JP2001048775A - Cosmetic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a cosmetic good in compatibility with hair or skin without stickiness and capable of imparting smoothness or a humectant feeling to the hair or skin, exhibiting effects on reduction in oily feeling in a cosmetic containing an oily substance and further imparting a refreshing finish feeling thereto. SOLUTION: This cosmetic is composed by including a silylated peptide-silane compound copolymer composition prepared by carrying out a condensation polymerization of a silylated peptide having two hydroxyl groups directly bound to silicon atom with one or more kinds of silane compounds capable of producing at least two hydroxyl groups directly bound to silicon atom by hydrolysis.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to cosmetics, and more particularly, to one or more silylated peptides having two hydroxyl groups directly bonded to silicon atoms, and a hydroxyl group directly bonded to silicon atoms by hydrolysis. A silylated peptide-silane compound copolymer composition obtained by condensation polymerization of at least one silane compound that produces two or more
The present invention relates to a cosmetic which imparts smoothness and moisturizing feeling to hair and skin, has no stickiness and further contains an oily substance, and further suppresses an oily feeling and gives a refreshing finish.

[0002]

2. Description of the Related Art Conventionally, hair cosmetics and skin cosmetics are blended with hydrolyzed peptides and derivatives thereof obtained by hydrolyzing proteins derived from natural products such as collagen, keratin, silk, soybean, and wheat. Has been done.
This is because their hydrolyzed peptides and their derivatives have good sorption properties to hair and skin, and hair cosmetics prevent hair damage, recover damaged hair, give gloss, glue, moisturize, Skin cosmetics have the effect of imparting a feeling of moisturizing and moisturizing to the skin, and because their hydrolyzed peptides and their derivatives are derived from natural proteins, are less irritating to hair and skin, and are highly safe. Things.

[0003] However, when the amount of the hydrolyzed peptide is large, the hair becomes hard in the case of hair cosmetics, the hair becomes sticky under high humidity, and the skin cosmetics give the skin a firm or sticky feeling. There is a problem that an amount sufficient to exert the effect of imparting gloss, moisture, and beams cannot be added.

[0004] Therefore, it has been practiced to combine a hydrolyzed peptide and a silicone with hair cosmetics and skin cosmetics. This is because of the excellent extensibility of silicone oil, the effect of giving gloss and luster to the hair and skin, the effect of giving smoothness, the protective effect by giving water repellency, and the effect of sorption of the hydrolyzed peptide on hair and skin. This is because it is intended to exert a protective action and a moisturizing action by film formation.

[0005] However, silicone oil is originally a lipophilic substance, and hydrolyzed peptides are essentially hydrophilic substances. Therefore, they are hardly compatible with each other. It was necessary to prevent the silicone oil from being separated by the emulsifier. In addition, in the case of hair cosmetics, the hydrolyzed peptide hardly adheres to the portion of the hair that has come into contact with the silicone oil first, and conversely, the silicone oil adheres to the portion that has contacted the hydrolyzed peptide first. There is a problem in that it is difficult to perform both properties sufficiently.

Accordingly, the present inventors have developed a silylated peptide in which a functional group containing only one silicon atom is covalently bonded to the amino group of a peptide containing an amino group in the amino acid side chain, and the peptide is used in hair cosmetics. By blending, it has been attempted to solve the above problem (for example, see Japanese Patent Application Laid-Open No. H8-813).
No. 38, JP-A-8-81339, JP-A-8-81339
133934, JP-A-8-157344 and the like).

However, since the silylated peptide used in the above publication has few silyl groups bonded to the peptide chain, the hydrolyzed peptide exerts the effect of imparting moisture retention, but has water repellency, extensibility, and smoothness. However, there is a problem that the silicone oil is inferior to the silicone oil in terms of the addition of silicone oil.

[0008]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, and in hair cosmetics,
Improves combability and imparts moisture by smoothing the hair surface, and in skin cosmetics, imparts smoothness and moisture (moisturizing sensation) to the skin, and has no stickiness, and further contains an oily substance. An object of hair cosmetics and skin cosmetics is to provide a cosmetic that can suppress an oily feeling and impart a refreshing finish feeling.

[0009]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, obtained by hydrolyzing one or more silylated peptides having two hydroxyl groups directly connected to a silicon atom. 2 hydroxyl groups directly connected to the silicon atom
When a cosmetic composition contains a silylated peptide-silane compound copolymer composition obtained by polycondensation of at least one silane compound with at least one silane compound in an aqueous solution, the hair surface is smoothened in a hair cosmetic. Improves combing and imparts moisture to hair, and in skin cosmetics,
It imparts smoothness and moisturizing feeling to the skin, can impart a refreshing finish without stickiness, and further contains an oily substance because the silylated peptide-silane compound copolymer composition has an emulsifying action. The inventors have found that the oily feeling can be easily added to cosmetics and that the oily feeling is reduced by the addition of the silylated peptide-silane compound copolymer composition, and the present invention has been completed.

[0010]

DETAILED DESCRIPTION OF THE INVENTION One or more silylated peptides having two hydroxyl groups directly bonded to silicon atoms contained in the cosmetic of the present invention, and a silane compound which produces two or more hydroxyl groups directly bonded to silicon atoms by hydrolysis A silylated peptide having two hydroxyl groups directly connected to a silicon atom used for the condensation polymerization of a silylated peptide-silane compound copolymer composition obtained by condensation polymerization of at least one of
It has two hydroxyl groups directly bonded to a silicon atom from the time of its synthesis, and has the following general structural formula (I)

[0011]

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[0012] ^wherein two of R ^1, R 2, ^{R 3} is a hydroxyl group and the rest represents an alkyl group having 1 to 3 carbon atoms, ^{R 4}
Represents a residue of a side chain excluding a terminal amino group of a basic amino acid having an amino group at a terminal of a side chain, R ⁵ represents an amino acid side chain other than R ⁴ , A represents —CH ₂ —, − (CH
_{2) 3} - and _{- (CH 2) 3 OCH 2} CH (OH) C
Represents at least one group selected from the group consisting of H ₂ —, m is 0 to 500, n is 0 to 500, and m + n is 1 to 5
00 (where m and n only indicate the number of amino acids, not the order of the amino acid sequences)] and the following general structural formula (I
I)

[0013]

Embedded image

[Wherein, R ^{6 to} R ⁸ each represent a hydroxyl group, an alkoxy group, a halogen group, a hydrogen atom or a carbon atom of 1 to 3;
Wherein R ^{6 to} R ⁸ may be the same or different, but two of R ^{6 to} R ⁸ are an alkoxy group or a halogen group, and R ⁴ , R ⁵ , A,
m and n are the same as those in the above general structural formula (I)], and some are obtained by hydrolyzing a silane compound represented by the general structural formula (I). The silylated peptides to be used are described in JP-A-8-59424, JP-A-8-67608, and JP-A-7-223.
No. 921, JP-A-7-228508 and the like can be easily synthesized in an aqueous solution.

In the silylated peptide represented by the general structural formula (I), R ⁴ is a residue of a side chain excluding a terminal amino group of a basic amino acid having an amino group at a terminal of the side chain. Examples of the basic amino acid having an amino group at the terminal of the side chain as described above include lysine, arginine, and hydroxylysine. Further, R ⁵ represents an amino acid side chain other than R ^4, but as such acids, e.g., glutamic acid, aspartic acid, alanine, serine, threonine, valine, methionine, leucine, isoleucine, tyrosine, phenylalanine, proline, Hydroxyproline and the like.

In the silylated peptide represented by the general structural formula (I), m is 0 to 500, preferably more than 0 and 200 or less (0 <m ≦ 200), more preferably more than 0 and 50 or less (0 <m <200). m ≦ 50), more preferably more than 0 and 10 or less (0 <m ≦ 10), and n is 0
５００500, preferably more than 0 and 200 or less (0 <n
≦ 200), more preferably 1 to 100, further preferably 2 to 40, and m + n is 1 to 500, preferably 1 to 200, more preferably 2 to 100, and still more preferably 3 to 50.

That is, when m is larger than the above range, the number of silyl functional groups bonded to the amino group in the side chain increases, and the sorption effect of the peptide on the original hair decreases. When the ratio of the silyl functional group portion to is small, the characteristics possessed by the silyl functional group portion cannot be sufficiently exhibited, and when m + n is larger than the above range, the sorption property and the permeability to the hair as a peptide become poor. In addition to the reduction compared to low-molecular-weight peptides, they tend to aggregate during storage and storage stability is reduced. The above m, n and m + n are theoretically integers. However, when the peptide portion is a hydrolyzed peptide as described below, the hydrolyzed peptide is obtained as a mixture of those having different molecular weights. The measured value will be the average value.

The peptides used for the silylated peptide represented by the above general structural formula (I) include amino acids, peptides and the like. Examples of the amino acids include alanine, glycine, valine, leucine, isoleucine and proline. Phenylalanine, tyrosine, serine, threonine, methionine, arginine, histidine, lysine, asparagine, aspartic acid, glutamine, glutamic acid, cystine, cysteine, cysteic acid, tryptophan, hydroxyproline, hydroxylysine, O-phosphoserine, citrulline and the like. .

Examples of the above-mentioned peptides include natural peptides, synthetic peptides, hydrolyzed peptides obtained by partially hydrolyzing proteins (proteins) with acids, alkalis, enzymes or a combination thereof.

Examples of the natural peptide include glutathione, bacitracin A, insulin, glucagon, oxytocin, and vasopressin, and examples of the synthetic peptide include polyglycine, polylysine, polyglutamic acid, and polyserine.

Examples of the hydrolyzed peptide include collagen (including gelatin as a denatured product thereof), keratin, silk fibroin (silk), sericin, casein,
Egg yolk protein (protein), egg white protein, egg white protein, soy protein, wheat protein, corn protein, rice (rice bran) protein, animal and plant-derived proteins such as potato protein in eggs such as conchiolin, elastin, chicken, and duck.
Alternatively, yeasts of the genera Saccharomyces, Candida and Endomycopsis, yeast proteins isolated from so-called beer yeasts, sake yeasts, proteins extracted from mushrooms (basidiomycetes), proteins isolated from chlorella, and the like. And a peptide obtained by partially hydrolyzing a protein derived from the microorganism with an acid, an alkali, an enzyme or a combination thereof.

The silylated peptide-silane compound copolymer composition contained in the cosmetic of the present invention is directly bonded to one or more silylated peptides represented by the above general formula (I) to a silicon atom by hydrolysis. Can be obtained by condensation polymerization of one or more silane compounds having two or more hydroxyl groups. The silane compound having two or more hydroxyl groups directly bonded to a silicon atom by hydrolysis is, for example, the following general structure Formula (III) R ⁹ pSiX (4-p) (III) wherein p is an integer of 0 to 2, R ⁹ is an organic group in which a carbon atom is directly bonded to a silicon atom, and p R ⁹ May be the same or different. (4-p) Xs are at least one group selected from the group consisting of a hydroxyl group, an alkoxy group, and a halogen group]. Structural formula (IV) R ¹⁰ pSi (OH) qY (4-q-p) (IV) wherein p is an integer of 0 to 2, q is an integer of 2 to 4,
When p + q ≦ 4, R ¹⁰ is an organic group having a carbon atom directly bonded to a silicon atom, and p R ¹⁰ may be the same or different. (4-q-p) Y are at least one group selected from the group consisting of an alkoxy group, a hydrogen atom, and a siloxy group.] The above general structural formulas (III) and (IV)
, P, (4-p), q, and (4-q-p) are subscripts.

Specific examples of the silane compound represented by the general structural formula (III) include, for example, tetramethoxysilane, methyltrimethoxysilane, methyldimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane. Silane, hexyltrimethoxysilane, decyltrimethoxysilane, vinyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxy Silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3
-Aminopropyltrimethoxysilane, N-phenyl-
3-aminopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycosidoxypropyltrimethoxysilane, 3-glycosidoxypropylmethyldimethoxysilane, Dimethyloctadecyl [3- (trimethoxysilyl) propyl] ammonium chloride, 3- (trimethoxysilyl) propylpolyoxyethylene (10)
Ether, tetraethoxysilane, methyltriethoxysilane, methyldiethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyl Methyldiethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N-
(2-aminoethyl) -3-aminopropylmethyldiethoxysilane, 3-aminopropyltriethoxysilane, 3-chloropropyltriethoxysilane, 3-chloropropylmethyldiethoxysilane, 3-glycosideoxypropylmethyldiethoxysilane , 3-isocyanatopropyltriethoxysilane, methyldichlorosilane, methyltrichlorosilane, dimethyldichlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, vinyltrichlorosilane, 3-chloropropylmethyldichlorosilane, and N- (2-amino Ethyl) -3-aminopropyltrimethoxysilane, N-
(2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycoside Xypropyltrimethoxysilane, 3-glycosideoxypropylmethyldimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane , N- (2-aminoethyl) -3-aminopropylmethyldiethoxysilane, 3
Silane coupling agents such as aminopropyltriethoxysilane, 3-chloropropyltriethoxysilane, 3-chloropropylmethyldiethoxysilane, 3-glycosidoxypropylmethyldiethoxysilane, and 3-isocyanatopropyltriethoxysilane; , An alkyl group, a polyoxyethylene ether, a polyoxypropylene ether, an acrylic polymer, a polyester, a resin acid, a dye, an ultraviolet absorber, a preservative, an antibacterial agent, an alkylammonium, and a compound having an aromatic ring bonded thereto. .

Next, a hydroxyl group directly bonded to a silicon atom is
The polycondensation reaction between a silylated peptide having two or more silane compounds in which two or more hydroxyl groups directly connected to a silicon atom are generated by hydrolysis will be described.
As the silylated peptide having two hydroxyl groups directly connected to the silicon atom, a silylated peptide represented by the general structural formula (I) or a silylated peptide represented by the general structural formula (II) will be described as a representative example. The silane compound having at least two hydroxyl groups directly bonded to a silicon atom by hydrolysis will be described with reference to a silane compound represented by the general structural formula (III).

The reaction between the silylated peptide represented by the general structural formula (I) and the silane compound represented by the general structural formula (III) is, for example, first represented by the general structural formula (I) The aqueous solution of the silylated peptide is adjusted to an acidic side with hydrochloric acid or sulfuric acid, or adjusted to a basic side with an aqueous solution of sodium hydroxide or potassium hydroxide, and a silane compound represented by the general structural formula (III) is added thereto. By dropping, the alkoxy group or halogen group of the silane compound is hydrolyzed to become a silane compound represented by the general structural formula (IV) having at least two hydroxyl groups directly bonded to silicon atoms, and then neutralized. By doing so, the hydroxyl group of the silylated peptide represented by the general structural formula (I) and the hydroxyl group of the silane compound represented by the general structural formula (IV) are polycondensed to form a copolymer composition. It is. As described above, the hydrolysis of the silane compound represented by the general structural formula (III) to the silane compound represented by the general structural formula (IV) is carried out with the silylated peptide represented by the general structural formula (I). It is not necessary to carry out the hydrolysis of the silane compound represented by the general structural formula (III) in a system different from the above-mentioned polycondensation system.

As described above, the silylated peptide represented by the general structural formula (II) is converted into the silylated peptide represented by the general structural formula (I) by hydrolysis. When the silylated peptide represented by the general structural formula (II) is used, an aqueous solution of the silylated peptide represented by the general structural formula (II) is adjusted to an acidic side with hydrochloric acid or sulfuric acid, When adjusted to the basic side with an aqueous sodium solution or aqueous potassium hydroxide solution, an alkoxy group or a halogen group bonded to a silyl group undergoes hydrolysis to become a hydroxyl group, and becomes a silylated peptide represented by the general structural formula (I). Therefore, thereafter, the silane compound represented by the general structural formula (III) is dropped into the silane compound represented by the general structural formula (III) in the same manner as described above. A silane compound represented by the general structural formula (IV) is hydrolyzed into a silane compound represented by the general structural formula (IV), and is then neutralized to be represented by the hydroxyl group of the silylated peptide and the general structural formula (IV). The hydroxyl group of the silane compound is polycondensed to obtain a copolymer composition.
As described above, even when the silylated peptide represented by the general structural formula (II) is used, the hydrolysis can be performed by adjusting the acid side or the basic side. Hydrolysis of the silylated peptide represented by Structural Formula (II) to the silylated peptide represented by Structural Formula (I) can also be achieved by the above-mentioned silylated peptide and the silane compound represented by Structural Formula (III) Can be carried out in the same system as the reaction system for the condensation polymerization, and need not be carried out in another system.

The hydrolysis reaction generally proceeds favorably at pH 2 to 3, but some silylated peptides represented by the general structural formula (I) are apt to generate insolubles on the acidic side. It is preferably carried out at pH 10-11. When an alkoxysilane compound is used as the silane compound represented by the general structural formula (III), the pH may be adjusted only before the dropwise addition of the silane compound. When reacting on the basic side using a compound or a carboxysilane compound, the pH drops during the reaction, so that an aqueous solution of sodium hydroxide or potassium hydroxide is added to adjust the pH to 10 to 10.
It must be kept at 11. In addition, when an aminosilane compound is used as the silane compound represented by the general structural formula (III) to react on the acidic side, the pH increases during the reaction,
It is necessary to maintain the pH at 2-3 by adding dilute hydrochloric acid or dilute sulfuric acid.

If the reaction temperature is too low, the reaction does not proceed easily. If the reaction temperature is too high, the alkoxy group or the halogen group of the silyl compound represented by the above general formula (III) is rapidly hydrolyzed. preferable. Further, the reaction time varies depending on the reaction amount, but the general structural formula (II)
It is preferable that the silane compound represented by I) is added dropwise over 30 minutes to 2 hours, and then stirring is continued for 1 to 6 hours.

At the end of the hydrolysis reaction, the silylated peptide represented by the general structural formula (I) and the silane compound represented by the general structural formula (III) are dissociated because the reaction solution is acidic or basic. If the reaction solution is acidic, add an alkaline aqueous solution such as aqueous sodium hydroxide or potassium hydroxide.If the reaction solution is basic, add an aqueous acid such as dilute hydrochloric acid or dilute sulfuric acid and stir. To neutralize the solution. By this neutralization, polycondensation proceeds to obtain a target silylated peptide-silane compound copolymer composition, and stirring after neutralization is preferably for about 2 to 24 hours.

The silylated peptide-silane compound copolymer composition to be incorporated in the cosmetic of the present invention is produced as described above, and when the composition is reacted with a silylated peptide having two hydroxyl groups, two or more hydroxyl groups are used. By appropriately selecting the type and reaction amount of the resulting silane compound, in cosmetics in which an oily substance is blended, a more compatible silylated peptide-
It can be a silane compound copolymer composition.

That is, it is obtained by condensation polymerization of an silylated peptide having two hydroxyl groups directly bonded to silicon atoms and at least one silane compound having two or more hydroxyl groups directly bonded to silicon atoms by hydrolysis in an aqueous solution. The silylated peptide-silane compound copolymer composition has a surface activity because it is a condensation-polymerized hydrophilic peptide portion derived from the silylated peptide and a silane compound having a hydrophobic group. Therefore, for example, when a cosmetic contains a higher fatty acid or a higher alcohol having a long carbon chain, in the silane compound represented by the general structural formula (III), an organic group having a long carbon chain is contained in R ^9. A bonded silane compound, for example, among the silane compounds exemplified above, when a silylated peptide-silane compound copolymer composition is manufactured using hexyltrimethoxysilane, decyltrimethoxysilane, etc., the carbon chain length is long. The stability of cosmetics containing higher fatty acids and higher alcohols can be improved.

In the reaction between a silylated peptide having two hydroxyl groups and a silane compound having two or more hydroxyl groups, an emulsifying property suitable for the cosmetic base material can also be obtained by adjusting the reaction ratio (molar ratio) of the two. You can also do so. That is, for example, by increasing the reaction ratio of a silane compound that generates two or more hydroxyl groups with respect to the silylated peptide, compatibility with the silicone oil is increased, and the stability of the cosmetic containing the silicone oil can be improved. .

The reaction ratio of the silylated peptide having two hydroxyl groups to be contained in the cosmetic of the present invention and the silane compound generating two or more hydroxyl groups is as follows: (two or more silylated peptides having two hydroxyl groups or two or more hydroxyl groups) When two or more silane compounds are used, the total amount thereof is preferably 1: 1 or more and 1: 300 or less, more preferably 1: 1 or more and 1: 200 or less. That is, when the hydroxyl group is 2
When the reaction ratio of the silylated peptide having two or more hydroxyl groups to the silylated peptide having two or more hydroxyl groups is less than the above range, when it is contained in cosmetics, smoothness and moisturizing feeling cannot be imparted to hair and skin, and This is because the effect of reducing the oily feeling may not be exhibited in cosmetics, and conversely, even if the reaction ratio between the silylated peptide having two hydroxyl groups and the silane compound generating two or more hydroxyl groups exceeds the above range, Not only the smoothness and the increase in the effect of imparting a moisturizing effect corresponding to the ratio are not observed, but also a silicone oil feeling is caused, and further, the silylated peptide-silane compound copolymer composition has a high viscosity and may be difficult to handle. It is.

The silylated peptide-silane compound copolymer composition obtained as described above can be used as it is in cosmetics, but a hydroxyl group remains in the terminal silyl group of the copolymer composition. Therefore, there is a possibility that the silylated peptide-silane compound copolymer composition may aggregate to form a polymer, and thus it is preferable to further add a silane compound in which one hydroxyl group is generated by hydrolysis.

Examples of the silane compound that produces one hydroxyl group by hydrolysis include, for example, the following general formula (V) R ¹¹ ₃ SiZ (V) [wherein three R ^{11 s} are carbon atoms directly to silicon atoms. This is an organic group to be bonded, and three R ^{11 s} may be the same or different. Z is at least one group selected from the group consisting of a hydroxyl group, an alkoxy group and a halogen group], and this silane compound is hydrolyzed to have the following general formula (VI) R ¹¹ ₃ Si (OH) (VI) [wherein three R ¹¹ are organic groups in which carbon atoms are directly bonded to silicon atoms, and three R ³ may be the same or different] Silane compound.

Examples of the silane compound represented by the general structural formula (V) in which one hydroxyl group directly bonded to a silicon atom by hydrolysis is dimethylvinylchlorosilane, n-butyldimethylchlorosilane, tert
-Butyldimethylchlorosilane, tert-butyldiphenylchlorosilane, octadecyldimethylchlorosilane, methyldiphenylchlorosilane, tri-n-butylchlorosilane, triethylchlorosilane, trimethylchlorosilane, tri-n-propylchlorosilane, triphenylchlorosilane, trimethylsilyl iodide,
Examples thereof include dimethylethoxysilane, dimethylvinylethoxysilane, dimethylvinylmethoxysilane, trimethylethoxysilane, trimethylmethoxysilane, and triphenylethoxysilane.

In addition to the above, silyl compounds having two silicon atoms, such as hexamethyldisilazane and hexamethyldisiloxane, can be used because one hydroxyl group directly connected to the silicon atom is generated by hydrolysis. it can.

As is apparent from the general structural formula (V), such a silane compound has one reactive group directly bonded to a silicon atom, and thus has a general structural formula (VI) obtained by hydrolyzing it. The represented silane compound reacts with the hydroxyl group present in the silylated peptide-silane compound copolymer composition to reduce the hydroxyl group in the silylated peptide-silane compound copolymer composition, and the silylated peptide-silane compound This prevents the copolymer compositions from aggregating. That is, by reacting the silane compound represented by the general structural formula (VI) obtained by hydrolyzing the silane compound represented by the general structural formula (V), a silylated peptide-silane having good storage stability is obtained. It can be a compound copolymer composition.

However, in the silane compound represented by the general formula (V), the silane compound having a halogen group as a functional group capable of generating a hydroxyl group by hydrolysis has good hydrolyzability. The above general structural formula (II
The reaction proceeds by directly dropping the silane compound represented by the general structural formula (V) into an aqueous solution of the silylated peptide-silane compound copolymer composition obtained by the condensation polymerization of I). In the case of a silane compound represented by the structural formula (V), in which a functional group that generates a hydroxyl group by hydrolysis is an alkoxy group, or a silane compound having two silicon atoms such as hexamethyldisiloxane, a silane compound having a pH of 2 to 3 is used in advance. Hydrolyzed with the general structural formula (V
The silane compound represented by I) is then dropped into an aqueous solution of a silylated peptide-silane compound copolymer composition obtained by condensation polymerization of the above general structural formulas (I) and (III). There is a need.

The silylated peptide-silane compound copolymer composition obtained by the condensation polymerization of the above general structural formulas (I) and (III) and the silane compound represented by the above general structural formula (V) Is preferably 30 to 60 ° C. The reaction time varies depending on the reaction amount, but is preferably about 30 minutes to 2 hours for dropping the silane compound represented by the general structural formula (V), and about 1 to 6 hours for subsequent stirring.

After the completion of the stirring, the reaction solution was neutralized with an aqueous alkali solution such as an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution, and further stirred for about 2 to 10 hours to complete the reaction, thereby preventing the aggregation. A silylated peptide-silane compound copolymer composition is obtained and used in the cosmetic of the present invention.

In the cosmetics of the present invention, hair cosmetics include, for example, hair rinses, hair treatments, hair conditioners, hair creams, split coat coatings, shampoos,
Skin cosmetics such as hair mousses, hair setting agents, hair blow lotions, and the like include, for example, skin creams, emulsions, facial cleansers, cleansing creams, lotions, skin care gels, serums, and the like.

The cosmetic of the present invention is constituted by adding a silylated peptide-silane compound copolymer composition to a conventional hair or skin cosmetic composition. May be used alone or in combination of two or more.

The content of the silylated peptide-silane compound copolymer composition in the cosmetic of the present invention (the amount blended into the cosmetic) varies depending on the type of cosmetic, such as a wash-off type and a non-wash-out type. Is 0.0
It is preferably from 5 to 20% by weight, more preferably from 0.1 to 10% by weight. That is, if the amount of the silylated peptide-silane compound copolymer composition is less than the above range, it is not possible to impart smoothness and moisturizing feeling to hair and skin, and the effect of reducing oily feeling in oily cosmetics. May not be exhibited, and conversely, the silylated peptide-
This is because even if the blending amount of the silane compound copolymer composition exceeds the above range, there is a possibility that the smoothing effect, the moisturizing effect imparting effect and the oily feeling reducing effect corresponding to the increasing blending amount are not increased.

The cosmetic of the present invention is prepared using the silylated peptide-silane compound copolymer composition as an essential component as described above, but within a range that does not impair the properties of the silylated peptide-silane compound copolymer composition. , Anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, cationic polymers, amphoteric polymers, anionic polymers, thickeners, animal and plant extracts, polysaccharides or derivatives thereof, animals and plants In addition, hydrolyzed peptides and derivatives thereof of microorganism-derived proteins, wetting agents, lower alcohols, higher alcohols, amino acids, oils and fats, silicone oils, various dyes and pigments, preservatives, fragrances, and the like can be added.

[0046]

Industrial Applicability The cosmetic of the present invention comprises a silylated peptide-
The silane compound copolymer composition has good familiarity with hair and skin, has no stickiness, imparts smoothness and moisturizing feeling to hair and skin, and, in cosmetics containing an oily substance, reduces oiliness. It exerts the effect of giving a refreshing finish feeling, and further improves the stability of cosmetics containing an oily substance.

[0047]

Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to only these examples. Prior to the examples, a method for producing the silylated peptide-silane compound copolymer composition used in the examples is shown as a reference example. Further, in the following Reference Examples, Examples, Comparative Examples, and the like,% indicating the concentration of the solution or dispersion is% by weight.

Reference Example 1 N- [2-hydroxy-3- (3'-methyldihydroxysilyl) propoxy] propyl hydrolyzed collagen
Production of dimethyldiethoxysilane-hexatriethoxysilane copolymer composition [1: 1: 1 (molar ratio)] In a round bottom cylindrical glass reaction vessel having an inner diameter of 12 cm and a capacity of 2 liters, 450 g of water and N- [ 50 g of 2-hydroxy-3- (3'-methyldihydroxysilyl) propoxy] propyl hydrolyzed collagen (the molecular weight of the hydrolyzed collagen is about 1500 in number average molecular weight) and 18%
Hydrochloric acid (18.2 g) was added thereto, and 5.0 g of dimethyldiethoxysilane (KBE-22 manufactured by Shin-Etsu Silicone Co., Ltd.) and hexyltriethoxysilane (A-13 manufactured by Nippon Unicar Co., Ltd.) were added.
7) After dripping 9.4 g of the mixture over 30 minutes, 55
Stirred at 2.5 ° C. for 2.5 hours. Next, the mixture was cooled to room temperature while stirring, 17.8 g of a 20% aqueous sodium hydroxide solution was added dropwise to adjust the pH to 7, and stirring was continued at room temperature for 15 hours. Further, 3.7 g of trimethylchlorosilane (KA-31 manufactured by Shin-Etsu Silicone Co., Ltd.) was added to the reaction solution while stirring at 250 rpm at room temperature. After stirring for 1 hour, the temperature of the reaction solution was raised to 80 ° C., and the mixture was stirred for 1 hour to complete the reaction. After the reaction, the reaction solution was concentrated under reduced pressure to adjust the concentration, and N- [2-hydroxy-3- (3′-methyldihydroxysilyl) propoxy] propyl hydrolyzed collagen-dimethyldiethoxysilane-hexyltriethoxysilane copolymer was used. 320% of a 20% aqueous dispersion of the composition
g was obtained.

Reference Example 2 N- [2-hydroxy-3- (3'-methyldihydroxysilyl) propoxy] propyl hydrolyzed sericin-dimethyldiethoxysilane-hexylliethoxysilane copolymer composition [1: 30: 2 ( Preparation of 270 g of water and N- [2-hydroxy-3- (3'-methyldihydroxysilyl) propoxy] propyl hydrolyzed sericin in a round bottom cylindrical glass reaction vessel having an inner diameter of 12 cm and a capacity of 2 liters. (The molecular weight of hydrolyzed sericin is about 2,000 in number average molecular weight) 30 g and 11.5 g of 18% hydrochloric acid were put therein, and 61.4 g of dimethyldiethoxysilane (KBE-22 manufactured by Shin-Etsu Silicone Co., Ltd.) and hexyltriethoxysilane (Japan) A-13 manufactured by Unicar
7) After dropping 7.6 g of the mixture over 30 minutes, 55
Stirred at C for 2 hours. Next, the mixture was cooled to room temperature while stirring, 11.8 g of a 20% aqueous sodium hydroxide solution was added dropwise to adjust the pH to 7, and the mixture was stirred at 50 ° C. for 15 hours. Further, 3.0 g of trimethylchlorosilane (KA-31 manufactured by Shin-Etsu Silicone Co., Ltd.) was added to the reaction solution at 50 ° C. while stirring at 400 rpm, and the mixture was stirred for 1 hour.
5.0 g of a 20% aqueous sodium hydroxide solution was added dropwise,
The mixture was stirred at 3 ° C. for 3 hours, then the temperature of the reaction solution was raised to 80 ° C. and stirred for 1 hour to complete the reaction. After the reaction, the reaction solution was concentrated under reduced pressure to adjust the concentration, and N- [2-hydroxy-3
270 g of a 20% aqueous dispersion of-(3'-methyldihydroxysilyl) propoxy] propyl hydrolyzed sericin-methyldiethoxysilane-hexyltriethoxysilane copolymer composition was obtained.

Reference Example 3 N- [2-hydroxy-3- (3'-methyldihydroxysilyl) propoxy] propyl hydrolyzed collagen
Production of dimethyldiethoxysilane-hexyltriethoxysilane copolymer composition [1: 60: 1 (molar ratio)] In a round bottom cylindrical glass reaction vessel having an inner diameter of 12 cm and a capacity of 2 liters, 270 g of water and N- [ 30 g of 2-hydroxy-3- (3'-methyldihydroxysilyl) propoxy] propyl hydrolyzed collagen (the molecular weight of the hydrolyzed collagen is about 1500 in number average molecular weight) and 18%
10.5 g of hydrochloric acid is added, and dimethyldiethoxysilane (KBE-22 manufactured by Shin-Etsu Silicone Co., Ltd.) 1 is added thereto while stirring.
A mixture of 70.6 g and 5.3 g of hexyltriethoxysilane (A-137 manufactured by Nippon Unicar) was added dropwise over 30 minutes, followed by stirring at 55 ° C. for 2 hours. Next, the mixture was cooled to room temperature with stirring, 8.8 g of a 20% aqueous sodium hydroxide solution was added dropwise to adjust the pH to 7, and stirring was continued at 50 ° C for 15 hours. Further, the reaction solution was heated at 50 ° C. for 40 minutes.
While stirring at 0 rpm, 4.2 g of trimethylchlorosilane (KA-31 manufactured by Shin-Etsu Silicone Co., Ltd.) was added and stirred for 1 hour, 7.2 g of a 20% aqueous sodium hydroxide solution was added dropwise, and the mixture was stirred at 50 ° C. for 1 hour. When the temperature of the reaction solution is 8
The temperature was raised to 0 ° C. and stirred for 1 hour to complete the reaction. After the reaction, the reaction solution was concentrated under reduced pressure to adjust the concentration, and N- [2-hydroxy-3- (3′-methyldihydroxysilyl) propoxy] propyl hydrolyzed collagen-dimethyldiethoxysilane-hexyltriethoxysilane copolymer was used. 280 g of a 20% aqueous dispersion of the composition was obtained.

Reference Example 4 N- [2-hydroxy-3-
Production of (3′-methyldihydroxysilyl) propoxy] propyl hydrolyzed collagen-dimethyldiethoxysilane copolymer composition [1: 150 (molar ratio)] In a round bottom cylindrical glass reaction vessel having an inner diameter of 12 cm and a capacity of 2 liters. 180 g of water and 20 g of N- [2-hydroxy-3- (3'-methyldihydroxysilyl) propoxy] propyl hydrolyzed collagen (the molecular weight of the hydrolyzed collagen is about 1500 in number average molecular weight) and 18%
After adding 7.2 g of hydrochloric acid, 300.9 g of dimethyldiethoxysilane (KBE-22 manufactured by Shin-Etsu Silicone Co., Ltd.) was added thereto, and the mixture was stirred at 55 ° C. for 2.5 hours. Next, the mixture was cooled to room temperature while stirring, 6.5 g of a 20% aqueous sodium hydroxide solution was added dropwise to adjust the pH to 7, and stirring was continued at room temperature for 15 hours. Further, this reaction solution was heated at room temperature for 250 r.
After adding 3.0 g of trimethylchlorosilane (KA-31 manufactured by Shin-Etsu Silicone Co., Ltd.) while stirring at pm,
5.4 g of a 0% aqueous sodium hydroxide solution was added dropwise, and the mixture was stirred at room temperature for 3 hours.
The reaction was completed by stirring for an hour. After the reaction, the reaction solution was concentrated under reduced pressure to adjust the concentration, and N- [2-hydroxy-3-
260 g of a 20% aqueous dispersion of (3′-methyldihydroxysilyl) propoxy] propyl hydrolyzed collagen-dimethyldiethoxysilane copolymer composition was obtained.

Example 1 Two types of non-flushable hair treatments having the composition shown in Table 1 were prepared, and each of the hair treatments was applied to shampoo-washed hair to hydrate the hair.
The smoothness, the combability, the feeling of touch and the degree of oiliness were evaluated. In addition, the compounding amount of each component in a table | surface is a part by weight, and when the compounding amount is not a solid content, the solid content concentration is shown in parentheses after the component name. These are the same in the following examples and comparative examples. In addition, although the expression is referred to as a blending amount here, this is an amount at the time of preparation, and is quantitatively the same as the content after preparation.

In Example 1, the silylated peptide-silane compound copolymer composition produced in Reference Example 1 was used.
In Comparative Example 1, an aqueous solution of silylated hydrolyzed collagen used as a raw material of the silylated peptide-silane compound copolymer composition produced in Reference Example 1 was used, and in Comparative Example 2, dimethylpolysiloxane of silylated hydrolyzed collagen and silicone was used. Is also used.

[0054]

[Table 1]

Prior to the treatment by the hair treatment, three hair bundles each having a length of 15 cm and a weight of 1 g were prepared, washed with a commercially available shampoo containing no hydrolyzed peptide or a derivative thereof, and rinsed with hot water. 0.2 g of each of the hair treatments of Example 1 and Comparative Examples 1 and 2 were applied to the washed hair bundles and dried with a hair dryer. Moisture, smoothness, combability, touch and oiliness after drying are low for 10 female panelists, the best is [2 points], and the second is [1 point]. And the bad thing was evaluated as [0 point]. The results are shown in Table 2 as an average value of 10 persons.

[0056]

[Table 2]

As shown in Table 2, the hair treated with the hair treatment of Example 1 had moisture, smoothness, combability, and hand feel compared to the hair treated with the hair treatment of Comparative Examples 1-2. The evaluation value was high in the evaluation item of the feeling. As is apparent from the results, Example 1 containing the silylated peptide-silane compound copolymer composition was used.
The hair treatment of Comparative Example 1 containing silylated hydrolyzed collagen and the hair treatment of Comparative Example 2 using silylated hydrolyzed collagen in combination with silicone moisturizes and imparts smoothness to the hair, The effect of improving the combability of hair was excellent.
Regarding the feel of the hair, the majority of panelists found that the hair treated with the hair treatment of Example 1 had smoothness and a moist feeling, but the hair treated with the hair treatment of Comparative Example 1 was hard. There was a feeling that the whole was dry, and the hair treated in Comparative Example 2 had a strong oily feeling and said that a natural finish could not be obtained.

Example 2 and Comparative Example 3 Two foam bases for hair mousse having the compositions shown in Table 3 were prepared, and the foam base and the liquefied petroleum gas of the propellant were filled in a spray container, respectively [foam base: Propellant (liquefied petroleum gas) = 80:20 (weight ratio)], and the hair was treated with each of the hair mousses to evaluate the ease of uniting (hair styling), moistness, smoothness, finger passing, and touch.

In Example 2, the silylated peptide-silane compound copolymer composition of the oxidized partially decomposed product of keratin prepared in Reference Example 2 was used. In Comparative Example 3, the silylated peptide-silane compound copolymer composition of Reference Example 2 was used. The aqueous solution of the silylated hydrolyzed sericin used as the raw material of the product is used.

[0060]

[Table 3]

For the above hair mousse, 10 female panelists were treated once daily with the hair mousse of Comparative Example 3 for the first 5 days and with the hair mousse of Example 2 for the next 5 days.

The treatment was carried out by taking 2 to 5 g of a hair mousse on the palm (the amount varies depending on the amount of hair), applying it to the hair by hand rubbing, and drying it with a hair dryer.

After the use period of 10 days (that is, after the use of the hair mousse of Example 2 for 5 days), the hair mousse of Comparative Example 3 was found to be easy to unite, moist, smooth, fingery and the feel of the hair. Asked if it was better, worse, or the same as when using. Table 4 shows the results.

[0064]

[Table 4]

As shown in Table 4, after the hair mousse of Example 2 containing the silylated peptide-silane compound copolymer composition was used, the hair was easier to unite, moisturized, and smoother than before use. Many, the number of people who answered that the finger passing property and touch feeling became better, the silylated peptide-silane compound copolymer composition was sorbed on the hair, and the hair was given cohesion, moisture, and smoothness, It was clear that it had the effect of improving finger penetration and improving the feeling of touch. In particular, regarding the finger passing property and the touch feeling, all the panelists answered that the hair mousse of Example 2 did not cause a squeaky feeling of the hair and had a smooth feeling.

Example 3 and Comparative Examples 4 to 5 Three types of hair treatment rinses having the compositions shown in Table 5 were prepared, and each of the hair treatment rinses was used for washed hair to hydrate and smooth hair. The combability and ease of cohesion (hair styling) were examined.

In Example 3, the silylated peptide-silane compound copolymer composition produced in Reference Example 3 was used. In Comparative Example 4, the silylated peptide-silane compound copolymer composition produced in Reference Example 3 was used. An aqueous solution of silylated hydrolyzed collagen used as a raw material was used. In Comparative Example 5, silylated hydrolyzed collagen and methylphenylpolysiloxane of silicone were used in combination.

[0068]

[Table 5]

Prior to the treatment with the above hair treatment rinse, three hair bundles having a length of 15 cm and a weight of 1 g were prepared, washed with a commercially available shampoo containing no hydrolyzed peptide or a derivative thereof, and rinsed with hot water. The hair bundle was treated with each of the hair treatment rinses of Example 3 and Comparative Examples 4 and 5 by 1 g, rinsed with hot water and dried with a hair dryer. This shampoo wash,
After repeating the process of rinsing, rinsing, rinsing, rinsing, and drying with a hair dryer three times, the moisturizing, smoothness, combability and unity (hair styling) of the hair of each hair bundle are given to ten female panelists. The evaluation was performed according to the same evaluation criteria as in Example 1. The results are shown in Table 6 as an average value of 10 persons.

[0070]

[Table 6]

As is evident from the results shown in Table 6, the hair treatment rinse of Example 3 showed that the majority of panelists were in the evaluation items of moisture, smoothness, combability and unity of hair. The hair treatment rinse of Example 3 in which the hair treatment rinse of Comparative Example 4 was superior to the hair treatment rinses of Comparative Examples 4 and 5, and which contained the silylated peptide-silane compound copolymer composition, contained silylated hydrolyzed collagen. Compared to the hair treatment rinse of Comparative Example 4 or the hair treatment rinse of Comparative Example 5 in which silylated hydrolyzed collagen and methylphenylpolysiloxane were used in combination, the action of imparting moisture to the hair, providing smoothness, and imparting good combability. It is clear that it has excellent action to make hair easier to unite and to make hair easier There was. In particular, most of the panelists evaluated that the hair treated with the hair treatment rinse of Example 3 had good combability and little rust.

Example 4 and Comparative Example 6 Two types of moisture gels having the compositions shown in Table 7 were prepared, and each of the moisture gels was applied to the skin. After application, the moisture, smoothness and low stickiness of the skin were measured. evaluated.

In Example 4, the silylated peptide-silane compound copolymer composition prepared in Reference Example 4 was used, and Comparative Example 6 was used.
Uses an aqueous solution of silylated hydrolyzed collagen used as a raw material of the silylated peptide-silane compound copolymer composition produced in Reference Example 4.

[0074]

[Table 7]

0.5 g each of the moisturizing gels of Example 4 and Comparative Example 6 were applied to 10 female panelists on the forearm and evenly stretched, after which the skin was moist, smooth, and less sticky. Was evaluated. Table 8
The number of persons who answered that Example 4 was superior, the number of persons who answered that Comparative Example 6 was superior, and the number of persons who could not say either.

[0076]

[Table 8]

As shown in Table 8, the majority of panelists
The skin to which the moisture gel of Example 4 was applied was described as having a moist feeling, smoothness, and less stickiness as compared with the skin to which the moisture gel of Comparative Example 6 was applied, and was included in the moisture gel of Example 4. The silylated peptide-silane compound copolymer composition is superior to the silylated hydrolyzed collagen contained in Comparative Example 6 in imparting a moist feeling and smoothness to the skin, and gives a sticky feeling. It was clear that no.

Example 5 and Comparative Example 7 Two types of hand creams having the compositions shown in Table 9 were prepared, and the respective hand creams were used to evaluate the moistness, smoothness, and low oiliness of the skin. . The skin was evaluated for moistness, smoothness, and low oiliness.

In Example 5, the silylated peptide-silane compound copolymer composition produced in Reference Example 1 was used.
Uses a methylsiloxane network polymer of silicone powder [Tospearl 145A (trade name) manufactured by Toshiba Silicone Co., Ltd.].

[0080]

[Table 9]

The hand creams of Example 5 and Comparative Example 7 were applied to the backs of the hands of 10 female panelists by 0.5 g each and spread evenly, and then the skin was less moist, smooth and less oily. Was evaluated according to the same evaluation criteria as in Example 4. Table 10 shows the results.

[0082]

[Table 10]

As shown in Table 10, the skin to which the majority of the panelists applied the hand cream of Example 5 was less moist, smooth and oily than the skin to which the hand cream of Comparative Example 7 was applied. The silylated peptide-silane compound copolymer composition contained in Example 5 imparts a moist feeling and smoothness to the skin and reduces the oily feeling of the cosmetic. It was clear to have. In particular, regarding the feel of the skin after use, the majority of panelists found that the skin to which the hand cream of Example 5 had been applied was not sticky and had a moist feeling, whereas the skin to which the hand cream of Comparative Example 7 had been applied had almost a moist feeling. He said that it would not remain.

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Claims (2)

[Claims] 1. An aqueous solution comprising one or more silylated peptides having two hydroxyl groups directly bonded to silicon atoms and one or more silane compounds having two or more hydroxyl groups directly bonded to silicon atoms by hydrolysis. A cosmetic comprising a silylated peptide-silane compound copolymer composition obtained by polymerization. 2. An aqueous solution comprising one or more silylated peptides having two hydroxyl groups directly bonded to silicon atoms and one or more silane compounds having two or more hydroxyl groups directly bonded to silicon atoms by hydrolysis. The cosmetic according to claim 1, wherein the content of the silylated peptide-silane compound copolymer composition obtained by polymerization is 0.05 to 20% by weight.