JP2002138033A - Anti-acne valgaris skin care preparation for external use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare an anti-acne valgaris skin care preparation for external use, excellent in curing effect on comedo, easily applicable, rapid in drying and which provides textures of the skin without giving sticky feeling. SOLUTION: This anti-acne valgaris skin care preparation for external use is obtained by incorporating, (I) a high molecular weight copolymer which is obtained by polymeriging (A) 15.0 to 90.0 wt.% specific amine-containing (meta)acrylic based monomer, (B) 10.0 to 80.0 wt.% specific vinyl monomer, (C) 1.0 to 60.0 wt.% specific (meta)acryloyl group-containing monomer, and (D) 0.1 to 25.0 wt.% crosslinkable vinyl monomer, (II) ethanol, and (III) one or at least two kinds selected from the group consisting of a keratin softening- peeling off agent, an antiinflammatory agent, an antimicrobal-disinfecting agent, a sebum secretion-inhibiting and absorbing agent, a protease inhibitor, an α- hydroxylic acid, vitamin B6 hydrochloride, sulfophenolates, arginine and arginine derivatives.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an anti-acne skin external preparation, and more particularly to an anti-acne skin external preparation which has an excellent acne treatment effect, is easy to apply, dries quickly and has a non-sticky feeling. .

[0002]

2. Description of the Related Art Acne is a skin disease that widely appears from puberty to adults, and its name is acne vulgaris.
It is defined as a chronic inflammatory change that occurs in the pores, mainly in the sebaceous gland system. Although the etiology of acne is complicatedly related to various factors, it is generally considered that hypersecretion of sebum, keratinization of the hair, and bacteria in the hair sac play an important role. Accordingly, as an external preparation for acne treatment, creams and ointments containing a sebum suppression / absorption component, a keratin softening / peeling component, an antibacterial / bactericidal component and an anti-inflammatory component are generally widely used in accordance with the above factors. ing.

[0003]

However, existing creams and ointments may give a psychological burden that an oily feeling may worsen acne, or they may be slow to dry, and other There was a tendency to get stuck in the place, and the usability was not very good.

[0004]

Means for Solving the Problems In view of the above circumstances, the present inventors have conducted intensive studies and as a result, have found that keratin softening and exfoliating agents, anti-inflammatory agents, antibacterial and bactericides, sebum suppressants and absorbents, protease inhibitors Agent, α-hydroxy acid, vitamin B6 hydrochloride, sulfocarbonate, arginine and one or more of arginine derivatives in combination with a specific high molecular weight copolymer and ethanol, if blended, easy to apply The present inventors have found that an external preparation for anti-acne skin which dries quickly and is excellent in feeling of use, the drug stays on the skin, and the purpose of acne treatment can be satisfactorily achieved, and the present invention has been completed.

That is, the present invention provides a polymer copolymer represented by the following component (A), (A) ethanol, (C)
One or two types selected from keratin softening and exfoliating agents, anti-inflammatory agents, antibacterial and bactericides, sebum depressants and absorbents, protease inhibitors, α-hydroxy acids, vitamin B6 hydrochloride, sulfocarbonate, arginine and arginine derivatives An external preparation for skin for anti-acne, comprising:

(A) A polymer copolymer obtained by polymerizing a monomer composition containing the following (A) to (D). (A) General formula (I):

[0007]

Embedded image

Wherein R ¹ is a hydrogen atom or a methyl group,
R ² and R ³ each independently represent a hydrogen atom, a methyl group,
An ethyl group or a t-butyl group, A is an oxygen atom, or-
An NH- group, B is a straight-chain or side-chain carbon atom having 1 to 4 carbon atoms;
Represents an alkylene group. 15.0 to 90.0% by weight of an amine-containing (meth) acrylic monomer represented by the formula (B): (B) a general formula (II):

[0009]

Embedded image

(Wherein R ¹ is the same as above, and R ⁴ is a general formula:

[0011]

Embedded image

(Wherein p represents 3 or 4) or a group represented by the following formula:

[0013]

Embedded image

The group represented by (C) General formula (III):

[0015]

Embedded image

(Wherein R ¹ and A are the same as above, and R ⁵ is a linear or side chain alkylene group having 8 to 17 carbon atoms or a compound represented by the general formula (IV):

[0017]

Embedded image

(Where n is an integer of 3-4, q is 10-2)
Represents an integer of 5. ), R ⁶ represents a hydrogen atom or a methyl group. (D) 1.0 to 25.0% by weight of a (meth) acryloyl group-containing monomer represented by

Hereinafter, the configuration of the present invention will be described in detail. The (A) polymer copolymer of the present invention is the above-mentioned (A) to
It is obtained by polymerizing a monomer composition containing (D). Hereinafter, each component constituting the polymer copolymer will be described in detail.

Representative examples of the amine-containing (meth) acrylic monomer represented by the general formula (I) include, for example, N, N-dimethylaminoethyl (meth) acrylate and N, N-dimethylaminoethyl (meth) acrylate. Examples include acrylate and N, N-dimethylaminopropyl (meth) acrylamide, but the present invention is not limited only to such examples. In the present invention, the amine-containing (meth) acrylic monomers are used alone or in combination of two or more.

Particularly preferred are amine-containing (meth) compounds.
The acrylic monomer is represented by the following general formula (V).

[0022]

Embedded image

The proportion of the amine-containing (meth) acrylic monomer in the monomer composition is from 15.0 to 9
0.0% by weight, preferably 25.0-75.0% by weight,
More preferably, it is adjusted to be 41.0 to 52.0% by weight. When the proportion of the amine-containing (meth) acrylic monomer is less than the above range, the emulsion stability is not good, and when it exceeds the above range, a tight feeling in use is likely to occur, which is not preferable.

Typical examples of the vinyl monomer represented by the general formula (II) include N-vinylpyrrolidone and
Examples thereof include N-vinylpiridone, acrylamide, methacrylamide, and the like, but the present invention is not limited to these examples. In the present invention, the vinyl monomers are used alone or in combination of two or more.

Particularly preferred vinyl monomers are:
It is represented by the following general formula (VI).

[0026]

Embedded image

The proportion of the vinyl monomer in the monomer composition is 10.0 to 80.0% by weight, preferably 2% by weight.
0.0 to 75.0% by weight, more preferably 40.0 to
It is adjusted to be 48.0% by weight. When the proportion of the vinyl monomer is less than the above range, the emulsion stability is not good, and when it exceeds the above range, the viscosity becomes difficult to be obtained, and the emulsion stability deteriorates, which is not preferable.

Specific examples of the (meth) acryloyl group-containing monomer represented by the general formula (III) include, for example, 2
-Ethylhexyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, Nt-octyl (meth) acrylamide, and the like. It is not limited only to the illustration. In the general formula (III), the group —R ⁵ —
R ⁶ must be hydrophobic, so that R ⁵ has at least 8 carbon atoms and _{n of the} — (C _n H _2n ) _q — group has at least 3;
Must be at least 10. In the present invention, the (meth) acryloyl group-containing monomers are used alone or in combination of two or more.

Among them, particularly preferred (meth) acryloyl group-containing monomers are those represented by the following formula (VII).

[0030]

Embedded image

The proportion of the (meth) acryloyl group-containing monomer in the monomer composition is 1.0 to 60.0% by weight, preferably 1.0 to 55.0% by weight, more preferably 1.5 to 3.5%. It is prepared so as to be% by weight. When the proportion of the (meth) acryloyl group-containing monomer exceeds the above range, the solubility in water is reduced, and the like, which is not preferable in the production process of the emulsion. When the proportion is less than the above range, the emulsion stability is poor. .

The crosslinkable vinyl monomer as the component (D) is a compound having two or more carbon-carbon unsaturated double bonds in one molecule, and has a property of crosslinking with other monomers. is there.

Representative examples of the crosslinkable vinyl monomer include, for example, ethylene glycol di (meth) acrylate, polyoxyethylene di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, polypropylene Having two or more carbon-carbon unsaturated double bonds in one molecule such as glycol di (meth) acrylate (meth)
Acrylic monomers; methylenebis (meth) acrylamide, 1,2-bis (meth) acrylamideethane,
1, such as 1,5-bis (meth) acrylamidopentane
(Meth) acrylamide monomers having two or more carbon-carbon unsaturated double bonds in the molecule; vinyl monomers having two or more carbon-carbon unsaturated double bonds in one molecule such as divinylbenzene; However, the present invention is not limited to only such examples. In the present invention, the crosslinkable vinyl monomers are used singly or as a mixture of two or more.

Among them, particularly preferred crosslinkable vinyl monomers are those represented by the following formula (VIII).

[0035]

Embedded image

The proportion of the crosslinkable vinyl monomer in the monomer composition is from 0.1 to 25.0% by weight, preferably from 1.0 to 10.0% by weight, and more preferably from 6.5 to 6.5% by weight.
It is prepared to be 7.5% by weight. When the ratio of the crosslinkable vinyl monomer is less than the above range,
If the emulsification stability is not good, and if it exceeds the above range, the solubility in water is reduced, so that it is difficult to emulsify.

The polymerization reaction of the monomer composition containing the amine-containing (meth) acrylic monomer, vinyl monomer, (meth) acryloyl group-containing monomer and crosslinkable vinyl monomer is carried out by a general solution polymerization method or a bulk polymerization method. The polymerization can be performed, for example, by a precipitation polymerization method, which is a polymerization method for obtaining a powder, and is usually performed while heating in a nonaqueous solvent under an atmosphere of an inert gas such as nitrogen gas. The reason why the polymerization reaction is performed in a non-aqueous solvent under an inert gas atmosphere is to prevent the monomer or the ester group present in the formed copolymer from being hydrolyzed. .

In the present invention, a good solvent alone or a mixed solvent of a good solvent and a poor solvent is used as the non-aqueous solvent.

In the present invention, a good solvent is used.
This is to suppress the formation of a homopolymer due to the difference in reactivity of each monomer and to obtain a uniform copolymer. In the present specification, the good solvent means the good solvent 1 at 25 ° C.
A solvent in which a copolymer having a molecular weight of 10,000 or more is dissolved in an amount of 20 g or more per 00 ml and no turbidity is observed. Specific examples of the good solvent include, for example, methanol, ethanol, isopropanol, acetone,
Examples include ethyl acetate, benzene, toluene, xylene and the like. Among these good solvents, ethanol, isopropanol and benzene are particularly preferable because they can obtain a copolymer having a relatively high molecular weight. Ethanol and isopropanol are most preferred because benzene and the like are harmful.

The reason why the poor solvent is used in the present invention is that the produced copolymer is easily precipitated from the polymerization solution. The poor solvent means a solvent which dissolves a copolymer having a molecular weight of 10,000 or more in 5 g or less in 100 ml of the poor solvent at 25 ° C. Specific examples of the poor solvent include linear, branched or cyclic aliphatic hydrocarbons having 15 or less carbon atoms, such as n-pentane, n-hexane and cyclohexane. Among these poor solvents, a linear, branched or cyclic aliphatic hydrocarbon having a relatively high boiling point and a carbon number of 7 or less is preferred. Among them, straight-chain, branched-chain or cyclic aliphatic hydrocarbons having 6 or 7 carbon atoms are particularly preferred because of their high boiling points. Further, n-hexane, cyclohexane, and the like are preferable because they are inexpensive and industrially easy to handle.

In order to synthesize a high molecular weight copolymer without impairing the properties of the obtained emulsifier, it is preferable to mix the good solvent and the poor solvent in appropriate ratios. If the proportion of the poor solvent is too large, the polymerization proceeds promptly, and a high molecular weight copolymer having desired physical properties is likely to be precipitated in a short period of time, so that it becomes difficult to obtain a high molecular weight copolymer. The ratio of the poor solvent to the mixed solvent of the good solvent and the poor solvent is 9
It is desirable that the content of the good solvent is 8% by weight or less, preferably 97% by weight or less, and the proportion of the good solvent is 2% by weight or more, preferably 3% by weight or more.

In order to efficiently obtain a high molecular weight copolymer from the reaction solution, it is preferable to use a reaction device for improving stirring during polymerization. When a commonly used stirrer for solution polymerization is used as the reaction apparatus, it is preferable to dilute the monomer composition with the solvent so that the concentration of the monomer composition becomes 30% by weight or less. At the time of the reaction, it is preferable to sufficiently stir using a stirrer or the like so that the reaction solution does not stay. The polymerization reaction is preferably performed under heating at 50 to 100 ° C., and is generally performed at the reflux temperature of the solvent used in the reaction. The time required for the polymerization reaction is usually 10 hours or more. In the polymerization reaction, the amount of the remaining monomer was 1
When the amount becomes 0% by weight or less, the process can be arbitrarily terminated. The amount of the remaining monomer is, for example, PS
It can be determined by adding an oxygen to a double bond by a known method such as a DB method, and measuring the double bond content.

Thus, a reaction solution containing a precipitate of the polymer copolymer is obtained. The mixed solvent can be removed by, for example, filtering the obtained polymer copolymer precipitate and drying it in vacuo. Alternatively, it can be carried out by distillation under normal pressure or reduced pressure.

At the time of the polymerization reaction, a polymerization catalyst may be used. Such polymerization catalysts include, for example, 2,2'-
Azobisisobutyronitrile, 2,2'-azobis (4
-Methoxy-2,4-dimethylvaleronitrile), azo compounds such as dimethyl-2,2'-azobisisobutyrate, diacyl peroxides such as benzoyl peroxide and lauroyl peroxide, and di-t-butylperoxide. There are peroxides represented by dialkyl peroxides such as oxides, peroxycarbonates such as diisopropylperoxydicarbonate, and peroxyesters such as t-butylperoxypivalate. These catalysts are used alone or in combination of two or more. These are used in combination. In addition, the present invention is not limited only to such an example. In addition, when a large amount of an amine monomer is used in the monomer composition, an excessive use of a peroxide catalyst may cause undesired side reactions such as an oxidation reaction at the same time, and may hinder polymerization. Cost. Generally, it is preferable to mainly use an azo-based catalyst, but it depends on the boiling point of the solvent used. For example, when ethanol or benzene is used, 2,2′-azobisisobutyronitrile is difficult to handle. Most preferred because it is good. The amount of the polymerization catalyst used is preferably 0.05 to 3.0% by weight, more preferably 0.1 to 1.0% by weight, based on the total weight of the monomers in the monomer composition.

In the course of the polymerization of the monomers,
Various aspects are exhibited. For example, when only the above-mentioned good solvent is used, the appearance is similar to that in the case where a general solution polymerization is performed in the initial stage of the polymerization reaction, but the crosslinking reaction proceeds with the progress of the reaction, and the gel state is obtained. And a grease-like product without a precipitate is obtained as the reaction further proceeds.

When a mixed solution of the above-mentioned good solvent and poor solvent is used, the initial stage of the polymerization exhibits the same appearance as that of the case where a general solution polymerization method is employed. Along with this, the crosslinking reaction progresses and the polymer becomes gel-like, and as the reaction further progresses, the obtained polymer can no longer be dissolved in the mixed solvent, becomes insoluble and precipitates as a precipitate.

Thus, (a) a high molecular weight copolymer is obtained.
No. 1, JP-A-6-316510.

The compounding amount of the high molecular weight copolymer in the external preparation for anti-acne skin is preferably 0.1 to 10.0% by weight,
More preferably, it is 0.5 to 2.0% by weight. 0.1
If the content is less than 10% by weight, a sufficient effect cannot be obtained in terms of usability.
If the content exceeds 0.0% by weight, the viscosity becomes too high.

When using the above-mentioned high molecular weight copolymer, it is desirable to neutralize it with a suitable acidic substance. Examples of the neutralizing agent include mineral acids such as sulfuric acid, hydrochloric acid, and phosphoric acid, and organic acids such as acetic acid, citric acid, lactic acid, succinic acid, malic acid, dimethyl sulfate, and diethyl sulfate.

The amount of ethanol used in the present invention is preferably 30.0 to 80.0% by weight, more preferably 40.0 to 50.0% by weight, based on the total amount of the external preparation.
It is. If the content is less than 30.0% by weight, drying becomes slow, and
When the content exceeds 0.0% by weight, irritation is too strong.

In the present invention, examples of the keratin softening / releasing agent used in combination with the polymer copolymer and ethanol include betaines, sulfur or sulfur compounds, selenium disulfide, salicylic acid, urea and derivatives and salts thereof. Preferably, at least one of them is used. By blending a high molecular weight copolymer and ethanol in combination with a keratin softening and exfoliating agent, abnormal keratinization can be mildly suppressed with respect to the skin, and keratotic plugs that cause comed formation can be removed.

The amount of the exfoliating and exfoliating agent to be added to the skin external preparation for anti-acne is 0.0001 with respect to the whole skin external preparation.
To 10.0% by weight is preferable, and 0.001 to 5.0% by weight is more preferable. If the content is less than 0.0001% by weight, it is difficult to exert a desired softening / peeling effect on the keratin, which is not preferable.
On the other hand, if it exceeds 10.0% by weight, the solubility tends to be inferior, which is not preferable in terms of formulation.

In the present invention, anti-inflammatory agents used in combination with the high molecular weight copolymer and ethanol include glycyrrhizic acid, glycyrrhetinic acid, allantoin, indomethacin, epsilon aminocaproic acid, butyl flufenamate, azulene, camphor, zinc chloride , Zinc flower, menthol, ibuprofen piconol, mefenamic acid and their derivatives and salts. By combining the high molecular weight copolymer and ethanol with an anti-inflammatory agent, it is possible to suppress the development of acne that is mild and highly inflammatory to the skin and to prevent deterioration.

The compounding amount of the anti-inflammatory agent to be used in combination is preferably 0.001 to 10.0% by weight, more preferably 0.01 to 5.0% by weight, based on the whole skin external preparation for acne.
If it is less than 0.001% by weight, the desired effect of suppressing inflammation is hardly exhibited, and if it is more than 10.0% by weight, an increase in the effect of inhibiting acne commensurate with the blending amount tends to not be observed, which is not preferred.

In the present invention, the antibacterial and bactericidal agents used in combination with the polymer copolymer and ethanol include sulfur or a sulfur compound, hinokitiol, triclosan, trichlorocarbanilide, chlorhexidine hydrochloride, chlorhexidine gluconate, Halocarban, chlorophenesin, benzethonium chloride, benzalkonium chloride, lysozyme chloride, alkyldiaminoethylglycine hydrochloride, isopropylmethylphenol, benzoic acid, photosensitizer 201, thymol, hexachlorophen, berberine, thioxolone, yukinoshita extract, oubaku extract , Gonid extract and at least one of their derivatives and salts. By combining the high molecular weight copolymer and ethanol with an antibacterial / bactericidal agent, the growth of Propionibacterium acnes can be suppressed, and the acne can be prevented from spreading and becoming worse.

The compounding amount of the antibacterial / bactericide to be used in combination is preferably 0.001 to 10.0% by weight, more preferably 0.01 to 5.0% by weight, based on the whole skin external preparation for acne. If the amount is less than 0.001% by weight, the desired antibacterial and bactericidal effects are hardly exhibited, so that it is not preferable. Even if the amount exceeds 10.0% by weight, the increase in acne suppression effect corresponding to the amount is not likely to be observed. Is not preferred.

In the present invention, the sebum-suppressing / absorbing agents used in combination with the high molecular weight copolymer and ethanol include burdock extract, oil-soluble burdock extract, peony extract, sage extract, calendula officinalis, bollige extract, cornflower extract , Pyridoxine hydrochloride, pyridoxine dicaprylate, pyridoxine dipalmitate, pyridoxine glycyrrhizinate, pyridoxine dilaurate, pyridoxine tripalmitate, pyridoxal phosphate, HP-β-CD, mica, pearlescent agents, talc, iron oxide, titanium oxide and titanium oxide Is preferably at least one of the derivatives and salts of By combining a high molecular weight copolymer and ethanol with a sebum suppressant / absorbent, mild secretion of excessive sebum to the skin is suppressed, and free fatty acids that cause irritation are suppressed. Exacerbation can be suppressed.

The amount of the sebum suppressant / absorbent used in combination is 0.001 to 30.0% with respect to the whole skin external preparation for anti-acne.
% By weight, and more preferably 0.01 to 10.0% by weight. If the content is less than 0.001% by weight, it is difficult to achieve the desired sebum suppression / absorption effect.
Even if the amount is more than 0.0% by weight, an increase in acne suppressing effect corresponding to the amount is not likely to be recognized, which is not preferable.

In the present invention, the protease inhibitors used in combination with the high molecular weight copolymer and ethanol include tranexamic acid, guanidinobenzoic acid, p-aminomethylbenzoic acid, guanidine, acetamide, benzamidine, antipine, plus It is preferably at least one of minostreptin, leupeptin, aprotinin, bovine pancreatic basic trypsin inhibitor, soybean trypsin inhibitor, corn protease inhibitor, lima bean protease inhibitor and derivatives and salts thereof. By combining high molecular weight copolymer and ethanol with protease inhibitors, it increases keratin water content, suppresses transepidermal water loss, and increases the resistance of the skin itself, making it difficult for acne Can be improved.

The amount of the protease inhibitor used in combination is
0.001 to 20. The total amount of the skin external preparation for acne.
0% by weight is preferable, and 0.01 to 10.0% by weight is more preferable. If the amount is less than 0.001% by weight, the desired effect of suppressing rough skin is difficult to be exhibited, so that it is not preferable. Even if the amount is more than 20.0% by weight, an increase in acne inhibiting effect commensurate with the compounding amount tends not to be recognized, Not preferred.

In the present invention, examples of the drug used in combination with the high molecular weight copolymer and ethanol include α-hydroxy acid, vitamin B6 hydrochloride, sulfocarbonate, arginine and an arginine derivative. .

The compounding amount of these drugs is preferably 0.01 to 10.0% by weight, more preferably 0.1 to 1.0% by weight, based on the whole skin external preparation for acne. If the amount is less than 0.01% by weight, the effect cannot be expected so much. Thus, it is not preferable. Even if the amount is more than 10.0% by weight, there is a tendency that no increase in acne suppression effect commensurate with the amount is found, which is not preferable.

In addition to the above-mentioned essential components, the skin external preparation for anti-acne according to the present invention includes components usually used in skin external preparations such as cosmetics and pharmaceuticals, for example, aqueous components, oily components, powder components, alcohols, humectants. , Thickeners, ultraviolet absorbers, whitening agents, preservatives, antioxidants, surfactants, fragrances, coloring agents,
Various skin nutrients and the like can be appropriately compounded as needed.

The properties of the skin external preparation for anti-acne of the present invention include:
For example, creams, lotions, ointments, emulsions, packs, bath preparations and the like may be used as long as they can be applied to conventional external preparations for the skin, and the dosage form is not particularly limited.

[0065]

Next, the present invention will be described in more detail with reference to Test Examples and Examples, but the present invention is not limited thereto. Unless otherwise specified, the compounding amount is% by weight based on the whole skin external preparation.

Production Example 1 (Production of high molecular weight copolymer) In a three-necked flask equipped with a thermometer, a reflux tube and a nitrogen introduction tube, 50 g of N, N-dimethylaminoethyl methacrylate as a monomer, N-vinylpyrrolidone 47.5
g, 2.5 g of stearyl acrylate and 1.9 g of tripropylene glycol diacrylate, and a mixed solvent (mixing ratio (weight ratio) of 4:96) of 23.1 g of ethanol and 554.3 g of cyclohexane were added, and the mixture was heated at 80 ° C. While refluxing, the mixture was stirred for 2 hours under a nitrogen stream to degas.

Next, 0.41 g of 2,2'-azobisisobutyronitrile was added to a three-necked flask, and polymerization was started at 80 ° C. After a lapse of 45 minutes from the start of the polymerization, 1.9 g of tripropylene glycol diacrylate was added, and after a lapse of 45 minutes, 1.9 g of tripropylene glycol diacrylate was added. After performing a polymerization reaction for about 10 hours while stirring under a nitrogen stream, the obtained polymer slurry solution was filtered under reduced pressure, and the solid component was dried under reduced pressure. The obtained dried polymer was pulverized with a pulverizer to obtain a white powdery polymer copolymer.

Next, test methods and evaluation criteria used for evaluating the skin external preparation for acne of the present invention will be described.

1. Utility (1) Test Method Twenty-five men and women suffering from acne from 13 to 25 years old were used for 4 weeks as a group, and the symptoms before and after use were observed and evaluated. After the face was thoroughly washed with toilet soap, each external preparation for skin was applied to the rash area 2-3 times a day. surface,
The severity of acne vulgaris was observed after 4 weeks by observing the three symptoms of alveoli, papules and pustules, and summing up the degree of each of the findings.

(2) Evaluation ：: Of the 20 patients, the symptom was improved in 20 or more, 15 or more ○: Among the 20 patients, the symptom was improved in 10 out of 20
14: △: Of the 20 patients, those whose symptoms were improved were 5 to 9 out of 20
Name ×: Out of 20, 4 or less of those with improved symptoms XX: Out of 20, 10 out of 20 with worsened symptoms
More than

2. Usability (1) Test method At the time of the above test, the feeling of use accompanying application was evaluated by a questionnaire for three items: stickiness, quick drying, and no irritability, and the individual items were combined to determine the feeling of use. did.

(2) Evaluation ：: Out of 20 persons who evaluated that the feeling of use was good overall,
15 or more ：: Out of 20 people who evaluated the overall usability as good,
10 to 14 △: Out of 20 people who evaluated that the feeling of use was good overall,
5 to 9 persons ×: Out of 20 persons who evaluated that the feeling of use was good overall,
4 or less

Examples 1 to 4 and Comparative Examples 1 to 5 Lotion-type skin external preparations having the formulations shown in Tables 1 and 2 were prepared by the following method, and their usefulness and usability were evaluated by the above-mentioned methods. evaluated. The results are also shown in Tables 1 and 2. The polymer obtained in Production Example 1 was used as the polymer copolymer.

(Production method) A high molecular weight copolymer is dissolved in ethanol, a solution in which various drugs are dissolved in purified water is added, and the mixture is stirred and mixed. When uniform, add lactic acid and mix again with stirring.

[0075]

[Table 1] ──────────────────────────── Examples Examples Ingredients ───────────── 1 2 3 4 ──────────────────────────── Solubilized sulfur 1.0 0.1 − − Peony extract 0.1 − 0.1 − Arginine hydrochloride 0.1 − − − Glycyrrhetinic acid 0.1 − − 0.1 Lactic acid 0.2 0.15 0.25 0.3 High molecular weight copolymer ^{* 1} 0.7 0.5 0.8 1.0 Ethanol 50.0 30.0 60.0 70.0 Purified water Residual Residual Residual ─────────────── ───────────── Utility ◎ ○ ○ ○ Usability ◎ △ ○ △ ───────────────────────── ───

[0076]

[Table 2] 例 Comparative Example Compounding ingredients 成分───── 1 2 3 4 5 ────────────────────────────── Solubilized sulfur-1.0---Peony extract − − 0.1 − − Arginine hydrochloride − − − 0.1 − Glycyrrhetinic acid − − − − 0.1 Lactic acid 0.2 − − − − High molecular weight copolymer ^{* 1} 0.6 − − − − Ethanol 40.0 50.0 50.0 50.0 50.0 Purified water Residual Residual Residual Residual ────────────────────────────── Utility × ○ ○ ○ ○ Usability ○ × × × × ───── ─────────────────────────

* 1: Vinylpyrrolidone / methacrylic acid N,
N-dimethylaminoethyl / stearyl acrylate / tripropylene glycol diacrylate copolymer (Production Example 1)

As shown in Tables 1 and 2, the high molecular weight copolymer and ethanol were combined with a component having a keratin softening / peeling action, anti-inflammatory action, antibacterial / bactericidal action, sebum suppression / absorption action, and anti-skin roughening action. The formulated skin external preparation for anti-acne of the present invention was more excellent in acne treatment effect than the lotion of each comparative example.

Examples of various external forms of the skin external preparation for acne according to the present invention according to the present invention will be shown below. The external preparations for skin in each of the examples were produced by a conventional method according to the specific dosage form. When the above-mentioned tests and evaluations were performed on the external preparations obtained in the respective examples, all the above-mentioned evaluations of the usefulness were “A”.

Example 5 Gel Ingredients Weight% Sulfur 3.0 Zinc White 2.0 Sulfocarbonate 0.1 Dipotassium glycyrrhizinate 0.1 Lactic acid 0.2 Hydroxypropylcellulose (HPC-H) 0.2 Polymer Polymer 0.5 (vinylpyrrolidone / N, N-dimethylaminoethyl methacrylate / stearyl acrylate / tripropylene glycol diacrylate copolymer) Ethanol 30.0 Purified water residue

Example 6 Gel Ingredients% by Weight Solubilized Sulfur 1.0 Salicylic Acid 0.1 Vitamin B ₆ Hydrochloride 0.05 Lactic Acid 0.25 Hydroxypropylcellulose (HPC-H) 0.1 High Polymer Copolymer 0 .9 (vinylpyrrolidone / N, N-dimethylaminoethyl methacrylate / stearyl acrylate / tripropylene glycol diacrylate copolymer) ethanol 70.0 purified water residue

[0082]

As described above, according to the present invention,
It is possible to provide an anti-acne skin external preparation having an excellent acne treatment effect with a non-greasy, dry and fast-wearing feeling.

Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat II (Reference) A61K 47/10 A61K 47/10 47/32 47/32 A61P 17/10 A61P 17/10 C08F 220/18 C08F 220/18 220/28 220/28 220/34 220/34 220/56 220/56 220/58 220/58 220/60 220/60 226/10 226/10 F term (reference) 4C076 AA09 AA12 BB31 CC03 CC04 CC18 CC24 CC31 DD37E DD43 EE13 FF12 FF15 FF17 FF35 GG41 4C083 AA111 AA112 AB111 AB112 AB211 AB212 AB231 AB241 AB331 AB431 AB501 AC031 AC101 AC102 AC301 AC302 AC471 AC472 AC551 AC581 AC582 AC621 AC641 AC681 AC691 AC711 AC741 AC742 AC791 AD82 AC742 AD791 AD551 AD631 AD632 BB48 BB51 CC03 DD23 DD27 DD41 EE06 EE07 EE14 FF01 4J100 AL08P AL08R AL66S AM15Q AM19P AM21R AQ08Q BA08R BA31P CA06 JA53

Claims (11)

[Claims] 1. A polymer copolymer represented by the following component (a), (a) ethanol, (c) a keratin softening / releasing agent,
Anti-inflammatory agent, antibacterial / bactericide, sebum suppressant / absorbent, protease inhibitor, α-hydroxy acid, vitamin B6 hydrochloride,
An external skin preparation for anti-acne, comprising: one or more selected from sulfocarbonate, arginine and arginine derivatives. (A) Next (A)
A polymer copolymer obtained by polymerizing a monomer composition containing (D). (A) General formula (I): (Wherein R ¹ is a hydrogen atom or a methyl group, R ² and R ³
Are each independently a hydrogen atom, a methyl group, an ethyl group or a t-butyl group, A is an oxygen atom, or a -NH- group,
Represents a linear or branched alkylene group having 1 to 4 carbon atoms. 15.0 to 90.0% by weight of an amine-containing (meth) acrylic monomer represented by the following formula (B): (B) a general formula (II): (In the formula, R ¹ is the same as described above, and R ⁴ is a general formula: (Wherein p represents 3 or 4) or a group represented by the following formula: Represents a group represented by Vinyl monomer 1)
0.0 to 80.0% by weight, (C) general formula (III): (Wherein R ¹ and A are the same as above, and R ⁵ is a linear or side chain alkylene group having 8 to 17 carbon atoms or a general formula (IV): (Wherein, n represents an integer of 3 to 4, q represents an integer of 10 to 25), and R ⁶ represents a hydrogen atom or a methyl group. (D) 1.0 to 25.0% by weight of a (meth) acryloyl group-containing monomer represented by 2. The amine-containing (meth) acrylic monomer of (A) is represented by the formula (V): The skin external preparation for anti-acne according to claim 1, which is: 3. The method according to claim 1, wherein the vinyl monomer (B) is of the formula (V)
I): The skin external preparation for anti-acne according to claim 1, which is: 4. The (meth) acryloyl group-containing monomer of (C) is represented by the formula (VII): The skin external preparation for anti-acne according to claim 1, which is: 5. The crosslinkable vinyl monomer of (D) has the formula (VIII): The skin external preparation for anti-acne according to claim 1, which is: 6. The anti-acne skin external use according to claim 1, wherein the exfoliating and exfoliating agent is at least one of betaines, sulfur or a sulfur compound, selenium disulfide, salicylic acid, urea and their derivatives and salts. Agent. 7. The anti-inflammatory agent may be glycyrrhizic acid, glycyrrhetinic acid, allantoin, indomethacin, epsilon aminocaproic acid, butyl flufenamic acid, azulene, camphor, zinc chloride, zinc white, menthol, ibuprofenpiconol, mefenamic acid and derivatives thereof. The skin external preparation for anti-acne according to claim 1, which is at least one of a salt and a salt. 8. The antibacterial / bactericidal agent is sulfur or a sulfur compound, hinokitiol, triclosan, trichlorocarbanilide, chlorhexidine hydrochloride, chlorhexidine gluconate, halocarban, chlorophenesin, benzethonium chloride, benzalkonium chloride, chloride. Lysozyme, alkyldiaminoethylglycine hydrochloride, isopropylmethylphenol, benzoic acid, photosensitizer No. 201, thymol, hexachlorophen, berberine, thioxolone, yukinoshita extract, oak extract, ogugon extract and at least one of their derivatives and salts The external preparation for skin for anti-acne according to claim 1. 9. The sebum suppressant / absorbent comprises burdock extract, oil-soluble burdock extract, peony extract, sage extract,
Calendula, Bodaiju extract, cornflower extract, pyridoxine hydrochloride, pyridoxine dicaprylate, pyridoxine dipalmitate, pyridoxine glycyrrhizinate, pyridoxine dilaurate, pyridoxine tripalmitate, pyridoxal phosphate, HP-β-CD,
2. The anti-acne skin external preparation according to claim 1, which is at least one of mica, pearl, talc, iron oxide, titanium oxide and derivatives and salts thereof. 10. The protease inhibitor may be tranexamic acid, guanidinobenzoic acid, p-aminomethylbenzoic acid,
Guanidine, acetamide, benzamidine, antipine, plasminostreptin, leupeptin, aprotinin, bovine pancreatic basic trypsin inhibitor, soybean trypsin inhibitor, corn protease inhibitor, lima bean protease inhibitor and at least one of their derivatives and salts. The external preparation for skin for anti-acne according to claim 1. 11. The polymer copolymer represented by the component (A) is 0.1 to 10.0% by weight, and (A) ethanol is 3%.
The anti-acne skin external preparation according to claim 1, comprising 0.0 to 80.0% by weight.