JP2003146863A - Emulsifying agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an emulsifying agent giving high emulsion stability, an emulsion composition containing the agent and a cosmetic. SOLUTION: The emulsifying agent is composed of a polyamino acid graft copolymer having the polymer unit (1) [X is a 1-22C alkylene or the like; Y is a group of formula (3), (4) or (5); R<1> , R<2> , R<3> , R<4> , R<5> and R<6> are each H, a 1-22C alkyl or the like; R<7> is H, a 1-22C alkyl or the like; R<8> is a 1-22C alkyl having anionic group; Z<-> is an anion; (p) is 0 or 1; and (n) is 1-500] and the polymer unit (2) (R<9> is H or CH3 ; and R<10> is a 1-22C alkyl or the like). The invention further provides an emulsion composition containing the emulsifying agent and an oil and a cosmetic containing the graft copolymer.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an emulsifier having excellent emulsion stability, an emulsion composition containing the emulsifier, and a cosmetic.

[0002]

2. Description of the Related Art Conventionally, the problems to be solved by the invention
Numerous studies on emulsification have been done and many emulsifiers have been developed. Further, the progress of emulsification technology is remarkable, and very stable emulsions are widely used in all industries.

However, most of them use a nonionic surfactant containing a polyoxyethylene chain, an anionic surfactant represented by an aliphatic soap, or an amphoteric surfactant as an emulsifier. In recent years, a method of obtaining an emulsion composition by utilizing an alkyl-modified water-soluble polymer without using a surfactant has been investigated. For example, CARBOPOL1 as an alkyl-modified carboxyvinyl polymer
342, PEMULEN TR-1, PEMULEN
Examples thereof include those known by trade names such as TR-2 (BF Goodrich).

However, these polymers have relatively small emulsifying power and poor emulsion stability. Therefore, in order to improve the stability, it is necessary to mix a large amount, but such a large amount of compound causes elasticity (gelation) at a low temperature and remarkably impairs the usability of the emulsion.

An object of the present invention is to provide an emulsifier showing high emulsion stability, an emulsion composition containing the emulsifier, and a cosmetic.

[0006]

The present invention is based on the general formula (1)
A polyamino acid graft copolymer (hereinafter referred to as a graft copolymer) having a polymerized unit represented by (hereinafter referred to as polymerized unit (1)) and a polymerized unit represented by the general formula (2) (hereinafter referred to as polymerized unit (2)) Called), this emulsifier,
Emulsified composition containing oil and water, cosmetic containing this emulsifier, and polymerized unit (1) and polymerized unit (2)
There is provided a cosmetic containing the polyamino acid graft copolymer having:

[0007]

[Chemical 6]

[Wherein, X is a linear or branched alkylene group having 1 to 22 carbon atoms, a cycloalkylene group having 3 to 22 carbon atoms, or a carbon number which may have a substituent containing a hetero atom. 7 to 22 is an alkylenearylene group or an arylenealkylene group, or an arylene group having 6 to 22 carbon atoms. Y represents a group represented by formula (3), (4) or (5).

[0009]

[Chemical 7]

R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same or different, and may be a hydrogen atom or a hetero atom-containing substituent, which is a straight chain having 1 to 22 carbon atoms. A chain or branched chain alkyl group, or a C3-C22 cycloalkyl group,
Aralkyl group having 7 to 22 carbon atoms or 6 to 22 carbon atoms
The aryl group of is shown. R ³ or R ⁴ and R ⁵ may together form a ring. R ⁷ is a hydrogen atom, or a linear or branched alkyl or alkenyl group having 1 to 22 carbon atoms, which may have a substituent containing a hetero atom, or a cycloalkyl group or carbon atom having 3 to 22 carbon atoms. Number 7 ~
22 represents an aralkyl group having 22 or an aryl group having 6 to 22 carbon atoms. R ⁸ has 1 to 22 carbon atoms having an anionic group
Is a linear or branched alkyl group. Z ⁻ represents an anion, p represents 0 or 1, and n represents a number of 1 to 500. ]

[0011]

[Chemical 8]

[In the formula, R ⁹ represents a hydrogen atom or a methyl group. R ¹⁰ represents a linear or branched alkyl group having 1 to 22 carbon atoms, a cycloalkyl group having 3 to 22 carbon atoms, an alkylaryl group or aralkyl group having 7 to 22 carbon atoms,
Alternatively, it represents an aryl group having 6 to 22 carbon atoms. ]

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION [Graft Copolymer] The graft copolymer of the present invention contains polymerization units (1) and (2), and the polymerization mode of the polymerization units (1) and (2) is a block. Alternatively, it may be random.

In the polymer unit (1), X is a linear or branched alkylene group having 1 to 8 carbon atoms or an alkylenearylene group having 7 to 10 carbon atoms, which may have a substituent containing a hetero atom. Alternatively, an arylene alkylene group or an arylene group having 6 to 9 carbon atoms is preferable. The hetero atom, hydrogen in the organic compound, refers to an atom other than carbon, as a substituent containing a hetero atom, a hydroxyl group, a carboxy group, a mercapto group, a dithioether group, an amino group, a guanidino group, an ester group, an ether Examples thereof include groups, amide groups, and acyl groups (hereinafter referred to as substituents of the present invention), and among these, amino groups, ester groups, and amide groups are preferable.

R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same or different and may have a substituent containing a hydrogen atom or a hetero atom, which may be a direct group having 1 to 8 carbon atoms. Chain or branched chain alkyl group, C3-6 cycloalkyl group, C7
An aralkyl group having 10 to 10 or an aryl group having 6 to 9 carbon atoms is preferable. R ³ or R ⁴ and R ⁵ may together form a ring. Examples of the substituent containing a hetero atom include the substituents of the present invention, and of these, an acyl group is preferable.

The average value of n is preferably 1 to 250, more preferably 5 to 100, particularly preferably 5 to 30. The n + 1 R ³ , R ⁴ , and R ⁵ may be the same or different.

In the formula (4), R ⁷ is preferably an alkyl group or an alkenyl group having 1 to 8 carbon atoms. Z ⁻ represents an anion, and may be an anion represented by Z ²⁻ or Z ³⁻ as a counter ion of 2 or 3 groups represented by the formula (4).
As such anions, chlorine, iodine, halogen ions such as bromine, sulfuric acid, inorganic anions obtained by removing a proton from an inorganic acid such as phosphoric acid, methosulfate, ethosulfate, metophosphate, etophosphate, or acetic acid, lactic acid. Alternatively, an organic anion obtained by removing a proton from an organic acid such as citric acid may be used.

In the formula (5), R ⁸ is an anionic group,
Preferably, it is a C1-C8 alkyl group having a carboxy group or a sulfonic acid group, more preferably a C1-C3 alkyl group, and the group represented by the formula (5) is a group showing carbobetaine or sulfobetaine. preferable.

In the polymerized unit (1), the formula (6)

[0020]

[Chemical 9]

Examples of the polyamino acid constituting the polyamino acid segment represented by the formula (wherein R ³ , R ⁴ , R ⁵ and n have the above-mentioned meanings) include, for example, polyglycine, polyalanine and polyN. -Methylglycine, polymers of neutral amino acids such as polyproline, polyglutamic acid, polymers of acidic amino acids such as polyaspartic acid, polyγ-methylglutamic acid, polymers of acidic amino acid esters such as poly β-methylaspartic acid, Poly ε-lysine, poly σ-
Polymers of basic amino acids such as ornithine, polyarginine and polyhistidine, polymers of acylated basic amino acids such as poly ε-N-acetyllysine and poly σ-N-carbobenzoxyornithine, polyserine and polycysteine. Examples thereof include polymers of amino acids having a hydroxyl group such as and a mercapto group, and polymers of derivatives thereof such as acetyl and isopropylidene. Among these, poly-N-methylglycine is particularly preferable because the obtained polymer has high emulsion stability. Further, the polyamino acid may be a copolymer composed of two or more kinds of amino acids.

In the polymerized unit (2), R ¹⁰ has 1 to ¹⁰ carbon atoms.
22 straight or branched chain alkyl groups, 7 to 1 carbon atoms
An alkylaryl group or aralkyl group having 0 or an aryl group having 6 to 9 carbon atoms is preferable, and a linear or branched alkyl group having 1 to 8 carbon atoms is more preferable.

The proportion of the polymerized units (1) and the polymerized units (2) in the graft copolymer of the present invention is 5:95 in terms of mass ratio.
To 95: 5 are preferable, and 10:90 to 9 are more preferable.
It is 0:10. Within the above range, an emulsifier having higher emulsion stability can be obtained.

The weight average molecular weight of the graft copolymer of the present invention is preferably 10,000 to 1,000,000. Within this range, an emulsifier having high emulsion stability can be easily obtained. The weight average molecular weight is measured by gel permeation chromatography by drying the polymer under reduced pressure at 105 ° C. for 2 hours, using polystyrene as a standard substance and chloroform as a solvent.

[Production Method of Graft Copolymer] The graft copolymer of the present invention has the general formula (7)

[0026]

[Chemical 10]

(Wherein X, Y, R ¹ , R ² , R ³ , R ⁴ and R
⁵ , p and n have the above-mentioned meanings. ) A macromonomer having a polyamino acid segment (hereinafter referred to as polyamino acid macromonomer (7)), and a general formula (8)

[0028]

[Chemical 11]

It can be obtained by copolymerizing with a monomer represented by the formula (wherein R ⁹ and R ¹⁰ have the above-mentioned meanings) (hereinafter referred to as monomer (8)).

Further, the graft copolymer of the present invention has 1
You may copolymerize other monomers more than a kind. Other monomers include, for example, JP-A-4-26830.
No. 5, page 3, column 3, line 50 to column 4, line 29, anionic monomers such as methacrylic acid, acrylic acid, maleic acid, fumaric acid or anhydrides thereof, or dimethyl methacrylate. Cationic monomers such as aminoethyl, diethylaminoethyl methacrylate, N- (3-dimethylaminopropyl) acrylamide, N- (3-dimethylaminopropyl) methacrylamide, N, N-dimethylaminoethyl diethylsulfate methacrylate, etc. Is mentioned.

As a method for copolymerizing the polyamino acid macromonomer (7) and the monomer (8) and, if necessary, other monomers, a polymerization method such as bulk polymerization or solution polymerization can be used.

A known radical polymerization initiator is used as the polymerization initiator. For example, hydroperoxides represented by t-butyl hydroperoxide, dialkyl peroxides represented by di-t-butyl peroxide, acetyl peroxide, diacyl peroxides represented by benzoyl peroxide,
Ketone peroxides represented by methyl ethyl ketone peroxide, and azo-based polymerization initiators are included.

For example, a radical polymerization initiator is added in an amount of 0.1 to 30 mol% based on all monomers, a chain transfer agent is used if necessary, and the solution is refluxed under a nitrogen gas stream at 50 to 300 ° C. under solvent reflux. By carrying out the polymerization, the graft copolymer of the present invention can be obtained.

Y in polyamino acid macromonomer (7)
Is a group represented by formula (3), R ⁵ and / or R ⁶
However, when it is a hydrogen atom, it may undergo a Michael addition reaction with the polymerizable vinyl bond of acrylic acid or methacrylic acid and its ester, amide, or salt which can be used as other monomers. When R ⁵ and / or R ⁶ is likely to be a hydrogen atom, it is preferable to polymerize after converting to an acylated product and the like.

In addition, if necessary, an inorganic acid such as sulfuric acid, hydrochloric acid or phosphoric acid, acetic acid or lactic acid may be added to the group represented by the formula (3).
An acid addition salt is formed with an organic acid such as citric acid, or is cationized with a cationizing agent such as an alkyl halide or an alkenyl halide, or a dialkyl sulfate or a dialkenyl sulfate to give a group represented by the formula (4). Good. Specific examples of the cationizing agent include alkyl halides having 1 to 8 carbon atoms such as methyl chloride, ethyl chloride, methyl bromide and methyl iodide, and carbon numbers such as dimethyl sulfate, diethyl sulfate and di-n-propyl sulfate. 1
Examples thereof include dialkyl sulfates having an alkyl group of ~ 8.

Further, the group represented by the formula (3) may be reacted with a halogenated alkylcarboxylic acid salt, a halogenated alkylsulfonic acid salt or the like to obtain the betaine represented by the formula (5). Examples of the halogenated alkyl carboxylate or halogenated alkyl sulfonate include sodium 3-chloropropylcarboxylate, sodium 3-chloropropylsulfonate, sodium chloroacetate and the like.

In the polyamino acid macromonomer (7), Y
Is a group represented by the general formula (9)

[0038]

[Chemical 12]

[Alpha] -amino acid-N-carboxylic acid anhydride (hereinafter referred to as [alpha] -amino acid NCA) represented by the formula (wherein R ³ , R ⁴ and R ⁵ have the above-mentioned meanings), In an inert solvent, the α-amino acid NCA and the compound represented by the general formula (1
0)

[0040]

[Chemical 13]

(In the formula, X, R ¹ , R ² and p have the above-mentioned meanings.) A primary and / or secondary amine having a polymerizable unsaturated group (hereinafter, a polymerizable unsaturated group). It is also referred to as an amine having a).

The α-amino acid NCA is, for example, Japanese Patent Publication No.
No. 9-5132, page 4, column 8, lines 20 to 44 may be mentioned. Among these, N-methylglycine NCA is preferable as the α-amino acid NCA.

The α-amino acid NCA can be used in either an optically active form or a racemic form. Two or more kinds of these α-amino acids NCA may be used in combination, and when two or more kinds of α-amino acids NCA are simultaneously added, two or more kinds of α-amino acids are randomly generated.
-A block in which the amino acids are arranged results. The second α-amino acid NCA after the polymerization of one α-amino acid NCA is completed.
Is added, a product in which two kinds of α-amino acids are arranged in a block form is obtained.

As the reaction solvent, an organic solvent that dissolves the α-amino acid NCA to be used and is inactive to the α-amino acid NCA and the amine having a polymerizable unsaturated group, that is, does not have active hydrogen is used. Is appropriate. Such a reaction solvent depends on the type of the α-amino acid NCA and needs to be selected, but is generally a halogenated hydrocarbon, for example, methylene chloride, chloroform, 1,1-dichloroethane, 1,2-dichloroethane, 1 , 1,2-Trichloroethane, 1,1,1-trichloroethane, tetrachloroethane, dichloropropane, dichlorobenzene and the like;
Fatty acid esters such as methyl acetate, ethyl acetate, butyl acetate, amyl acetate, ethyl propionate and the like; cyclic ethers such as dioxane and tetrahydrofuran;
Other examples include N-methylpyrrolidone, dimethylformamide, dimethylsulfoxide and the like. The reaction solvent may be a mixed system. Further, if necessary, it is also possible to mix a non-solvent with the α-amino acid NCA having no active hydrogen and carry out solid phase polymerization.

When a predetermined amount of amine having a polymerizable unsaturated group and α-amino acid NCA are added and mixed in the above reaction solvent, generation of carbon dioxide is recognized and the reaction starts immediately. Poly-α defined by the equivalent ratio of α-amino acid NCA to amine having a polymerizable unsaturated group
-High yields of polyamino acids with amino acid segment lengths are obtained. The equivalent ratio of the α-amino acid NCA to the equivalent of the amine having a polymerizable unsaturated group (hereinafter, NCA / AM
1 to 250 is preferable (α-amino acid N).
1 mol of CA is 1 equivalent because of reactivity).

The reaction components may be added and mixed by any method such as simultaneous addition, sequential addition, total amount addition, partial sequential addition, etc., but it is easy to adjust the polyamino acid segment length, change the polyamino acid composition, etc. In order to carry out reliably, the amine having a polymerizable unsaturated group is uniformly dissolved or dispersed in the reaction solvent in advance, and then the α-amino acid NCA is added in total amount or sequentially added according to the reaction rate. The method is suitable and desirable.

The reaction temperature is determined in consideration of the properties of the resulting polyamino acid macromonomer (7), the reactivity of the α-amino acid NCA with an amine having a polymerizable unsaturated group, the boiling point of the reaction solvent, and the like. Generally -5 ° C to 20
It is desirable to carry out in the temperature range of 0 ° C.

The polyamino acid macromonomer (7) is preferably a polyamino acid macromonomer represented by the general formula (11) or (12).

[0049]

[Chemical 14]

The graft copolymer of the present invention exhibits high emulsion stability and is useful as an emulsifier.

[Emulsion Composition] The emulsion composition of the present invention contains the graft copolymer of the present invention, an oil agent and water,
Since the graft copolymer serves as an emulsifier, the oil agent can be stably retained in the composition.

In the emulsion composition of the present invention, the amount of the oil agent is preferably 1 to 10000 parts by mass, more preferably 10 to 1000 parts by mass, based on 100 parts by mass of the graft copolymer. Water is 1 part by weight of the graft copolymer,
It is preferably 0.1 to 1000 parts by mass, and 1 to 1
000 parts by mass is more preferable.

As the oil agent used in the present invention, it is preferable to use a general cosmetic oil agent usually used in cosmetics. These oil agents are not particularly limited, but include cyclic silicones such as octylmethylcyclotetrasiloxane and dodecamethylcyclohexasiloxane, silicone oils such as chain silicones such as dimethylpolysiloxane and methylphenylpolysiloxane; avocado oil, camellia oil, macadamia nuts. Vegetable oils such as oil, olive oil and jojoba oil; fatty acids such as oleic acid and isostearic acid; alcohols such as hexadecyl alcohol, stearyl alcohol, oleyl alcohol and behenyl alcohol; cetyl 2-ethylhexanoate, 2-ethylhexyl palmitate,
2-Octyldodecyl myristate, neopentyl glycol di-2-ethylhexanoate, glycerol tri-2-ethylhexanoate, 2-octyldodecyl oleate, isopropyl myristate, glycerol triisostearate, tri-2-ethyl Esters such as glycerol hexanoate, 2-octyldodecyl oleate, isopropyl myristate, glycerol triisostearate, diglyceride 2-ethylhexanoate, di-paramethoxycinnamic acid-mono-2-ethylhexanoate glyceryl; liquid paraffin, Liquid hydrocarbon oils such as squalene, squalane; beeswax, spermaceti, microcrystalline wax, carnauba wax, candelilla wax,
Examples thereof include waxes such as petroleum wax and polyethylene wax; vitamins such as vitamin A, vitamin E, panthenol and pantothenyl ethyl ether; ceramide and its similar structural substances; and other substances such as petrolatum, lanolin and ceresin. These oil agents can be used alone or in combination of two or more kinds.

In the method for producing the emulsion composition of the present invention, it is preferable that the graft copolymer and the oil agent are mixed with an organic solvent and then mixed with water. As the organic solvent, methanol, ethanol, isopropyl alcohol, tetrahydrofuran,
Water-soluble solvents such as acetone and methyl ethyl ketone are preferred. The emulsion composition of the present invention can be preferably used for cosmetics and the like.

[Cosmetic] The graft copolymer of the present invention is
Since it has a hydrophobic polymerized unit, it is preferably self-emulsified in water, and a cosmetic containing it is preferable in terms of skin feel.

The content of the graft copolymer in the cosmetic is
The amount is preferably 0.01 to 90% by mass, more preferably 0.
05-70% by mass, particularly preferably 0.1-30% by mass
Is.

Furthermore, the cosmetic of the present invention preferably contains an oil agent, and the graft copolymer serves as an emulsifier.
The oil agent can be stably retained in the cosmetic. Examples of the oil agent include those described in the section of the above emulsified composition. The content of the oil agent in the cosmetic of the present invention is preferably 0.5 to 30% by mass, more preferably 1 to 20% by mass.

The cosmetic of the present invention may contain a water-soluble solvent, and examples thereof include lower alcohols or polyols such as ethanol, glycerin, sorbitol, propylene glycol and 1,3-butylene glycol.

As the viscosity modifier, a high molecular compound such as polyvinyl alcohol, carboxyvinyl polymer, carboxymethylcellulose, polyvinylpyrrolidone, hydroxyethylcellulose, methylcellulose and the like may be contained.

Furthermore, the cosmetics of the present invention may contain other emulsifiers, if necessary, within a range not impairing the effects of the present invention. Examples of such emulsifiers include glycerin fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyethylene glycol fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene hydrogenated castor oil derivative, and alkyl. Preferred examples include glyceryl ether and polyoxyalkylene-modified polysiloxane.

The cosmetics of the present invention further include water-soluble and oil-soluble polymers, inorganic and organic pigments, coloring materials such as organic dyes, anion activators, cation activators, and nonionic activators as components usually used in cosmetics. Agents, surfactants such as polyether modified silicone, etc., other, water, preservatives, antioxidants, thickeners, pH adjusters, dyes, fragrances, ultraviolet absorbers,
A moisturizing agent, a blood circulation promoting agent, a cooling sensation agent, an antiperspirant, a bactericidal agent, a skin protecting agent, a chelating agent and the like can be appropriately added within a range not impairing the effects of the present invention.

The cosmetics to which the present invention is applied are not limited to general skin cosmetics, but include hair cosmetics, quasi drugs, external medicines, and the like, for example, face care cream or Creams such as emulsion, hand / body care cream or emulsion, hair milk, hair cream, etc.
Emulsions; basic cosmetics such as lotions, beauty essences, moisturizers, and emulsions; liquid or cream type foundations; and external medicines such as anti-inflammatory creams and insect bite creams;
Skin cleansing agents, whole body cleansing agents, shampoos, rinses and other cleansing agents can be mentioned. These are prepared from the above components by a conventional method.

[0063]

EXAMPLES Parts and% in the examples are based on mass unless otherwise specified.

Synthesis Example 1 (Synthesis of Macromonomer) 100 parts of methylene chloride and 7 parts of p-aminomethylstyrene were charged, and after substitution with nitrogen gas, N-methylglycine-N- was used.
A solution of 77 parts of carboxylic acid anhydride in methylene chloride (500 parts) was added dropwise at room temperature over about 2 hours (NCA / AMI).
= 13). Carbon dioxide gas was generated during the dropping, and ring-opening polymerization of N-methylglycine-N-carboxylic acid anhydride proceeded. Further, after stirring at room temperature for 1 hour, 26 parts of triethylamine was added. After cooling the flask with an ice bath, 20 parts of acetyl chloride was added dropwise over 15 minutes. After stirring overnight at room temperature, the reaction mixture was put into 3000 parts of hexane, and the generated precipitate was dissolved in 1000 parts of ion-exchanged water. Ion exchange resin (Amberlite MB-1 manufactured by Organo Corporation)
After adding 500 parts and stirring for about 2 hours, the ion-exchange resin was filtered off and freeze-dried to give a macromonomer having a poly-N-methylglycine chain (molecular weight 1, 10
0) was obtained.

Synthesis Example 2 30 parts of macromonomer having poly-N-methylglycine chain obtained in Synthesis Example 1, 70 parts of methyl acrylate,
2,2-azobis (2,4-dimethylvaleronitrile)
0.5 part of chloroform 300 parts and methanol 100
Part of the mixed solvent, and after purging with nitrogen gas, at 50 at 65 ℃
Stir for hours. The solvent was distilled off from the reaction mixture under reduced pressure, and the obtained residue was subdivided and washed with 500 parts of hexane. Furthermore, after washing with 500 parts of ion-exchanged water and drying under reduced pressure, a p-aminomethylstyrene-methyl acrylate copolymer (molecular weight 30,000) grafted with a poly-N-methylglycine chain was obtained.

Synthesis Example 3 A p-aminomethylstyrene-butyl acrylate copolymer grafted with a poly-N-methylglycine chain (molecular weight 30,000) was prepared in the same manner as in Synthesis Example 2 except that butyl acrylate was used instead of methyl acrylate. Got

Example 1 10 parts of p-aminomethylstyrene-methyl acrylate copolymer grafted with the poly-N-methylglycine chain obtained in Synthesis Example 2 was dissolved in 30 parts of ethanol, and 120 parts of deionized water was slowly added. Dropped. Ethanol and water were distilled off under reduced pressure to obtain an emulsion having a polymer content of 10%.

Example 2 The poly-N-methylglycine chain obtained in Synthesis Example 3 was replaced by the poly-N-methylglycine chain grafted with the poly-N-methylglycine chain obtained in Synthesis Example 2. An emulsion having a polymer content of 10% was obtained in the same manner as in Example 1 except that the grafted p-aminomethylstyrene-butyl acrylate copolymer was used.

Example 3 1 part of p-aminomethylstyrene-butyl acrylate copolymer grafted with the poly-N-methylglycine chain obtained in Synthesis Example 3 and 1 part of squalane were dissolved in 4 parts of ethanol and slowly ion-exchanged. Drop 94 parts of water,
An emulsified composition was obtained.

Formulation Example A lotion containing the emulsions or emulsion compositions obtained in Examples 1 to 3 was produced according to the following formulation, and a sensory evaluation of the feeling of use was performed by one expert evaluator by the following method. I did.
In addition, the emulsion stability was evaluated by the following method. The results are shown in Table 1.

<Formulation of Lotion> Emulsions or emulsified compositions of Examples 1 to 3 1.0% ethanol 5.0 glycerin 10.0 dipropylene glycol 3.0 preservative proper amount perfume proper amount pH adjuster proper amount purified water Remaining amount <feeling of use> The feel when the lotion is applied on the skin (at the time of application) and the feel after the application and drying on the skin (at the time of application) are sensory-evaluated according to the following criteria. Evaluation criteria ⊚: Very good, ◯: Good, Δ: Normal, ×: Poor <Emulsion stability> Emulsion stability was visually evaluated immediately after emulsification and after storage in a thermostatic chamber at 50 ° C for 1 week.

[0072]

[Table 1]

As shown in Table 1, the cosmetics of the present invention had good feeling in use and good emulsion stability.

[0074]

INDUSTRIAL APPLICABILITY The graft copolymer of the present invention can be used as an emulsifier for oils such as fragrances, vitamins and ceramides, and cosmetics containing the same give a protective film to the skin and give a pleasant feeling. Can be given.

Continued front page    F-term (reference) 4C083 AC102 AC122 AD042 AD071                       AD072 BB41 BB44 BB48                       CC03                 4D077 AA09 AB11 AC01 BA02 BA03                       BA07 DD06X DD12Y DD18Y                       DE04Y DE10Y DE24Y                 4J027 AD01 BA07 CD00

Claims (4)

[Claims] 1. An emulsifier comprising a polyamino acid graft copolymer having a polymerized unit represented by the general formula (1) and a polymerized unit represented by the general formula (2). [Chemical 1] [In the formula, X may have a substituent containing a hetero atom, and may be a linear or branched alkylene group having 1 to 22 carbon atoms, a cycloalkylene group having 3 to 22 carbon atoms, or 7 to carbon atoms.
22 shows an alkylenearylene group having 22 or an arylenealkylene group, or an arylene group having 6 to 22 carbon atoms.
Y represents a group represented by formula (3), (4) or (5). [Chemical 2] R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same or different,
A hydrogen atom, a linear or branched alkyl group having 1 to 22 carbon atoms, or a cycloalkyl group having 3 to 22 carbon atoms, which may have a substituent containing a hetero atom, or 7 carbon atoms
Is an aralkyl group having 22 to 22 or an aryl group having 6 to 22 carbon atoms. R ³ or R ⁴ and R ⁵ may together form a ring. R ⁷ is a hydrogen atom, or a linear or branched alkyl or alkenyl group having 1 to 22 carbon atoms, which may have a substituent containing a hetero atom, or a cycloalkyl group or carbon atom having 3 to 22 carbon atoms. An aralkyl group having 7 to 22 carbon atoms or an aryl group having 6 to 22 carbon atoms is shown. R ⁸ represents a linear or branched alkyl group having 1 to 22 carbon atoms having an anionic group. Z ^- is an anion,
p represents 0 or 1, and n represents a number of 1 to 500. ] [Chemical 3] [In the formula, R ⁹ represents a hydrogen atom or a methyl group. R ¹⁰ is a linear or branched alkyl group having 1 to 22 carbon atoms, a cycloalkyl group having 3 to 22 carbon atoms, an alkylaryl group or aralkyl group having 7 to 22 carbon atoms, or 6 carbon atoms.
The aryl groups of 22 are shown. ] 2. An emulsified composition containing the emulsifier according to claim 1, an oil agent, and water. 3. A cosmetic containing the emulsifier according to claim 1. 4. A cosmetic containing a polyamino acid graft copolymer having a polymerized unit represented by the general formula (1) and a polymerized unit represented by the general formula (2). [Chemical 4] [Wherein X, Y, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , p and n
Indicates the above meaning. ] [Chemical 5] [In the formula, R ⁹ and R ¹⁰ have the above-mentioned meanings. ]