JP2011162516A - Oily cosmetic containing hydrophilic substance - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an oily cosmetic with which water-soluble ascorbic acid derivatives and the salts thereof, and N-glyceryl amino acids and the salts thereof difficult to obtain a stable mixture with oily cosmetics are easily, homogenously, and stably blended and which has excellent moisture retention and feel of use. <P>SOLUTION: A hydrophilic substance is easily and stably blended in a cosmetic mainly composed of an oily ingredient by including a silylated peptide-silane compound copolymer composition and one kind or more selected from among water-soluble ascorbic acid derivatives and the salts thereof, and N-glyceryl amino acids and the salts thereof in the cosmetic. Preferably, the blend ratio of the hydrophilic substance to the silylated peptide-silane compound copolymer composition is 1:0.05-20 by mass. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to oily cosmetics, and more specifically, to oily cosmetics such as lipstick, lip gloss, concealer, oily mascara, oily cosmetic liquid, powder foundation, hair stick, water soluble ascorbic acid derivative or salt thereof, N-glyceryl. Oily cosmetics containing hydrophilic substances that contain hydrophilic substances such as amino acids or their salts, have high effects on rough skin, lips, etc., have a good feel when applied, and have excellent stability. Regarding fees.

  Oily cosmetics are lipsticks, lip balms, concealers, powder foundations, oil-based formulations that contain liquid oily ingredients and wax esters such as candelilla wax and carnauba wax as dosage forms that have excellent occlusive properties on the skin and lips. There are hair sticks, etc., blending with hydrophilic substances such as water and polyhydric alcohol, improving rough skin and lips due to drying etc., improving the feeling of use such as extensibility to skin and wrinkles, hard to discolor Technologies and technologies aimed at preventing sweating of oily cosmetics and improving stability over time have been proposed. For example, there are a technique for dispersing water in a non-emulsified state in a semi-solid oil and / or a solid oil and a fluid oil, and a technique for blending water into an oily cosmetic using a water-soluble polymer.

  However, blending hydrophilic substances into oily cosmetics (external skin preparations and hair cosmetics) has been carried out, but it is complicated or difficult in process, stable over time such as color change and sweating. There are problems such as there being a problem of the property and the oily component is limited, and it is not always satisfactory.

  In addition, since hair is damaged by chemical treatment such as hair color and permanent wave, fading over time and reduction in hair strength occur, and thus a hair cosmetic that can improve these and provide moisture retention is desired. However, there is no oily cosmetic for hair aimed at solving such problems.

JP 4-40324 JP 2005-263694 A JP 2005-255639 A

  Therefore, the present invention uniformly blends a hydrophilic substance, has a high improvement effect on rough skin, lips, etc., has a good touch (smoothness, extensibility, etc.) during application, and changes in color over time. It is an object to provide less oily cosmetics.

  As a result of intensive studies in order to solve the above problems, the present inventors have used a silylated peptide-silane compound copolymer composition to obtain a water-soluble ascorbic acid derivative or a salt thereof, an N-glyceryl amino acid or a salt thereof. Hydrophilic substances such as salt can be easily blended into oily cosmetics such as lipsticks, lip glosses, concealers, oily mascaras, and hair sticks, and these oily cosmetics can be applied to rough skin, lips, and hair. It has been found that the effect of improving the color is high, the stability over time such as color change is improved, the feeling in use is good, and the function of imparting and sustaining moisture is exhibited, and the present invention has been completed.

  That is, the present invention is a group of hydrophilic substances consisting of a silylated peptide-silane compound copolymer composition, a water-soluble ascorbic acid derivative and a salt thereof, an N-glyceryl amino acid and a salt thereof, in a cosmetic mainly composed of an oily substance. An oily cosmetic characterized by containing one or more selected from the above (claim 1).

〔式中、Ｒ^１は水酸基または炭素数１〜３のアルキル基を示し、Ｒ^２は側鎖の末端にアミノ基を有する塩基性アミノ酸の末端アミノ基を除く側鎖の残基を示し、Ｒ^３はＲ^２が結合するアミノ酸以外のアミノ酸側鎖を示し、Ａは結合手で、メチレン、プロピレン、−（ＣＨ_２）_３ＯＣＨ_３ＣＨ（ＯＨ）ＣＨ_２−、−（ＣＨ_２）_３Ｓ−、−（ＣＨ_２）_３ＮＨ−および−（ＣＨ_２）_３ＯＣＯＣＨ_２ＣＨ_２−からなる群から選ばれる少なくとも１種の基を表し、ｘは０〜５０、ｙは１〜１００、ｘ＋ｙは１〜１００である（ただし、ｘおよびｙはアミノ酸の数を示すのみで、アミノ酸配列の順序を示すものではない）〕で表されるシリル化ペプチドの１種以上と、下記の一般式（ＩＩ）
Ｒ^４ _ｍＳｉ（ＯＨ）_ｐＹ_{（４−ｐ−ｍ）} （ＩＩ）
〔式中、ｍは０から２の整数で、ｐは２から４の整数、ｍ＋ｐ≦４で、Ｒ^４は炭素原子がケイ素原子に直接結合する有機基であり、ｍ個のＲ^４は同じでもよく、異なっていてもよい。（４−ｐ−ｍ）個のＹはアルコキシ基または水素原子である〕で表されるシラン化合物の１種以上とを、反応モル比がシリル化ペプチド：シラン化合物＝１：２０〜１：８０の範囲で水溶液中で縮重合させた後、下記の一般式（ＩＩＩ）
Ｒ^５ _３Ｓｉ（ＯＨ） （ＩＩＩ）
〔式中、３個のＲ^５は炭素原子がケイ素原子に直接結合する有機基であり、３個のＲ^５は同じでもよく、異なっていてもよい〕で表されるシラン化合物を水溶液中で付加させることにより得られるものであり、このシリル化ペプチド−シラン化合物共重合組成物を用いることによって、油性物質を主成分とする油性化粧料に親水性物質を容易に配合できるようになる。 In the present invention, the oily cosmetic refers to those in which the oily substance such as the lipstick, lip gloss, concealer, oily mascara, powder foundation, and hair stick is the main constituent, and the oily cosmetic of the present invention includes the main ingredient and 1 or 2 selected from the group consisting of an oily substance, a silylated peptide-silane compound copolymer composition, and a hydrophilic substance consisting of a water-soluble ascorbic acid derivative and salt thereof, N-glyceryl amino acid and salt thereof Although it is composed of more than one species, the silylated peptide-silane compound copolymer composition is as follows. That is, the following general formula (I)

[Wherein R ¹ represents a hydroxyl group or an alkyl group having 1 to 3 carbon atoms, R ² represents a residue of a side chain excluding a terminal amino group of a basic amino acid having an amino group at the end of the side chain; ³ represents an amino acid side chain other than the amino acid to which R ² is bonded, A is a bond, methylene, propylene, — (CH ₂ ) ₃ OCH ₃ CH (OH) CH ₂ —, — (CH ₂ ) ₃ S— , — (CH ₂ ) ₃ NH— and — (CH ₂ ) ₃ OCOCH ₂ CH ₂ — represents at least one group selected from the group consisting of 0 to 50, y to 1 to 100, and x + y to 1 1 or more of the silylated peptides represented by the following general formula (II): wherein x and y only indicate the number of amino acids, not the order of amino acid sequences)
R ⁴ _m Si (OH) _p Y _(4-p-m) (II)
[Wherein, m is an integer of 0 to 2, p is an integer of 2 to 4, m + p ≦ 4, R ⁴ is an organic group in which a carbon atom is directly bonded to a silicon atom, and m R ⁴ are the same. But it may be different. (4-pm) Y is an alkoxy group or a hydrogen atom], and the reaction molar ratio is silylated peptide: silane compound = 1: 20 to 1:80. The following general formula (III)
R ⁵ ₃ Si (OH) (III)
[Wherein, three R ⁵ are organic groups in which a carbon atom is directly bonded to a silicon atom, and three R ⁵ may be the same or different] in an aqueous solution. By using this silylated peptide-silane compound copolymer composition, it becomes possible to easily add a hydrophilic substance to an oily cosmetic mainly composed of an oily substance.

  The hydrophilic substance used in the present invention is one or two or more selected from water-soluble ascorbic acid derivatives and salts thereof, N-glyceryl amino acids and salts thereof, and aqueous solutions containing these and water-soluble alcohol mixtures are also included. It is included in the category of the hydrophilic substance of the present invention.

  Examples of water-soluble ascorbic acid derivatives and salts thereof include ascorbic acid, ascorbic acid glycosides such as ascorbic acid glucoside, ascorbic acid phosphate magnesium, ascorbic acid phosphate sodium salt such as ascorbic acid sodium phosphate, ascorbine Ascorbic acid sulfate such as magnesium acid sulfate, magnesium ascorbyl sulfate, sodium glyceryl ascorbate such as 2-glyceryl ascorbic acid, 3-glyceryl ascorbic acid, 6-glyceryl ascorbic acid, 2,3-diglyceryl ascorbic acid Etc.

  Examples of N-glyceryl amino acids or salts thereof include N-glyceryl glycine, N-glyceryl alanine, N-glyceryl alanine sodium, N-glyceryl valine, N-glyceryl valine sodium, N-glyceryl threonine, N-glyceryl threonine potassium, N-glyceryl glutamic acid, sodium N-glyceryl glutamate, N-glyceryl aspartic acid, potassium N-glyceryl aspartate, N-glyceryl lysine, N-glyceryl lysine hydrochloride, N-α, ε-diglyceryl lysine, N-glyceryl arginine N-glyceryl arginine hydrochloride, N-glyceryl phenylalanine, N-glyceryl phenylalanine sodium, N-glyceryl hydroxyproline, N-glyceryl hydroxyproline potassium N-glyceryl β-alanine sodium, N-glyceryl γ-aminobutyric acid and the like.

〔式中、Ｒ^６はＨ、炭素数１〜４のアルキル基、Ｒ^８−Ｏ−ＣＨ_２−ＣＨ（ＯＨ）−ＣＨ_２−、Ｒ^９−Ｏ−ＣＨ_２−ＣＨ（ＣＨ_２ＯＨ）−、Ｒ^７はＨ、炭素数１〜４のアルキル基、Ｒ^１０−Ｏ−ＣＨ_２−ＣＨ（ＯＨ）−ＣＨ_２−、Ｒ^１１−Ｏ−ＣＨ_２−ＣＨ（ＣＨ_２ＯＨ）−であり、Ｒ^８およびＲ^９はＨ、炭素数１〜４のアルキル基であり、Ｒ^１０およびＲ^１１はＨ、炭素数１〜４のアルキル基である〕で表されるものが保湿性、肌荒れ防止効果などに優れ、これら化合物の一種以上を配合した油性化粧料は皮膚に保湿性を付与し、肌荒れ防止効果発揮するので、より好ましい態様である（請求項２）。 Among the above hydrophilic substances, among the water-soluble ascorbic acid derivatives, the following general formula (IV)

[Wherein R ⁶ is H, an alkyl group having 1 to 4 carbon atoms, R ⁸ —O—CH ₂ —CH (OH) —CH ₂ —, R ⁹ —O—CH ₂ —CH (CH ₂ OH) — , R ⁷ is H, an alkyl group having 1 to 4 carbon atoms, R ¹⁰ —O—CH ₂ —CH (OH) —CH ₂ —, R ¹¹ —O—CH ₂ —CH (CH ₂ OH) —, R ⁸ and R ⁹ are H and an alkyl group having 1 to 4 carbon atoms, and R ¹⁰ and R ¹¹ are H and an alkyl group having 1 to 4 carbon atoms]. Oil-based cosmetics formulated with one or more of these compounds are more preferred because they impart moisture retention to the skin and exhibit an effect of preventing rough skin (Claim 2).

  The water-soluble ascorbic acid represented by the general formula (IV) can be produced, for example, by reacting ascorbic acid with glycidol.

（式中、Ａはα−アミノ酸の側鎖を示し、Ｚは水素原子、アルカリ金属、アンモニウムまたは有機アンモニウムである）で表されるものが、保湿性、肌荒れ防止効果などに優れ、これらの物質の一種以上を配合した油性化粧料は皮膚に保湿性を付与し、肌荒れ防止効果発揮するので、より好ましい態様である（請求項３）。 Among the above hydrophilic substances, among N-glyceryl amino acids, the following general formula (V)

(Wherein A represents a side chain of an α-amino acid and Z is a hydrogen atom, an alkali metal, ammonium or organic ammonium) is excellent in moisture retention, rough skin prevention effect, etc., and these substances An oily cosmetic containing one or more of these is a more preferred embodiment because it imparts moisture retention to the skin and exhibits an effect of preventing rough skin (Claim 3).

  The N-glyceryl amino acid represented by the general formula (V) can be produced, for example, by the method described in WO2004 / 052318 A1.

  Among the ascorbic acid derivatives represented by the general formula (IV), 2-O-glyceryl ascorbic acid or a salt thereof, 3-O-glyceryl ascorbic acid or a salt thereof, 2,3-di-O-glyceryl ascorbic acid or One or more selected from the group consisting of the salts is a more preferable embodiment because it is particularly excellent in imparting moisture retention and preventing rough skin (Claim 4).

  Further, among N-glyceryl amino acids or salts thereof, N-glyceryl arginine or a salt thereof, N-glyceryl lysine or a salt thereof, N-glyceryl glutamic acid or a salt thereof, N-glyceryl aspartic acid or a salt thereof is selected. One or more of these are more preferable because they are particularly excellent in imparting moisture retention and preventing rough skin (Claim 5).

  The mixing ratio of the hydrophilic substance and the silylated peptide-silane compound copolymer composition is a mass ratio, and the ratio of the silylated peptide-silane compound copolymer composition to the hydrophilic substance 1 is in the range of 0.05 to 15. (Claim 6).

  This is because when the ratio of the silylated peptide-silane compound copolymer composition to the hydrophilic substance 1 is 0.05 or less in mass ratio, it becomes difficult to uniformly mix the hydrophilic substance in the oily cosmetic. In other words, even if the ratio of the silylated peptide-silane compound copolymer composition is 15 or more by mass ratio, the effect of uniformly dispersing the hydrophilic substance commensurate with the amount cannot be obtained.

  The oily cosmetic composition of the present invention has a hydrophilic substance uniformly incorporated in the oily component by using the silylated peptide-silane compound copolymer composition, and has an improvement effect on rough skin, lips, etc. It is high, has a good feeling during use (smoothness, extensibility, etc.), has little color change over time, and hardly separates oils and pigments.

  The oily substance that is the main component of the oily cosmetic of the present invention includes hydrocarbons, natural waxes, ester oils, fats and oils, higher fatty acids, higher alcohols, fluorine-based oils, and the like that can be used for normal cosmetics. There is no restriction | limiting, These oily substances are used individually or in mixture of 2 or more types.

  Examples of hydrocarbons include paraffin, isoparaffin, squalane, petrolatum, ceresin wax, paraffin wax, microcrystalline wax, polyethylene wax, ozokerite, polybutene, α-olefin oligomers, and natural waxes include, for example, Candelilla wax, carnauba wax, beeswax, lanolin, gayrow, mole, rice bran, shellac wax, orange luffy oil, jojoba oil, hydrogenated jojoba oil, montan wax, palm wax, sugar cane wax and the like.

  Examples of ester oils include diisostearyl malate, isopropyl myristate, neopentyl glycol dicaprate, glyceryl tri-2-ethylhexanoate, glyceryl tri (capric acid / caprylic acid), (hydrogenated rosin / diisostearic acid) Glyceryl, ethyl oleate, butyl myristate, isopropyl palmitate, ethyl stearate, butyl stearate, ethyl linoleate, isopropyl linoleate, cetyl caprylate, hexyl laurate, decyl myristate, cetyl myristate, cetyl palmitate, Myristyl myristate, stearyl stearate, decyl oleate, oleyl oleate, cetyl ricinoleate, isostearyl laurate, isotridecyl myristate, 2-hexyl myristate Rudecyl, isostearyl myristate, octyldodecyl myristate, octyl palmitate, isocetyl palmitate, isostearyl palmitate, octyl stearate, isocetyl stearate, isododecyl oleate, octyldodecyl oleate, octyldodecyl lisinoleate, isopropyl isostearate , Ethyl isostearate, cetyl 2-ethylhexanoate, cetostearyl 2-ethylhexanoate, stearyl 2-ethylhexanoate, hexyl isostearate, propylene glycol dicaprate, glyceryl triundecylate, isocetyl isostearate, octyldodecyl dimethyloctanoate, Myristyl lactate, cetyl lactate, trioctyldodecyl citrate, glyceryl triisostearate, Toraokutan acid pentaerythritol, diisobutyl adipate, diethyl sebacate, cholesteryl stearate, hydroxystearic acid cholesteryl, phytosteryl isostearate, such as acetic acid polyoxyethylene (3) mono-oxypropylene cetyl ether Ageraru.

  Examples of oils and fats include olive oil, macadamia nut oil, soybean oil, castor oil, hydrogenated castor oil, kukui nut oil, wheat germ oil, rice germ oil, shea butter, avocado oil, sesame oil, rice bran oil, safflower oil , Corn oil, Rapeseed oil, Persic oil, Palm kernel oil, Sunflower oil, Grape seed oil, Cottonseed oil, Palm oil, Emu oil, Hardened oil, Horse oil, Mink oil, Egg yolk fat oil, Evening primrose oil, Mango butter, Rose hip Examples of the fatty acids include oleic acid, behenic acid, isostearic acid, lauric acid, myristic acid, palmitic acid, stearic acid, 12-hydroxystearic acid, and undecylenic acid. Examples of higher alcohols include oleyl alcohol, behenyl alcohol, stearyl alcohol, isostearyl alcohol, octyldodecanol, cholesterol, sitosterol, cetanol, cetostearyl alcohol, ceralkyl alcohol, decyltetradecanol, batyl alcohol, phytosterol, Examples include hexyl decanol, lauryl alcohol, lanolin alcohol, hydrogenated lanolin alcohol, and myristyl alcohol. Examples of the fluorinated oil include perfluoropolyether and perfluorooctane.

  Furthermore, high-polymerized dimethylpolysiloxane, low-polymerized dimethylpolysiloxane, methylphenylpolysiloxane, cyclic polysiloxane, alcohol-modified silicones, alkyl-modified silicone oils, silicone oils such as amino-modified silicones, chimyl alcohol, seraalkyl alcohol, batyl Alkyl glyceryl ethers such as alcohol can also be used.

  The content of the oily substance that is the main ingredient in the oily cosmetic is various, such as liquid, solid, and powdery oily cosmetics, and can vary greatly depending on the cosmetic, and the oily cosmetic of the present invention is not limited. An oily substance is the main constituent.

  As described above, the silylated peptide-silane compound copolymer composition used in the oily cosmetic composition of the present invention is synthesized by condensation polymerization of a silylated peptide and a silane compound in an aqueous solution. For example, JP-A-2001-48732 And the method disclosed in Japanese Patent Application Laid-Open No. 2001-48775. The silylated peptide that is a constituent of the silylated peptide-silane compound copolymer composition can be synthesized, for example, by the methods disclosed in JP-A-8-59424 and JP-A-8-67608.

  Examples of the peptide portion of the silylated peptide include natural peptides, synthetic peptides, and protein hydrolysates. However, protein hydrolysates are used because of their ease of availability and ease of control of the number average molecular weight of peptide portions. preferable.

  The protein hydrolyzate is obtained by partially hydrolyzing a protein with acid, alkali, enzyme, or a combination thereof. Examples of the protein source include animal protein, plant protein, and microorganism-derived protein. Examples of animal protein include egg yolk protein and egg white protein such as collagen (including gelatin which is a modified product thereof), keratin, fibroin, sericin, casein, conchiolin, elastin, protamine and chicken. Examples of plant proteins include proteins contained in soybeans, wheat, rice (rice bran), sesame seeds, peas, corn, and potatoes. Proteins derived from microorganisms include Saccharomyces, Candida, and Endomico. Yeast fungus belonging to the genus Psis And yeast proteins isolated from yeast which is said to be sake yeast, fungi (Basidiomycetes) and proteins separated from Chlorella, and the like spirulina protein from seaweed.

The silylated peptide-silane compound copolymer composition includes the silylated peptide and the following general formula (I):
R6 _n SiX _(4-n) (V)
[Wherein, n is an integer of 0 to 2, R6 is an organic group in which a carbon atom is directly bonded to a silicon atom, and n R1s may be the same or different. (4-n) X is at least one group selected from a hydroxyl group, an alkoxy group and a halogen group] obtained by hydrolyzing in a water solution the following general formula (II)
_{R4 m Si (OH) p Y} (4-p-n) (II)
[Wherein, m is an integer from 0 to 2, p is an integer from 2 to 4, m + p ≦ 4, R4 is an organic group in which a carbon atom is directly bonded to a silicon atom, and m R1s may be the same. , May be different. (4-pn) Y is an alkoxy group or a hydrogen atom] is subjected to condensation polymerization of a hydrolyzate of a silane compound represented by the following general formula (III)
R ⁵ ₃ Si (OH) (III)
[Wherein, three R ⁵ are organic groups in which a carbon atom is directly bonded to a silicon atom, and three R ⁵ may be the same or different] in an aqueous solution. The added silylated peptide-silane compound copolymer composition is not limited to one type, and two or more types may be used in combination.

  Examples of commercially available silylated peptide-silane compound copolymer compositions that can be used in the oily cosmetic composition of the present invention include PROTESIL FN, PROTESIL F, PROTESIL LH, and PROTESIL GLH manufactured by Seiwa Kasei Co., Ltd. Name).

  The hydrophilic substance used in the oily cosmetic of the present invention can be used alone or in combination of two or more from the group consisting of water-soluble ascorbic acid derivatives and salts thereof, N-glyceryl amino acids and salts thereof.

〔式中、Ｒ^６はＨ、炭素数１〜４のアルキル基、Ｒ^８−Ｏ−ＣＨ_２−ＣＨ（ＯＨ）−ＣＨ_２−、Ｒ^９−Ｏ−ＣＨ_２−ＣＨ（ＣＨ_２ＯＨ）−、Ｒ^７はＨ、炭素数１〜４のアルキル基、Ｒ^１０−Ｏ−ＣＨ_２−ＣＨ（ＯＨ）−ＣＨ_２−、Ｒ^１１−Ｏ−ＣＨ_２−ＣＨ（ＣＨ_２ＯＨ）−であり、Ｒ^８およびＲ^９はＨ、炭素数１〜４のアルキル基であり、Ｒ^１０およびＲ^１１はＨ、炭素数１〜４のアルキル基である〕で表されるものが好ましく、その中でも、２−Ｏ−グリセリルアスコルビン酸またはその塩、３−Ｏ−グリセリルアスコルビン酸またはその塩、２，３−ジ−Ｏ−グリセリルアスコルビン酸またはその塩がさらに好ましい。 Among the water-soluble ascorbic acid derivatives, the following general formula (IV)

[Wherein R ⁶ is H, an alkyl group having 1 to 4 carbon atoms, R ⁸ —O—CH ₂ —CH (OH) —CH ₂ —, R ⁹ —O—CH ₂ —CH (CH ₂ OH) — , R ⁷ is H, an alkyl group having 1 to 4 carbon atoms, R ¹⁰ —O—CH ₂ —CH (OH) —CH ₂ —, R ¹¹ —O—CH ₂ —CH (CH ₂ OH) —, R ⁸ and R ⁹ are H and an alkyl group having 1 to 4 carbon atoms, and R ¹⁰ and R ¹¹ are H and an alkyl group having 1 to 4 carbon atoms]. Among them, 2 -O-glyceryl ascorbic acid or a salt thereof, 3-O-glyceryl ascorbic acid or a salt thereof, or 2,3-di-O-glyceryl ascorbic acid or a salt thereof is more preferable.

  The water-soluble ascorbic acid represented by the general formula (IV) can be produced, for example, by reacting ascorbic acid with glycidol, alkyl glycidyl ether, alkenyl glycidyl ether or the like in an aqueous solvent. In addition, the ascorbic acid derivative of the above general formula (IV) in which R6 or R7 is a hydrogen atom forms a salt formed by substituting a hydrogen ion from which H is dissociated with a cation such as a metal ion or an ammonium ion. Examples of the salt include inorganic salts such as sodium, potassium, magnesium, and calcium salts, and organic salts such as triethanolamine salt, diethanolamine salt, and basic amino acid salt.

（式中、Ａはα−アミノ酸の側鎖を示し、Ｚは水素原子、アルカリ金属、アンモニウムまたは有機アンモニウムである）で表されるものが好ましく、その中でも、Ｎ−グリセリルアルギニンまたはその塩、Ｎ−グリセリルリシンまたはその塩、Ｎ−グリセリルグルタミン酸またはその塩、Ｎ−グリセリルアスパラギン酸またはその塩など、Ｎ−グリセリル塩基性アミノ酸、Ｎ−グリセリル酸性アミノ酸、および、それらの塩類がより好ましい。 Among N-glyceryl amino acids, the following general formula (V)

(Wherein A represents a side chain of an α-amino acid and Z is a hydrogen atom, an alkali metal, ammonium or organic ammonium), among which N-glycerylarginine or a salt thereof, N -N-glyceryl basic amino acids, N-glyceryl acidic amino acids, and salts thereof, such as glyceryl lysine or a salt thereof, N-glyceryl glutamic acid or a salt thereof, N-glyceryl aspartic acid or a salt thereof, are more preferable.

  The N-glyceryl amino acid represented by the above general formula (V) can be produced, for example, by the method described in WO2004 / 052318 A1, and specifically, in an amino acid aqueous solution, glycidol or 1-halo It can be produced by dropping -2,3-dihydroxypropane.

  A commercially available product of N-glyceryl amino acid that can be used in the oily cosmetic of the present invention is Amitose R (trade name) manufactured by Seiwa Kasei Co., Ltd.

  A hydrophilic substance selected from a hydrophilic substance group consisting of a silylated peptide-silane compound copolymer composition and a water-soluble ascorbic acid derivative and salt thereof, N-glyceryl amino acid and salt thereof is mixed with an oily substance or a mixture thereof. It is preferable to add to the solution used as the main agent. The hydrophilic substance may be mixed with water and then mixed with the silylated peptide-silane compound copolymer composition.

  The mixing ratio of the hydrophilic substance to the silylated peptide-silane compound copolymer composition is preferably in the range of 0.05 to 15 for the silylated peptide-silane compound copolymer composition relative to the hydrophilic substance 1 in terms of mass ratio. The range of 0.1-10 is more preferable.

  If the mass ratio of the silylated peptide-silane compound copolymer composition to the hydrophilic substance 1 is less than the above range, the hydrophilic substance may not be uniformly blended in the oily cosmetic, and the silylated peptide- Even if the ratio of the silane compound copolymer composition exceeds the above range by mass ratio, a uniform dispersion effect of a hydrophilic substance commensurate with the amount used cannot be expected.

  The oily cosmetics of the present invention are usually prepared by mixing a silylated peptide-silane compound copolymer composition and a hydrophilic substance, then adding other ingredients including the main oily substance, heating and mixing, and cooling. Can be manufactured.

  The oily cosmetic of the present invention comprises a hydrophilic substance selected from the group consisting of an oily substance as a main ingredient, a silylated peptide-silane compound copolymer composition, a water-soluble ascorbic acid derivative and a salt thereof, N-glyceryl amino acid and a salt thereof. Although one or more kinds are essential components, other components that are usually blended in cosmetics may be blended within a range not impairing the effects of the present invention. Examples of such components include humectants, surfactants, whitening agents, effective ingredients such as anti-inflammatory agents, antioxidants, thickeners, polymer compounds, inorganic powders, coloring materials, and oily substances other than the main agent. Etc.

  Examples of the humectant include amino acids such as glycine and alanine, saccharides such as trimethylglycine, sodium pyrrolidonecarboxylate and trehalose, and glucosamine.

  Examples of the nonionic surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene alkyl ether such as polyoxyethylene oleyl ether, polyoxyethylene alkenyl ether, polyoxyethylene sorbitan fatty acid ester, Examples include an oxyethylene hydrogenated castor oil, sorbitan fatty acid ester, sucrose fatty acid ester, alkyl polyglycoside, glycerin fatty acid ester, fatty acid polyglyceryl, and polyether-modified silicone. Examples of the anionic surfactant include fatty acid sodium, alkyl Examples thereof include sulfates, polyoxyethylene alkyl sulfates, alkyl phosphates, acylated amino acid salts, and acylated peptide salts. Examples of amphoteric surfactants include alkyldimethylaminoacetic acid betaines and alkylamidopropylalkyldimethylaminoacetic acid betaines. Examples of cationic surfactants include alkyltrimethylammonium chloride and dialkyldimethylammonium chloride. Can be mentioned.

  Examples of effective ingredients include arbutin, kojic acid, ascorbic acid glucoside, magnesium ascorbyl phosphate, glycyrrhizic acid or its salt, glycyrrhetinic acid or its salt, vitamins A, carotene, lycopene, nicotinic acid, pantothenic acids, ubiquinones, Examples thereof include γ-aminobutyric acid.

  Examples of polymers (thickeners) include methyl cellulose, xanthan gum, guar gum, ethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose salt, polyvinyl alcohol, polyvinyl pyrrolidone, sodium polyacrylate, carboxyvinyl polymer, chitin, chitosan, quince. Seed, hyaluronic acid and salts thereof, polyacrylamide, (hydroxyethyl acrylate / sodium acryloyldimethyltaurate) copolymer, etc. Inorganic powders and coloring materials include, for example, titanium oxide, zinc oxide, talc, mica, iron oxide Etc.

  EXAMPLES Next, although an Example is given and this invention is demonstrated concretely, this invention is not limited to these Examples. In the following examples, all the percentages are% by mass, and in the tables showing the formulations of the examples and comparative examples, the amount of each component is based on parts by mass, and the amount is solid. For non-quantity, the solid content concentration is shown in parentheses after the ingredient name. Prior to the examples, production examples of the silylated peptide-silane compound copolymer composition, the glyceryl ascorbic acid derivative, and the N-glyceryl amino acid used in the examples are shown as reference examples.

Reference Example 1: Production of Silylated Peptide-Silane Compound Copolymer Composition-A N- [2-hydroxy-3- [3- (dihydroxymethylsilyl) propoxy was placed in a 2 liter round bottom cylindrical glass reaction vessel. ] Propyl] Hydrolyzed silk (molecular weight of hydrolyzed silk is about 500 in terms of number average molecular weight) 240 g of 20% aqueous solution and 24 g of 17% hydrochloric acid were added and heated to about 60 ° C. While stirring, a mixed solution of 134.0 g of dimethyldiethoxysilane and 250.0 g of octyltriethoxysilane was added dropwise. Next, an aqueous sodium hydroxide solution was gradually added dropwise with stirring to adjust the pH to about 6 and stirred. While stirring this reaction solution at about 60 ° C., 20.0 g of trimethylchlorosilane was added. Then, 144.0 g of an aqueous sodium hydroxide solution was added dropwise to adjust the pH to about 6, and then the temperature of the reaction solution was raised to 80 ° C. and stirred for about 1 hour. Thereafter, the reaction solution was concentrated under reduced pressure using a rotary evaporator to adjust the solid content concentration to 70%, and N- [2-hydroxy-3- [3- (dihydroxymethylsilyl) propoxy] propyl] hydrolyzed silk-dimethyldi 370 g of an ethoxysilane-octyltriethoxysilane copolymer composition (abbreviated as silylated peptide-silane compound copolymer composition-A) was obtained.

Reference Example 2: Production of 2-O-glyceryl ascorbic acid L-ascorbic acid (10.0 g) and sodium hydrogen carbonate (9.54 g) were added to water under an argon atmosphere, and the mixture was stirred at room temperature for 30 minutes. 8.41 g) was added, and the mixture was heated to 60 ° C. and stirred for 5 hours. Methanol was added to the reaction product and filtered, the filtrate was concentrated under reduced pressure, and 19.0 g of the resulting residue was subjected to silica gel column chromatography. Elution was performed with chloroform / methanol / water = 6/4/1, and concentration was performed under reduced pressure to obtain 2-O-glyceryl ascorbic acid (1.21 g) represented by Chemical formula 6. The obtained product was subjected to 1H-NMR and 13C-NMR measurements. From these measurement results, it was confirmed that this product was 2-O-glyceryl ascorbic acid represented by the following formula (IV). It was. After dissolving this product in water, the pH was adjusted to 6 using an aqueous KOH solution to make a 50% aqueous solution, which was used in the examples.

The analysis results by NMR (Nuclear Magnetic Resonance Analysis) were as follows.
1H-NMR (400 MHz, CD3OD): δ ppm 3.61 (2H, m), 3.67 (2H, m), 3.90 (1H, m), 3.92 (1H, dt-like), 3 .92 (1H, m), 4.07 / 4.09 (1H, dd), 4.86 (1H, d)
13C-NMR (100 MHz, CD3OD): δ ppm 63.3, 63.7, 70.4, 72.0, 74.6, 76.8, 122.2, 161.6, 172.9

Reference Example 3: Production of 2,3-di-O-glyceryl ascorbic acid Under argon atmosphere, L-ascorbic acid (100 g) and sodium hydrogen carbonate (14.4 g) were added to water, and the mixture was stirred at room temperature for 30 minutes. Glycidol (42.0 g) was added. The mixture was heated to 50 ° C. and stirred for 5 hours. Thereafter, glycidol (57.5 g) was added, heated to 80 ° C., stirred for 4 hours, and then concentrated under reduced pressure. 232 g of the obtained residue was subjected to alumina column chromatography, eluted with chloroform / methanol / water = 6/4/1 mixed solution, concentrated under reduced pressure, and 2,3-diglyceryl ascorbic acid (23. 0 g) was obtained. The obtained product was subjected to 1H-NMR and 13C-NMR measurements in the same manner as in Reference Example 2, and from these measurement results, the product was 2,3-di-- represented by the following formula (VII). It was confirmed to be O-glyceryl ascorbic acid. After dissolving this product in water, the pH was adjusted to 6 using an aqueous KOH solution to make a 50% aqueous solution and used in the following examples.

The analysis results by NMR (Nuclear Magnetic Resonance Analysis) were as follows.
1H-NMR (400 MHz, CD ₃ OD): δ ppm 3.58 (2H, m), 3.61 (2H, m), 3.99 (1H, m), 4.16 (1H, m), 4 .53 (1H, m), 4.65 (1H, dd), 4.88 (1H, m)
13C-NMR (100 MHz, CD ₃ OD): δ ppm 63.22, 63.60, 63.63, 63.95, 63.98, 64.44, 70.57, 70.60, 71.68, 71 .94, 71.98, 73.87, 74.27, 74.33, 75.06, 76.83, 123.02

Reference Example 4: Production of 3-O-butylglyceryl ascorbic acid Under argon atmosphere, L-ascorbic acid (100 g) and sodium hydrogen carbonate (14.3 g) were added to water, and the mixture was stirred at room temperature for 30 minutes. Ether (73.8 g) was added. The mixture was heated to 80 ° C. and stirred for 12 hours. Then, it extracted with n-butanol. The extract was dried over anhydrous sodium sulfate and concentrated under reduced pressure. 96.8 g of the obtained residue was subjected to silica gel column chromatography. Elution was performed with a mixed solution of chloroform / methanol / water = 20/3 / 0.3, and concentration was performed under reduced pressure to obtain 3-O-butylglyceryl ascorbic acid (74.2 g). The obtained product was subjected to 1H-NMR and 13C-NMR measurements in the same manner as in Reference Example 2, and from these measurement results, the product was 3-di-- represented by the following formula (VIII) It was confirmed to be O-butylglyceryl ascorbic acid. After dissolving this product in water, the pH was adjusted to 6 using an aqueous KOH solution to make a 50% aqueous solution and used in the following examples.

The analysis results by NMR (Nuclear Magnetic Resonance Analysis) were as follows.
1H-NMR (500 MHz, CD ₃ OD): δ ppm 0.93 (3H, m), 1.38 (2H, m), 1.56 (2H, m), 3.49 (2H, m), 3 .50 (2H, m), 3.66 (2H, m), 3.88 (1H, m), 4.03 (1H, m), 4.44 / 4.46 (1H, dd), 4. 59 / 4.62 (1H, dd), 4.81 (1H, m)
13C-NMR (125 MHz, CD ₃ OD): δ ppm 14.2, 20.3, 32.8, 36.63, 70.2, 71.4, 70.56, 70.61, 72.4, 72 5, 72.6, 73.8, 73.9, 76.8, 121.1, 121.2, 151.7, 151.8, 172.9, 173.0

Reference Example 5: Production of N-glycerylglycine 75.1 g of glycine and 675 g of water were charged into a 3 liter three-necked round bottom flask, and the pH was adjusted to 9.5 by adding an aqueous sodium hydroxide solution, and then heated to 60 ° C. While stirring, 59.3 g of glycidol was gradually added dropwise over 1 hour, and after completion of the addition, stirring was continued for 6 hours to complete the reaction. After cooling to room temperature, diluted hydrochloric acid was added to adjust the pH to 6.5, and water was distilled off under reduced pressure to obtain a viscous substance. 1344 g of methanol was added to the viscous material and stirred to obtain a powdery precipitate, which was then filtered off. The solvent was distilled off under reduced pressure from the methanol solution from which the powdery precipitate had been removed to obtain 101.5 g of a glycerin derivative of glycine, which was a viscous substance. When the total nitrogen content, total carbon content and amino nitrogen content of the glyceryl derivative of glycine thus obtained and the raw material glycine were measured, the following values were obtained. About 69% of the amino groups of glycine were glycerylated. This N-glyceryl derivative of glycine was made into a 30% aqueous solution and used in the following examples.

Glyceryl derivative of glycine Total nitrogen content: 10.68%
Total carbon content: 36.68%
Amino nitrogen content: 3.54%
Glycine (numbers in parentheses are calculated values)
Total nitrogen content: 18.29% (18.66%)
Total carbon content: 31.36% (32.00%)
Amino nitrogen content: 18.47% (18.66%)

Reference Example 6: Production of N-glyceryl lysine 182.7 g of lysine hydrochloride was dissolved in a 3 liter three-necked round bottom flask containing 1644 mL of water, and 20% aqueous sodium hydroxide solution was added to adjust the pH to 9.5. Adjusted. This aqueous solution was heated to 60 ° C., and 74 g of glycidol was added dropwise over 30 minutes while stirring. After completion of the dropwise addition, the reaction was completed by further stirring for 5 hours while maintaining the liquid temperature at 60 ° C. After completion of the reaction, the reaction solution was cooled to room temperature and adjusted to pH 6.8 by adding hydrochloric acid, and then water was distilled off under reduced pressure to obtain 258 g of glyceryl derivative of lysine. When the total nitrogen amount, total carbon amount and amino nitrogen amount of the glyceryl derivative of lysine and the raw material lysine hydrochloride were measured, the following values were obtained: 65.5% of the two amino groups of lysine It was glycerylated. This N-glyceryl derivative of lysine was made into a 30% aqueous solution and used in the following examples.

Glyceryl derivative of lysine Total nitrogen content: 8.25%
Total carbon content: 33.74%
Amino nitrogen content: 5.63%
Lysine hydrochloride (numbers in parentheses are calculated values)
Total nitrogen content: 14.71% (15.33%)
Total carbon content: 39.02% (39.41%)
Amino nitrogen content: 14.60% (15.33%)

Reference Example 7: Production of N-glyceryl glutamic acid 118 g of glutamic acid was added to and dispersed in a 3 liter three-necked round bottom flask containing 1060 mL of water, and 20% aqueous sodium hydroxide solution was converted to adjust the pH to 9.4. Was dissolved. After this aqueous solution was heated to 65 ° C., 58 g of glycidol was added dropwise over 30 minutes while stirring. After completion of the dropping, the reaction was completed by further stirring for 6 hours while maintaining the liquid temperature at 65 ° C. After completion of the reaction, the reaction solution was cooled to room temperature and adjusted to pH 6.6 by adding hydrochloric acid, and then water was distilled off under reduced pressure to obtain 241 g of glyceryl derivative of glutamic acid. Of these, 19% is considered to be salt with neutralized salt. The total amount of nitrogen, the total amount of carbon and the amount of amino nitrogen of the resulting glyceryl derivative of glutamic acid and raw material glutamic acid were measured, and the following values were obtained. 74% of the amino groups of glutamic acid were glycerylated. Since glutamic acid is hardly soluble in water, sodium glutamate monohydrate was used for analysis. This N-glyceryl derivative of glutamic acid was made into a 30% aqueous solution and used in the following examples.

Glyceryl derivative of glutamic acid Total nitrogen content: 4.57%
Total carbon content: 31.32%
Amino nitrogen content: 1.21%
Sodium glutamate monohydrate (numbers in parentheses are calculated)
Total nitrogen content: 7.36% (7.49%)
Total carbon content: 31.25% (32.09%)
Amino nitrogen content: 7.36% (7.49%)

Example 1 and Comparative Examples 1-2: Lipstick A lipstick having the composition shown in Table 1 was prepared by the following preparation method, and the stability of the prepared lipstick (whether oil or pigment was separated, sweating, blooming, color change) The feeling of use and moisture retention were evaluated. A part of the lipstick was taken and the dispersion state of the hydrophilic substance was observed with a microscope.

  In Examples 1 and 2, a silyl peptide-silane compound copolymer composition and glyceryl arginine as a hydrophilic substance were used, and Comparative Example 1 did not use a silylated peptide-silane compound copolymer composition, and the same glyceryl as a hydrophilic substance. Arginine is used. Comparative Example 2 uses PEG-10 dimethicone instead of silylated peptide-silane compound copolymer, and uses the same glyceryl arginine as the hydrophilic substance. In addition, the difference of the total amount by the presence or absence of the blending of silylated peptide-silane compound or PEG-10 dimethicone was adjusted with diisostearyl malate so that the total amount was 100 for each preparation.

  In Table 1, * 1 is PROTESIL FN (trade name) [(hydrolyzed silk / PG-propylmethylsilanediol) crosspolymer] manufactured by Seiwa Kasei Co., Ltd., and * 2 is manufactured by Seiwa Kasei Co., Ltd. Amitose R (trade name). * 3 represents the ratio of red 202, yellow 4, blue 1 and titanium oxide diisostearyl malate dispersion (50% concentration for each pigment dispersion) at a ratio of 14: 50: 1: 30 (mass ratio) The pearl agent of * 4 is a 5: 2 mixture (mass ratio) of silver and gold based on titanium oxide coated with mica.

<Preparation method>
After part A was put into a stirring vessel and mixed well, part B was added and stirred and mixed at 90 ° C. Next, part D was added, and mixing and stirring were repeated until the color tone became uniform while removing the generated bubbles under reduced pressure. Next, part C was added, and after confirming dissolution, the mixture was taken out of the stirring vessel, filled into a lipstick mold and cooled.

(1) Evaluation of stability For the lipstick prepared as described above, immediately after preparation, and after storage for 1 month at 40 ° C., when returned to room temperature, whether oil or pigment is separated, whether sweat is present, Blooming and color change were visually judged by five testers with and without, and lipsticks prepared based on the following stability evaluation criteria were evaluated based on the results. In addition, about the thing already isolate | separated at the time of preparation, only the presence or absence of isolation | separation was evaluated. The results are shown in Table 2. The phrase “after storage at 40 ° C. for 1 month” is abbreviated as “after storage at 40 ° C.” because of the space in the table.
〔Evaluation criteria〕
Presence or absence of separation of oil and / or pigment ○: No separation (3 or more people judged that there was no separation)
×: Separation (determined that 3 or more are separated)
Presence / absence of sweat ○: No sweat (3 or more people judged that there was no sweat)
×: sweating (3 or more people judged sweating)
Presence / absence of blooming ○: No blooming (3 or more people judged no blooming)
×: Blooming (3 or more people judge blooming)
Presence or absence of color change ○: No color change (3 or more people judged that there was no color change)
×: Color change (3 or more people judged that there was a color change)

  As can be seen from Table 2, the lipstick of Example 1 shows excellent results in any of the evaluation items of separation of oil and / or pigment separation, sweating, presence or absence of blooming, and change in color. There is no problem in separation, sweating, blooming, color change, etc. even after storage for months, and the silylated peptide-silane compound copolymer composition has a high ability to stably mix N-glyceryl arginine hydrochloride into oily substances. It has shown that it has.

(2) Evaluation of feeling of use Applying lipstick on the thumb base of the palm of 10 subjects, making the moist feeling, adhesion feeling, and color development good / bad, and determining the lipstick according to the following evaluation criteria based on the results. evaluated.
Evaluation criteria for feeling of use ◎: Eight or more out of 10 judged good for each evaluation item ○: 5-7 out of 10 judged good for each evaluation item △: 2 out of 10 ~ 4 people judged that each evaluation item was good ×: 0 to 1 out of 10 people judged that each evaluation item was good

(3) Evaluation of moisture retention About 6 mg was applied to a 6 cm 2 (2 × 3) cm range inside the subject's forearm, and the corneal moisture content for 10, 20, 30, 45, 60, 90, 120 minutes after application was CORNEOMETER CM825. It was measured by (Courage + Khazaka electronic GmbH). Measurement was performed with 10 test subjects, and the rate of change after 30 minutes was determined on the basis of the value immediately after application, and the moisture retention was evaluated by the average value of 10 subjects.
Evaluation standard of moisture retention ◎: Change rate is 20% or more ○: Change rate is 10-20%
Δ: Change rate is 5 to 10%
×: Change rate is 5% or less

  The results of evaluation of the feeling of use and evaluation of moisture retention are shown in Table 3, but these evaluations were not performed for Comparative Example 1 that had already been separated at the time of preparation.

  As is apparent from Table 3, the evaluation value of the lipstick of Example 1 was high in any of the evaluation items of the feeling of use and the moisturizing property. This is because the hydrophilic substance is uniformly dispersed and blended in the lipstick. It is thought that.

(4) Observation of dispersion state with a microscope In order to confirm the dispersion state of the hydrophilic substance, a small amount of fluorescein (fluorescent reagent) was added to N-glycerylarginine hydrochloride, and the formulations of Example 1 and Comparative Example 2 were used. Lipstick was prepared, applied to a slide glass, and the dispersion state was evaluated with a fluorescence microscope. In the evaluation, five testers visually judged whether the dispersibility was good or bad, and the dispersibility was evaluated based on the following criteria.
Evaluation standard of dispersibility ○: 3 or more people judged that dispersibility was good ×: 3 or more people judged that dispersibility was bad

  The results are shown in Table 4. In the lipstick of Example 1, it was often determined that the hydrophilic substance N-glyceryl arginine hydrochloride was uniformly dispersed, whereas the lipstick of Comparative Example 2 Therefore, it was evaluated that the dispersion of N-glyceryl arginine hydrochloride was poor, and it was clear that the silylated peptide-silane compound copolymer composition uniformly dispersed N-glyceryl arginine hydrochloride in the oil component. It was.

Example 2 and Comparative Examples 3 to 4: Liquid Gloss Liquid gloss having the composition shown in Table 5 was prepared by the following preparation method. For the prepared liquid gloss, the appearance and color immediately after preparation and after storage for 1 month at 40 ° C Changes and feel were evaluated. In Example 3, the silylated peptide-silane compound copolymer composition and 2-O-glyceryl ascorbic acid produced in Reference Example 2 were used as hydrophilic substances, and in Comparative Example 3, the silylated peptide-silane compound copolymer composition was used. Without using 2-O-glyceryl ascorbic acid, in Comparative Example 4, using PEG-10 dimethicone instead of silylated peptide-silane compound copolymer and using 2-O-glyceryl ascorbic acid as a hydrophilic substance It is. The difference in the total amount depending on whether or not the silylated peptide-silane compound was blended was adjusted with hydrogenated polyisobutene so that the total amount was 100 for each preparation.

  In Table 5, * 5 indicates the red 202, yellow 4, and blue 1 diisostearyl malate dispersions (50% concentration for each dye dispersion) in a ratio (mass ratio) of 14: 50: 1. Mix and knead well with three rollers. * 6 is a silver-based pearling agent obtained by coating mica on titanium oxide.

<Preparation method>
After part A was put into a stirring vessel and mixed well, part B was added and stirred and mixed at 90 ° C. Next, part D was added, and mixing and stirring were repeated until the color tone became uniform. At the same time, bubbles generated by decompression were removed. Next, part C was added, and after confirming that it was dissolved, it was removed from the stirring vessel, filled into a container and cooled.

(1) Stability evaluation For liquid gloss prepared as described above, immediately after preparation and after storage at 40 ° C. for 1 month, the liquid gloss is returned to room temperature and the liquid gloss oil or pigment is separated or the color changes. The same evaluation method and evaluation criteria as in Example 1 were used for evaluation.

(2) Evaluation of use feeling Liquid gloss was applied to the base of the thumb of the palm of 10 subjects, and the moist feeling and color development were evaluated using the same criteria and evaluation method as in Example 1.

  The results of the evaluation of the stability and the feeling in use are shown in Table 6. In Comparative Example 3, which had already been separated at the time of preparation, the stability and the feeling in use were not evaluated. In the table, “after storage at 40 ° C.” means “after storage at 40 ° C. for one month”.

  The liquid gloss of Example 2 is an excellent evaluation value for all items of separation of oil and pigment for stability evaluation, color change, moist feeling for evaluation of use feeling, and color development. It was clear that by blending the polymerization composition, a water-soluble component can be blended and used in a formulation mainly composed of an oily substance, and liquid gloss excellent in stability and use feeling can be prepared.

Example 3 and Comparative Examples 5 to 6: Solid Gloss A solid gloss having the composition shown in Table 7 was prepared by the following preparation method, stability was evaluated, and skin roughness improvement effect by continuous use was further evaluated. In Example 3, the silylated peptide-silane compound copolymer composition and the ascorbic acid derivative produced in Reference Example 3 were used as hydrophilic substances, and in Comparative Example 5, the silylated peptide-silane compound copolymer composition was not used. The ascorbic acid derivative produced in Reference Example 3 is used as the active substance. In Comparative Example 6, PEG-10 dimethicone was used instead of silylated peptide-silane compound copolymer, and the ascorbic acid derivative produced in Reference Example 3 was used as the hydrophilic substance. The difference in the total amount depending on whether or not the silylated peptide-silane compound is mixed is adjusted with mineral oil so that the total amount is 100 for each preparation.

  In Table 7, * 1 is the same as Table 1 of Example 1, and * 5 and * 6 are the same as Table 5 of Example 2.

<Preparation method>
After part A was put into a stirring vessel and mixed well, part B was added and stirred and mixed at 90 ° C. Next, part D was added, and mixing and stirring were repeated until the color tone became uniform while removing bubbles generated under reduced pressure. Next, C part was added, and after confirming that it was dissolved, the mixture was taken out of the stirring vessel, filled into a container and cooled.

(1) Evaluation of stability Evaluation was performed using the same evaluation method and evaluation criteria as in Example 1.

(2) Evaluation of skin roughness improvement effect by continuous use Ten subjects were allowed to use the sample continuously for 1 month instead of the lips for 1 month, and evaluated the skin roughness improvement effect according to the following five evaluation criteria. An average score was calculated based on the evaluation score, and the skin roughness improvement effect of the prepared solid gloss was evaluated according to the following three-stage criteria.
5-point evaluation for continuous test subjects 2 points: very good 1 point: good 0 point: cannot say either -1 point: somewhat bad -2 point: bad
The average value of 10 people in the 3 grades of the continuous test
1.5 points or more: ◎ (very good)
0 to less than 1.5 points: ○ (good)
Less than 0: x (defect)

  Table 8 shows the results of the evaluation of stability and the effect of improving skin roughness by continuous use. In Comparative Example 5, which had already been separated at the time of preparation, the stability and feel of use were not evaluated. In the table, “after storage at 40 ° C.” means “after storage at 40 ° C. for one month”.

  As is apparent from Table 8, the solid gloss of Example 3 was excellent in all the items of oil / pigment separation / no sweating / blooming / color change, and the silylated peptide-silane compound. By blending the copolymer composition, it was possible to blend a hydrophilic substance into a formulation mainly composed of an oil component, and it was possible to prepare a solid gloss excellent in stability. Moreover, it was recognized that roughening of the skin was improved by using this solid gloss continuously.

Example 4 and Comparative Examples 7 to 8: Concealer A concealer having the composition shown in Table 9 was prepared by the following preparation method, and the stability and feel of use were evaluated. In Example 5, the silylated peptide-silane compound copolymer composition and the ascorbic acid derivative (3-O-butylglyceryl ascorbic acid) produced in Reference Example 4 were used as the hydrophilic substance. In Comparative Example 7, the silylated peptide-silane was used. Without using the compound copolymer composition, only the hydrophilic substance 3-O-butylglyceryl ascorbic acid was used, and Comparative Example 8 used PEG-10 dimethicone instead of silylated peptide-silane compound copolymer to make the hydrophilic substance In addition, 3-O-butylglyceryl ascorbic acid is used. The difference in the total amount depending on whether or not the silylated peptide-silane compound was blended was adjusted with diisostearyl malate so that the total amount was 100 for each preparation.

  * 1 is the same as Example 1 in Table 1, * 7 is a mixed pigment in which titanium oxide, yellow iron oxide, red iron oxide, and black iron oxide are mixed in a ratio (mass ratio) of 2940: 436: 88: 35 It is.

<Preparation method>
After part A was put into a stirring vessel and mixed well, part B was added and stirred and mixed uniformly with a homomixer. Next, part C was added, stirring and mixing at 90 ° C. while removing bubbles generated under reduced pressure, and mixing and stirring were repeated until the color tone became uniform. After confirming that it was sufficiently dissolved, the mixture was taken out of the stirring vessel, filled into a container and cooled.

(1) Evaluation of stability The concealer prepared as described above was checked for oil / pigment separation, sweating and blooming immediately after preparation and when stored at 40 ° C. for 1 month and then returned to room temperature. Evaluation was performed in the same manner as in Example 1.

(2) Evaluation of feeling of use A concealer was applied to 10 subjects on the inner side of the forearm, and the ease of spreading, adhesion and familiarity were evaluated using the same evaluation method and evaluation criteria as the feeling of feeling of use in Example 1. .

(3) Evaluation of whitening effect by continuous use Ten test subjects were allowed to use the sample for a month for a part where the spots etc. were worried, and the whitening effect was evaluated and evaluated in the same manner as the skin roughening effect by continuous use of Example 4. Evaluated by criteria.

  The evaluation results of stability, feel in use and whitening effect are shown in Table 10, but Comparative Example 9 which had already been separated at the time of preparation did not perform these evaluations. In the table, “after storage at 40 ° C.” means “after storage at 40 ° C. for one month”.

  As is clear from Table 10, the concealer of Example 4 is excellent in stability such as separation of oil and pigment, sweating, blooming and the like, and also has good use feeling such as ease of spreading, adhesion, and familiarity. Moreover, the whitening effect was recognized by using repeatedly. It was clear that by using the silylated peptide-silane compound copolymer composition, a hydrophilic substance can be stably blended into a formulation mainly composed of an oil component, and a concealer excellent in use feeling can be prepared.

Example 5 and Comparative Examples 9 to 10: Oily Mascara Oily mascara having the composition shown in Table 11 was prepared by the following preparation method, and the stability and feel of use were evaluated. In Example 5, N-glycerylglycine produced in Reference Example 5 was used as a silylated peptide-silane compound copolymer composition and a hydrophilic substance, and in Comparative Example 9, a silylated peptide-silane compound copolymer composition was not used. The hydrophilic substance N-glycerylalanine was used, and Comparative Example 10 used PEG-10 dimethicone instead of silylated peptide-silane compound copolymerization and N-glycerylalanine as the hydrophilic substance. The difference in the total amount depending on whether or not the silylated peptide-silane compound was blended was adjusted with neopentyl glycol dicaprate so that the total amount was 100 for each preparation.

  In Table 11, * 1 is the same as Example 1 in Table 1.

<Preparation method>
Part A is put into a stirring vessel and mixed well, then part B is added, then added to the mixture of part A and part B into part C previously dissolved at 90 ° C., and bubbles generated under reduced pressure Mixing and stirring were repeated until the mixture became uniform. After confirming that all the additives were sufficiently dissolved and mixed, the mixture was taken out of the stirring vessel, filled into a container and cooled.

(1) Evaluation of Stability The stability of Example 1 with respect to the presence or absence of separation of oil and pigment immediately after preparation and when returned to room temperature after storage at 40 ° C. for 1 month. Evaluation was performed using the same evaluation method and evaluation criteria as in the above.

(2) Evaluation of feeling of use Applying an oily mascara to 10 subjects, ease of spreading, difficulty of dropping, and curling for 12 hours after application, the same evaluation method as that of Example 1 feeling of use, Evaluation was based on the evaluation criteria.

  The evaluation results of these stability and feel in use are shown in Table 12, but Comparative Example 11 in which the oil and pigment were separated immediately after the preparation was not evaluated. In the table, “after storage at 40 ° C.” means “after storage at 40 ° C. for one month”.

  As is clear from Table 12, the oily mascara of Example 6 had no separation of oil and pigment, and was excellent in all items of curl holding, ease of spreading and resistance to dropping. From this result, it is clear that by using a silylated peptide-silane compound copolymer composition, a hydrophilic substance can be blended in an oily mascara, and an oily mascara excellent in stability and usability can be obtained. It became.

Example 6 and Comparative Examples 11 to 12: Hair Sticks Hair sticks having the compositions shown in Table 13 were prepared by the following preparation methods, and the stability of the preparation, the feeling of use, and the effect of preventing color hair from fading were evaluated. . In Example 6, the silylated peptide-silane compound copolymer composition and the ascorbic acid derivative produced in Reference Example 2 and the N-glyceryl glutamic acid produced in Reference Example 7 were used as hydrophilic substances, and in Comparative Example 11, the silylated peptide- Ascorbic acid derivatives and N-glyceryl glutamic acid, which are hydrophilic substances, are used without using a silane compound copolymer composition, and in Comparative Example 14, PEG-10 dimethicone is used instead of silylated peptide-silane compound copolymer. Ascorbic acid derivatives and N-glyceryl ascorbic acid are used. The difference in the total amount depending on whether or not the silylated peptide-silane compound was blended was adjusted with diisostearyl malate so that the total amount was 100 for each preparation.

  In Table 13, * 1 is the same as Example 1 in Table 1.

<Preparation method>
Part A was put into a stirring kettle and mixed well, then part B was added and stirred and mixed at 90 ° C. while removing bubbles generated under reduced pressure. The mixture was removed from the stirring kettle, filled into a container and cooled.

(1) Evaluation of stability The hair sticks prepared as described above were subjected to oil separation and pigment separation and sweating immediately after preparation and when returned to room temperature after storage at 40 ° C for 1 month. Evaluation was performed by the same evaluation method and evaluation criteria as those of Example 1 for stability evaluation.

(2) Evaluation of use feeling About hair sticks immediately after preparation, 10 test subjects were allowed to apply hair sticks to the inner part of the forearm, and the same evaluation method as the evaluation of use feeling in Example 1 was applied to ease of spreading and non-stickiness. Evaluation was made based on evaluation criteria.

(3) Evaluation of anti-fading effect of color hair by continuous use The hair stick prepared for 10 subjects who are coloring is used continuously for 1 month. Evaluation was performed by the same evaluation method and evaluation standard as the evaluation of the roughness improvement effect.

  Table 14 shows the results of evaluation of the stability, feel of use, and anti-fading effect of color hair by continuous use of the prepared hair stick. Comparative Example 11 was evaluated because it was separated from immediately after preparation and did not form a hair stick body. I have not done it. In the table, “after storage at 40 ° C.” means “after storage at 40 ° C. for one month”.

  The hair stick of Example 6 has excellent results in all evaluation items of oil and pigment separation, sweating, ease of spreading, and non-stickiness. By blending the silylated peptide-silane compound copolymer composition, It was clear that the water-soluble component can be blended in a formulation mainly composed of an oil component, and that a hair stick excellent in stability and use feeling can be prepared. Moreover, the anti-fading effect of color hair was also recognized by using the hair stick of Example 6 continuously.

Example 7: Lipstick A lipstick having the composition shown in Table 15 was mixed well by introducing part A into a stirring vessel, and then part B was introduced. The temperature was 90 ° C. while removing bubbles produced under reduced pressure. After stirring and mixing and adding part C and confirming that it was dissolved, the mixture was taken out of the stirring vessel, filled into a container, and cooled to prepare.

  In Table 15, * 1 is the same as Example 1 in Table 1.

  The obtained lipstick had excellent usability and had an effect of improving lip roughness.

Example 8: Powder foundation The powder foundation of the composition shown in Table 16 was uniformly mixed with part A using a juicer mixer, part B was added to part A, and mixed uniformly with a juicer mixer. It was prepared by pressing.

  In Table 16, * 1 is the same as Example 1 in Table 1.

The obtained powder foundation was excellent in moisturizing feeling.

Claims (6)

The following general formula (I)

[Wherein R ¹ represents a hydroxyl group or an alkyl group having 1 to 3 carbon atoms, R ² represents a residue of a side chain excluding a terminal amino group of a basic amino acid having an amino group at the end of the side chain; ³ represents an amino acid side chain other than the amino acid to which R ² is bonded, A is a bond, methylene, propylene, — (CH ₂ ) ₃ OCH ₃ CH (OH) CH ₂ —, — (CH ₂ ) ₃ S— , — (CH ₂ ) ₃ NH— and — (CH ₂ ) ₃ OCOCH ₂ CH ₂ — represents at least one group selected from the group consisting of 0 to 50, y to 1 to 100, and x + y to 1 1 or more of the silylated peptides represented by the following general formula (II): wherein x and y only indicate the number of amino acids, not the order of amino acid sequences)
R ⁴ _m Si (OH) _p Y _(4-p-m) (II)
[Wherein, m is an integer of 0 to 2, p is an integer of 2 to 4, m + p ≦ 4, R ⁴ is an organic group in which a carbon atom is directly bonded to a silicon atom, and m R ⁴ are the same. But it may be different. (4-pm) Y is an alkoxy group or a hydrogen atom], and the reaction molar ratio is silylated peptide: silane compound = 1: 20 to 1:80. The following general formula (III)
R ⁵ ₃ Si (OH) (III)
[Wherein, three R ⁵ are organic groups in which a carbon atom is directly bonded to a silicon atom, and three R ⁵ may be the same or different] in an aqueous solution. A silylated peptide-silane compound copolymer composition obtained by addition, and one or more selected from the group of hydrophilic substances consisting of a water-soluble ascorbic acid derivative or salt thereof, N-glyceryl amino acid or salt thereof, or An oily cosmetic comprising two or more. The water-soluble ascorbic acid derivative is represented by the following general formula (IV)

[Wherein R ⁶ is H, an alkyl group having 1 to 4 carbon atoms, R ⁸ —O—CH ₂ —CH (OH) —CH ₂ —, R ⁹ —O—CH ₂ —CH (CH ₂ OH) — , R ⁷ is H, an alkyl group having 1 to 4 carbon atoms, R ¹⁰ —O—CH ₂ —CH (OH) —CH ₂ —, R ¹¹ —O—CH ₂ —CH (CH ₂ OH) —, The R ⁸ and R ⁹ are H and an alkyl group having 1 to 4 carbon atoms, and the R ¹⁰ and R ¹¹ are H and an alkyl group having 1 to 4 carbon atoms]. Oily cosmetics. N-glyceryl amino acid is represented by the following general formula (V)

The oily cosmetic according to claim 1 or 2, wherein A represents a side chain of an α-amino acid, and Z represents a hydrogen atom, an alkali metal, ammonium, or organic ammonium.   Ascorbic acid derivatives represented by the general formula (IV) are 2-O-glyceryl ascorbic acid or a salt thereof, 3-O-glyceryl ascorbic acid or a salt thereof, 2,3-di-O-glyceryl ascorbic acid or a salt thereof The oily cosmetic according to claim 1, wherein the cosmetic is at least one selected from the group consisting of:   N-glyceryl amino acid or a salt thereof is one or more selected from the group consisting of N-glyceryl arginine or a salt thereof, N-glyceryl lysine or a salt thereof, N-glyceryl glutamic acid or a salt thereof, N-glyceryl aspartic acid or a salt thereof The oily cosmetic according to claim 1, wherein The mixing ratio of one or more selected from the hydrophilic substance group and the silylated peptide-silane compound copolymer composition is one or more selected from the hydrophilic substance group by mass ratio: silylated peptide The oily cosmetic according to any one of claims 1 to 3, wherein the silane compound copolymer composition is 1: 0.05 to 15.