JPS5929562B2 - Cosmetic composition containing a filtering polymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a cosmetic composition containing a novel ▲photosensitive, ie selective light blocking, polymer or copolymer, particularly a tanning cosmetic composition that tans the skin an attractive brown color. It is something.

When the human body is exposed to sunlight without special protection,
In some cases, it causes skin irritation, even burns of various degrees.

The ultraviolet rays that cause this inflammation are in the so-called “inflammatory zone,” or 2
This is light in the wavelength range between 80 and 315 nm.

The UV rays that have the effect of browning the skin are 315 to 400.
This is light in the wavelength range between 500 nm and 300 nm.

Therefore, if you want to tan your skin by exposing it to sunlight, you can filter out the UV rays in the inflamed area while allowing the wavelengths of light that are useful for tanning the skin to pass through. It is important to protect the skin with compositions containing such substances, which has the advantage of avoiding all burns.

Many substances have been proposed for this purpose, most of which are aromatic compounds having absorption in the wavelength range of 280 to 315 nm, particularly 295 to 305 nm.

▲In addition to photoactivity, these aromatic compounds must also have other properties, in particular they must not block light in the wavelength range of 315-400 nm, they must not be volatile, and they must be sweat resistant. It must also have good cosmetic properties for various cosmetic formulations, must not have a bad odor, and must be non-toxic and non-irritating.

Among these properties, the most important one is that it is non-toxic and usable from a dermatological point of view.

Aromatic compounds said to have such effects include para-aminobenzene derivatives, anthranilic acid derivatives, cinnamic acid derivatives, dihydroxy and trihydroxycinnamic acid derivatives, and coumarin derivatives.

Although these aromatic compounds are currently extremely widely used as photosensitive substances (filters), they are not without drawbacks.

In fact, some of these aromatic compounds do not have sufficient optical effects, nor do they have the necessary solubility for various formulations, and due to their low molecular weight they do not penetrate the human body through the epidermis of the skin. It can penetrate tissues and in some cases cause secondary side effects. In order to overcome the drawbacks of these aromatic compounds, it has been proposed to bind a photosensitive substance that selectively absorbs ultraviolet rays in inflammatory areas to the polymer chains of certain copolymers.

Among polymers of this type described in the literature, in particular 2-hydroxy-(3-acryloxy or methacryloxy-2-hydroxy-4-propoxy)benzophenone and methyl methacrylate or acrylic acid, methacrylic acid,
Examples include copolymers obtained by copolymerizing comonomers of unsaturated carboxylic acids such as itaconic acid and crotonic acid.

However, these copolymers cannot be used to create tanning agents with various formulations, and on the other hand, these copolymers only block part of the inflammatory wavelength range, so they cannot be used effectively as cosmetics. I couldn't find a way.

In fact, ▲Due to the type of functional groups that create the bond between the photoactive substance and the polymer chain, very few aromatic molecules are attached to the polymer chain, so that the selective light-blocking properties of aromatic molecules are always There was no way it could be preserved.

In order to compensate for these drawbacks, the inventors of the present invention have conducted intensive research and succeeded in synthesizing a new polymer or copolymer having excellent selective light-blocking properties or light properties.

This polymer or copolymer has molecules of known UV-absorbing aromatic compounds attached to the polymer chain by means of a special type of chemical functionality. Therefore, the present invention provides a photopolymer or copolymer having an ultraviolet absorbing ability in the range of 280 to 315 nm selected from the following formulas (1) to (7): It is an aromatic group imparted to the polymer and contains at least one of the following groups in the polymer chain. The present invention provides a cosmetic composition having the following characteristics.

The selective light-blocking polymers of the present invention can be used because the penetration of UV molecules through the skin can be avoided or significantly slowed down by attaching UV-absorbing molecules to the polymer chains. Its use as a cosmetic has many benefits. In fact, compounds that can have side effects on skin tissue are currently widely used as cosmetic solar brighteners, and for this reason, the photopolymer component of the composition of the present invention hardly penetrates the epidermis. It is important that it is not absorbed.

Since it is no longer necessary to pre-apply prophylactic compositions that protect the skin from low-molecular ▲photoactive compounds, it is desirable to use ▲photoactive polymers that do not penetrate into skin tissues in cosmetic compositions. It is easy to understand why this is advantageous.

The photopolymer used in the composition of the present invention also has many other advantages as described below.

The photopolymer used in the present invention generally has a molecular weight of 2,000 to 100
It has an average molecular weight of between 0,000 and 0,000.

The photopolymer used in the present invention may be a homopolymer or a copolymer. In the case of a homopolymer, the above formula (
It contains the group 1) as a repeating polymer unit, and the groups Z at this time are of the same type.

Also, does the photopolymer used in the present invention have different aromatic groups Z? It may also be a copolymer containing two or more of the groups I) as repeating polymer units.

The ability to use copolymers in which different types of aromatic groups Z are attached to the polymer chain is of great advantage. In other words, by selecting an appropriate number of aromatic groups z to be present in the copolymer molecule, only one type of copolymer can be used to absorb and block light throughout the inflammatory wavelength band. This can be a very effective solar irradiant. Furthermore, the photopolymer used in the present invention is a copolymer containing both a group of formula () having the same or different aromatic group z and one or more groups derived from an ethylenically unsaturated monomer or comonomer. It can also be a polymer or interpolymer.

The ethylenically unsaturated monomers or comonomers used in making this type of copolymer are selected depending on the use of the photopolymer used, or more precisely, on the purpose of making it. It is selected depending on the type of cosmetic composition to be used.

That is, the various properties of the photosensitive copolymer used in the present invention can be variously modified simply by selecting the type of comonomer constituting the polymer chain of the copolymer.

Examples of comonomers used in the production of this type of copolymer include the following, but the present invention is not limited thereto.

N-vinylpyrrolidone, N-methacryloyl-D-glucosamine, dimethylaminoethyl methacrylate, stearyl acrylate, stearyl methacrylate, methyl methacrylate.

Among these comonomers, some have the property of imparting water solubility to the photosensitive copolymer, and others have the property of imparting oil solubility.

A preferred example of the photosensitive copolymer used in the present invention is the following general formula: [where z has the same meaning as above, R represents a hydrogen atom or a methyl group, and Y represents the following formula: (X is methyl Group, D
- indicates a glucosamine group, a dimethylaminoethyl group that may be quaternized, or a group (representing Cl8H37)]
It is expressed as

The proportion of the comonomer used in the production of the photosensitive copolymer used in the present invention varies, but is generally in the range of 20 to 90% based on the total weight of the copolymer.

The photopolymer used in the present invention can generally contain groups of formula (1) in a content ranging from 10 to 100% based on the total weight of the polymer. As already mentioned, the content of groups of formula () can vary within a very wide range and will vary depending on the intended use of the particular polymer.

The photopolymer used in the present invention has the following formula: [wherein Z is an aromatic group within the range described above that provides the desired polymer or copolymer with ultraviolet absorption ability within the range of 280 to 315 nm. In the first step, an unsaturated compound represented by It is produced by copolymerizing an unsaturated compound with at least one comonomer.

The monomeric unsaturated compound represented by the formula is prepared by a conventional method by reacting N-methylol acrylamide with an aromatic compound Z in a cold sulfuric acid medium, and the reaction time is about 10 hours at room temperature. It will take about 4 days.

The polymerization reaction is carried out according to the general method of polymerization.

That is, polymerization is performed using solid polymerization, solution polymerization, suspension polymerization, or emulsion polymerization. It is desirable to carry out solution or suspension polymerization. A general radical polymerization initiator is used as the polymerization initiator, and the choice of which one to use depends mainly on the type of monomer used and the reaction medium.

Among the various initiators that may be used, in particular peroxides such as benzoyl peroxide, lauroyl peroxide, acetyl peroxide, tertiary butyl hydroperoxide, benzoyl hydroperoxide; such as azobisisobutyronitrile. Catalysts which decompose to generate inert gases; redox catalysts such as sodium persulfate; sodium sulfide and hydrogen peroxide may be mentioned. The concentration of initiator generally ranges from 0.2 to 35%, preferably from 0.5 to 20%, based on the total weight of monomers. The molecular weight of the photopolymer used in the present invention is determined by the amount of aldehydes such as butyraldehyde or a small amount (0.05 to 0.15 % by weight) during the polymerization. After polymerization,
If desired, the resulting polymer can be purified by means such as treatment with an ion exchange resin.

The cosmetic composition of the present invention can be made into various dosage forms depending on its use.

The compositions of the present invention include aqueous emulsions, lotions, creams,
Preferably, it is used in the form of an emulsion, gel or aerosol. The compositions of the invention may also be used in the form of aqueous solutions, hydroalcoholic solutions (ethanol or isopropanol) or oily solutions. When the composition of the present invention is used in the form of an aerosol, it is enclosed in a pressure container together with an atomizing gas, and the atomizing gas is a halogenated hydrocarbon or a halogenated hydrocarbon such as a mixture of trichlorofluoromethane and dichlorodifluoromethane. Preferably, a mixture of hydrocarbons is used.

The concentration of photopolymers as described above in the cosmetic compositions of the present invention will vary depending on the degree of protection intended.

However, it is generally desirable that the photopolymer concentration be in the range of 0.2 to 20% based on the total weight of the composition. The compositions of the present invention may further contain common ingredients such as fats (oils, greases, waxes), emulsifiers, surfactants, fragrances, silicone oils, pigments, dyes and preservatives.

Addition of coloring pigments to the compositions of the present invention can color the epidermis, thereby masking skin imperfections.

When the composition of the present invention is used on the skin, it forms a film with good affinity for the epidermis and exhibits an excellent protective effect against the sun's ultraviolet rays included in the inflammatory wavelength range.

The glossy polymer, which is a feature of the present invention, is hardly absorbed through the skin, and this was confirmed by the following experiment.

Five male rabbits weighing approximately 2.2K9 each with a skin diameter of 2C7 on the abdomen! 8 circular exposed locations of l are provided.

Twelve of these areas will be covered with opaque tape to protect them from UV rays.

- Two locations are not protected in any way. 0.1 ml of the test compound was applied to the two locations immediately before UV irradiation.

12 locations were treated with 0.1 m of test compound 3 hours before UV irradiation.
Apply 1.

Ultraviolet irradiation was performed for 5 minutes using a lamp with a wavelength of 290 nm located at a distance of 30 CWL from the abdomen of the test rabbit.

The compound of Example 6 (homopolymer of 3-(acrylamidomethylbenzylidene)-D/L-ganfer) was used as a test compound, and as a comparative example, benzylidene-D which was not bonded to the polymer was used as a photopolymer of the present invention. -L-ganfer was selected, dissolved in paraffin oil, and applied to the above circular area.

24 hours after the above irradiation experiment, the anti-ultraviolet activity of the test compounds was determined by the inhibition rate of increase in capillary permeability.

The following results were obtained. The compound of Example 6 (invention) showed a 17% reduction in anti-UV activity when applied 3 hours prior.

The comparative compound also showed a 63% decrease in anti-UV activity when applied 3 hours earlier.

On the other hand, when liquid solutions of both test compounds were simply applied onto a glass plate, the decrease in anti-ultraviolet activity measured by the rate of decrease in absorption of ultraviolet light at 290 nm was about 10% after 3 hours in both cases. These test results indicate that most of the decrease in anti-UV activity of the active compound not bound to the polymer chain (comparative example) is not due to decomposition of the active compound, but is due to its absorption through the skin. On the other hand, it is clearly observed that the photopolymer of the present invention is hardly absorbed through the skin.

Furthermore, the toxicity of the photopolymers of Examples 2, 6, and 17 was investigated by applying them to the skin of rabbits and humans. As a result, no signs of toxicity were observed in rabbits, and there was no skin irritation in humans. It was not detected and no abnormality was observed.

In addition to its protective effect on the epidermis against the sun's ultraviolet rays, the photopolymer of the present invention can be included in various cosmetics, such as coloring compositions, nuance compositions, and hair styling lotions. It can also be used to protect dyes from deterioration.

In the following, a number of production examples of the photopolymer used in the present invention and a number of examples of cosmetic compositions containing the photopolymer used in the present invention are given for explanation, but these are not intended to limit the present invention in any way.

Example 1 3-Acrylamidomethyl-4-hydroxybenzophenone 500 equipped with a cooler, nitrogen introduction tube and stirrer
Pour 19.87 m of benzophenone dissolved in 70 f7 of sulfuric acid into a flask, and add 107 m of N while cooling.
- Add methylol acrylamide in portions.

The mixture was stirred vigorously to homogenize, resulting in a bright yellow solid.

Stirring is continued for 36 hours and then the solution is left at room temperature for 48 hours. The mixture is precipitated into a mixture of water and ice, and the precipitate is dried, washed and extracted with ether.

Wash the organic layer with water until neutral. After drying the ether phase, the ether is driven off and the 3 residue is dried in vacuo. Recrystallization twice from acetone gives pure product 20f.

Melting point -159°C λNlaXl in EtOH 236 nm,. Ksp=E
λMax2=296 nm during t0H, . Ksp example 23
- Preparation of a copolymer of acrylamide methyl-4-hydroxy-benzophenone and stearyl methacrylate. A solution of phenone, 1.57 g of stearyl methacrylate and 0.25 f7 of azobisisobutyronitrile in 5 ml of acetone is introduced.

The mixture is heated to 80° C. for 8 hours. Dilute with acetone,
The copolymer is precipitated in methanol.

A pure copolymer of 167 was obtained.

λMax-295nm in hexane, . Ksp example 33-
Preparation of Acrylamidomethyl-4-Methoxy-2-Hydroxy-benzophenone.22.
Add a solution of 4-methoxy-2-hydroxybenzophenone (No. 87) dissolved in sulfuric acid (No. 607), and add N-methylolacrylamide (No. 107) little by little.

The solution is stirred for 24 hours and then left at room temperature for 2 days.

When the mixture is added to ice a light brown precipitate forms which is dried and washed with water and ethyl acetate.

After drying, the product is recrystallized from isopropanol. Melting point = 194°C λN lax in CHCl3 - 293 nm,. Ksp Example 4 Preparation of a copolymer of 3-acrylamidomethyl-4-methoxy-2-hydroxy-benzophenone and stearyl methacrylate. In 11 reactors equipped with a mechanical stirrer, a condenser and a calcium chloride tube, 3 of 120y. -(acrylamidomethylbenzylidene)-D. L-ganfer is dissolved in 2407 pure sulfuric acid.

After dissolution, 17 sodium nitrite is added and the mixture is cooled in an ice bath. When the internal temperature reaches 0°C, add 5 to this
Add 6f7 N-methylolacrylamide over 1 hour.

The mixture is kept at room temperature with stirring for 48 hours. The brown viscous solution is slowly added to a mixture of 500 y of ice and 500 y of water with vigorous stirring.

A light beige precipitate is obtained which is collected, washed with water and dissolved in 500 ml of ethyl acetate.

The organic layer is washed with water until the washing solution becomes neutral, and then dried with anhydrous sodium sulfate.

. After filtration and evaporation of the solvent, the product is dried under reduced pressure to give 607 oil, which is allowed to cool and crystallize.

The crude product is washed with 90 ml of diethyl ether.

Dehydration and drying of the remaining solid gives the product 317, which is recrystallized from carbon tetrachloride (28f7). Melting point 134°C λMax-295nm in CHCl3,. Ksp=Example 6
3-(acrylamidomethylbenzylidene)-D. L-
Preparation of Ganfer's Homopolymer In a 25 ml flask equipped with a condenser, a nitrogen inlet tube and a stirrer, the above 3-(acrylamidomethylbenzylidene)-D. Add L-Gamphir 4y and Azobisisobutyronitrile 0.47.

The mixture is heated under methanol reflux for 24 hours and, after cooling, the precipitated homopolymer is dissolved in chloroform. Add this solution to methanol, filter the precipitated polymer,
Drying under reduced pressure gives 2.57 product.

λMax-296 nm, . in CHCl3. Ksp example 7
3-(acrylamidomethylbenzylidene)-D. L-
Production of copolymer of gunfer and stearyl methacrylate 100m1 equipped with a cooler, nitrogen inlet pipe and stirrer
607 of 3-(acrylamidomethylbenzylidene)-D. dissolved in acetone in a flask of Add L-Gamphir 157, Stearyl Methacrylate 157 and Azobisisobutyronitrile 3y.

The solution is heated to 80° C. for 24 hours with stirring. After cooling, the polymer precipitates and is filtered. The polymer is dissolved in heptane and then added to the absolute ethanol of 21 to precipitate it to obtain a pure product of 15y. λMa in heptane
x=291 nm,. Ksp example 83-(acrylamidomethylbenzylidene)-D. Preparation of a copolymer of L-ganfer and dimethylaminoethyl methacrylate quaternized with dimethyl sulfuric acid In a 250 ml flask equipped with a condenser, a nitrogen inlet tube and a stirrer, 15y of 3-(acrylamidomethylbenzylidene)- D. L- Ganfer,
Add 5y dimethylaminoethyl methacrylate, 2y azobisisobutyronitrile, and 407 dioxane.

The liquid solution was stirred at 80° C. for 24 hours, and then 57 dimethyl sulfate dissolved in 207 methanol was added.

The temperature is maintained at 80° C. for 4 hours and the polymer is precipitated in ethyl acetate of 21 to yield the desired copolymer of 177.

λMax=295nm1KSP= in EtOH+H2O
25500 Example 9 3-(acrylamidomethylbenzylidene)-D. L-
Production of copolymer of gunfer, methyl methacrylate, and dimethylaminoethyl methacrylate quaternized with dimethyl sulfuric acid 10 equipped with a cooler, nitrogen inlet tube, and stirrer
In a 0me flask, 87 3-(acrylamidomethylbenzylidene)-D. Add L-gamphor, 8y methyl methacrylate, 8y dimethylaminoethyl methacrylate, 0.24y azobisisobutyronitrile, and 24y absolute ethanol.

The solution was stirred at 80°C for 10 hours, then 57 dimethyl sulfate dissolved in 2.5y methanol was added, and the temperature was lowered to 80°C.
Hold at ℃ for 4 hours.

Precipitation of the copolymer in ethyl acetate gives 227 pure product.

λNlax=295nm1KsP in EtOH+H2O
-8500 Example 10 3-(acrylamidomethylbenzylidene)-D. L-
Preparation of Copolymer of Ganfer and N-vinylpyrrolidone In a 2.5 ml flask equipped with a condenser, a nitrogen inlet tube and a stirrer, 0.5y of 3-(acrylamidomethylbenzylidene)-D. Charge L-ganfer, 27% N-vinylpyrrolidone, 0.157% azobisisobutyronitrile, and 3y ethanol.

The mixture was heated to 80°C for 8 hours, then ethyl ether,
Precipitation of the copolymer by addition to a 8:1 mixture of isopropanol gives a pure 1.5y copolymer. Et
λNlax = 298 nm in OH+H2O, Ksp-1
8100 Example 11 3-(acrylamidomethylbenzylidene)-D. L-
Production of copolymer of Ganfer, methyl acrylate, and dimethylaminoethyl methacrylate quaternized with dimethyl sulfuric acid 250 equipped with a cooler, stirrer, and nitrogen inlet tube
m1 flask, 12y of 3-(acrylamidomethylbenzylidene)-D. L-ganfer, 87 dimethylaminoethyl methacrylate, 87 methyl acrylate, 0.3y azobisisobutyronitrile and 2
.

Add 8y of absolute ethanol.

The liquid solution is heated to 80° C. for 8 hours and then cooled, 77 dimethyl sulfate dissolved in methanol is added thereto, and the solution is heated to 80° C. for 24 hours.

The copolymer is precipitated by adding it to a 50:50 mixture of ethyllidioxane acetate to obtain a pure copolymer of 24y. λMax-295nm1K in EtOH+H2O
sp=17800 Example 12 3-(acrylamidomethylbenzylidene)-D. L-
Production of copolymer of gunfer and N-methacrylic-D-glucosamine 5 equipped with a stirrer, nitrogen inlet tube and cooler
In a 0 ml flask, 5y N-methacryl-D-glucosamine, 5y 3-(acrylamidomethylbenzylidene)-D. Charge L-Gamphir, 0.57 azobisisobutyronitrile and 30y dimethyl formate.

Heat the solution to 80° C. for 24 hours. The copolymer was precipitated by adding it to water, cooled with a mixture of 50:50 ethanolimethanol, and 8% ethyl ether lysipropanol.
: Precipitation in a mixture of 1 to 67 gives a pure copolymer of 67.

λMax=297nm1Ksp- in EtOH+H2O
24200 Example 13 3-(acrylamidomethylbenzylidene)-D. L-
Preparation of Copolymer of Ganfer and Stearyl Acrylate In a 10 ml flask equipped with a condenser, a nitrogen inlet tube and a stirrer, 1.6 f7 of 3-(acrylamidomethylbenzylidene)-D. Charge L-Gamphir, 0.67 stearyl acrylate, 0.27 azobisisobutyronitrile and 3y acetone.

The solution is heated under reflux for 18 hours. 250WL of polymer
Precipitation of I in methanol gives 0.8y pure copolymer. λMax in CH3Cl=295
nm,. Ksp example 143-(acrylamidomethylbenzylidene)-D. Production of copolymer of L-ganfer, stearyl methacrylate, and methyl acrylate 10! Equipped with a cooler, nitrogen inlet tube, and stirrer! In a flask of RL1, 1.27 of 3-(acrylamidomethylbenzylidene)-D. L-ganfer, 0.67 stearyl methacrylate, 0.27 methyl acrylate, 0
．． Add 2y of azobisisobutyronitrile and 37% of acetone, and keep the filtrate at 80°C for 18 hours.

Then diluted with 10ml of heptane and then diluted with 500WLt.
of methanol gives a pure copolymer of 1.37. λMax-295 nm in CHCl3, . Ksp example 153-(acrylamidomethylbenzylidene)-D.
Preparation of copolymer of L-ganfer, stearyl acrylate and methyl acrylate In a 10 ml flask equipped with a condenser, a nitrogen inlet tube and a stirrer, 1.2 f of 3-
(acrylamidomethylbenzylidene)-D. L-ganfer, 0.6y stearyl acrylate, 0.2y
of methyl acrylate, 0.27 of azobisisobutyronitrile and 37 of acetone.

The solution was refluxed for 18 hours, then diluted with 10 ml of heptane and precipitated into 500 ml of methanol to give a 0.8y copolymer. λNl in CHCI3
ax=294nm,. Example of Ksp Preparation of 163-acrylamidomethyl-J[hydroxy-14-methylcoumarin] In a 250a flask equipped with a condenser, nitrogen inlet tube and stirrer, 17.67 parts of 7-hydroxy-14-methylcoumarin and 60 f7 of ice were added. Add cooled pure sulfuric acid and add 1
Add 07 N-methylolacrylamide.

The mixture is stirred for 2 days at room temperature and then left for 2 days.
The resulting precipitate is dissolved in ethyl acetate, washed with water, and dried under reduced pressure.

Recrystallization from ethanol gives 10t of pure product.
λMax = 323 nm in CHCl3 Example 17 Preparation of a copolymer of 3-acrylamidomethyl-J-hydroxy-4-methylcoumarin and stearyl methacrylate In a 50 Wt flask equipped with a condenser, a nitrogen inlet and a stirrer, 17 3-acrylamide methyl-J me
[Hydroxy-4-methylcoumarin, 27 stearyl methacrylate, 0.3t azobisisobutyronitrile and 6? Add DMF.

After heating the mixture to 80 DEG C. for 8 hours, the solution is diluted with benzene and the copolymer is precipitated in methanol to yield 1.2 f/p of pure copolymer. λN in hexane
lax=324nm,. Ksp = Example 18 3-(acrylamidomethyl)-4-hydrosigmarin production cooler;
In a 250 ml flask equipped with a nitrogen inlet and a stirrer, 16.2 f 4-hydroxycoumarin is dissolved in 507 g pure sulfuric acid.

The reaction is exothermic and the temperature rises to 80°C. Cool to 0° C. with an ice/salt mixture and then slowly add 11 tf) N-methylolacrylamide. Next, the temperature is returned to room temperature, and stirring is continued for an additional 4 days. When the solution is added to an ice/water mixture, the product precipitates as a beige powder, which is dehydrated, washed with water, dried under vacuum, and recrystallized from ethanol to give 15r of the product. obtain.

Melting point = 194°C λMaxl in EtOH+H2O = 28
8nm, Ksp=48000λM in Et0H+H2O
ax2 = 304 nm, Ksp = 50000 Example 19 Preparation of homopolymer of 3-(acrylamidomethyl)-4-hydroxycoumarin In a 50 d flask equipped with a condenser, a nitrogen inlet tube and a stirrer, 2.5 f of 3-( Acrylamidomethyl)-4-hydroxycoumarin, 0.25P
of azobisisobutyronitrile and 15- of DMF.

The mixture is heated to 100° C. for 24 hours and then precipitated into lukewarm dichloromethane to yield a 0.6y homopolymer. λMax in MeOCH2CH2OH=3
10 nm 1 Ksp = 14200 Example 20 Production of copolymer of 3-(acrylamidomethyl)-4-hydroxycoumarin and N-vinylpyrrolidone Cooler,
In a 50 WLI flask equipped with a nitrogen inlet tube and a stirrer, 3f 3-(acrylamidomethyl)-4-hydroxycoumarin, 7y N-vinylpyrrolidone, 0.5
Add 7 parts of azobisisobutyronitrile and 107 parts of DMF.

Heat to 100° C. for 24 hours and then add to dimethyl ether.

The solution is filtered and the precipitate is redissolved in methanol and cooled in nitromethane to yield pure copolymer 37. Et
λMaxl in OH=282 nm, . λMax2-305 nm in KspEtOH, . Ksp Example 21 Preparation of a copolymer of 3-(acrylamidomethyl)-4-hydroxycoumarin and dimethylaminoethyl methacrylate quaternized with dimethyl sulfuric acid In a 50 ml flask equipped with a condenser, a nitrogen inlet tube and a stirrer, 77 3-(acrylamidomethyl)-4-hydroxycoumarin, 3y dimethylaminoethyl methacrylate quaternized with dimethyl sulfate, 17 azobisisobutyronitrile and 30V
f) Add DMF.

The mixture is heated to 100° C. for 24 hours and then poured into lukewarm dichloromethane. After drying, a pure copolymer of 5V is obtained. λMaxl in H2O=302 nm, . λMax2 in Ksp-H20 = 290 nm, . Ksp=Example 22
stearyl acrylate, 3-(acrylamidomethyl)-4-hydroxycoumarin, 3-acrylamidomethyl-4-hydroxy-benzophenone, and 3-(acrylamidomethylbenzylidene)-D. Preparation of copolymer with L-ganfer In a 50 ml flask equipped with a condenser, a nitrogen inlet tube and a stirrer, 2f of 3-(acrylamidomethyl)-4-hydroxycoumarin, 1f of 3-(acrylamidomethyl)-4 -Hydroxy-benzophenone,
0.5f7 of 3-(acrylamidomethylbenzylidene)-D. L-ganfer, 3.5y stearyl acrylate, 0.7y azobisisobutyronitrile and 1
5ff) Add DMF.

The mixture is heated at 80 DEG C. with stirring for 24 hours, then diluted with chloroform, filtered, and precipitated into 800 ml of lukewarm acetone. ▲ Copolymer
After filtering, washing and drying under reduced pressure, a pure product of 4.17 is obtained.

λMOI in CHCl3 - 284 nm. Ksp=CHC
λNlax2 in 13 = 298 nm, . Ksp example 23
-24 Acrylamidomethyl compounds having the groups of the formulas (6) and (7) as the group Z were prepared in the same manner as in Examples 1, 16 and 18.

Maximum ultraviolet absorption wavelength λNlax of the obtained monomer compound
is as follows. The light-absorbing ability of the copolymer produced in the above example, which indicates photoactivity, is defined by Ksp, which is determined by the concentration of the photosensitive substance contained in the sample, the measured optical density, and a constant specific to the device. is a function of The definition of Ksp is given by Gillan and Stern “IntrOd
uctiOntOelectrOnicabsOrpt
iOn◆●●NspectrOscOpyinOrga
nickchemistryl (ArnOld Publishing, London, 1954, p. 10).

d = measured optical density 1 = liquid length in the device cell ((V7!) Examples of the cosmetic composition of the present invention are shown below.

Example A A tanning oil (sun oil) is prepared according to the invention by mixing the following ingredients.

Polymer produced according to Example 2...10r fragrance
...0.57 Vaseline oil (appropriate amount) ...100y in total In this example, the copolymer of Example 2 was used as the copolymer of Examples 4, 7, 17, 22
can be replaced with any of the same amounts of copolymers prepared in .

Example B A tanning lotion is prepared according to the invention by mixing the following ingredients.

In this example, the polymer of Example 13 was combined with Examples 14, 15,
22 can be substituted with one of the same amounts of copolymers prepared by any of the following.

Example C A tanning aerosol composition is prepared according to the invention by mixing the following ingredients.

Copolymer produced according to Example 13
5f7 Anhydrous ethyl alcohol ・・・・・・・・・
・・・30f isopropyl palmitate ・・・・・・
...20y sesame oil...
・・・・・・ 2y lanolin
・・・・・・・・・ 2y fragrance ・・・・・・
...17 In this example, the copolymer prepared according to Example 13 can be replaced by the same amount of the copolymer prepared according to Example 22.

Example D A tanning aerosol foaming cream is prepared according to the invention by mixing the following ingredients.

Copolymer produced according to Example 4...10V
Stearic acid ・・・・・・ 0.
57 Palmitic acid ・・・・・・
0.5r Vaseline oil...
・45.7tp-hydroxybenzoic acid ethyl ester
・・・・・・ 0.3y
Triethanolamine ・・・・・・ 1,
5t fragrance...0.5f7 The above composition 857 is sealed in an aerosol bomb along with 137 Fl2 (dichlorodifluoromethane).

In this example, the copolymer made according to Example 4 can be replaced with the same amount of copolymer made according to either Example 7 or 17.

Example E A tanning cream is prepared according to the invention by mixing the following ingredients.

In this example, the polymer produced according to Example 15 can be replaced by the same amount of the polymer produced according to Example 14, again yielding an excellent tanning cream.

Example F A sunscreen emulsion is prepared according to the invention by mixing the following ingredients.

In this example, the polymer produced according to Example 8 was:
It can be replaced by the same amount of polymer prepared by any of Examples 9, 10, 11 and 12.

Example H A cosmetic emulsion is prepared according to the invention by mixing the following ingredients.

Example 1 A cosmetic composition is prepared according to the invention by mixing the following ingredients.

Claims (1)

[Claims] Primary formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) (1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (2) ▲ Numerical formulas, chemical formulas,
There are tables, etc. ▼ (3) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ R = H or CH_3 R_1 = CH_3 or OCH_3 (4) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (5) ▲ Mathematical formulas, chemical formulas, tables, etc. There are ▼ (6) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (7) ▲ There are mathematical formulas, chemical formulas, tables, etc. At least one of the filtering polymers or copolymers containing at least one of the following aromatic groups in the polymer chain is blended into an appropriate cosmetic medium. It is characterized by:
Cosmetic composition.