JPS5825324B2 - Light-shielding polymer, method for producing the same, and cosmetic composition containing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel light-blocking polymer, a method for producing the same, and a cosmetic composition containing the same.

According to the present invention, a light-shielding compound containing at least one repeating polymer unit corresponding to the following formula (■): (representing a group represented by) and having an average molecular weight in the range of 2,000 to 1,000,000 A polymer is provided.

This new polymer is capable of producing ultraviolet rays in the ``inflammation zone'' (280 to 3
It has the characteristic of absorbing not only light in the wavelength range (between 15 nm) but also light in the wavelength range (up to 350 nm) that browns the skin, so it can prevent burns caused by sunlight and 280 to 350 nm.
It is possible to simultaneously and generally protect against the effects of ultraviolet radiation between 100 nm and 200 nm.

The novel polymer of the present invention is a light-shielding copolymer (dipolymer, terpolymer, etc.), that is, a polymeric unit of the formula (n) and other polymeric units derived from an ethylenically unsaturated monomer. It is desirable to contain one or several kinds at the same time.

The ethylenically unsaturated monomer or comonomer used in preparing the copolymer of the present invention is selected depending on the type of cosmetic composition to be prepared.

In fact, by changing the type of comonomer, it is possible to impart various properties to the light-shielding copolymer.

Examples of preferred comonomers include, inter alia, N-vinylpyrrolidone, N-methacryloyl-D-glucosamine, dimethylamine ethyl methacrylate, stearyl acrylate, stearyl acrylate, vinyl stearate.

The former three types of comonomers provide solubility in aqueous solutions, and the latter three types provide solubility in oil.

A preferred copolymer of the present invention has the following general formula: [wherein Z1 has the same meaning as above, R' represents a hydrogen atom or a methyl group, and Y represents the following formula: (wherein, X is a quaternized or a non-quaternized dimethylaminoethyl group or Cl8H3□, and (wherein A is a glucosamine residue) a repeating unit represented by a group selected from the group of is 2,000 to 1,000,0
It is in the range of 00.

According to the present invention, the light-shielding polymer generally contains groups of formula (II), that is, polymerized units, in an amount of 15 to 100 based on the total weight of the polymer.
%, preferably in the range of 20 to 80%.

The present invention relates to a method for producing novel light-shielding polymers of formulas (II) and (ll[).

That is, in the present invention, in the first step, the following formula: % formula %
() (in which Z1 has the same meaning as below) is prepared as a so-called "furnace photosensitive monomer", and then this monomer is homopolymerized or copolymerized with one or more other comonomers. A light-shielding polymer containing at least one polymerized unit of the following formula ■: (wherein Z1 represents a group represented by the following formula: or) or the following formula ■: [wherein Z1 represents a group represented by the following formula: Z1 has the same meaning as above, R' represents a hydrogen atom or a methyl group, and Y represents the following formula: (However, X represents a quaternized or non-quaternized dimethylaminoethyl group or Cl8H37) The present invention also provides a method for producing a light-shielding copolymer having a repeating unit selected from the group consisting of: and (where A is a glucosamine residue).

The p-photomonomer is prepared by cold reaction of N-methylolacrylamide and aromatic compound Z1H in the presence of sulfuric acid.

The above polymerization reaction is carried out by a conventional polymerization method, that is, bulk polymerization,
It is carried out by solution, suspension or emulsion polymerization using conventional polymerization initiators.

The molecular weight of the light-shielding polymer of the present invention is determined by aldehydes such as butyraldehyde, chloroform, bromoform,
This can be controlled by adding small amounts (0.05 to 0.15% by weight) of chain length regulators such as chlorides such as carbon tetrachloride during the polymerization.

At the end of the polymerization, if desired, the resulting polymer can be purified, for example by treatment with an ion exchange resin.

The present invention also provides a sunscreen cosmetic composition containing at least one of the above-mentioned polymers of repeating units of formula (1) or copolymers of repeating units of formula (2) as a UV-active substance. It is also a gist of things.

The cosmetic compositions of the present invention can be made into various forms depending on the intended use.

Preferably, the composition is used in the form of an aqueous emulsion, lotion, cream, emulsion, gel or aerosol.

The compositions may also be used in the form of aqueous, hydroalcoholic (ethanol or isopropanol) or oily solutions.

When the composition of the invention is used in the form of an aerosol,
Preferably, the atomizing gas is enclosed in a bellows vessel, and the atomizing gas is a halogenated hydrocarbon or a mixture of halogenated hydrocarbons, such as a mixture of trichlorofluoromethane and dichlorodifluoromethane.

The concentration of light-blocking polymers as described above in the cosmetic compositions of the invention will vary depending on the degree of protection desired.

However, it is generally desirable that the concentration of the light blocking polymer be in the range of 0.2 to 20% based on the total weight of the composition.

The compositions may also contain common ingredients such as fats (oils, greases, waxes, etc.), emulsifiers, surfactants, fragrances, silicone oils, pigments, dyes, and preservatives.

Addition of coloring pigments to the composition can color the epidermis, thereby masking skin imperfections.

When the cosmetic composition of the present invention is used on the skin, it forms a film that has good affinity for the epidermis and exhibits an excellent skin protection effect against sunlight.

In the following examples, the UV absorption capacity of the manufactured photochromic material is defined by Ksp, which is a numerical value related to the amount of photochromic material contained in the sample, the measured absorbance and constants specific to the apparatus. It is.

The definition of Ksp is by Gillam and 5tern” I
introduction to electronic
absorption spectroscopy i
organic chemistry” (Arno
(ed., London, 1954, p. 10).

d = absorbance that can be measured l - Thickness of the sample container of the device, α The present invention will be explained below with reference to Examples.

Reference Example: A photosensitive monomer of the following formula, 2-((2'-hydroxy-5'-methylacrylamidemethyl)phenylcy 2
Preparation of H-benzotriazole: 192 g of pure sulfuric acid and 72 g of 2-((2'-hydroxy-5'-methyl)phenyl)-2H-benzotriazole are placed in a flask under nitrogen.

The mixture is cooled to 0 DEG C. and then 31.5 g of N-hydroxymethylacrylamide are added.

Allow to return to room temperature and then continue stirring for 18 hours.

Pour the mixture into water and separate in the oven.

Recrystallization in chloroform gives 55 g of pure product.

Yield: 56% Melting point -204°C λmaxl(THF) -302nm, Ksp=55
,000λmax2(THF)-339nm Ks
p=57,000 Acrylamidomethyl derivatives of 2-phenylbenzimidazole can be produced in a similar manner.

Example 1 2-[(acrylamidomethyl-27-hydroxy-5
Preparation of copolymer of N,N-dimethyl-2-aminoethyl methacrylate quaternized with dimethyl sulfate and N,N-dimethyl-2-aminoethyl methacrylate quaternized with dimethyl sulfate , 8 g of N,N-dimethyl-2-aminoethyl methacrylate quaternized with dimethyl sulfate, dimethylformamide (DMF) 2
0 g and 1 g of azobis-isobutyronitrile are placed in the flask under nitrogen.

The mixture was heated to 80 °C for 24 h and then cooled to 20 °C.
Dilute with TLl methanol and pour dropwise into 500 ml acetone.

The polymer is separated and dried on top and bottom.

8 g of water-soluble copolymer are obtained. Yield: 80% λmax1(DMF)-298nm, Ksp=6
,200λmax2(DMF)-335nm, K
sp=5,200 A copolymer of an acrylamide methyl derivative of 2-phenylbenzimidazole and N,N-dimethyl-2-aminoethyl methacrylate quaternized with dimethyl sulfate can be produced in a similar manner.

Example 2 2-[(acrylamidomethyl-2'-hydroxy-5
7-Methyl)phenyl:]-]2H-Pentztriazo and stearyl acrylate copolymer production: 50.9 g of the photosensitive monomer prepared in the above reference example, 33.4 g of stearyl acrylate, tetrahydrofuran (T
HF) 150 g and azobis-isobutyronitrile 5
Put g into the flask.

The mixture is heated to 80° C. for 9 hours and then poured into 71 methanol.

After separating in a furnace and drying under a reduced temperature, 70g of oil-soluble copolymer
is obtained.

Yield: 85% λmax1(THF)-303nm, Ksp=28
,300λmax2(THF)-339nm, Ks
p=28,000 A copolymer of an acrylamide methyl derivative of 2-phenylbenzimidazole and stearyl acrylate can be produced in a similar manner.

Example 3 Production of copolymer of 2-((2'-hydroxy-5'-methyl-acrylamidomethyl)phenyl)-2H-benzotriazole and vinyl stearate 6.6 g of vinyl stearate, 2-((2 13.3 g of '-hydroxy-5'-methyl-acrylamidomethyl)phenyl)-2H-penztriazole and 2 g of azobisisobutyronitrile were dissolved in dimethylformamide.
Dissolve in 200 ml of a 50:50 mixture of tetrafuran and then heat to reflux temperature for 24 hours under an atmosphere of nitrogen.

The reaction mixture is then poured into 21 methanol and the precipitated copolymer is dried (50% yield).

Ultraviolet absorption spectrum: λmax1 (CHCA3) - 304 nm λmax2 (CHC13) - 338 nm Example 4 Co-existence of 2-((2'-hydroxy-57-methyl-acrylamidomethyl)phenyl)-2H-benzotriazole and N-vinylpyrrolidone Preparation of polymer 2-((2'-hydroxy-5'-methyl-acrylamidomethyl)phenyl)-2H-benzotriazole 1
2.9 is dissolved in 80.9 g of N-methylpyrrolidone, and then 28 g of N-vinylpyrrolidone is added.

This mixture is heated to 80° C. under an atmosphere of nitrogen.

The resulting crude solution is poured into 31 parts of toluene, and the precipitated copolymer is collected and dried (77% yield).

Ultraviolet absorption spectrum: λrn aX 1 (ethanol) - 303 nm λm
aX 2 (ethanol) = 338 nm Example 5 Preparation of copolymer of 2-((2'-hydroxy-57-methyl-acrylamidomethyl)phenyl)-2H-penztriazole and N-methacryloylglucosamine 2-((2 '-Hydroxy-57-methyl-acrylamidomethyl)phenyl)-2H-benzotriazole8
g and 32 g of N-methacryloylglucosamine are dissolved in 20.9 g of N-methylpyrrolidone, and 2 g of azobisisobutyronitrile is added.

After heating to 80° C. for 24 hours under an atmosphere of nitrogen, the crude solution was poured into toluene and the precipitated copolymer was collected;
Dissolve in 150 ml of N-methylpyrrolidone.

The resulting solution is dialysed against water for 24 hours.

By concentrating this aqueous solution, 23 g of pure copolymer is obtained (60% yield).

Ultraviolet absorption spectrum: λrnaX1 (ethanol) = 303nmλrnaX
2 (ethanol) = 338 nm or less The cosmetic composition of the present invention will be explained with examples.

Example I A light-blocking (sunscreen) cream is prepared by mixing the following ingredients.

Polymer produced according to Example 1...1
5.9 Cetylstearyl alcohol...
...2g glycerol monostearate...
・・・・・・ 4g cetyl alcohol ・
・・・・・・・・・ 4g Vaseline oil
・・・・・・・・・ 5g butyl stearate
・・・・・・・・・ 5g Propylene glycol ・・・・・・・・・ 79 Silicone oil
・・・・・・・・・0.125gU
A 5% aqueous solution of a high molecular weight nonionic polymer commercially available from NIONCARBIDE under the trade name POLYOX.
3.5gp-hydroxybenzoic acid methyl ester...
・・・・・・0.3g fragrance
・・・・・・・・・0.5g water ・
・・・・・・Amount to make the whole 100g Example ■ The following ingredients are mixed to produce a light-shielding oil (for sunscreen).

Claims (1)

[Scope of Claims] It is characterized by containing at least one repeating polymer unit of the primary formula (■: representing a group represented by) and having an average molecular weight in the range of 2,000 to 1,000,000. A light-shielding polymer. 2nd formula ■: [In the formula, Z represents a group represented by the following formula: R' represents a hydrogen atom or a methyl group, Y represents the following formula: (However, X is a quaternized or non-quaternized (represents a dimethylaminoethyl group or Cl8H3□) and (represents a group selected from the group of groups) (where A is a glucosamine residue), and has an average molecular weight of 2,000 to 1,0σo,oo. A light-shielding copolymer characterized by being in the range of. 3 15 to 100%, preferably 20 to 80% by weight of repeating polymer units having light-shielding properties based on the total weight of the copolymer
The copolymer according to claim 2, which contains the copolymer in the following range. 4 The copolymer is 2-[(acrylamidomethyl-21-
Copolymer of hydroxy-5/-methyl)phenyl)-2H-benzotriazole and N,N-dimethyl-2-amine ethyl methacrylate quaternized with dimethyl sulfate and 2-[(acrylamidomethyl-27-hydroxy- The copolymer according to claim 2, which is selected from the group consisting of copolymers of 57-methyl)phenyl]-2H-benzotriazole and stearyl acrylate. 5 In the first step, an unsaturated derivative of the following formula: (wherein Z1 represents a group represented by the following formula: or) is first prepared, and then, in the second step, this derivative is homopolymerized. , a method for producing a light-shielding polymer containing at least one polymerized unit of the following formula (2): (representing a group represented by the following formula). 6 In the first step, an unsaturated derivative of the following formula: (wherein Z' has the meaning below) is first prepared, and then in the second step, this derivative is added in a proportion corresponding to the desired light-shielding copolymer. is copolymerized with at least one comonomer, with the following formula (■): [wherein Z1 represents a group represented by the following formula:, R' represents a hydrogen atom or a methyl group, and Y represents a The following formula: represents a group selected from the group of groups (wherein X represents a quaternized or non-quaternized dimethylaminoethyl group or Cl8H3□) (wherein A is a glucosamine residue) A method for producing a light-shielding copolymer having the following repeating unit. 7 Contains at least one polymerized unit of the following formula ■: (in the formula, Z represents a group represented by the following formula: or), and has an average molecular weight of 2,
A sunscreen cosmetic composition comprising at least one light-shielding polymer in the range of 000 to 1,000,000 in a suitable cosmetic medium. 8 The light-shielding polymer is added in an amount of 0.2 to 2% based on the total weight of the composition.
Cosmetic composition according to claim 7, containing in a proportion in the range of 0%. 9. The cosmetic composition according to claim 7 or 8, which is used in the form of an aqueous solution, hydroalcoholic solution, oily solution, gel, cream, emulsion or aerosol. 10 The following formula ■: [In the formula, Z1 represents a group represented by the following formula:, R' represents a hydrogen atom or a methyl group, and Y represents the following formula: (However, X is a quaternized or non-quaternized (represents a dimethylaminoethyl group or Cl8H3□) and (where A is a glucosamine residue), and has an average molecular weight of 2,000 to i , o o o, o o. 1. A sunscreen cosmetic composition comprising at least one light-shielding copolymer in a suitable cosmetic medium.