DE2347928A1 - PROTECTIVE AGENTS AGAINST ACTINIC RADIATIONS AND AGENTS CONTAINING THEM - Google Patents

Description

PAT ENTA N W XLT E

DR.-ING. WOLFRAM BUNTE DR. KARL GEORG LÖSCH

D-8OOO MUNICH 13, BAUERSTRASSE 22. POST BOX 78O FERNRUF (OBII) 37 65 83 TELEX 521520B ISAR CJ

Munich, September 24, 1973 M / 12 7Q8

- ',, L' O R E-A L

¹ I.

14, rue Royale, Paris, - France

Protective agents against actinic rays and containing them '

middle

The present invention relates to new derivatives which are used in a specific area of ultraviolet radiation have an absorbent effect and due to this property the ' Frequently against the harmful effects of the human actinic rays protect and the retention time certain cosmetic 'preparations can increase. It is known that the part of the actinic radiation between 280 and 400 nanometers (nm) 'the tan- the human Skin allowed. It is also known to be the most effective

409815/1125

Zone for this browning is between 280 and 315 nm and 'that this zone corresponds to the wavelengths that cause erythema and sunburn. It is therefore important to be human Protect skin from the wavelengths between 280 and 315 nm and allow it to radiate with a Wavelength above 315 nm can be exposed to to create the conditions for a tan without erythema. In particular, it is important that you get the rays with a Wavelengths around 340 nm which give maximum tan without erythema.

The protective agent must therefore have an increased absorbing effect between 280 and 315 nm and a weak one above 315 nm. It has _one beyond a good hardiness

[j.

! ability to _{: show} external influences, that is, a good one

photochemical stability, 'good thermal stability

! and ej.ne sufficient affinity for the skin and chemical "'

Have stability. So that it is not sweaty or slight-

'Is removed or degraded with docile washing.

'On the other hand, it is known that the dyes used in certain cosmetic "preparations, in particular hair preparations, such as.

: Dyes and colored hair varnishes, shampoos, colored Water wave lotions öote'r nail polish or tinted creams are not always sufficiently stable to light. . '

ι I

I ■

These agents can be in the form of a solution, emulsion, gel, suspension, or dispersion, and it is general

It is customary to put them in small bottles made of white glass or transparent ■ To pack plastic. The paints in particular often become grounded j offered in a transparent spray bottle so that the consumer can assess the color. ;

_ 2 -

■ 4 09815/1125

The remedy is like this during storage and consumption

exposed to light. !

I Also, the dyes do not always have sufficient stability to light rays. This is particularly the case Triphenylmethane derivatives the case (for example crystal violet, methyl violet, methyl green), although they are a very interesting color scales have the disadvantage of being quickly destroyed by light. This is also the case with one large number — other dyes — the case under certain Concentration conditions are stable and when they are used in great dilution a pronounced photosensitivity exhibit.

On the other hand, it also happens quite often that colorless agents, for example colorless nail varnishes, change and turn yellow when exposed to light for long periods of time

It follows that these agents, whether they are colored or not, only for a certain period of time, generally on the order of a few weeks can. In order to remedy this disadvantage, one can include a compound in these preparations, which the rays of light can filter. In addition to good filter properties, this connection must have good stability and sufficient stability Solubility range in the commonly used in cosmetics The present invention relates to precisely new ones. Compounds that are different from the above Meet criteria and are particularly effective for the purposes proposed.

409815/1125

M / 12 708

The present invention relates to a cosmetic agent, which is characterized in that it is used as a means for Protection against light rays contains a compound of the general formula (I), · ■ ·

CH,

⁺ N - ■ CH,

(D

wherein "R is hydrogen or an alkyl group having 1 to 12 carbon atoms; ι Y signify a halogen, a methyl group or a hydrogen atom. X ~ means a 'halide, a Aryl sulfonate, an alkyl sulfonate, a camphor sulfonate or

an alkyl sulfate. ■

The present invention also relates to a means of protection the skin against ultraviolet rays. Unless it contains opacifying agents, it allows or facilitates such Means a safe tanning of the skin. Such an agent can be in solution, in the form of lotion, in emulsion, in the form of cream, gel, foam or milk or any other in the

^: Cosmetic usual form / present. It can also contain cosmetic auxiliaries such as thickeners, emollients, greasing agents, emollients, wetting agents, surfactants, preservatives, antifoams, perfumes and any other ingredient commonly used in cosmetics. This remedy can also be a

; or contain more propellants to make it aerosolized can be used.

_ 4 _ 409815/1125

ι

M / 12 708

This agent is characterized in that it contains 0.5 to 10 % of its weight in compound (I). The solvent can be water. use a mono-alcohol or a lower polyol or an aqueous-alcoholic solution.

; The preferred monoalcohol or lower polyol is ethanol,

! Isopropyl alcohol, propylene glycol, glycerin, or sorbitol.

y _

\ This agent is often colorless, but it can also be colored.

The 'present' invention also relates to a 'cosmetic agent which contains components which are sensitive to ultraviolet rays, in particular one or more photosensitive dyes, often in very low concentrations of the order of ten thousandths or one hundred thousandths of the total weight of the agent, and which is characterized in that it also contains one or more compounds of the formula (I) in a concentration of 0.05 to 5 % by weight on the total weight of the agent., "

In addition to the dye and the compound of the formula (I), such an agent can be surfactants, swelling agents, Thickening agents, softening agents, greasing agents, decolorizing agents, film-forming agents, cosmetic resins, Wetting agents, foaming agents, synergistic foaming agents, preservatives, perfumes and any other conventionally Contains ingredient used in cosmetics.

4098 15/1125

M / 12 708

Examples of cosmetic agents that use a compound of formula (I) as a filter for ultraviolet rays contain the hair products and especially the hair lacquers, the softening water wave lotions, the nourishing ones and the combing-through water wave lotions, the shampoos, the coloring shampoos, the hair coloring solutions, the nail polishes, the skin care creams, the funds de teint;

These remedies are often packaged in glass bottles or clear plastic. You can also use a Containing propellants and being conditioned so that they can be used in "aerosol form".

The present invention also relates to a method for protecting cosmetic agents which can be changed by light rays, which is characterized in that a compound of the formula (i) is included in these solutions in an amount of from 0.15 to 5 % .

The present. The invention also relates to the new compounds of formula (I).

The compounds of formula (I) can be regarded as derivatives of benzylide_enkamphor_ of ₍ formula (II)),.

(II)

which itself is a good light ray filter and in the French patent 2 004 142 is described.

- ⁶ "A 0 9 8 1 5/112 5

The compounds of formula (i) have very interesting solubility properties. The compounds of the formula (I) have better solubility than benzylidene camphor in certain media. I.

It is known that the use of filter media is often limited by insufficient solubility. Certain connections of formula I have in particular the great advantage of good solubility in water or in aqueous alcoholic Medium.

The table below gives the solubilities in water, ethanol and in a 50:50 water-ethanol mixture for

(A) 4 - [(2-0xo-3-bornylidene) methyl] phenyl trimethylammonium methyl sulfate of formula (I),

(B) 4 - [(2-0xo-3-bornylidene) -methyl] -phenyl-trimethyl- ■ ai & aionium p-toluenesulfonate of the formula (I),

• '■ ■ - "!

(C) 4 - [(2-0xo-3-bornylidene.) - methyl] -phenylrtrimethyl-, ammonium methanesulfonate, _

(D) 4 - [(2-0xo-3-bornylidene) -methyl! -Phenyltrimethylammonium chloride, -. i ·· <

(E) i, 7, .7-Trimethyl-3-benzylidene- [2,2,1] -bicyclo-2-heptanone i or benzylidene camphor of formula (II):

- 7 40981 5/1125

M / 12 708

j solubility in

^: 100 cm of water

I solubility in

! 100 cur ⁵ ethanol

100 %

0.2 % 50 %

1 %

50%

80 %

E!

insoluble;

95 % 14

Solubility in 50 cm of water. 50 cnr ethanol "

100 %

■ ίο

50 % 120 % 0.5 %

It is found that the compounds according to the invention have better solubility in water and in a ^ ί:, 1 mixture of ^! Water and ethanol have the same properties as benzylidene camphor. In addition, these solubility properties do not result in poor retention in the skin. On the contrary, these compounds show a considerable increase in the substantivity of the skin.

The compounds of formula (I). have good absorption properties for light rays. In the table below: are the transmittance for two of them for 1.5% solutions ; in ethanol given as 96 ° with a thickness of 0.01 mm.

409815/1125

! M /] 2,708

I I

ι,

X (mn) AB

270 12th 275 9 " 280 8th 285 7.5 290 8th 295 14th 300 19th 310 40. 320- 86

30. % 21 20 19 20 30 '41 • 58 85

In addition, "the compounds of the formula (I) have a

good thermal and photochemical stability. If you can!

3 hours of a tanning lamp with ultraviolet radiation ^:

suspends or ^{holds at 60 0} C for a week, that changes the.! Transmission curve not. In addition, the experiments let go!

visibly 'dermatoxicity on the harmlessness of this

close ties. ..!

The compounds of formula (I) are prepared according to the method of j Haller by condensation of a substituted or unsubstituted p-dimethylaminobenzaldehyde in an inert solvent, such as benzene, toluene, ether, dimethylformamide, dimethoxy-ethane, with sodium salt. of camphor, which by the action of j from sodium or a strong base such as a sodium alcoholate, sodium amide or sodium hydride. Then i

depending on a quaternization or 'introduces in',

Salt over. '\> ■ ■ \

- 9 - 409815/1125

M / 12 708

! Preparation of '1,7,7-trimethyl-4-dimethylamino-3-benzylidene ' · [2,2,1] -bicyclo-2-heptanone or 4-dimethylamino-benzylidene camphor.

"CH

ClII)

577.5 g (3.8 mol) of synthetic camphor and 205 g of sodium methylate are refluxed in anhydrous toluene for 30 minutes. Probably one has again reached ambient temperature ~ ^ The solution is added all at once 566 g of p-dimethylaminobenzaldehyde. The mixture is then refluxed for 4 hours. After cooling to ambient temperature, the reaction mixture is extracted with water. Then it is dried and the toluene fraction is evaporated to dryness. 1013 g of a solid yellow residue are obtained. Recrystallization from absolute ethanol gives 711 g of shiny yellow crystals which melt at 110.degree.

Elemental analysis:

calculated: found:

The compounds det formula (I) is obtained from 4-Dimethylaminobenzylidenkampher of formula (III) by quaternizing or converting into a salt. ■ ''. ·· ■

: -; C , 56 H 83 N 94 80 , 54 8th, 04. 4, 87 80 9, 4,

09 8 1

2 5

As a quaternizing agent you can use:

: .j

the alkyl sulfates, for example methyl sulfate or ethyl sulfate, | -

! the alkyl alkyl sulfonates, for example methyl methane sulfonate,

_; the alkylarylsulfonates, for example methyl p-toluenesulfonate
or. Methyl p-bromobenzenesulfonate.

■ The anion X "can also be obtained by anion exchange,
; for example by using a compound of the formula (i)

■ via an anion exchange resin that has a different anion

■ contains as X ".

- · j ¹

The agents according to the invention can also have one or more j

water-soluble filters of the formula (-1) together with other \

Filters, for example one or more other water .. -;

soluble filters or one or more fat-soluble ι

Filters "included.. ^;

If the agents are in the form of an emulsion, the; simultaneous presence of water-soluble and fat-soluble. UV filters are very beneficial because they provide protection at the same time
for the aqueous and ... for the oily phase is obtained.

On the other hand, the good affinity properties of the; Compounds according to the invention for the skin that part
the protective effect, for example after immersion in fresh water
or sea water is preserved if the agent used
in addition to the filters according to the invention, other less substantive: contains water-soluble filters.

- 11 409815/1125

; The compounds in which the radical R is hydrogen,

j is obtained by protonation of the tertiary amine, which the

; Compounds of formula (I) corresponds, for example

j with the help of a strong acid ..

i The following examples illustrate the manufacture and

; Application of. Compounds of formula (I).

1 · 'I.

I /

> - ■ »■

- 12 4098 15/1

M / 12 708 production examples

Example I.

Preparation of 4 - [(2-0xo-3-bornylidene) methyl] phenyltrimethylammonium methyl sulfate

¹ CB

SO / .CH,

750 g of 4-dimethylamino-benzylidene camphor (prepared as described above) and 334 g of Μβΐ1 ^ ΐ3μ1Ϊ3ΐ are gradually heated in ethyl acetate to reflux. Suddenly an exothermic precipitation sets in and when it has calmed down, the mixture is refluxed for 3 hours. The pale yellow solid is filtered off with suction, washed with ethyl acetate and recrystallized from a benzene-acetonitrile mixture. Man "erhall: 866 g weiße.s product, which melts at 210 ⁰ C.

Elementary analysis

>, Molecular weight = 409

calculated: found:

61.61

'61, 31

7.58

7.75

- 13 -. '. 409815/1125

3.42 3.40

7.82 % 7.93 %

M / 12 708

Example II

Preparation "of 4 - [(2-0xo-3-bornylidene) methyl] phenyltrimethylammonium p-toluenesulfonate

-CH

283 g of 4-dimethylamino-benzylidene camphor (such as prepared as described above) and 186 g of methyl p-toluenesulfonate in toluene with vigorous stirring for 8 hours under reflux. The white solid is filtered off with suction and dried him. 417 g of product are obtained, after recrystallization from ethanol gives 362 g of white crystals.

F 3Ö5 ° C

Elemental analysis

calculated: found:

C. , 08 H 46 IT 98 % 69 , 08 7, 50 2, 90 % 69 7, 2,

- 14 409815/1125

M / 12 708 '

Example III

Preparation of 4 - [(2-0xo-3-bornylidene) methyl] phenyltrimethylammonium methanesulfonate

• CH

'. N - CH

CH ₃ SO ₃

A mixture of 28.3 g of p-diethylamino benzylidene camphor and 16.5 g of methyl methanesulfonate in 50 ml of toluene is refluxed for 10 hours with vigorous stirring. The precipitate formed is filtered off and washed. with toluene and then recrystallized it from a mixture of benzene and acetonitrile. Are thus obtained 26.6 g we'iße crystals, melting at 265 ⁰ C.

Analysis"

calculated found:

64, 12th 7th , 88 3, 56 ■ 64, 16 7th , 62 3, 53

- 15 409815 / T125

M / ₁₂₇ 08 _m

Example IV j

ι j _ ·

j Production of 4- [(2-0xo-3-t) ornylidene) methyl] phenyl : trimethylammonium chloride

A solution of 10 g of methyl sulfate, which has been obtained according to Example I ■ ^: in 20 ml of water, is added to an anion dispenser

Exchange resin, in the form of chloride ions, is then eluted with 'Water. The eluates are concentrated to dryness under reduced pressure and the solid residue that is obtained

is crystallized from a mixture of ethanol and benzene I. Is obtained as 6.4 g of white crystals, melting at 240 ° '. ''. . .. ■

analysis

calculated: found:

C. 96 H 39 N 19th Cl 64 ■ 71, 78 ' 8th, 37 · 4, 11 10, 84 71 OO 4, 10,

- 16

409815/1125

M / 12 708

'•• Example V j

Production of 3-methyl-4- [2-oxo-3-bornylidene-methyl] -phenyl- \ trimethylaminonium methyl sulfate · - ■

(a) first stage; Preparation of l, 7,7-trimethyl-3- (4-dimethyl-; amino-2-methyl-benzylidene) - [2,2, l] ~ bicyclo-2-heptanone; of the formula: - i

The mixture is stirred 2.3 "g sodium vigorously in 100 ml of boiling ^toluene: then decanted to the toluene from and covers the obtained
Sodium pearls with 100 ml of anhydrous diethyl ether. Under
Stir, the temperature being reduced by cooling to 25
holds, one adds 15.2 g / kamphor. ¥ §nn, a ^ les sodium implemented
is · (4 to 5 hours) one cools to 0 ° and gives 16.3 g
4-dimethylamino-2-methyl- + benzaldehyde to. The mixture is stirred for 3 hours at 0 ° and 30 minutes at the reflux temperature of the
Ether '. After cooling, 100 ml of water are poured in, and the
ethereal phase, dry over sodium sulfate and evaporate
the ether. The oily residue is fractionated
and wins the fraction (23.8 g) which is below 1 mm Hg at 243 °
distilled. The product can crystallize out
Diethyl ether to be purified. It is in the form of yellow
Crystals that melt ^{at 115 ° C.}

409815/1125 ^:

- 17 -

Μ / 12 708

Elemental analysis

calculated: found:

C. , 81 H 09 N 71 80 , 88 9, 83 4, 59 80 8th, 4,

(b) Second stage: Production of 3-methyl-4- [2-oxo-3-bornylidenemethyl] -phenyl-trimethyl-ammonium methyl sulfate of the formula:

CH,

SO ₄ CH ₃

14.9 g of the compound prepared in step (a) and 6.3 g Methyl sulfate is gradually heated in ethyl acetate to reflux and this is maintained for 3 hours a white solid which is washed with ethyl acetate. 12 g of white crystals which melt at 245 ° C. are obtained.

Elemental analysis:

... ·, 'C 41 H 80 N 31 S. 56 calculated: / "62, 78 7, 88 3, 24 7, 63 found: - ' 61, 7, 3, 7,

- 18 - ■
40981 5/1125

M / 12 708

., .. Example VI

Preparation of 3-chloro-4- [2-oxo-3-bornylidene-methylI-phenyl-trimethylammonium methyl sulfate

(a) first stage; Preparation of 1,7,7-trimethyl-3- (4-dimethyl-. Amino-2-chlorobenzylidene) - [2,2,1] -bicyclo-2-heptanone! of the formula: i

¹ CH,.

CH

N
t

CH

Cl.

A mixture of 76 g of camphor and 19.5 g of sodium amide in 150 ml of dry toluene is stirred for 3 hours at reflux temperature. After cooling to ambient temperature, 92 g of o-chloro-p-dimethylaminobenzaldehyde are added and the mixture is refluxed for 5 hours. About 400 ml of water are poured into the cooled mixture and the toluene phase is separated off. It is dried and concentrated to dryness . Ben residue crystallized man.aus Is'opopanol to give 82 g of yellow crystals give 'which melt at 128 ⁰ C.

Elemental analysis

- 40 9 8th 1 5/1 1 • 2 C. j H , 56 N 41 % calculated: ■ 19 - 71 , 81 ' • 7 , 90 4, 38 % found: 71 , 53 7th 4, 5

M / 12 708

23A7928

(b) Second stage: Preparation of 3-chloro-4- [2-oxo-3-bornylidene methyl] phenyl trimethylammonium methyl sulfate of the formula: |

•• CH

SO ₄ CH

A mixture of 42 g of the above product (a) '' is heated! and 15.2 g of methyl sulfate in 400 ml of acetonitrile for about 10 hours, to reflux. The precipitate obtained is recrystallized from a mixture of benzene and acetonitrile. ■

The product obtained is in the form of pale yellow platelets ^: "which ^{melt at 210 °} C. · · ·. I

Elemental analysis Cp-;

calculated ^ found:

ClS

I /

3 * 16

3.12

S · ■ 7.19 % 7.18 %

-. 20 409815/1125

M / 12 708 ι

Example VII

Preparation of 4 - [(2-0xo-3-bornylidene) methyl] phenyltrime thylammonium camphor sulfonate

N-CH.

56.6 g of 4-dimethylamino-benzylidene camphor are heated and '

49.2 g of methyl camphor sulfonate in 300 ml of ethyl acetate for 15 hours!

to reflux. After cooling down, the precipitate is sucked off ^;

off,. Wash it with ethyl acetate and crystallize it from j

a toluene-acetonitrile mixture. Man; receives 73 g j

snow-white crystals that melt at 260_C. '

analysis

C. .. H 13th N. 64. S. 05 calculated: 68 , 05 8th, Il 2, 51 · 6, 29 found: ¹ <68
ί ·, , 00 8th, 2, 6,

- ■ • 21 '"- ■"

409815/1125

M / 12 708

Example VIII

Production of 4- [(2-0xo-3-t> ornylidene) methyl] phenylethyl dimethylammonium ethyl sulfate

14 g of 4-dimethylaminobenzylidene camphor and 8 g are heated Dietary sulfate in 100 ml · ethyl acetate for 6 hours under reflux. After cooling down one sucks. the precipitate and washes it with ethyl acetate. ·

This gives 9.9 g of white hygroscopic crystals having a melting point 126 to .127 ⁰ C. The yield is 45%.

Analysis:

calculated: found:

• N ■

3.21

2.93

7.32

7.52

. - 22 -

409815/1125

M / 12 708

Example IX

Preparation of 4- [(2-0xo-3-'bornylidene) methyl] phenyldo de cyclo-dimethylammonium-p-1οluo1sulfonat

The mixture is heated ^ 2.8 g 4-dimethylamino-benzylidenkampher and 3.4 g tauryltosylat-6 1/2 hours elna temperature 130-140 ⁰ C. "

You take the "whole" in a sufficient amount of isopropanol on to solve the product.

The isopropanol is then evaporated off and 4.6 g of des is obtained desired product, which is in the form of whitish crystals with a melting point of 135 ° C.

The yield amounts to 72 % i S. 13th Analysis: I.
t
C. VJl 69 ·· N 5, calculated: ¹ ^ • 2.25 found: '2.32,

40981 5/1125

m / 12 708? 3Λ7928

«Υ

Application examples

Example 1

i sun protection lotion

ι Lanolin '"■ 2.5 g

'■■ Butylhydroxyanisole "- · 0.025 g

i butyl hydroxytoluene * x 0.025 g

I octyl gallate -... -. . '"0.0125 g

I triglyceride of fatty acid with 8 to 12

j carbon atoms. 40 g

i perfume "/ ·. '- l, 25._g

; 4 - [(2-0xo-3-bornylidene) -methyl! -Phenyl -

j trimethylammonium methyl sulfate. "" ■ '4g

i Ethanol at 96 ° as much as necessary for 1Ö0 g

"- · Example 2 ,

j sun protection lotion

ι Glycerin .. '

' Polyethylene glycol' * 4po

! ethoxylated lanolin

¹ soluble perfume,

; 4 - [(2-0xo-3-bornylidene) methyl] phenyl

! trimethylammonium methyl sulfate

j alcohol with 96 ° _# . '

: Water as much as' required for

- 24 '■■ - ^: 4098 15/1125

VJl g " ο, 5 g 1" G 2 G 2 G 50 G 100 G

30th G 20th G 2 G 5 G 1 G . 2 G 40 G

! tr

Example '3

Aero sol sunscreen

absolute ^; Ethanol isopropyl myristate castor oil
lanolin
Perfume

4- [(2-0xo-3-13ornylidene) methyl] phenyltrimethylammonium methyl sulfate . . Dichlorodifluoromethane, under the trade name Freon 12 distributed

· '. ■ Example -4 ' sun protection aerosol foam

t

Sipol- ¥ axis "" ·, '- ··; '■ Vaseline oil

! Isopropyl myristate

Preservatives,. . . ·

j glycerin .. '".., j perfume

ι 4 - ['(2-0xo-3-bornylidene) methyl] -phehyltr ime thylammonium-methyl'sulf a t water, as much as necessary for Dichlorodifluoromethane, under the trade name "Freon 12" distributed '. 15 g

3.5 G i 6 g 1
i
i 3 g .0.3 G !
I. 10'g i
1 0.3 G I.
j I. 2.5 G 100 g

'- - 25 .-;.; 40981 5/1125

K / 12 708

example

Sunscreen

Cetyl stearyl alcohol.

GIyc erinmono ste arat Cetyl alcohol petroleum jelly butyl stearate; Propylene glycol ..

Silicone oil '· ■ ·

Ethylene oxide polymer with a molecular weight of 100,000 to 1,000,000, which is below the Union Carbide trade name "Polyox"

Preservatives are sold

Perfume.. ' · .;.---··

4 - [(Ζ ^ Οχα-3-.bornylidene) -methyl] -phenyl-

trimethylammonium methyl sulfate

Water, as much as required for

2 g

4th G 4th σ
ο VJl G 5 G 7th G ο, 125 g

3, 5 he
O .. o, ■ z G •O, 4th G ti G 100 G

■ Example

, ι -40 98 - 2 B - 5 g 1 5/1 125 Sunscreen milk
* »"
I. ■ - - - 6 g 4th
I V
Sipol wax. / '' / 3 g SAD ORIGINAL Petroleum jelly ■. ' ₍ " 1 g Isopropyl myristate 1 g Silicone oil. 2nd Floor Cetyl alcohol ·· ■ ■ ■. 0.3 g Glycerin 0.3 pounds Preservatives Perfume h- \, (2-Oxo-3-bornylidene) -methyl'-phony 1- trimethylammonium methyl sulfate

m / 12 708? 3A7928

Water as much as necessary for 100 g

Example, 7 colored water wave lotion

50 g G .pH 7 cnr 0.2 100

Vinylpyrrolidone-vinyl acetate copolymer 70/30 2 g Victoria blue BSA, Color Index 44 045 0.001g

_Ethyl alcohol - 'ώ'

Triethanolamine, as much as necessary for 4- [('2-0xo-3 ~ bornylidene) methyl] phenyltrimethylainmonium methyl sulfate , · Water as much as needed for. · ·

- ~ ' B, ei' s ό 1 e 1 · "S · '*

Colored water wave lotion

• i

Croton axles / vinyl acetate copolymer 90/10. 2 g

CI. Basic violet no. 3 '' 0.01 g

Color Index 42 555. '· ■. "' '' '

Ethyl alcohol · · '- ··, ^ .50 g

Triethanolamine as much as required for pH 7 4 - [(2-Oxo-3-bornylidene) methyl] phenyl

trimethylammonivun-p-toluenesulfonate 0.2 g

/ Ί 3

Water as much as required for 100 cnr

409815/1125

5 G I. 1 G j 15th G 5 G ο, 2 g 1 G

M / 12 708 7347928

«P

Example 9 Sun milk _y medium protection

Cetostearyl alcohol condensed with

25 moles of ethylene oxide, cetyl alcohol, 2-octyl-dodecanol Vaseline Oil Codex

unsaponifiable components of alfalfa

Benzylidene camphor

4- [(2-Oxo-3-b'orriylidene) -methyl] -phenyl-tr imethyl- ■

ammonium methyl sulfate 2.5 g ■ '

"Nipa-Ester 82 '521" (mixture of methyl, ethyl, j

Butyl-r. and benzyl esters of p-hydroxybenzoic acid)!

as much as- required - · j

Perfume . ,. . ; - ... '. * _T 0.5 g '\

"Water, as much as necessary for. 100 gj

Example '10 ^r ■

Sun cream, strong protection ■ - ·

Hydrogenated, poloxyethylene palm oil 5 g, cetyl stearyl alcohol, 'condensed with 15 mol

Ethylene oxide "';' ■,, 5 g

Lanolin - 3g;

Lanolin Alcohols'. Ig

Litmus oil. . 5 g- ^:

Vaseline oil '*> ■ 10 g

Benzylidene camphor 2.5 g ι

4- [(2-.0xo-3-bornylidene) methyl] phenyl trimethyl:

ammonium methyl sulfate '... ^ ^,

409815/1125 i

- 28 - - 1

m / 12 708 2 3 U 7 9 2 8

Propylene glycol,

"Nipa-Ester 82 521" as much as required

Perfume 0.5 g

Water as much as needed for. 100 g

, Each of the compounds of the formula (I) can be in each of the in - ■ ; cosmetic agents mentioned in the above examples within a concentration range of 0.05 to 10% by weight, based on the compound or compounds of the formula (I).

A 0 9 8 1 5 £ 3 12 5

Claims (10)

Claims 1. Cosmetic agent, characterized in that it contains at least one compound of the general formula (I) as a protective agent against the light rays, - CH- (D wherein R is hydrogen or an alkyl group having 1 to 12 carbon atoms, Y is a halogen atom, a methyl group or a hydrogen atom, and X ~ a halide, 'an aryl sulfonate, an alkyl sulfonate, a camphor sulfonate or an alkyl sulfate mean. ,. · ■ 2. Agent according to claim 1, characterized in that it contains 0.05 to 10% compounds of the formula (i) in the form of a solution, emulsion, gel, dispersion or suspension. 3- Cosmetic agent according to claims 1 and 2 for protecting the Η3μτ against ultraviolet rays, characterized in that it contains 0.5 to 10 % compound of formula (I) mixed with cosmetic auxiliaries. ·· 4 0 9 8 15/1125 - 30 - . 4. Cosmetic agent according to claim 1 and 2, characterized in that it contains a.auser a photosensitive dye and cosmetic auxiliaries 0.05 to 10 % of compounds of the formula (I). .. ". · 5. Agent according to one of claims 1 to 4, characterized in that it is in the form of aqueous, alcoholic or aqueous alcoholic solution is present. 6. ', means according to claim 5, characterized in that the alcohol used is ethanol. 7. Agent according to one of claims 1 to 6, characterized in that it ¹ also contains a propellant and is conditioned so that it can be used in aerosol form. ■■. ■ 8. Agent according to .einem of claims 1 to 7, characterized characterized in that, in addition to the compounds of the formula (I), it contains at least one other UV filter. 9. Agent according to one of claims 1 to 8, characterized characterized in that it also contains at least one fat-soluble UV filter ... --- 31 ..-; 409815/1125 i M / 12 708 10. A method for protecting cosmetic agents which can be changed by light rays, characterized in that a compound of the formula (i) is taken up in amounts of 0.05 to 5 % in these solutions. Compounds of the formula N- - CH- wherein R is a hydrogen atom or an alkyl group having 1 to j 12 carbon atoms, Y is a halogen atom, a methyl group _; - mm ^V or a hydrogen atom, and X a halide, an aryl sulfonate, an alkyl sulfonate, a camphor sulfonate or an alkyl sulfate! mean. · ·. · ■ '' ι I - 32 0 $ β 1-5 / 1 1 2 5