JPH09241126A - Cosmetic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a cosmetic having excellent use feeling, high absorptivity of water and sebum as components of sweat, excellent in moisture-holding property and durability, and hardly inducing crumbling of makeup by using a specific poly α-amino acid or its derivative as a particle component. SOLUTION: This cosmetic uses a particle of a poly α-amino acid obtained by emulsion polymerizastion or heterogeneous polymerization of an α-amino acid-N-carbonate anhydride or a particle of its derivative. Preferably, the pole α-amino acid or its derivative has a weight-average molecular weight within the range of 5×10<3> -5×10<5> , 100-1,000ml/100g oil absorption and 50-400% water absorption. The average diameter of the particle is preferably in the range of 0.1-10μm, and its blending amount in the cosmetic is 0.1-80wt.%, preferably 0.5-60wt.% based on the weight of the cosmetic. This cosmetic can impact wet feeling and fresh feeling to the skin. As the form of the cosmetic, a foundation, a rouge, baby powder and a sweat-controlling powder, etc., are exemplified.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to α-amino acid-N
-Contains particles of poly α-amino acid or a derivative thereof obtained by emulsion polymerization or heterogeneous polymerization of carbonic anhydride, has a good feeling in use, absorbs water and sebum, which are components of sweat, and retains moisture. The present invention relates to a cosmetic material that is excellent in durability and does not easily cause makeup breakdown.

[0002]

2. Description of the Related Art Various powders are blended in cosmetics depending on the application. The characteristics of the powders are that it is easy to mix with other components used in cosmetics and dispersibility. Other important factors are the texture and safety when applied to the skin. Conventionally, such powders include talc, kaolin, mineral fine powder such as titanium oxide, or nylon,
Synthetic polymer fine powders such as polyacrylic acid ester are used, but these mineral fine powders or synthetic polymer fine powders often have insufficient affinity with human skin. From this point of view, polyamino acids, which have properties close to those of natural proteins and can be said to be synthetic proteins, are expected to have a good affinity with the skin when used as an additive for cosmetics. For example, JP-A-52-145527. The publication discloses a cosmetic containing polyamino acid particles. However, since the polyamino acid particles of the publication are particles formed from a solution or sol of a pre-synthesized polyamino acid by a spray method, a re-emulsification method, etc., the oil absorption amount and the water absorption rate that affect the quality of cosmetics It is difficult to control, and it is also difficult to form uniform particles, and as a result, the spreadability of the cosmetic containing the particles to the skin cannot be said to be sufficient. On the other hand, polyamino acids have been conventionally used as a material for synthetic leather and as a solution for processing papers and fibers.However, since these raw material monomers are very easily hydrolyzed, the solution It is produced by a polymerization method and is not a particulate polymer. As another method for obtaining the polyamino acid in the form of particles, for example, (i) α-amino acid-N-carbonic anhydride is solution-polymerized in a halogenated hydrocarbon solvent, and this solution is added dropwise to the non-solvent. Method of forming fine powder or emulsion (for example, Japanese Patent Publication 5-1
No. 3168), (ii) a method of obtaining a polyamino acid powder by polymerizing glutamic acid-γ-methyl ester-N-carbonic anhydride dissolved in a solvent of ethyl acetate using an amine compound as a polymerization initiator (for example, JP-B-52). No. 9477), (iii) solid-state polymerization of α-amino acid-N-carbonic anhydride using a vaporizable amine compound as a polymerization initiator,
Method for obtaining polyamino acid powder (for example, JP-A-49-38)
Japanese Patent Laid-Open No. 995) and the like are known. However,
The method for obtaining these polyamino acid particles has no problem at the laboratory level, but has various industrial problems. That is, the method (i) requires three steps of solution polymerization, re-emulsification and solvent removal, and at the stage of granulation, the particle size and particle size distribution, which are important factors as a cosmetic ingredient, are accurately determined. It is difficult to control, and in the method (ii),
It is limited to the case of polymerizing a specific α-amino acid in a specific solvent, and it is difficult to control the particle size and particle size distribution generated by the polymerization.Furthermore, in the method (iii), a vaporizable amine compound is also used. Since the polymerization method is limited to the polymerization using the polymerization initiator and the vaporized amine compound is continuously supplied to the solid phase polymerization system, it is difficult to control the reaction, and it is difficult to stir the solid phase monomer. There is also a problem that sufficient reproducibility of the molecular weight of the polymer obtained cannot be obtained. Moreover, from the above-mentioned problems, all of the above methods (i) to (iii) are similar to those in JP-A-52-145527.
It is also unsatisfactory in terms of the properties of the obtained polyamino acid particles as a cosmetic ingredient.

[0003]

The present invention has been made as a result of earnestly studying the particle component added to cosmetics from such a viewpoint, and the problem is that it can be industrially advantageously produced. Another object of the present invention is to provide a cosmetic which has a good feeling in use, has high absorbability of water and sebum which are components of sweat, has excellent moisturizing properties and durability, and does not easily cause makeup collapse.

The gist of the present invention is a cosmetic characterized by containing particles of poly α-amino acid or a derivative thereof obtained by emulsion polymerization or heterogeneous polymerization of α-amino acid-N-carbonic anhydride, Consists of.

Hereinafter, the present invention will be described in detail. Particles of the poly α-amino acid (hereinafter abbreviated as “polyamino acid”) or a derivative thereof used in the present invention include α-amino acid-N-carbonic anhydride (hereinafter, “amino acid-NCA”).
That. A) is obtained by emulsion polymerization or heterogeneous polymerization of polyamino acid or a derivative thereof. The α-amino acid constituting the amino acid-NCA in the present invention is not particularly limited, and examples thereof include glycine, alanine, valine, norvaline, leucine, isoleucine, norleucine, phenylalanine,
Neutral amino acids such as methionine and proline; acidic amino acids such as glutamic acid-γ-ester and aspartic acid-β-ester-ω-ester (in this case, the organic group constituting the ester group is a methyl group, an ethyl group, a butyl group). Group, cyclohexyl group, phenyl group, benzyl group, naphthylmethyl group and the like having 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms
The alkyl, cycloalkyl, aryl or aralkyl groups of are suitable. ); N-acylated basic amino acids such as N-carbobenzoxylidine, N-carbobenzoxyornithine and N-acetyllysine (in this case, the acyl group has 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms).
Is appropriate. ); Esters of hydroxyl group-containing α-amino acids such as serine, threonine, and tyrosine (in this case,
The organic group constituting the ester group includes a methyl group, an ethyl group, a butyl group, an octyl group, a cyclohexyl group, a phenyl group, a benzyl group, a naphthylmethyl group and the like having 1 to 1 carbon atoms.
Suitable are 20, preferably 1 to 15 alkyl, cycloalkyl, aryl or aralkyl groups. )
And the like. However, among these α-amino acids,
Α-amino acid having a functional group such as a carboxyl group, a hydroxyl group, a thiol group, an amino group, and a guanidyl group in its side chain is
As a derivative in which the functional group is protected by a suitable protecting group,
Need to convert to amino acid-NCA. Particularly preferable amino acid-NCA includes NCA of glutamic acid or aspartic acid ester, NCA of lysine N-acyl compound, NCA of glycine or alanine, and the like. Further, the amino acid-NCA may be an optically active substance, a racemate, or a mixture thereof, and if necessary, two or more kinds of amino acid-NCA may be mixed and used as a copolymer. You can

The polyamino acid particles are produced by an emulsion polymerization method or a heterogeneous polymerization method. Specific examples of these polymerization methods include the following methods (1) to (4). (1) A method of emulsion-polymerizing amino acid-NCA in water containing a polymerization initiator and an emulsifier. (2) The solubility of water at 1 atm and 25 ° C is 10 g / 1.
A method of emulsifying an organic solvent in an amount of 00 ml or less in water to prepare a basic emulsion, adding amino acid-NCA to the emulsion to effect emulsion polymerization, and then removing the organic solvent. (3) Solubility of water at 1 atm and 25 ° C is 10 g / 1
A basic emulsion is prepared by emulsifying an organic solvent in an amount of 00 ml or less in water, and in this basic emulsion, amino acid-NCA is emulsion-polymerized in the presence of a polymer having a terminal amino group, and then the organic solvent is removed. hand,
A method for obtaining a block copolymer in which a polyamino acid is bound to a polymer having a terminal amino group. (4) The solubility of amino acid-NCA and the solubility of the produced polyamino acid are both 0.1 g / 25 ° C.
A method of heterogeneously polymerizing the amino acid-NCA in an organic medium of 100 ml or less.

Hereinafter, these polymerization methods will be sequentially described. First, in the above method (1), the polymerization initiator is
The compound is not particularly limited as long as it is a compound capable of causing the amino acid-NCA polymerization reaction. Specific examples thereof include primary amines such as methylamine, ethylamine, isopropylamine, butylamine, hexylamine, heptylamine and octylamine; dimethylamine, diethylamine, dibutylamine, dihexylamine, diheptylamine, dioctylamine and the like. Secondary amines; trimethylamine, triethylamine, tributylamine, trihexylamine, triheptylamine,
Tertiary amines such as trioctylamine; ethanolamine, diethanolamine, triethanolamine, N,
Alkanolamines such as N-dimethylethanolamine; ethylenediamine, hexamethylenediamine, N,
Examples include polyamines such as N-dimethyl-1,3-propanediamine and triethylenediamine. These polymerization initiators can be used alone or in combination of two or more kinds. The proportion of the polymerization initiator used is usually 1/2 to 1/500 relative to 1 mol of amino acid-NCA.
It is 0 mol, preferably 1/5 to 1/1000 mol.

As the emulsifier, amino acid-NCA is used.
It is not particularly limited as long as it does not hinder the polymerization reaction, but a nonionic emulsifier is particularly preferable. Specific examples of the nonionic emulsifier include polyoxyethylene alkyl ether, polyoxyethylene alkylphenol ether, polyoxyethylene / polyoxypropylene alkyl ether, polyoxyethylene fatty acid ester, polyoxyethylene alkyl ester, sorbitan fatty acid ester, polyoxyethylene. Examples thereof include sorbitan fatty acid ester and glycerin fatty acid ester.
These nonionic emulsifiers can be used alone or in combination of two or more kinds. The ratio of the emulsifier to be used is usually 0. 1 with respect to 1 part by weight of amino acid-NCA.
05 to 100 parts by weight, preferably 0.01 to 50 parts by weight.

The ratio of amino acid-NCA to water as a polymerization reaction medium is usually 1: 0.5 to 1: 100, preferably 1: 1 in terms of weight ratio of amino acid-NCA: water.
~ 1:50. In the method (1), it is necessary to emulsify the amino acid-NCA before the amino acid-NCA is hydrolyzed. Therefore, while stirring the water containing the polymerization initiator and the emulsifier, the amino acid-NC
It is preferable to add A. Examples of the stirring means in this case include mechanical stirring means, ultrasonic irradiation means, and a combination thereof. According to such a method, the polymerization reaction medium is in a state in which the conditions necessary for immediate polymerization of the amino acid-NCA are in order, so that the polymerization reaction proceeds from the surface of the amino acid-NCA at the same time when the amino acid-NCA is added. Since this polymerization reaction is preferentially performed over the hydrolysis reaction of amino acid-NCA, the polymerization reaction is not hindered by the hydrolysis reaction, and polyamino acid particles are produced. The polymerization temperature is amino acid-N
Although it depends on the type of CA and the polymerization initiator, it is usually 0.
˜100 ° C., preferably 5-90 ° C. By adjusting the polymerization temperature, a polyamino acid having a desired molecular weight can be obtained. The polymerization pressure is not particularly limited. During the polymerization reaction, it is necessary to stir the system to maintain the emulsified state. This stirring is preferably carried out, for example, by means of mechanical stirring, and the number of rotations thereof is usually 20 to 3000 rpm. p. m. It is.
The polyamino acid particles obtained by the method (1) are usually porous.

Next, the method (2) will be described.
The organic solvent used in the preparation of the basic emulsion in the method (2) has a water solubility of 10 g / 100 ml or less at 1 atm and 25 ° C., preferably 5 g / 1.
It is less than 00 ml. In this case, when an organic solvent having a water solubility of more than 10 g / 100 ml is used, the amount of water dissolved in the organic solvent increases in the step of preparing the basic emulsion, resulting in the amino acid-NC.
The hydrolysis of A becomes nonnegligible, which lowers the polymerization yield and makes it difficult to obtain a high molecular weight polyamino acid (derivative). As the organic solvent, at 1 atm and 25 ° C., amino acid-NCA is at least 0.1 g / 100 ml or more, and particularly 0.3
It is preferable that it can be dissolved at a ratio of g / 100 ml or more, and 0.3 g of the produced polyamino acid is further added.
What can be dissolved at a ratio of / 100 ml or more, particularly 0.5 g / 100 ml or more is preferable.

Specific examples of such organic solvents include chloromethane, dichloromethane, chloroform and 1,1-
Dichloroethane, 1,2-dichloroethane, 1,1,2
-Aliphatic halogenated hydrocarbons such as trichloroethane;
Chlorobenzene, o-dichlorobenzene, 1,2,4-
Aromatic halogenated hydrocarbons such as trichlorobenzene;
Esters such as ethyl acetate, butyl acetate, ethyl butyrate;
Ethers such as diethyl ether, dibutyl ether, dihexyl ether, dioctyl ether, anisole, ethoxybenzene, tetrahydrofuran and dioxane; hydrocarbon compounds such as pentane, hexane, heptane, octane, cyclohexane, benzene, toluene and xylene. These organic solvents can be used alone or in combination of two or more kinds.
The ratio of water to the organic solvent used is usually 90:10 to 50:50, preferably 80 :, by weight ratio of water: organic solvent.
20-55: 45.

The polymerization initiator is not particularly limited as long as it is a compound capable of causing a polymerization reaction of amino acid-NCA and soluble in the organic solvent used, but in particular, amine compounds, metal alcoholates and the like. preferable. Specific examples of such an amine compound include the compounds exemplified in the above method (1). Further, specific examples of the metal alcoholate include methyl alcohol,
Examples thereof include alcohol components such as ethyl alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, 2-ethylhexyl alcohol and benzyl alcohol, and metal components such as lithium, sodium and potassium. These polymerization initiators can be used alone or in combination of two or more kinds. The ratio of the polymerization initiator to be used is usually 1/10 to 1/5000 mol, preferably 1 to 1 mol of amino acid-NCA.
/ 30 to 1/1000 mol. As a method of adding the polymerization initiator, a method of previously dissolving the polymerization initiator in an organic solvent used for preparation of the basic emulsion, a polymerization initiator in an organic solvent different from the organic solvent used for preparation of the basic emulsion And the like, or a solution in which amino acid-NCA is dissolved together is added to the basic emulsion.

The emulsifier is not particularly limited as long as it does not inhibit the polymerization reaction of amino acid-NCA and has a function of uniformly emulsifying an organic solvent in water. For example, the method of the above (1) is used. The exemplified nonionic emulsifiers and anionic emulsifiers are preferably used. The ratio of the emulsifier to be used varies depending on the amino acid-NCA used, the type of organic solvent or the type of emulsifier, but is preferably 0.1 to 10% by weight, and more preferably the total amount of water and the organic solvent. It is 0.2 to 5% by weight. The means for emulsifying the organic solvent in water to prepare the basic emulsion is not particularly limited, but examples thereof include mechanical stirring means, ultrasonic irradiation means, and combinations thereof.

Then, the base emulsion was added with amino acid-N.
Add CA and polymerize. Amino Acid in this case-NCA
The use ratio is usually 1 to 100 parts by weight, preferably 5 to 90 parts by weight, based on 100 parts by weight of the organic solvent used. However, in the method (2), amino acid-
NCA does not need to be completely dissolved because the polymerization reaction proceeds even in the state in which a part of NCA is dispersed and present in an organic solvent. Therefore, the maximum amount of amino acid-NCA used is:
The amount of the organic solvent used is not strictly limited. Examples of the method of adding the amino acid-NCA to the basic emulsion include a method of adding the amino acid-NCA powder as it is and a method of adding an amino acid-NCA organic solvent solution. The polymerization temperature varies depending on the type of amino acid-NCA, organic solvent or polymerization initiator, but is usually -5 to + 100 ° C, preferably 0 to 90 ° C.
By selecting such a polymerization temperature, a polyamino acid having a desired molecular weight can be obtained. The polymerization pressure is not particularly limited. During the polymerization reaction, it is necessary to stir the system to maintain the emulsified state. This agitation is preferably carried out, for example, by a mechanical agitation means, and the rotation speed thereof is usually 20 to 3000 rpm.

After the polymerization reaction of amino acid-NCA is completed, the organic solvent is removed to obtain an emulsion of polyamino acid. As means for removing the organic solvent, various means such as vacuum distillation and steam stripping can be used. At this time, in order to stabilize the emulsion, the emulsifier can be added in a proportion of 0.05 to 10% by weight of the emulsion to be treated, if necessary. The polyamino acid emulsion can also be obtained by adding a poor solvent miscible with both water and an organic solvent to the polyamino acid emulsion after the polymerization reaction, and then removing the organic solvent. In this case, the obtained polyamino acid particles are hollow. The poor solvent used in this case is compatible with both water and the organic solvent used, and does not dissolve the produced polyamino acid, and specific examples thereof include methyl alcohol, ethyl alcohol, isopropyl alcohol, and the like. Lower alcohols; lower ketones such as acetone and methyl ethyl ketone. The addition ratio of the poor solvent is usually 1 to 50 parts by weight, preferably 2 to 30 parts by weight, based on 100 parts by weight of the emulsion after the polymerization reaction. As the means for removing the organic solvent after adding the poor solvent, the same means as for removing the organic solvent described above can be used. By stirring the system during this removal process, the medium located on the surface of each oil drop is renewed, the poor solvent makes sufficient contact with the oil drop surface, and the organic solvent is removed efficiently together with some water. To be done. Examples of stirring means in this case include mechanical stirring means, ultrasonic stirring means, and a combination thereof.

Next, the method (3) will be described.
The organic solvent used in the preparation of the basic emulsion in the method (3) has a water solubility of 10 g / 100 ml or less at 1 atm and 25 ° C., preferably 5 g / 1.
It is less than 00 ml. Water solubility is 10
When an organic solvent exceeding g / 100 ml is used, the amount of water dissolved in the organic solvent increases in the step of preparing the basic emulsion, and hydrolysis of amino acid-NCA becomes nonnegligible, which results in a polymerization yield. As a result, it becomes difficult to produce a high molecular weight polyamino acid block copolymer having a high content of amino acid constituent units. Further, as the organic solvent, at least 0.1 g / 100 amino acid-NCA is prepared under the conditions of 1 atm and 25 ° C.
Those capable of dissolving at least milliliters, particularly at least 0.3 g / 100 milliliters are preferred. Specific examples of such an organic solvent include the organic solvents exemplified in the above method (2). The ratio of water and organic solvent used is
The weight ratio of water: organic solvent is usually 95: 5 to 50: 5.
0, preferably 80:20 to 55:45. Also,
Specific examples of the emulsifier used for the preparation of the basic emulsion also include the emulsifiers exemplified in the method (1), and the nonionic emulsifier is particularly preferable. The use ratio of the emulsifier varies depending on the type of the amino acid-NCA, the organic solvent or the emulsifier, but is usually 0.1 to 10% by weight, preferably 0.2 with respect to the total amount of water and the organic solvent.
~ 5% by weight. The means for emulsifying the organic solvent in water to prepare the basic emulsion is not particularly limited, but includes mechanical stirring, ultrasonic irradiation, or a combination thereof.

The polymer having an amino group at the terminal (hereinafter referred to as "amino group-containing prepolymer") present in the basic emulsion during the polymerization of amino acid-NCA has the ability to initiate polymerization at one or both of its terminals. There is no particular limitation as long as it has an amino group and is soluble in the organic solvent used. By polymerizing amino acid-NCA in the presence of such an amino group-containing prepolymer, and assuming that the polyamino acid block is A and the amino group-containing prepolymer block is B, the amino group-containing prepolymer is present on only one of its terminals. When it has an amino group, an AB type polyamino acid block copolymer is obtained, and when the amino group-containing prepolymer has an amino group at both of its terminals, A-B-A
A type of polyamino acid block copolymer is obtained. Specific examples of the polymer that constitutes the amino group-containing prepolymer include diene-based polymers such as polybutadiene, polyisoprene, styrene-butadiene copolymer, and acrylonitrile-butadiene copolymer; polyethylene, polypropylene, ethylene-propylene copolymer. Olefinic polymers such as coalescing; polar vinyl polymers such as poly (meth) acrylic acid, poly (meth) acrylic acid ester, (meth) acrylic acid ester copolymers; polyvinyl acetate, ethylene-vinyl acetate copolymer Examples thereof include vinyl acetate polymers such as coalesced materials, polyvinyl alcohol, polyurethane, polyamide, polycaprolactone, and polydimethylsiloxane. The weight average molecular weight of these polymers is not particularly limited, but is preferably 500 to 600,000, which can be selected according to the properties required for the particles of the block copolymer obtained. it can.

Examples of the method for producing the amino group-containing prepolymer include the following methods (a) to (e). (A) A method of radically polymerizing a monomer in the presence of a chain transfer agent having an amino group. (B) an organolithium and a protective group and primary amino group (e.g., [(CH _{3) 3} Si] _{2 N-C 6 H 4 -Li} )
Is used as an anionic polymerization initiator to polymerize the conjugated dienes and then perform hydrolysis. (C) A method of treating a cationic living polymer with ammonia. (D) An anionic living polymer obtained by polymerizing at least one monomer of a conjugated diene and / or an α-olefin with an organic alkali metal as a polymerization initiator, and a general formula X-R ⁴ -N (SiR ¹ R ² R ³ ) ₂ or (R ⁵ ) (R ⁶ ) C = NY (where X is a halogen atom,
R ¹ , R ² and R ³ are hydrocarbon groups having 1 to 12 carbon atoms,
R ⁴ is an alkylene group having 1 to 12 carbon atoms, R ⁵ and R ⁶
Is a hydrocarbon group having 1 to 10 carbon hydrogen atom or carbon, Y is a hydrocarbon group having 1 to 12 carbon ^{atoms, -Si (R 7) (R} 8) (R
⁹ ) (wherein R ⁷ , R ⁸ and R ⁹ represent a hydrocarbon group having 1 to 12 carbon atoms) or —S—C ₆
It represents a group represented by H ₅ . ), And a primary amino group or secondary amino group is introduced into the terminal. (E) A chlorine gas is blown into the anionic living polymer obtained in the above (D), and a chlorinated end of the polymer is reacted with ammonia or an amine to give a primary amino group or a secondary amino group at the end. How to introduce a group. The ratio of the amino group-containing prepolymer used is amino acid-N
It is usually 1/10 to 1/5000 mol, preferably 1/30 to 1/1000 mol, relative to 1 mol of CA.

Then, in this base emulsion, the amino acid-N was prepared in the presence of the amino group-containing prepolymer.
The amino acid-NCA is polymerized in the oil droplets of the organic solvent by adding CA. In this polymerization reaction, the terminal amino group of the amino group-containing prepolymer acts as a polymerization initiator, and an AB type or ABA type block copolymer is obtained. Amino acid-N in the base emulsion
Examples of the method of adding CA include a method of adding the amino acid-NCA powder as it is and a method of adding an amino acid-NCA organic solvent solution. As a method of adding the amino group-containing prepolymer, a method of previously dissolving the amino group-containing prepolymer in the organic solvent used for preparing the basic emulsion, and a method different from the organic solvent used for preparing the basic emulsion Examples include a method of adding the amino group-containing prepolymer alone or as a solution in which it is dissolved together with amino acid-NCA in an organic solvent. The use ratio of amino acid-NCA is 10
It is usually 1 to 100 parts by weight, preferably 5 to 90 parts by weight, relative to 0 parts by weight. The amino acid-NCA does not need to be completely dissolved because the polymerization reaction proceeds even in the state where a part of the amino acid-NCA is dispersed in the organic solvent. Therefore, the maximum amount of the amino acid-NCA used is the amount of the organic solvent used. It is not strictly limited to. The polymerization temperature varies depending on the type of amino acid-NCA, organic solvent or polymerization initiator, but is usually -30 to + 100 ° C, preferably 0 to 90 ° C. The polymerization pressure is not particularly limited. During the polymerization reaction, it is necessary to stir the system to maintain the emulsified state. The stirring is preferably mechanical stirring, for example, and the rotation speed thereof is usually 20 to 3000 rpm. After the completion of the amino acid-NCA polymerization reaction, the organic solvent is removed to obtain an emulsion of the polyamino acid block copolymer. As means for removing the organic solvent, various means such as vacuum distillation and steam stripping can be used. Also in the method of (3), a hollow polyamino acid block copolymer can be obtained by adding a poor solvent to the emulsion after the amino acid-NCA polymerization and then removing the organic solvent. The treatment method in this case is the same as that of the method (2).

Next, the method (4) will be described.
The organic medium used in the method (4) is amino acid-NC.
Both A and the polyamino acid produced have a solubility of 2
It is 0.1 g / 100 ml or less, preferably 0.05 g / 100 ml or less at 5 ° C., and is not particularly limited as long as it is an organic medium that does not hinder the polymerization of amino acid-NCA. As such an organic medium, for example, n
-Pentane, n-hexane, n-heptane, n-octane, isooctane, cyclohexane and the like having 5 to 2 carbon atoms
0, preferably 5 to 10 aliphatic hydrocarbons; benzene, toluene, xylene and other aromatic hydrocarbons having 6 to 9 carbon atoms, preferably 6 to 8 carbon atoms; diethyl ether, diisopropyl ether, dibutyl ether, dihexyl ether , Dioctyl ether, ethoxybenzene and the like having 4 to 20 carbon atoms, preferably 4 to 16 ethers and the like. These organic media can be used alone or in admixture of two or more. A preferred combination of the amino acid-NCA and the organic medium in the method (4) is:
It is as follows. That is, glutamic acid-γ-methyl ester-NCA, glutamic acid-γ-ethyl ester-N
In the case of CA, glutamic acid-γ-benzyl ester-NCA or aspartic acid-β-ester-NCA, hydrocarbons or ethers are preferable as the organic medium, and alanine-NCA, leucine-NCA or N-carbobenzoxylyl is preferable. In the case of syn-NCA, ethers are preferred as the organic medium.

As the polymerization initiator, for example, the amine compounds or metal alcoholates exemplified in the above method (2) are preferably used. The amount of the polymerization initiator used is usually 1/2 to 1/500, based on 1 mol of amino acid-NCA.
It is 0 mol, preferably 1/5 to 1/1000 mol.
The ratio of amino acid-NCA used to the organic medium is usually 1 to 50% by weight, preferably 5 to 30% by weight. The polymerization of amino acid-NCA is preferably carried out with mechanical stirring, and the stirring speed is usually 10 to 3
000 rpm, preferably 20 to 3000 rpm. The polymerization temperature is usually -30 to + 100 ° C, preferably 0 to 90 ° C. The polymerization pressure is not particularly limited. In the method (4), the amino acid-NCA is suspended in an organic medium, and the polymerization initiator dissolved in the organic medium uniformly acts on the suspended particles of the amino acid-NCA to initiate polymerization. Resulting in the production of uniform particles of polyamino acid. The obtained particles can be easily separated by, for example, filtration or the like, and an additive such as an emulsifier is not required. Therefore, highly pure polyamino acid particles can be easily obtained. The polyamino acid particles obtained by the method (4) are usually porous.

By the methods (1) to (3), an emulsion of polyamino acid particles can be obtained. As a method of separating the particles from water, a method of evaporating water all at once by a spray dryer or the like, or a method of centrifugation is used. In addition to the method of precipitating and separating the particles and then drying, the method of concentrating and drying using a water separation membrane, and the freeze-drying method, etc., the freeze-drying method is effective when the particle concentration of the emulsion is low. is there. Further, if necessary, the separated polyamino acid particles can be washed with water or the like to remove the emulsifier. In the case of the method (4), after the polymerization, the polyamino acid particles are collected by filtration or the like, washed with an organic solvent such as methanol or acetone, and then dried to obtain purified particles.

In the present invention, the obtained polyamino acid may be used as an emulsion or as particles separated from water or an organic medium, and further chemically modified to obtain particles of a polyamino acid derivative. Specific examples of such a modification reaction include the case where the amino acid-NCA is an NCA of an acidic amino acid ester such as a glutamic acid ester or an aspartic acid ester, or a base such as N-carbobenzoxylysine or N-carbobenzoxyornithine. When the polyamino acid is NCA of a neutral amino acid, or when the polyamino acid is obtained by copolymerization of NCA of an acidic amino acid ester or basic amino acid and NCA of a neutral amino acid, the particle surface of the polyamino acid is hydrolyzed, By generating an amino group or a carboxyl group, the surface of the particle can be made hydrophilic. Further, the polyamino acid particles can be made hydrophilic by reacting them with alkanolamines such as ethanolamine, propanolamine and butanolamine. Furthermore, reacting the polyamino acid particles with diamines such as ethylenediamine, propylenediamine, hexamethylenediamine, octamethylenediamine, glycols such as ethylene glycol and propylene glycol, or dicarboxylic acids such as malonic acid, succinic acid, and adipic acid. Thus, the crosslinking reaction can be performed inside the polyamino acid particles. In the present invention, the particles of the polyamino acid derivative thus obtained can be used as such or in combination with unmodified polyamino acid particles.

The weight average molecular weight of the polyamino acid and its derivative used in the present invention (hereinafter referred to as "Mw").
Is preferably 3,000 or more, more preferably 5,
000 to 500,000. In this case, if the molecular weight is less than 3,000, the properties as a polyamino acid may not be sufficiently exhibited. The polyamino acid and its derivative in the present invention preferably have an oil absorption of 100.
-1000 ml / 100 g, more preferably 120-800 ml / 100 g,
Further, it is desirable that the water absorption rate is in the range of preferably 30 to 500%, more preferably 50 to 400%. In this case, the oil absorption amount and the water absorption rate are within the above ranges, so that sweat and extra sebum can be sufficiently absorbed, and the moisturizing property and the durability are particularly excellent, and a cosmetic that does not easily cause makeup collapse is provided. be able to. The average particle diameter of the polyamino acid and its derivative in the present invention is preferably 0.1 to 100 μm, more preferably 0.2 to
It is preferably in the range of 50 μm. In this case, if the average particle diameter is less than 0.1 μm, the elongation to the skin tends to decrease, and if it exceeds 100 μm, the surface may be rough.

Particles of the polyamino acid or its derivative thus obtained are used as makeup cosmetics such as foundation, lipstick, powder lip, blusher, eye shadow, eyeliner, mascara, dusting powder, baby powder and shaving. It is used as a compounding ingredient in basic cosmetics such as lotions, calamine lotions, face wash creams, emulsions, peel-off packs, antiperspirant powders. The content of the polyamino acid or its derivative particles in the cosmetic of the present invention varies depending on the intended use of the cosmetic, but is usually 0.1 to 80% by weight, preferably 0.5 to 60% by weight. . In this case, the blending amount is 0.1
If it is less than 80% by weight, the effect of the polyamino acid particles is unlikely to appear, and if it exceeds 80% by weight, the sticking to the skin tends to decrease.

Further, in the present invention, other than the particles of the polyamino acid or its derivative, the ingredients to be mixed in the cosmetic are:
It is selected according to the intended use of the cosmetic. For example,
Makeup cosmetics such as foundation, lipstick, powder lipstick, blusher, eye shadow, eyeliner, mascara, dusting powder, inorganic powders such as talc, mica, kaolin, sericite, muscovite; titanium oxide, oxidation Inorganic pigments such as zinc, yellow iron oxide, black iron oxide, titanium mica; red 201 (barium lake), red 226
Organic pigments such as No. 4 (calcium lake) and Yellow No. 4 (aluminum lake); hydrocarbons such as squalane, vaseline, liquid paraffin; oil components such as higher fatty acids, oils and fats, esters, higher alcohols, silicone oils, and ultraviolet rays Absorbents, antioxidants, preservatives, fragrances and the like are added.
In addition, basic cosmetics such as baby powder, shaving lotion, calamine lotion, facial cleansing cream, milky lotion, peel-off pack, antiperspirant powder, alcohols such as ethanol, butylene glycol, glycerin, cetanol, polyethylene glycol; stearic acid etc. Higher fatty acids; surfactants such as polyoxyethylene monostearate and polyoxyethylene sorbitan monolaurate; antiperspirants such as aluminum chloride and chlorohydroxyaluminum; germicides such as benzalkonium chloride and resorcin, and water , An antiseptic, a thickener, a moisturizer, and a fragrance. Furthermore, in the case of particles of porous polyamino acid or its derivative obtained by the method (1) or (4), and hollow polyamino acid obtained by the method (2) or (3) or its In the case of the particles of the derivative, the active ingredients such as the ultraviolet absorber, the bactericide, the fragrance, and the oil can be included or adsorbed in the inner pores of the particles to be used as a cosmetic.

[0027]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be specifically described below with reference to examples. Each measurement in the examples was performed as follows. From the value of the intrinsic viscosity measured at 30 ° C. in molecular weight dichloroacetic acid,
It calculated | required using the following formula. Poly-γ-benzyl-L-
In case of glutamate-NCA: [η] = 2.78 × 10 ⁻⁵ × Mw ^{0.87 In case of} poly-γ-methyl-L-glutamate-NCA: [η] = 2.90 × 10 ⁻⁴ × Mw ^0.74 [Η] is the intrinsic viscosity. While stirring 1 g of oil absorption particles, hydrocarbons or oil components (squalene, liquid paraffin or linseed oil) were added, and the amount added when the whole was collected was measured,
Oil absorption (milliliters / 100g)
100 g). Water absorption particles were placed in a 550 mesh nylon bag, immersed in water for 2 hours, and then air-dried (Ww) and 100 ° C.
It was calculated from the weight (Wo) after drying for 6 hours by the following formula. Water absorption rate (%) = [(Ww-Wo) / Wo] × 100

[0028]

【Example】

Example 1 To 300 ml of water, 1.5 g of polyoxyethylene sorbit tetraoleate (trade name "Reodol 440", manufactured by Kao Corporation) as an emulsifier and 0.6 ml of triethylamine as a polymerization initiator were added and stirred. ,
γ-benzyl-L-glutamate-NCA (hereinafter referred to as “B
LG-NCA ". ) Add 30 g and add 5 at room temperature.
By polymerizing for a time, an emulsion of poly-γ-benzyl-L-glutamate (hereinafter referred to as "PBLG") was obtained. This emulsion was freeze-dried to obtain 24 g of PBLG particles having an average particle size of 9 μm. The molecular weight of this PBLG was 41,000. As a result of measuring the oil absorption of the obtained PBLG particles, squalane 220 ml / 100 g, liquid paraffin 190 ml / 1
The amount was 00 g and linseed oil 180 ml / 100 g. Since the oil absorption of talc, kaolin or nylon particles is in the range of 50 to 70 ml / 100 g, it can be seen that the oil absorption of PBLG particles is very large. The water absorption rate of PBLG particles is 200.
%, And the water absorption rate of talc, kaolin, or nylon particles is in the range of 40 to 60%, which indicates that PBLG particles have a very high water absorption rate.

Next, the obtained PBLG particles (hereinafter referred to as "P
BLG-1 ”. ) Was used to prepare a powder foundation according to the formulation shown in Table 1. The preparation method is as follows. The powder parts were uniformly mixed and pulverized with a pulverizer. Separately, the binder was uniformly dissolved, and the powder portion and the binder were mixed using a Henschel mixer until the mixture became uniform, and the whole was crushed and then passed through a sieve. Then 1
It was pressed at a pressure of 00 to 200 kgf / cm ² and compression-molded in an appropriate container to obtain a powder foundation having a diameter of 5.8 cm. The oil absorption of the obtained powder foundation is squalane 460 ml / 1
00g, liquid paraffin 430ml / 100
g, linseed oil 450 ml / 100 g, the water absorption rate was 170%, which was considerably larger than that of the comparative example. When applied to the face, the cake is easily removed, spreads well on the skin, has a moist feel, and gives a natural finish. It was difficult.

Example 2 300 ml of dry diethyl ether and BLG-NCA were placed in a dry flask having an inner volume of 500 ml.
30 g, 0.2 ml of n-butylamine as a polymerization initiator
Was added and polymerized for 15 hours at room temperature with stirring. After the completion of the polymerization, the polymer was filtered and dried to obtain 24 g of PBLG particles having an average particle size of 11 μm. The molecular weight of this PBLG is 2
It was 3,000. The oil absorption of the obtained PBLG particles was as follows: squalane 460 ml / 100 g, liquid paraffin 430 ml / 100 g, linseed oil 36
It is 0 ml / 100 g and has a water absorption rate of 170.
%Met. Let this PBLG particle be PBLG-2, and
A powder foundation was prepared in the same manner as in Example 1 except that PBLG-2 was used instead of BLG-1 and the formulation of Table 1 was used. The oil absorption of the obtained powder foundation was 320 ml of squalane /
100 g, liquid paraffin 280 ml / 100
g, 260 ml of linseed oil / 100 g, the water absorption rate was 210%, which was considerably larger than that of the comparative example. Also, when applied to the face, the cake can be easily taken off, spreads well on the skin, spreads smoothly, has a moist feel, and gives a natural finish, and makeup makeup does not easily occur when sweating. It was a thing.

Example 3 BLG-NCA was converted to γ-methyl-L-glutamate-NC
The same operation as in Example 2 was carried out except that A was changed to 23 g of poly-γ-methyl-L-glutamate (hereinafter referred to as “PMLG”) particles having an average particle diameter of 14 μm. The molecular weight of this PMLG was 11,000. The oil absorption of the obtained PMLG particles was as follows: squalane 320 ml / 100 g, liquid paraffin 280 ml / 1
The amount was 00 g, the linseed oil was 200 ml / 100 g, and the water absorption rate was 210%. This PMLG particle is referred to as PMLG-1, and PMLG is used instead of PBLG-1.
-1 was used to prepare a powder foundation in the same manner as in Example 1 according to the formulation shown in Table 1. The oil absorption of the obtained powder foundation was 43.8 ml of linseed oil / 100 g, which was considerably larger than that of the comparative example. Also, when applied to the face, the cake can be easily taken off, spreads well on the skin, spreads smoothly, has a moist feel, and gives a natural finish, and makeup makeup does not easily occur when sweating. It was a thing.

Comparative Example 1 Nylon 1 was used instead of PBLG-1 used in Example 1.
2 particles (Brand name "Olgasol 2002 EX DN
A powder foundation was prepared in the same manner as in Example 1 by using “TCOS”, manufactured by Atochem Co., Ltd. and having the formulation shown in Table 1. The oil absorption of the obtained powder foundation was linseed oil 36.6 ml / 1.
00 g. Further, when applied to the face, the removal of the cake, the adhesion to the skin, and the spread were worse than those of Example 1, and the makeup loss when sweating was large. Further, when the oil absorption was increased to 40 ml / 100 g or more, cake cracking occurred.

Comparative Example 2 Instead of PBLG-1 used in Example 1, polymethylmethacrylate particles (trade name "Matsumoto Microsphere M-100", manufactured by Matsumoto Yushi Co., Ltd.) were used, and the formulation shown in Table 1 was used. Thus, a powder foundation was prepared in the same manner as in Example 1. The oil absorption of the obtained powder foundation was linseed oil 33.8 ml / 1
00 g. Further, when applied to the face, removal of the cake, adhesion to the skin, and spread were worse than those of Example 1, and makeup loss when sweating was large. Further, when the oil absorption was increased to 40 ml / 100 g or more, cake cracking occurred.

[0034]

[Table 1]

Example 4 Using the PBLG-1 used in Example 1 and according to the formulation shown in Table 2, a dual-purpose type cake foundation was prepared. The preparation method is as follows. The powder parts were mixed well and then pulverized with a pulverizer. The obtained powder was transferred to a high speed blender and mixed with a binder and other components, and then a pigment was further added and mixed. This mixture was crushed with a crusher, passed through a sieve, and compression-molded in an appropriate container to obtain a dual-purpose type cake foundation. The resulting dual-purpose type cake foundation spreads well when applied to the face, gives a moist feel, gives a natural finish, and is resistant to makeup loss when sweating. there were.

[0036]

[Table 2]

Example 5 A lipstick was prepared using the PBLG-1 used in Example 1 and the formulation shown in Table 3. The preparation method is as follows. A part of the castor oil in the base component and the coloring material were kneaded with a roller mill and uniformly dispersed. Separately, the remaining base component was heated to 75 to 85 ° C. to be uniformly dissolved, and the coloring material treated with the roller mill was added to and uniformly dispersed. Next, other components were added and mixed uniformly, and then the mixture was degassed under reduced pressure, and the temperature was adjusted to 70 to 75 ° C. while stirring so that bubbles were not mixed. Then
It was poured into an appropriate mold and rapidly cooled and solidified. The solidified product was taken out of the mold and filled in a container, and then framing was carried out to make the surface uniform and lipstick was obtained. The obtained lipstick spread well, had gloss, and had good moisturizing properties.

[0038]

[Table 3]

Example 6 Using PBLG-1 used in Example 1, a pressed lip powder was prepared according to the formulation shown in Table 4. The preparation method is as follows. Mix the talc and the fragrance in the powder component beforehand and disperse them evenly.
LG-1, preservative and pigment were added, and the mixture was pulverized with a pulverizer. This pulverized product was transferred to a high speed blender, a pearlescent agent was added, and the mixture was mixed uniformly. Separately, heat the binder and dissolve it evenly, add this to the powder part and the pearlescent agent,
Mix evenly. The mixture was crushed with a crusher, passed through a sieve, and compression-molded in an appropriate container to obtain a pressed lip powder. The obtained pressed lip powder spread well, had excellent adhesiveness, and moisturized the lips.

[0040]

[Table 4]

Example 7 PBLG-1 used in Example 1 was used to prepare a blusher according to the formulation shown in Table 5. The preparation method is as follows. The powder portion was uniformly mixed with a high speed blender. Separately, the binder was uniformly stirred, and this was added to a high speed blender to uniformly mix the whole. The mixture was crushed with a crusher, passed through a sieve, and compression-molded in an appropriate container to obtain a blusher. The obtained blusher had good spreadability, excellent adhesiveness, and was resistant to makeup breakage.

[0042]

[Table 5]

Example 8 Using PBLG-1 used in Example 1, an eye shadow was prepared according to the formulation shown in Table 6. The preparation method is
It is as follows. The powder portion was uniformly mixed with a high-speed blender, a binder was added to this, and the whole was uniformly mixed. This mixture was crushed with a crusher, passed through a sieve, and compression-molded in an appropriate container to obtain an eye shadow. The obtained eye shadow had excellent adhesion, good color development, and a moist feeling.

[0044]

[Table 6]

Example 9 Using PBLG-1 used in Example 1, a dusting powder was prepared according to the formulation shown in Table 7. The preparation method is as follows. The powder portion was uniformly mixed with a high-speed blender, and other components were sprayed on the powder portion, and then the whole was uniformly mixed. This mixture was ground with a grinder and passed through a sieve to obtain a dusting powder.
The resulting dusting powder spread well, had a refreshing finish, and had good moisturizing properties.

[0046]

[Table 7]

Example 10 Using PBLG-1 used in Example 1, a preshaving lotion was prepared according to the formulation shown in Table 8. The preparation method is as follows. Stir the aqueous phase,
Uniformly dissolved. Separately, the alcohol part was stirred and uniformly dispersed, and then this was added to the aqueous phase part with stirring to uniformly mix the whole. This mixture was filled into a suitable container with stirring to obtain a preshaving lotion. The resulting pre-shaving lotion had a dry feel, good slipperiness, and a moist feeling after use.

[0048]

[Table 8]

Example 11 Using the PBLG-1 used in Example 1, a calamine lotion was prepared according to the formulation shown in Table 9. The preparation method is as follows. The aqueous phase was thoroughly stirred to wet-disperse the powder component. Separately stir the alcohol part,
Disperse evenly, add this to the aqueous phase with stirring,
The whole was mixed uniformly. Add this mixture to a coarse filter cloth (8
After filtering with 0 to 120 mesh), the whole was filled into a suitable container with stirring to obtain a calamine lotion. The resulting calamine lotion was well spread, had a dry feel, and gave a moist feeling after use.

[0050]

[Table 9]

Example 12 Using PBLG-1 used in Example 1, a face cleansing cream was prepared according to the formulation shown in Table 10. The preparation method is as follows. The components (a) to (h) were mixed and dissolved by stirring at 70 to 75 ° C. Separately, the components (i) and (j) were mixed and uniformly dispersed, and this was added to the components (a) to (h) and mixed uniformly. The mixture was stirred and cooled to 40 ° C. to obtain a face cleansing cream. The obtained face cleansing cream had a fine foaming and had no firm skin after use.

[0052]

[Table 10]

Example 13 An emulsion was prepared using the PBLG-1 used in Example 1 and the formulation shown in Table 11. The preparation method is as follows. 77 to 8 by mixing the components (a) to (e)
It was dissolved by stirring at 0 ° C. Separately, the components (f) to (j) are put into a container having a capacity capable of charging the whole amount, and the components are dissolved by stirring at 75 to 78 ° C., while stirring the components (a) to
The component (e) was added and emulsified. To this emulsion, the components (k) and (l), which had been uniformly dispersed in a separate container, were added, and the mixture was uniformly mixed with a homogenizer, then cooled to 30 ° C. with stirring and filled in an appropriate container. , An emulsion was obtained. The obtained emulsion had good spreadability and excellent moisturizing sensation.

[0054]

[Table 11]

Example 14 Using PBLG-1 used in Example 1, a peel-off pack was prepared according to the formulation shown in Table 12. The preparation method is as follows. After swelling the components (b) and (c) with the component (a), the components (d) to (f) were added and heated at about 80 ° C. to dissolve them. to this,
The components (g) and (h), which had been uniformly dispersed in a separate container, were added, and the whole was mixed uniformly.
It was cooled to 30 ° C. and filled in a suitable container to obtain a peel-off pack. The peel-off pack obtained had good elongation and had a moist feeling despite a refreshing finished feeling.

[0056]

[Table 12]

[0057]

Industrial Applicability The cosmetic composition of the present invention can be produced industrially advantageously, has a good feeling in use, and is highly water-absorbent and oil-absorptive, which polyamino acids and their derivatives have. With high absorbency of sebum, it can give the skin a moist feeling and a refreshing feeling, and in the case of makeup cosmetics, the particles of polyamino acid or its derivative absorb water and sebum well, so that moisturizing property, It has the characteristics of excellent durability and less likely to cause makeup breakdown.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location A61K 7/031 A61K 7/031 7/15 7/15 7/32 7/32 C08G 69/10 NRN C08G 69/10 NRN (72) Inventor Takatsugu Yoshioka 1-7-11 Doshomachi, Chuo-ku, Osaka City, Osaka Prefecture Iwase Cosfa Co., Ltd. (72) Norio Matsuda 1-7 Doshomachi, Chuo-ku, Osaka City, Osaka Prefecture No. 11 Iwase Cosfa Co., Ltd.

Claims (1)

[Claims] 1. A cosmetic comprising particles of poly α-amino acid or a derivative thereof obtained by emulsion polymerization or heterogeneous polymerization of α-amino acid-N-carbonic anhydride.