JP2002145724A - Cosmetic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cosmetic having high absorbing property to skin and hair and exhibiting natural gloss, smoothness, powdery feeling and water- repelling property of skin and skin-protecting effect. SOLUTION: This cosmetic comprises a modified silicone having a polyamino acid segment and an organopolysiloxane segment.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to cosmetics useful for skin and hair.

[0002]

2. Description of the Related Art
Oil-like polyorganosiloxanes (commonly known as silicone oils) represented by polydimethylsiloxane have properties such as water repellency, lubricity, and gloss imparting properties.
It has been applied to mold release agents, defoamers, polishes, fabric softeners, cosmetics, and the like. However, the silicone oil is well soluble in low-polarity n-hexane and the like, but is inherently hardly soluble in other solvents, particularly in highly polar solvents such as water. In addition, since it is difficult to emulsify in water, there is a limitation in its use. That is, when a silicone oil is blended with a cosmetic, it is necessary to uniformly disperse, emulsify or solubilize the silicone oil in order to exhibit the above properties, and a large amount of a surfactant is required in the blending. In addition, silicone oil is structurally
Since it has no adsorption points to the hair, the residual state is merely physical attachment. Due to these factors, the amount of adhesion to skin and hair is extremely low, and sufficient performance is not exhibited.

In order to improve such disadvantages and to impart new properties to silicone oils, modification by introducing long-chain alkyl groups, polyoxyalkylene groups, amino groups, carboxyl groups and epoxy groups has been carried out. Have been done. However, in such an oil agent, the proportion of the polyoxyalkylene portion relative to the whole becomes high in order to balance hydrophilicity and hydrophobicity, and the performance as silicone may not be exhibited.

[0004] As described above, the conventional modified silicone has the performance as a component for cosmetics, that is, the properties (lubricity, water repellency, gloss imparting, and dry feeling) of the silicone oil, skin and hair. All performances such as adsorptivity and solubility in water and other highly polar solvents could not be satisfied.

[0005] An object of the present invention is to provide a cosmetic composition having a high adsorptivity to the skin and hair, and exhibiting natural luster, smoothness, dry feeling, water repellency of the skin and skin protective effects.

[0006]

The present invention relates to a cosmetic containing a modified silicone having a polyamino acid segment and an organopolysiloxane segment (hereinafter referred to as a polyamino acid modified silicone).

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS [Polyamino acid-modified silicone]
The polyamino acid-modified silicone used in the present invention has an alkylene group containing a hetero atom between at least one silicon atom at the terminal and / or side chain of the organopolysiloxane segment and the carbonyl group of the polyamino acid. Is preferred.

The alkylene group containing a hetero atom is more preferably at least one selected from groups represented by the general formula (I) or (II).

[0009]

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(Wherein R ¹ , R ² and R ³ are the same or different and each may have a substituent containing a heteroatom, a linear or branched alkylene group having 2 to 22 carbon atoms; An alkenylene group or an arylene group having 6 to 22 carbon atoms is shown.) In the general formula (I) or (II), R ¹ and R ² represent a linear or branched alkylene group having 2 to 8 carbon atoms. Preferably, a trimethylene group is more preferable. R ³ is preferably a linear or branched alkylene group having 2 to 8 carbon atoms, and more preferably an ethylene group. Examples of the substituent containing a hetero atom in R ¹ , R ² and R ³ include an ester group and an ether group.

The polyamino acid constituting the polyamino acid segment preferably has a repeating unit represented by the general formula (III).

[0012]

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(Wherein R ⁴ , R ⁵ and R ⁶ are the same or different and each may have a straight-chain or branched chain having 1 to 22 carbon atoms, which may have a substituent containing a hydrogen atom or a hetero atom). An alkyl group, a cycloalkyl group having 6 to 22 carbon atoms, an aralkyl group having 7 to 22 carbon atoms or an aryl group having 6 to 22 carbon atoms, and R ⁴ or R ⁵ and R ⁶ together form a ring In formula (III), R ⁴ and R ^{5 each} represent a hydrogen atom or a carbon atom
To 8 linear or branched alkyl groups are preferred.
⁶ is preferably a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms. Examples of the substituent containing a hetero atom include a hydroxyl group, a mercapto group, a dithioether group, an amino group, a guanidino group, an ester group, an ether group, and an amide group.

As such a polyamino acid, for example,
Polymers of neutral amino acids such as polyglycine, polyalanine, poly N-methylglycine, polyproline; polymers of acidic amino acids such as polyglutamic acid and polyaspartic acid; polyγ-methylglutamic acid, polyβ-methylaspartic acid Polymer of acidic amino acid ester of poly ε
Polymers of basic amino acids such as lysine and poly-σ-ornithine; polymers of acylated basic amino acids such as polyε-N-acetyllysine and polyσ-N-carbobenzoxyornithine; polyserine and polycysteine And polymers of amino acids having a hydroxyl group, a mercapto group and the like such as polyarginine and polyhistidine, and polymers of derivatives thereof such as acetyl and isopropylidene. Among these polyamino acids, from the viewpoint of solubility in water and organic solvents,
Poly N-alkylamino acids in which R ⁶ is not a hydrogen atom are more preferred, and among them, poly N-methyl glycine and polyproline are more preferred. Poly N because of its high hydrophilicity
-Methylglycine is particularly preferred.

The molecular weight of the polyamino acid-modified silicone used in the present invention is preferably from 2.5 to 1,000,000,
0 to 500,000 is more preferable, and 1000 to 100,000 is particularly preferable. The molecular weight can be determined by GPC in terms of polystyrene.

[Synthesis of Polyamino Acid-Modified Silicone]
The polyamino acid-modified silicone used in the present invention is, for example, an organopolysiloxane having primary and / or secondary amino groups (hereinafter, referred to as aminopolysiloxane).
And the general formula (IV)

[0017]

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(Wherein, R ⁴ , R ⁵ and R ⁶ have the same meanings as above) (hereinafter referred to as α-amino acid NCA). It can be obtained by: Aminopolysiloxane is represented by the general formula (V) at the terminal and / or side chain of polydimethylsiloxane.
Or those having a group represented by (VI) are preferred.

[0019]

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(Wherein, R ¹ , R ² and R ³ have the same meanings as above.) The aminopolysiloxane has a molecular weight of 200 to 500,
The molecular weight is preferably 000 or less, more preferably 800 or more and 100,000 or less, and may be linear or branched. The molecular weight can be determined in terms of styrene by GPC (gel permeation chromatography). Such an aminopolysiloxane is
For example, those described in JP-A-5-25025, page 4, column 6, line 23 to page 5, column 8, line 1 can be mentioned.

The α-amino acid NCA includes, for example, N
-Methylglycine-NCA, proline-NCA and column 4 lines 20 to 44 of page 4 of JP-B-59-5132.
What is described in the line is mentioned. Among these,
A preferred α-amino acid NCA is N-methylglycine-
NCA, proline-NCA.

As the α-amino acid NCA, any of an optically active form and a racemic form can be used. Two or more of these α-amino acid NCAs may be used in combination, and when two or more α-amino acid NCAs are added simultaneously, two or more α-amino acid NCAs are randomly added.
A block of amino acids is produced. After completion of the polymerization of the first α-amino acid NCA, the second α-amino acid NCA
Is obtained, two α-amino acids are arranged in a block form.

The reaction solvent may be any organic solvent that dissolves the α-amino acid NCA to be used and is inert to the α-amino acid NCA and the aminopolysiloxane to be used. As such a reaction solvent, α
-It depends on the type of amino acid NCA and requires selection but is generally a halogenated hydrocarbon such as 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,
For example, methyl acetate, ethyl acetate, butyl acetate, amyl acetate, ethyl propionate and the like; cyclic ethers, for example,
Dioxane, tetrahydrofuran and the like; and N-methylpyrrolidone, dimethylformamide, dimethylsulfoxide and the like. The reaction solvent may be the one described above alone or a mixed system. In addition, for an α-amino acid NCA having no active hydrogen, it is possible to carry out solid phase polymerization by mixing a non-solvent.

By adding and mixing a predetermined amount of aminopolysiloxane and α-amino acid NCA in the above reaction solvent, generation of carbon dioxide gas is recognized, the reaction starts immediately, and α -Equivalent ratio of amino acid NCA (hereinafter abbreviated as NCA / AMI)
A polyamino acid-modified silicone having a polyamino acid segment length determined by the formula (1) is obtained in high yield. NCA
/ AMI is preferably from 0.5 to 200, more preferably from 1 to 100 (1 mol of α-amino acid NCA is 1 equivalent in terms of reactivity).

The addition and mixing of the two components of the reaction may be carried out by any method such as simultaneous addition, sequential addition, whole amount addition and partial sequential addition.
In order to easily and surely change the composition of the polyamino acid, etc., the aminopolysiloxane is uniformly dissolved or dispersed in advance in the reaction solvent, and then the whole amount of the α-amino acid NCA is added or the reaction rate is adjusted. The method of successive addition is suitable and desirable.

The reaction temperature is determined in consideration of the properties of the resulting polyamino acid-modified silicone, the reactivity of the α-amino acid NCA with the corresponding aminopolysiloxane, the boiling point of the reaction solvent, and the like. It is preferable to carry out in a temperature range of from 40C to 40C.

[0027] The polyamino acid-modified silicone used in the present invention includes a type of organopolysiloxane segment,
It shows various states ranging from a viscous oil to a solid resin, depending on the type of polyamino acid segment and the combination of both segments. The weight ratio between the polyamino acid segment and the organopolysiloxane segment is 1 /
It is preferably in the range of 20 to 20/1.

[Cosmetic] The amount of the polyamino acid-modified silicone in the cosmetic of the present invention is preferably 0.01 to 20% by weight, more preferably 0.1 to 10% by weight.

As the raw material components other than the polyamino acid-modified silicone used in the present invention, components usually used in cosmetics, for example, surfactants, foam improvers, alcohols, oils, thickeners Agents, humectants, wetting agents, feel improvers, anti-inflammatory agents (anti-inflammatory agents), ultraviolet absorbers, antioxidants,
Preservatives, bactericides, antibacterial agents, powders, fragrances, pigments, coloring pigments, scrubbing agents, pearlizing agents, warming agents, medicinal ingredients (anti-dandruff agents, etc.), as long as the effects of the present invention are not impaired. They can be blended, and are appropriately selected and blended according to the purpose, application, dosage form, and the like.

The cosmetic of the present invention can be applied to the skin and hair, and as skin cosmetics, it can be any dosage form applicable to the skin, for example, mascara, nail enamel, cream for skin, milky lotion, lotion, skin Cleaning agents, skin massage agents,
Esthetic agents and the like. As hair cosmetics, hair shampoo, hair rinse, scalp massage agent, esthetic agent,
Hair coloring agents, hair modifying agents, hair styling agents, hair permanent agents and the like can be mentioned. In addition, it can be used as an oral care agent for toothpaste, a shaving agent and the like.

In particular, it is preferable to use a film-forming polymer in combination, and to provide a cosmetic having excellent film properties with good film-forming ability while maintaining the properties inherent to silicone, such as smoothness, gloss, and smoothness. Obtainable. Examples of the film-forming polymer used in the present invention include, for example,
No. 112423, page 11, column 11, line 45 to page 8, column 13, line 33.
The amount of the film-forming polymer in the cosmetic of the present invention is 0.05
-20% by weight is preferred. Examples of cosmetics using a film-forming polymer in combination include skin cosmetics such as mascara and nail enamel, and hair styling agents such as hair mist, hair foam, hair spray, hair set lotion, hair gel, hair mousse, and hair cream.

The surfactant used in the cosmetic of the present invention includes a linear or branched alkylbenzene sulfonate, an alkyl or alkenyl ether sulfate to which ethylene oxide and / or propylene oxide is added,
Olefin sulfonates, alkane sulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates to which ethylene oxide and / or propylene oxide are added, α-sulfo fatty acid salt esters,
Amino acid type surfactant, phosphate ester type surfactant,
Anionic surfactants such as sulfosuccinic surfactants; amphoteric surfactants such as sulfonic amphoteric surfactants and betaine amphoteric surfactants; alkylamine oxides, alkyltrimethylammonium having 16 to 22 carbon atoms, Cationic surfactants such as aramidopropyl betaine; polyoxyalkyl or alkenyl ethers,
Nonionic surfactants such as polyoxyalkyl phenyl ether, higher fatty acid alkanolamide or alkylene oxide adduct, polyhydric alcohol and fatty acid ester, sorbitol and fatty acid ester, sucrose and fatty acid ester, higher alcohol and sugar ether Agents.

The amount of the surfactant in the cosmetic of the present invention is preferably 0.01 to 60% by weight, particularly 5 to 50% by weight as a detergent, and 0.05 to 20% by weight for other cosmetics. Is preferred.

In addition, examples of the high molecular compound used as a thickener or a feel improver include a cationized cellulose derivative, a cationic starch, a cationized guar gum derivative, a carboxyvinyl polymer, xanthan gum, methylcellulose, hydroxyethylcellulose and the like.
The blending amount of these polymer compounds in the cosmetic of the present invention is 0.1.
It is preferably from 0.5 to 20% by weight.

As the oil component, higher fatty acids such as stearic acid, higher alcohols such as cetanol, cholesterol,
Examples include solid fats such as petrolatum, cholesteryl isostearate, sphingolipids, and liquid fats such as squalene, jojoba oil, and other silicone derivatives.

As alcohols, ethanol, n-
Monohydric alcohols such as propanol, isopropanol, n-butanol and benzyl alcohol, glycerin,
1,3-butylene glycol, propylene glycol,
Examples include polyhydric alcohols such as dipropylene glycol, polyethylene glycol, and sorbitol.

Other components include triclosan and trichlorocarban as fungicides, potassium glycyrrhizinate and tocophenol acetate as anti-inflammatory agents, zinc pyrithione and octopirox as anti-dandruff agents, and methyl parapen as an antiseptic agent. Can be arbitrarily added within a range that does not impair.

[0038]

EXAMPLES In the examples, parts and percentages are by weight unless otherwise specified.

Synthesis Example 1 (polyamino acid-modified silicone with NCA / AMI = 70) 100 parts of methylene chloride, 3-aminopropyl-substituted polydimethylsiloxane (KF-8, manufactured by Shin-Etsu Silicone Co., Ltd.)
003, amine equivalent 2,000, molecular weight 30,000) 20
And after replacing with nitrogen gas, N-methylglycine-N
-80 parts of carboxylic anhydride in methylene chloride (500 parts)
The solution was added dropwise at room temperature over about 2 hours. During the dropwise addition, carbon dioxide gas was generated, and the ring-opening polymerization of N-methylglycine-N-carboxylic anhydride proceeded. The solvent was distilled off under reduced pressure to obtain a graft copolymer having a poly (N-methylglycine) chain attached to the side chain of polydimethylsiloxane (molecular weight: 5000).
0) was obtained. This copolymer was a colorless hard solid.

Synthesis Example 2 (polyamino acid-modified silicone having NCA / AMI = 22) 100 parts of methylene chloride, 3-aminopropyl-substituted polydimethylsiloxane at both ends (manufactured by Chisso Corporation, FM-33)
25, amine equivalent 5000, molecular weight 10,000), 20 parts, and after replacement with nitrogen gas, N-methylglycine-N-
A solution of 10 parts of carboxylic anhydride in methylene chloride (100 parts) was added dropwise at room temperature over about 30 minutes. During the dropwise addition, carbon dioxide gas was generated, and the ring-opening polymerization of N-methylglycine-N-carboxylic anhydride proceeded. By distilling off the solvent under reduced pressure, a block copolymer having a poly N-methylglycine chain at both ends of polydimethylsiloxane (molecular weight: 110
00) was obtained. This copolymer was a colorless elastic solid.

Example 1 A cream for skin was prepared by mixing the following components.

<Components> Polyamino acid-modified silicone obtained in Synthesis Example 1 0.3% Stearic acid 2.0 Cetanol 1.0 Cholesterol 1.0 Squalane 10.0 Jojoba oil 10.0 Polyoxyethylene (40) cured castor Oil 0.5 cetyl phosphate 0.5 sorbitan monostearate 2.0 butyl parapen 0.1 methyl parapent 0.2 glycerin 10.0 1,3-butylene glycol 5.0 fragrance 0.1 potassium hydroxide 0.1 water balance Example 2 The following components were mixed to prepare an emulsion for skin.

<Ingredients> Polyamino acid-modified silicone obtained in Synthesis Example 1 0.2% cetanol 1.0 Squalane 5.0 Olive oil 3.0 Jojoba oil 2.0 Polyoxyethylene (10) hydrogenated castor oil 1.0 Mono Sorbitan stearate 1.0 Butyl parapen 0.1 Methyl parapen 0.1 Glycerin 2.0 1,3-butylene glycol 2.0 Fragrance 0.1 Ethanol 3.0 Water Balance Example 3 A lotion for skin by mixing the following ingredients Was prepared.

<Ingredients> Polyamino acid-modified silicone obtained in Synthesis Example 2 4.0% Dimethylpolysiloxane 1.0 Polyoxyethylene (60) hydrogenated castor oil 1.0 Lactic acid proper amount Sodium lactate proper amount Glycerin 3.0 1,3 -Butylene glycol 1.5 polyethylene glycol 1500 0.5 fragrance 0.1 ethanol 10.0 water balance Example 4 Two kinds of compositions shown in Table 1 were obtained using the polyamino acid-modified silicone obtained in Synthesis Examples 1 and 2. A mist was prepared. The resulting mist was applied to the hair, and the set holding power, slipperiness, gloss, and comb of the hair were evaluated by the following methods.
Table 1 also shows the results.

<Evaluation method> Set holding power A hair bundle having a length of 18 cm and a weight of 1.5 g was wetted with water, dried with a towel, applied with 2 g of a mist, wound around a rod having a diameter of 2 cm, and air-dried. After drying, the rod was removed from the curled hair. Place this in a thermostatic chamber (20 ° C, 98%
RH) for 30 minutes, the curl elongation was observed, and the set holding power was evaluated according to the following criteria.

◎: Very good ○: Good △: Normal ×: Slightly poor ××: Poor slipperiness, glossiness, hair combs Wet a hair bundle of 18 cm in length and 10 g in weight with water, dry with a towel and mist 0.2 g was applied and air dried.
Based on the following criteria, the slipperiness, gloss, and comb of the hair were evaluated by an expert according to the following criteria.

◎: Very good ○: Good △: Normal ×: Somewhat bad ××: Bad

[0048]

[Table 1]

Example 5 A blowing agent was manufactured by mixing the following components.

<Ingredients> Polyamino acid-modified silicone obtained in Synthesis Example 2 0.5% amphoteric polymer (Yukaforma M-75) 0.5 Fragrance trace amount of ethanol 30.0 Purified water qs 100.0 Example 6 The mixture was mixed to produce a hair foam.

<Components> Polyamino acid-modified silicone obtained in Synthesis Example 1 1.0% chitin liquid (manufactured by Ichimaru Falcos) 5.0 Nonionic surfactant 1.0 (sophthalanol 90, manufactured by Nippon Shokubai Co., Ltd.) ) Fragrance trace amount liquefied petroleum gas 10.0 purified water qs 100.0 Example 7 The following components were mixed to produce a hair spray.

<Ingredients> Polyamino acid-modified silicone obtained in Synthesis Example 1 1.5% nonionic polymer (Luviskol VA37, manufactured by BASF) 5.0 Fragrance trace amount Liquefied petroleum gas 50.0 Ethanol Appropriate meter 100.0 Example 8 A set lotion for hair was prepared by mixing the following ingredients.

<Components> Polyamino acid-modified silicone obtained in Synthesis Example 2 1.0% amphoteric polymer (Yukaformer M-75) 2.0 Fragrance trace amount Purified water 10.0 Ethanol qs 100.0

[0054]

EFFECT OF THE INVENTION The cosmetic of the present invention containing a polyamino acid-modified silicone, when applied to hair, has a natural luster, smoothness, suppleness, good combability, without reducing the setting power of hair. It is excellent in water repellency, and when applied to the skin, it is excellent in natural luster, smoothness, dry feeling, water repellency of the skin and skin protective effect.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4C083 AA122 AB032 AC012 AC022 AC072 AC102 AC122 AC182 AC242 AC302 AC432 AC442 AC482 AC902 AD042 AD072 AD092 AD161 AD162 AD322 AD492 CC02 CC05 CC32 CC33 DD08 EE06 EE12 FF01 4J035 BA01 BA06 CA01N GA05

Claims (5)

[Claims] 1. A cosmetic comprising a modified silicone having a polyamino acid segment and an organopolysiloxane segment (hereinafter referred to as a polyamino acid modified silicone). 2. A modified polyamino acid silicone having an alkylene group containing a hetero atom between at least one silicon atom at the terminal and / or side chain of the organopolysiloxane segment and the carbonyl group of the polyamino acid. The cosmetic according to claim 1, which is silicone. 3. The cosmetic according to claim 2, wherein the alkylene group containing a hetero atom is at least one selected from groups represented by formula (I) or (II). Embedded image (Wherein, R ¹ , R ² and R ³ are the same or different and each may have a substituent containing a hetero atom, and may have 2 to 22 carbon atoms)
A linear or branched alkylene group, alkenylene group or arylene group having 6 to 22 carbon atoms. ) 4. The cosmetic according to claim 1, wherein the polyamino acid has a repeating unit represented by the general formula (III). Embedded image (Wherein, R ⁴ , R ⁵ and R ⁶ are the same or different and each may have a hydrogen atom or a substituent containing a hetero atom, a linear or branched alkyl group having 1 to 22 carbon atoms, Or a cycloalkyl group having 6 to 22 carbon atoms, an aralkyl group having 7 to 22 carbon atoms or an aryl group having 6 to 22 carbon atoms, and R ⁴ or R ⁵ and R ⁶ together form a ring. May be.) 5. A polyamino acid-modified silicone comprising an organopolysiloxane having a primary and / or secondary amino group, and an organopolysiloxane having the general formula (IV): (Wherein, R ⁴ , R ⁵ and R ⁶ have the same meanings as described above), which is obtained by reacting an α-amino acid-N-carboxylic anhydride represented by the formula: The cosmetic according to any one of the above items.