU637596B2
(en)

Applications Claiming Priority (2)

Application Number
Priority Date
Filing Date
Title

FR8901989A

FR2642967B1
(en)

1989-02-15
1989-02-15

COSMETIC USE OF BENZALMALONATE FUNCTIONAL DIORGANOPOLYSILOXANES AND NOVEL COSMETIC COMPOSITIONS CONTAINING THESE COMPOUNDS FOR PROTECTION OF THE SKIN AND HAIR

FR8901989

1989-02-15

Publications (2)

Publication Number
Publication Date

AU4970090A

AU4970090A
(en)

1990-08-23

AU637596B2
true

AU637596B2
(en)

1993-06-03

Family
ID=9378822
Family Applications (1)

Application Number
Title
Priority Date
Filing Date

AU49700/90A
Ceased

AU637596B2
(en)

1989-02-15
1990-02-14
Cosmetic use of benzalmalonate diorganopolysiloxanes and novel cosmetic compositions containing such compounds for the protection of skin and hair

Country Status (11)

Country
Link

US
(1)

US5415854A
(en)

EP
(1)

EP0392882B1
(en)

JP
(1)

JP2984300B2
(en)

AT
(1)

ATE81768T1
(en)

AU
(1)

AU637596B2
(en)

BR
(1)

BR9000672A
(en)

CA
(1)

CA2010161C
(en)

DE
(1)

DE69000409T2
(en)

ES
(1)

ES2046718T3
(en)

FR
(1)

FR2642967B1
(en)

MX
(1)

MX170783B
(en)

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1989-03-22
1994-04-15
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COSMETIC USE OF DIORGANOPOLYSILOXANES WITH 2-HYDROXY-BENZOPHENONE FUNCTION AND COSMETIC COMPOSITIONS CONTAINING THESE COMPOUNDS FOR PROTECTION OF THE SKIN AND HAIR

GB9110123D0
(en)

1991-05-10
1991-07-03
Dow Corning
Organosilicon compounds their preparation and use

FR2680683B1
(en)

1991-08-29
1993-11-12
Oreal

COSMETIC FILTERING COMPOSITION CONTAINING A HYDROCARBON STRUCTURED FILTER POLYMER AND A FILTERED SILICONE.

FR2680684B1
(en)

1991-08-29
1993-11-12
Oreal

COSMETIC FILTERING COMPOSITION COMPRISING A METAL OXIDE NANOPIGMENT AND A FILTERED POLYMER.

FR2684551B1
(en)

1991-12-05
1995-04-21
Oreal

COSMETIC FILTERING OIL CONTAINING A FILTERED SILICONE AND A MIXTURE OF A VOLATILE SILICONE AND A SILICONE OIL OR A SILICONE GUM AND COSMETIC FILTERING EMULSION CONTAINING SUCH AN OIL.

ATE354605T1
(en)

1994-10-14
2007-03-15
Dsm Ip Assets Bv

ORGANOSILOXANE CONTAINING BENZALMALONATE GROUPS

ES2170116T3
(en)

1994-10-14
2002-08-01
Hoffmann La Roche

PHOTOSTABLE COSMETIC LIGHT FILTER COMPOSITIONS.

FR2754446B1
(en)

1996-10-15
2004-10-15
Oreal

USE OF A SILICONE FILTER FOR THE PROTECTION OF THE COLOR OF KERATINIC FIBERS NATURALLY OR ARTIFICIALLY COLORED

FR2756287B1
(en)

1996-11-28
1998-12-24
Oreal

NOVEL DERIVATIVES OF SILICON FILTERS ON THEIR AROMATIC PART, PHOTOPROTECTIVE COSMETIC COMPOSITIONS CONTAINING THEM AND USES THEREOF

FR2757057A1
(en)

1996-12-17
1998-06-19
Oreal

COMPOSITIONS COMPRISING A DIBENZOYLMETHANE DERIVATIVE, A 1,3,5-TRIAZINE DERIVATIVE, AND A BENZALMALONATE FUNCTIONAL SILICY DERIVATIVE AND USES THEREOF

FR2760464B1
(en)

1997-03-07
2005-07-01
Oreal

PROCESS FOR IMPROVING THE PHOTOSTABILITY OF A DIBENZOYLMETHANE DERIVATIVE BY SILANE, BENZALMALONATE, PROCESS FOR THE PREPARATION OF BENZALMALONATE SILANES

FR2771630B1
(en)

1997-12-03
2000-03-31
Oreal

AQUEOUS DISPERSION COMPRISING A BENZOSMALONATE FUNCTION ORGANOSILOXANE UV FILTER AND A WATER-INSOLUBLE CATIONIC SURFACTANT

US6365141B2
(en)

1998-11-06
2002-04-02
General Electric Company
Method of using an aralkylsiloxane

DE102005022790A1
(en)

2005-05-12
2006-11-16
Henkel Kgaa

Agent for dyeing keratinous fibers

GB0611770D0
(en)

2006-06-15
2006-07-26
Givaudan Sa
Compounds

ATE544805T1
(en)

2008-12-01
2012-02-15
Dsm Ip Assets Bv

NEW PROCESS

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FR
FR8901989A
patent/FR2642967B1/en
not_active
Expired – Fee Related

1990

1990-02-08
ES
ES199090400345T
patent/ES2046718T3/en
not_active
Expired – Lifetime

1990-02-08
AT
AT90400345T
patent/ATE81768T1/en
not_active
IP Right Cessation

1990-02-08
DE
DE9090400345T
patent/DE69000409T2/en
not_active
Expired – Fee Related

1990-02-08
EP
EP90400345A
patent/EP0392882B1/en
not_active
Expired – Lifetime

1990-02-14
BR
BR909000672A
patent/BR9000672A/en
unknown

1990-02-14
MX
MX019498A
patent/MX170783B/en
unknown

1990-02-14
AU
AU49700/90A
patent/AU637596B2/en
not_active
Ceased

1990-02-15
JP
JP2035066A
patent/JP2984300B2/en
not_active
Expired – Fee Related

1990-02-15
CA
CA002010161A
patent/CA2010161C/en
not_active
Expired – Fee Related

1993

1993-06-22
US
US08/081,064
patent/US5415854A/en
not_active
Expired – Lifetime

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1978-03-08
1983-09-20
Consortium Fur Elektrochemische Ind. Gmbh
Greases prepared from organosiloxanes with SiC-bonded groups

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1983-08-18
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Organosilicon compounds and preparation and use thereof

Also Published As

Publication number
Publication date

ATE81768T1
(en)

1992-11-15

JPH02270816A
(en)

1990-11-05

DE69000409T2
(en)

1993-03-18

AU4970090A
(en)

1990-08-23

EP0392882A1
(en)

1990-10-17

MX170783B
(en)

1993-09-14

BR9000672A
(en)

1991-01-15

CA2010161A1
(en)

1990-08-15

DE69000409D1
(en)

1992-12-03

JP2984300B2
(en)

1999-11-29

US5415854A
(en)

1995-05-16

ES2046718T3
(en)

1994-02-01

CA2010161C
(en)

2002-01-01

FR2642967A1
(en)

1990-08-17

FR2642967B1
(en)

1991-06-07

EP0392882B1
(en)

1992-10-28

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