JP2948278B2 - Skin cosmetics - Google Patents

Description

The present invention relates to cosmetics for skin, and more particularly, the present invention relates to antibacterial, antibacterial, sterilizing and disinfecting effects on skin, and deodorant and deodorant effects such as body odor. It has odor and deodorant effects, has good affinity for skin, has the effect of moisturizing and smoothing skin, and has low irritation and high safety to skin. The present invention relates to a cosmetic for skin containing an N-quaternary ammonium-derived peptide having self-confident surface activity and emulsifying action and dispersing action.

[Conventional technology]

Peptides obtained by hydrolyzing proteins such as collagen, keratin, and silk have already been incorporated into cosmetics for hair (see, for example,
No. 183298), and it has also been proposed to incorporate these peptides into cosmetics for skin (for example,
“Cosmetics and Toiletries” Vol. 87, p65, 1972).

This means that these peptides have good affinity for the skin, have the effect of imparting moisture and smoothness to the skin, and are natural protein derivatives with little irritation to the skin and high safety It is for a reason.

[Problems to be Solved by the Invention] However, for those engaged in the research of skin cosmetics, it is necessary to impart more useful properties to the peptide without impairing the above-mentioned properties of the peptide, and blend it into the skin cosmetic. Therefore, there is a demand for obtaining higher quality skin cosmetics. Also, not only ordinary skin cosmetics, but also creams, ointments, emulsions, etc. for the purpose of preventing acne, rough skin, rash, bruises, etc., have an antibacterial effect and have little skin irritation. Requested.

[Means for solving the problem]

In view of such circumstances, the present invention has synthesized various peptide derivatives and studied their properties repeatedly. As a result, the following general formula (I) was obtained. (Wherein at least one of R ₁ , R ₂ , and R ₃ has at least 8 carbon atoms)
22 alkyl groups or alkenyl groups having 8 to 22 carbon atoms,
The rest is an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group having 1 to 3 carbon atoms or a benzyl group. A is a hydroxyalkylene having 2 to 3 carbon atoms or an alkylene having a prime number of 2 to 3, R ₄ is a side chain of various amino acids constituting the peptide, and n is 1 to 50. The quaternary ammonium-derived peptide has antibacterial, antibacterial, bactericidal and disinfecting effects on the skin,
Has deodorant and deodorant effects, and has good affinity for skin,
Moisturizes the skin, has the effect of imparting smoothness,
In addition, it is less irritating to the skin, has a mild surface activity by itself, and has an emulsifying action and a dispersing action. Finding that high-quality skin cosmetics that take advantage of the properties of the derived peptide can be obtained,
The present invention has been completed.

The N-quaternary ammonium-derived peptide represented by the above general formula (I) is combined with a peptide, for example, by the following general formula (I)
I) [R _1, R _2, R ₃ in the formula is the same as in the general formula (I), X is _{Cl, Br, I, NO 3} , SO 4/2, R 5 OSO 3 (R 5 is A lower alkyl group) or R ₅ SO ₃ (R ₅ is the same as described above)], or the following general formula (III) (Wherein R ₁ , R ₂ , R ₃ and X are the same as those in the general formula (II), and Y represents a halogen atom such as Cl, Br, and I). -Hydroxypropyl ammonium salt, or the following general formula (IV) (R ₁ , R ₂ , R ₃ , X and Y in the formula are the same as those in the general formula (III)
3-halogenpropylammonium salt represented by the following general formula (V): (R ₁ , R ₂ , R ₃ , X and Y in the formula are the same as those in the general formula (III)
Is the same as in the above case)).

Examples of the peptide in the N-quaternary ammonium-derived peptide represented by the general formula (I) include naturally-occurring proteins such as collagen or a denatured product thereof such as gelatin, keratin, silk, casein, Akoya shellfish, and mussel. Shellfish conchiolin, soy protein, wheat protein,
It can be obtained by hydrolyzing proteins such as egg whites and egg yolks, complex proteins containing sugars, phosphate esters, fats and the like with acids, alkalis, enzymes and the like.

The above-mentioned peptide is derived from a natural protein, has a chemical structure similar or similar to that of the constituent proteins of the skin, and has an amino group, a carboxyl group, or a side chain of various amino acids. And has the effect of moisturizing the skin and imparting smoothness. Moreover, since it is derived from a natural protein, it is safe with little irritation to the skin.

The N-quaternary ammonium-derived peptide represented by the general formula (I) is quaternized by reacting the peptide with any one of the ammonium salts represented by the general formulas (II) to (V). By doing so, the affinity for the skin is further increased, and the action of the above-mentioned peptide is further remarkably made. In addition, since the quaternization is performed with a quaternary ammonium salt in which a higher alkyl group or a higher alkenyl group is introduced into the nitrogen (N) atom, the quaternary ammonium salt in which a lower alkyl group is introduced is used.
Affinity to the skin is improved more than in the case of grading, and the moisturizing power is improved by an increase in the lipophilic portion due to the higher alkyl group or higher alkenyl group, and the effect of imparting moisture to the skin is increased, and The effect of imparting smoothness to the skin is increased by increasing the oily portion. Furthermore, by increasing the lipophilic moiety due to the higher alkyl group or higher alkenyl group, it has a surfactant itself, acts as a cationic surfactant, and covers, bactericidal, sterilizes, disinfects the skin. As a result, it has antibacterial, antibacterial, sterilizing and disinfecting effects, resulting in anti-odor, deodorizing and deodorizing effects such as body odor, and has an emulsifying and dispersing effect by itself. doing.

Therefore, when the N-quaternary ammonium-derived peptide represented by the general formula (I) is blended into skin cosmetics, the skin cosmetics have antibacterial, antibacterial, antiseptic and disinfecting effects on skin, It has a deodorant and deodorant effect, and also has an enhanced affinity for the skin, moisturizes the skin, and has a stronger effect of imparting smoothness. Preparation becomes easy and storage stability after preparation improves. In addition, since it is highly safe, it can be applied to the oral cavity and mucous membranes.

In the general formula (I), the amino acid side chain of the peptide moiety represented by R _4, for example, alanine, glycine, valine, leucine, isoleucine, proline, phenylalanine, tyrosine, serine, threonine, methionine, arginine, Histidine, lysine, asparagine, aspartic acid, glutamine, glutamic acid, cystine, tryptophan, hydroxyproline,
Examples include hydroxylysine and O-phosphoserine.

Table 1 shows an example of the amino acid composition of typical peptides.

However, usually, when performing amino acid analysis of proteins, the complete hydrolysis of the sample is performed using 6N hydrochloric acid before the amino acid analysis, so that the amide bond between asparagine and glutamine is hydrolyzed by the complete hydrolysis, and aspartic acid, respectively. And glutamic acid, and O-phosphoserine becomes serine. Therefore, in Table 1, asparagine, glutamine, and O-phosphoserine are respectively added to aspartic acid, glutamic acid, and serine, and tryptophan is decomposed and disappeared by hydrolysis, and thus cannot be quantified. Therefore, they are not shown in Table 1.

Hydrolysis of proteins to obtain peptides involves acid,
Performed by alkali or enzyme.

In acid hydrolysis, hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid,
Inorganic acids such as hydrobromic acid and organic acids such as acetic acid and formic acid are used.

For alkali hydrolysis, sodium hydroxide, potassium hydroxide, lithium hydroxide, barium hydroxide, sodium carbonate, lithium carbonate and the like are used.

In the case of hydrolysis by an enzyme, an acidic proteolytic enzyme such as pepsin, proctase A and proctase B, a neutral proteolytic enzyme such as papain, bromelain, thermolysin, trypsin, pronase and chymotrypsin are used. Bacterial neutral proteases such as subtilisin and staphylococcal protease can also be used. When using enzymes, cells containing those bacterial proteolytic enzymes,
Alternatively, it can be used in the form of a film, granules or the like on which an enzyme or a cell containing the enzyme is immobilized. Details of the hydrolysis of proteins such as collagen, keratin, silk, and casein are described in, for example, JP-A-61-69717 and JP-A-63-105000.

As a peptide obtained by hydrolysis with an acid, alkali or enzyme as described above, n in the general formula (I) is 1 to 50 (however, the value of n is an average value, and n is 1 to 50) Is about 75 by the average molecular weight of the peptide
~ Equivalent to about 8,000). This is n
If is less than 1, there is no affinity for the skin due to the amino acid or peptide structural portion, and if n exceeds 30, the water solubility is reduced, making it difficult to handle, and the affinity for the skin is reduced. The above n is particularly 3
-25 (corresponding to an average molecular weight of the peptide of about 250-3,800) is preferred.

As described above, the N-quaternary ammonium-derived peptide represented by the general formula (I) is different from the peptide represented by the general formula (II) to
It is obtained by a reaction with an ammonium salt represented by (V). The reaction formulas are as follows. In addition, in showing the reaction formula, the peptide is represented by the following general formula (VI).

A peptide represented by the above or, a glycidyl ammonium salt represented by the general formula (II), a 3-halogen-2-hydroxypropylammonium salt represented by the general formula (III), and a peptide represented by the general formula (IV) The reaction with -halogenpropylammonium salt or 2-halogenethylammonium salt represented by the general formula (V) is usually carried out by adding an aqueous solution of a peptide to a glycidylammonium salt represented by the general formula (II) or a glycidylammonium salt represented by the general formula (III) A solution of a 3-halogen-2-hydroxypropylammonium salt, a 3-halogenpropylammonium salt represented by the general formula (IV), or a 2-halogenethylammonium salt represented by the general formula (V) is dropped into This is performed by bringing the two into contact. During the reaction, the pH in the reaction system is preferably maintained at 8 to 12, particularly 9 to 11, and for this purpose, an alkaline solution such as sodium hydroxide, potassium hydroxide, lithium hydroxide or the like is added dropwise to the reaction solution as required. Is done. During the reaction, the pH in the reaction system is maintained in the above range because the amino group of the peptide is a glycidyl ammonium salt represented by the general formula (II) or a 3-halogen-2-hydroxyl represented by the general formula (III). In order to react with a propylammonium salt, a 3-halogenpropylammonium salt represented by the general formula (IV), or a 2-halogenethylammonium salt represented by the general formula (V), the alkali side having a pH of 8 or more is required. Desirably, when the pH exceeds 12, the peptide, the glycidyl ammonium salt represented by the general formula (II), the 3-halogen-2-hydroxypropyl ammonium salt represented by the general formula (III), the general formula (I
V) a 3-halogenpropylammonium salt represented by the formula:
This is because a 2-halogenethylammonium salt represented by the general formula (V) causes hydrolysis. The reaction proceeds at room temperature, but the higher the temperature, the faster the reaction. However, when the temperature is increased in a state where the pH is high, the glycidyl ammonium salt represented by the general formula (II), the 3-halogen-2-hydroxypropyl ammonium salt represented by the general formula (III), and the glycidyl ammonium salt represented by the general formula (IV) Since the hydrolysis of 3-halogenpropylammonium salt and 2-halogenethylammonium salt represented by the general formula (V) is promoted, the temperature is preferably at most 80 ° C. General formula (I
A glycidyl ammonium salt represented by the general formula (II)
3-halogen-2-hydroxypropyl ammonium salt represented by I), 3-halogen propyl ammonium salt represented by general formula (IV), 2-halogen propyl ammonium salt represented by general formula (V)
The halogen ethyl ammonium salt or the like may be used as a crystal, but it is preferable to drop an aqueous solution or an alcohol solution such as methanol, ethanol, n-propyl alcohol, or isopropyl alcohol, or a mixed solution thereof. A glycidyl ammonium salt represented by the general formula (II), a 3-halogen-2-hydroxypropyl ammonium salt represented by the general formula (III), a 3-halogen propyl ammonium salt represented by the general formula (IV) in a peptide solution, The dropping of the 2-halogenethylammonium salt represented by the general formula (V) or the like is preferably completed in 15 minutes to 6 hours.

In these reactions, the reaction produces a hydrogen halide and lowers the pH of the reaction solution.Therefore, the alkali is dropped at the same time as the start of the reaction, and the mixture is stirred and maintained in the above range so as to be suitable for the pH in the solution. It is necessary.

The progress and completion of the reaction can be confirmed by measuring the amino nitrogen of the peptide in the reaction solution by the Van Slyke method for the reaction to the amino group. After completion of the reaction, the reaction solution can be appropriately concentrated or purified by ion exchange resin, gel filtration, electrodialysis, or the like, and then appropriately concentrated to be used as a solid or a concentrated liquid.

As described above, the glycidyl ammonium salt represented by the general formula (II) used for the reaction with the peptide, the 3-halogen-2-hydroxypropyl ammonium salt represented by the general formula (III), and the glycidyl ammonium salt represented by the general formula (IV) Specific examples of the 3-halogenpropylammonium salt shown and the 2-halogenethylammonium salt shown by the general formula (V) are as follows.

Examples of the glycidyl ammonium salt represented by the general formula (II) include glycidyl lauryl dimethyl ammonium chloride, glycidyl myristyl dimethyl ammonium chloride, glycidyl cetyl dimethyl ammonium chloride, glycidyl stearyl dimethyl ammonium chloride, glycidyl lauryl dimethyl ammonium bromide, glycidyl myristyl dimethyl ammonium bromide, Glycidyl cetyl dimethyl ammonium bromide, glycidyl stearyl dimethyl ammonium bromide, glycidyl decyl dimethyl ammonium chloride, glycidyl eicosyl dimethyl ammonium chloride, glycidyl decyl dimethyl ammonium bromide, glycidyl eicosyl dimethyl ammonium bromide, glycidyl Lurauryl dibenzyl ammonium chloride, glycidyl cetyl dibenzyl ammonium chloride, glycidyl stearyl dibenzyl ammonium chloride, glycidyl lauryl diethanol ammonium chloride, glycidyl cetyl diethanol ammonium chloride, glycidyl stearyl diethanol ammonium chloride, glycidyl dilauryl methyl ammonium chloride, glycidyl dicetyl methyl Ammonium chloride, glycidyl stearyl methyl ammonium chloride, glycidyl dilauryl ethanol ammonium chloride, glycidyl dicetyl ethanol ammonium chloride, glycidyl distearyl ethanol ammonium chloride and the like are used.

Examples of the 3-halogen 2-hydroxypropyl ammonium salt represented by the general formula (III) include lauryl (3-chloro-2-hydroxypropyl) dimethyl ammonium chloride, myristyl (3-chloro-2-hydroxypropyl) dimethyl ammonium chloride, Cetyl (3-chloro-2-hydroxypropyl) dimethyl ammonium chloride, stearyl (3-chloro-2-hydroxypropyl) dimethyl ammonium chloride,
Decyl (3-chloro-2-hydroxypropyl) dimethylammonium chloride, eicosyl (3-chloro-
2-hydroxypropyl) dimethylammonium chloride, lauryl (3-chloro-2-hydroxypropyl) dimethylammonium bromide, myristyl (3
-Chloro-2-hydroxypropyl) dimethylammonium bromide, cetyl (3-chloro-2-hydroxypropyl) dimethylammonium bromide, stearyl (3-chloro-2-hydroxypropyl) dimethylammonium bromide, lauryl (3-chloro-2- Hydroxypropyl) dibenzylammonium chloride, myristyl (3-chloro-2-hydroxypropyl) dibenzylammonium chloride, cetyl (3-
Chloro-2-hydroxypropyl) dibenzylammonium chloride, stearyl (3-chloro-2-hydroxypropyl) dibenzylammonium chloride, lauryl (3-chloro-2-hydroxypropyl) diethanolammonium chloride, myristyl (3-chloro-2) -Hydroxypropyl) diethanolammonium chloride, cetyl (3-chloro-2-hydroxypropyl) diethanolammonium chloride, stearyl (3-chloro-2-hydroxypropyl) diethanolammonium chloride, dilauryl (3-chloro-2-hydroxypropyl) methyl Ammonium chloride, dimyristyl (3-chloro-2-hydroxypropyl) methyl ammonium chloride, dicetyl (3-
Chloro-2-hydroxypropyl) methylammonium chloride, distearyl (3-chloro-2-hydroxypropyl) methylammonium chloride, lauryl (3-bromo-2-hydroxypropyl) dimethylammonium chloride, myristyl (3-bromo-2- Hydroxypropyl) dimethylammonium chloride,
Cetyl (3-bromo-2-hydroxypropyl) dimethyl ammonium chloride, stearyl (3-bromo-
2-Hydroxypropyl) dimethylammonium chloride and the like are used.

Examples of the 3-halogenpropylammonium salt represented by the general formula (IV) include lauryl (3-chloropropyl) dimethylammonium chloride, myristyl (3-chloropropyl) dimethylammonium chloride, cetyl (3-chloropropyl) dimethylammonium chloride, Stearyl (3-chloropropyl) dimethyl ammonium chloride, decyl (3-chloropropyl) dimethyl ammonium chloride, eicosyl (3-chloropropyl) dimethyl ammonium chloride, lauryl (3-chloropropyl) dimethyl ammonium bromide, myristyl (3-chloropropyl) ) Dimethylammonium bromide, cetyl (3-chloropropyl) dimethylammonium bromide, stearyl (3-chloropropyl) dimethyl Nmo bromide, lauryl (3-chloropropyl) dibenzyl ammonium chloride, myristyl (3-chloropropyl) dibenzyl ammonium chloride, cetyl (3-chloropropyl)
Dibenzyl ammonium chloride, stearyl (3-
Chloropropyl) dibenzylammonium chloride,
Lauryl (3-chloropropyl) diethanolammonium chloride, myristyl (3-chloropropyl) diethanolammonium chloride, cetyl (3-chloropropyl) diethanolammonium chloride, stearyl (3-chloropropyl) diethanolammonium chloride, dilauryl (3-chloropropyl) ) Methylammonium chloride, dimyristyl (3-chloropropyl) methylammonium chloride, dicetyl (3-chloropropyl) methylammonium chloride, distearyl (3-chloropropyl) methylammonium chloride, lauryl (3-bromopropyl) dimethylammonium chloride, Myristyl (3-bromopropyl) dimethyl ammonium chloride, cetyl (3-bromopropyl ) Dimethyl ammonium chloride, and stearyl (3-bromopropyl) dimethyl ammonium chloride is used.

Further, as the 2-halogenethylammonium salt represented by the general formula (V), lauryl (2-chloroethyl)
Dimethyl ammonium chloride, myristyl (2-chloroethyl) dimethyl ammonium chloride, cetyl (2-chloroethyl) dimethyl ammonium chloride, stearyl (2-chloroethyl) dimethyl ammonium chloride, decyl (2-chloroethyl) dimethyl ammonium chloride, eicosyl (2-chloroethyl) Dimethyl ammonium chloride, lauryl (2-
Chloroethyl) dimethylammonium bromide, myristyl (2-chloroethyl) dimethylammonium bromide, cetyl (2-chloroethyl) dimethylammonium bromide, stearyl (2-chloroethyl) dimethylammonium bromide, lauryl (2-chloroethyl) dibenzylammonium chloride, myristyl (2 -Chloroethyl) dibenzylammonium chloride, cetyl (2-chloroethyl) dibenzylammonium chloride, stearyl (2-chloroethyl) dibenzylammonium chloride, lauryl (2-chloroethyl) diethanolammonium chloride, myristyl (2-chloroethyl) diethanolammonium chloride, Cetyl (2-chloroethyl) diethanolammonium chloride , Stearyl (2-chloroethyl)
Diethanol ammonium chloride, dilauryl (2
-Chloroethyl) methylammonium chloride, dimyristyl (2-chloroethyl) methylammonium chloride, dicetyl (2-chloroethyl) methylammonium chloride, distearyl (2-chloroethyl) methylammonium chloride, lauryl (2-chloroethyl) dimethylammonium chloride, myristyl ( For example, 2-bromoethyl) dimethylammonium chloride, cetyl (2-bromoethyl) dimethylammonium chloride, stearyl (2-bromoethyl) dimethylammonium chloride and the like are used.

R ₁ , R ₂ and R ₃ in the general formula (I) are the same as those in the general formula (I)
A glycidyl ammonium salt represented by the general formula (II)
3-halogen-2-hydroxypropylammonium salt represented by I), 3-halogenpropylammonium salt represented by general formula (IV), or 2-halogenethylammonium salt represented by general formula (V) In the present invention, at least one of R _{1 to} R ₃ is an alkyl group having 8 to 22 carbon atoms or an alkyl group having 8 to 22 carbon atoms.
It is necessary that the alkenyl group has a strong affinity for the skin, and has a surfactant, antibacterial, antibacterial, sterilization, disinfecting action on the skin, and deodorant such as body odor, deodorize,
This is for obtaining an N-quaternary ammonium-derived peptide having a deodorizing effect. If all of R _{1 to} R ₃ have less than 8 carbon atoms, the affinity for skin will not be sufficiently increased, and It is difficult to impart surface activity, and therefore antibacterial, antibacterial, sterilizing, disinfecting action of the skin, deodorant such as body odor, deodorant,
When it has no deodorant effect, on the other hand, if the carbon number of the alkyl group or alkenyl group exceeds 22, it becomes too oily and difficult to handle, and when used in skin cosmetics, This is because the skin becomes sticky.

The N-quaternary ammonium-derived peptide represented by the above general formula (I) can be used in place of a conventional skin cosmetic compound or in combination with a conventional skin cosmetic compound.
It is blended in various skin cosmetics.

Examples of skin cosmetics to which the N-quaternary ammonium derived peptide represented by the general formula (I) is blended include body shampoo, face wash, body lotion, burnishing cream, hand cream, face wash cream, face pack, Soap (soap), inverse soap, skin lotion, face lotion, antiperspirant deodorant (liquid roll-on type, stick type, aerosol type,
Powder), after shave lotion, after shave gel, after shave latex, after shave cream, face, limbs, whole body latex, face, limbs, whole body gel, pre shave lotion, pre shave gel, pre shave latex, pre shave cream, shaving cream, shaving Foam, body shampoo for baby, baby soap, lotion for baby,
Baby latex, baby gel, baby cream, acne, skin roughness prevention, rash prevention face wash, pack,
Ointments, creams, emulsions, lotions, creams, gels, ointments to prevent bruising, creams, various cosmetics for hypoallergenic sensitive skin, soaps or soaps for hospitals, hotels and restaurants, foot sprays, pet shampoos, In addition, makeup products, sunscreen products, etc.
It can be applied to various skin cosmetics. The present invention utilizes the antibacterial action of the N-quaternary ammonium-derived peptide represented by the general formula (I) and the like, and uses not only ordinary skin cosmetics but also the above-exemplified antiperspirant and deodorant. It can also be applied to those which are usually classified as quasi-drug skin external preparations, and the skin cosmetics of the present invention include such ordinary quasi-drug skin external preparations. Includes those that are classified.

The amount of the N-quaternary ammonium-derived peptide represented by the general formula (I) in the skin cosmetic is adjusted to be about 0.1 to 20% (weight%, hereinafter the same) in pure content. Is preferred.

In addition, components that can be added to the skin cosmetics in combination with the N-quaternary ammonium derived peptide represented by the general formula (I) include, for example, ammonium lauryl sulfate, ethanolamine lauryl sulfate, sodium lauryl sulfate, lauryl sulfate Alkyl sulfates such as triethanolamine, polyoxyethylene (2EO) triethanolamine lauryl sulphate (EO is ethylene oxide, the number before EO indicates the number of moles of ethylene oxide added), polyoxyethylene (3EO) alkyl (any one or a mixture of two or more of 11 to 15 carbon atoms) polyoxyethylene alkyl ether sulfates such as sodium ether sulfate, alkylbenzene sulfones such as sodium laurylbenzenesulfonate and triethanolamine laurylbenzenesulfonate Polyoxyethylene alkyl ether acetates such as sodium polyoxyethylene (3EO) tridecyl ether acetate, coconut oil fatty acid sarcosine sodium, lauroyl sarcosine triethanolamine, sodium lauroylmethyl-β-alanine, lauroyl-L-glutamic acid N-acyl amino acid salts such as sodium, lauroyl-L-glutamate triethanolamine, coconut oil fatty acid-sodium L-glutamate, coconut oil fatty acid-L-glutamate triethanolamine, coconut oil fatty acid methyltaurine sodium, sodium lauroylmethyltaurine, Sodium ether sulfate sodium alkane sulfonate, hydrogenated coconut oil fatty acid sodium glycerin sulfate, disodium undecylenoylamidoethyl sulfosuccinate, octylfe Carboxymethyl sodium diethoxyethyl sulfonic acid, amide sulfosuccinate disodium oleate, dioctyl sodium sulfosuccinate, sodium lauryl sulfosuccinate, disodium polyoxyethylene alkyl (carbon number 12-1
5) Ether phosphoric acid (8-10EO) sodium polyoxyethylene oleyl ether phosphate, sodium polyoxyethylene cetyl ether phosphate, disodium lauryl polyoxyethylene sulfosuccinate, sodium polyoxyethylene lauryl ether phosphate, sodium lauryl sulfoacetate , Anionic surfactants such as sodium tetradecene sulfonate, distearyl dimethyl ammonium chloride, dipolyoxyethylene oleyl methyl ammonium chloride, stearyl dimethyl benzyl ammonium chloride, stearyl trimethyl ammonium chloride,
Cationic surfactants such as cetyltrimethylammonium chloride, tri (polyoxyethylene) stearylammonium chloride, polyoxypropylenemethyldiethylammonium chloride, myristyldimethylbenzylammonium chloride, and lauryltrimethylammonium chloride;
Alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, undecylhydroxyethylimidazolium betaine sodium, undecyl-
N-hydroxyethyl-N-carboxymethylimidazolinium betaine, stearyl dihydroxyethyl betaine, stearyl dimethylaminoacetic acid betaine, coconut oil alkylbetaine, coconut oil fatty acid amide propyl betaine, coconut oil alkyl N-carboxyethyl-N-hydroxyethylimidazo Linium betaine sodium, coconut oil alkyl N-carboxyethoxyethyl-N-carboxyethylimidazolinium disodium hydroxide, coconut oil alkyl N-carboxymethoxyethyl-N
-Amphoteric surfactants such as -carboxymethyl imidazolinium disodium lauryl sulfate, N-coconut fatty acid acyl L-arginine ethyl / DL-pyrrolidone carboxylate, polyoxyethylene alkyl (C12-14) ether (7EO) , Polyoxyethylene octyl phenyl ether, polyoxyethylene oleyl ether, polyoxyethylene glyceryl oleate, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene cetyl stearyl diether,
Polyoxyethylene sorbitol lanolin (40EO),
Nonionic surfactants such as polyoxyethylene nonyl phenyl ether, polyoxyethylene polyoxypropylene cetyl ether, polyoxyethylene polyoxypropylene decyl tetradecyl ether, polyoxyethylene lanolin, polyoxyethylene lanolin alcohol, and polyoxypropylene stearyl ether Cationized cellulose, cationized hydroxyethylcellulose, poly (diallyldimethylammonium chloride), cationic polymers such as polyvinylpyridine, polyethyleneimine, synthetic polymers such as amphoteric polymers and anionic polymers, diethanolamide isostearate, monoethanolamide undecylenate , Oleic acid diethanolamide, bovine fatty acid monoethanolamide, hardened bovine fatty acid dietanol Amide, diethanolamide stearate, diethylaminoethylamide stearate, monoethanolamide stearate, diethanolamide myristate, coconut oil fatty acid ethanolamide, coconut oil fatty acid diethanolamide, lauric acid isopropanolamide, lauric acid ethanolamide, lauric acid diethanolamide , Thickeners such as lanolin fatty acid diethanolamide, waxes, paraffins, fatty acid esters, glycerides, oils and fats such as animal and vegetable oils, animal and plant extracts, polysaccharides or derivatives thereof, linear or cyclic methylpolysiloxane, methylphenylpolysiloxane, Dimethylpolysiloxane polyethylene glycol copolymer, dimethylpolysiloxane polypropylene copolymer, amino-modified silicone oil, 4th Silicone oils such as ammonium-modified silicone oils, wetting agents such as propylene glycol, 1,3-butylene glycol, ethylene glycol, glycerin and polyethylene glycol; lower alcohols such as ethanol, methanol, propyl alcohol and isopropyl alcohol; L-aspartic acid , Sodium L-aspartate, DL-alanine, L-arginine, glycine, L-glutamic acid, L-cysteine, L-threonine and the like.

〔Example〕

Next, the present invention will be described more specifically with reference to examples. Prior to the embodiment, the N-fourth
Production examples of quaternary ammonium-derived peptides are shown as reference examples.

Reference Example 1 Collagen peptide [n (n in general formula (I))
= 3] was heated under stirring and kept at 40 ° C, and 290 g of a 50% solution of glycidyl lauryl dimethyl ammonium chloride [water-isopropyl alcohol (1: 1) solution] in 290 g for 1 hour. It was dropped. During this time, the pH of the reaction solution was maintained at pH 9.5 using a 20% aqueous sodium hydroxide solution. After stirring at 40 ° C for 3 hours, keep at 40 ° C
The reaction was completed by standing for 24 hours. The reaction solution was neutralized to pH 7, desalted by electrodialysis, and then concentrated under reduced pressure.
N- (3-Lauryldimethylammonio-2-hydroxypropyl) as a quaternary ammonium derived peptide
A 30% aqueous solution of collagen peptide was obtained.

It was confirmed as follows that the obtained reaction product was N- (3-lauryldimethylammonio-2hydroxypropyl) collagen peptide.

(1) When the total amount of amino nitrogen of the collagen peptide before the reaction and the total amount of amino nitrogen of the reaction product were measured by the Van Slyke method, the amino nitrogen of the collagen peptide before the reaction was measured. The total amount is 484
In mmol, the total amount of amino nitrogen in the reaction product was 48 mmol, and the reaction reduced amino nitrogen. This decrease in amino nitrogen indicates that the amino group in the collagen peptide has reacted with glycidyl lauryl dimethyl ammonium chloride. From the amount of decrease in amino nitrogen, 90% of the amino nitrogen in the collagen peptide was determined. It turns out that is reacting.

(2) Gel filtration was performed under the following conditions, and the average molecular weight of the product after the reaction of the collagen peptide before the reaction was measured.

Average molecular weight before reaction 490 Average molecular weight after reaction 820 Measurement conditions: Column: TSK gel G3000PW _XL diameter 7.8 mm x length 30 cm Solvent: 0.05% trifluoroacetic acid, 48% acetonitrile-water Flow rate: 0.3 ml / min Detection : UV absorbance detector (wavelength 210 nm) Standard substance: aprotinin (MW6500) α-MSH (MW1665) Bradykinin (MW1060) Glutathione (MW307) The above increase in molecular weight is due to the glycidyl lauryl dimethylammonium moiety when the collagen peptide reacts. Is thought to be due to an increase in the molecular weight due to the introduction of the compound. The collagen peptide reacts with glycidyl lauryl dimethyl ammonium chloride to give N- (3-lauryl dimethyl ammonium 2-hydroxypropyl) as a reaction product.
It can be seen that collagen peptide is produced.

Reference Example 2 A 25% aqueous solution of keratin peptide (n = 10) was used instead of the aqueous collagen peptide solution in Reference Example 1, and a 50% solution of glycidyl stearyl dimethyl ammonium chloride [water-isopropyl alcohol] was used instead of the glycidyl lauryl dimethyl ammonium chloride solution. (1:
1) Solution] The reaction was carried out in the same manner as in Reference Example 1 except that 81 g was used.
Through similar operations, N- (3-stearyldimethylammonio-) as an N-quaternary ammonium-derived peptide was obtained.
A 25% aqueous solution of (2-hydroxypropyl) keratin peptide was obtained.

The total amount of amino nitrogen of the keratin peptide subjected to the reaction was 102 mmol, the total amount of amino nitrogen of the reaction product was 12 mmol, and 86% of the amino nitrogen of the keratin peptide had reacted.

The average molecular weights of the keratin peptide and the reaction product before the reaction were measured by gel filtration under the same conditions as in Reference Example 1. The average molecular weight of the keratin peptide before the reaction was 2,2.
At 200, the average molecular weight of the reaction product was 2,800. From the increase in molecular weight and the decrease in the amino nitrogen, the reaction product was N- (3-stearyldimethylammonio-2-hydroxypropyl) keratin peptide. It was confirmed that there was.

Reference Example 3 Instead of the collagen peptide aqueous solution in Reference Example 1, 500 g of a 30% aqueous solution of casein peptide (n = 7) was used.
The reaction was carried out in the same manner as in Reference Example 1, except that 165 g of a 50% solution of glycidyl coconut oil alkyldimethylammonium chloride [water-isopropyl alcohol (1: 1) solution] was used instead of the glycidyl lauryl dimethyl ammonium chloride solution. Through operation, a 30% solution of N- (3-coconut oil alkyldimethylammonio-2-hydroxypropyl) casein peptide as N-quaternary ammonium derived peptide was obtained. In addition, the coconut oil alkyl of the glycidyl coconut oil alkyl dimethyl ammonium chloride used is a mixture of alkyl having 8 to 18 carbon atoms and partially contains alkenyl having 18 carbon atoms.

The total amount of amino nitrogen of the casein peptide subjected to the reaction was 185 mmol, the total amount of amino nitrogen of the reaction product was 15 mmol, and 92% of the amino nitrogen of the casein peptide reacted. Was.

The average molecular weights of the keratin peptide and the reaction product before the reaction were measured by gel filtration under the same conditions as in Reference Example 1. The average molecular weight of the casein peptide before the reaction was 1,
At 600, the average molecular weight of the reaction product was 2,100. From the increase in molecular weight and the decrease in amino nitrogen, the reaction product was found to be N- (3-cocoalkyl dimethylammonio-).
(2 hydroxypropyl) casein peptide.

Reference Example 4 Instead of the collagen peptide aqueous solution in Reference Example 1, 500 g of a 10% aqueous solution of silk peptide (n = 2) was used, and instead of the glycidyl lauryl dimethyl ammonium chloride solution, a 50% solution of glycidyl tallow alkyldimethyl ammonium [water-isopropyl Alcohol (1: 1) solution] was reacted in the same manner as in Reference Example 1 except that 220 g was used, and N- (3-tallowalkyldimethylammonio as an N-quaternary ammonium-derived peptide was obtained through the same operation. −
A 20% aqueous solution of (2-hydroxypropyl) silk peptide was obtained.

The total amount of amino nitrogen in the silk peptide subjected to the reaction was 281 mmol, the total amount of amino nitrogen in the reaction product was 11 mmol, and 96% of the amino nitrogen in the silk peptide had reacted. Was.

The average molecular weights of the silk peptide and the reaction product before the reaction were measured by the gel filtration method under the same conditions as in Reference Example 1. The average molecular weight of the silk peptide before the reaction was 390.
The average molecular weight of the reaction product power is 800. From the increase in the molecular weight and the decrease in amino nitrogen, the reaction product is N- (3-tallowalkyldimethylammonio-2hydroxypropyl) silk peptide. It was confirmed that there was. In addition, the tallow alkyl of glycidyl tallow alkyl dimethyl ammonium used is a mixture of alkyl having 12 to 18 carbon atoms and partially contains alkenyl.

Reference Example 5 30 of collagen peptide (n = 30) different from Reference Example 1
Glycidyl lauryl dimethyl ammonium chloride solution was replaced with a glycidyl stearyl dimethyl ammonium chloride 50% solution [water-isopropyl alcohol (1: 1) solution] 36 g instead of the glycidyl lauryl dimethyl ammonium chloride solution.
The reaction was performed in the same manner as in Reference Example 1, and the N-
A 25% aqueous solution of N- (3-stearyldimethylammonio-2-hydroxypropyl) collagen peptide as a quaternary ammonium derived peptide was obtained.

The total amount of amino nitrogen in the collagen peptide subjected to the reaction was 48 mmol, the total amount of amino nitrogen in the reaction product was 8 mmol, and 84% of the amino nitrogen in the collagen peptide had reacted. Was.

The average molecular weight of the collagen peptide and the reaction product before the reaction was measured by gel filtration under the same conditions as in Reference Example 1. The average molecular weight of the collagen peptide was 9,800.
The average molecular weight of the reaction product was 11,000. From the increase in molecular weight and the decrease in amino nitrogen, the reaction product was N- (3-stearyldimethylammonio-2-hydroxypropyl) collagen peptide. It was confirmed that there was.

Next, the N-quaternary ammonium-derived peptide obtained in Reference Examples 1 to 5 described above was used for Staphyloco
2 shows the results of examining the antibacterial activity against ccus aureus, Bacillus subtilus, and Escherichia coli by the inhibition zone formation assay.

Test method: Sterilized SCD agar medium (tryptosoya agar medium)
Is poured into a Petri dish having a diameter of 90 mm in an amount of about 20 ml to coagulate. The culture medium is inoculated with 0.05 ml of a culture solution adjusted to about 10 ⁵ / ml and evenly spread.

Absorb a necessary and sufficient amount of the sample solution of a certain concentration into a filter paper of 8 mm in diameter, place the filter paper on the culture medium in a sterile petri dish,
Incubate at 18 ° C for 18 hours. The concentration of the sample solution (that is, the concentration of the solution of the N-quaternary ammonium-derived peptide in Reference Examples 1 to 5) was 1.0 wt% and 0.5 wt%.

The evaluation is performed by measuring the diameter of the inhibition zone formed after the culture and determining the size of the inhibition zone according to the following equation.

W = diameter of inhibition zone (mm) T = diameter of inhibition zone including filter paper (mm) D = diameter of filter paper (mm) Test results: Antibacterial activity of N-quaternary ammonium-derived peptides of Reference Examples 1 to 5 The test results are shown in Table 2. Unreacted peptide does not form any inhibition zone.

As shown in Table 2, the N-quaternary ammonium-derived peptides of Reference Examples 1 to 5 slightly vary depending on the type and concentration of the bacterium, but form a zone of inhibition except in specific cases, and have an antibacterial effect. Was.

 Next, examples of the present invention will be described.

Example 1 A body shampoo having the following composition, in which the N- (3-lauryldimethylammonio-2-hydroxypropyl) collagen peptide obtained in Reference Example 1 was blended, was prepared.
In addition, what does not add the component concentration in parentheses (parentheses) after each substance name is the compounding amount in terms of pure components. The amounts of the components are all based on weight%. These are the same in each of the following embodiments.

Reference Example 1-N- (3-lauryldimethylammonio-
2-Hydroxypropyl) collagen peptide (30%) 7.5 Hydrolyzed collagen coconut oil fatty acid condensate triethanolamine salt (30%) (Promois ECT manufactured by Seiwa Kasei Co., Ltd.) 10.0 2-Alkyl-carboxymethyl-N-hydroxyethylimidazo Linium betaine (40%) 20.0 Coconut oil fatty acid sodium methyltaurine 15.0 Hydrolyzed keratin (25%) (Promois manufactured by Seiwa Kasei Co., Ltd.)
WK) 1.0 Diethanolamide laurate 4.0 Diethylaminoethylamide stearate 2.0 Polyoxyethylene glycol dioleate 1000 1.5 Ethylene glycol monostearate 0.5 Mixture of paraoxybenzoate and phenoxyethanol (Secept, Seiwa Chemical Co., Ltd.) 0.3 EDTA-2Na 0.1 Fragrance Appropriate amount Sterilized ion-exchanged water Totally 100.0 In addition, except that the N- (3-lauryldimethylammonio-2-hydroxypropyl) collagen peptide of Reference Example 1 was not added and sterilized ion water was increased, A body shampoo having the same composition as in Example 1 was prepared,
This was designated as Comparative Example 1.

The body shampoos of Example 1 and Comparative Example 1 were divided into 20 panelists, 10 men and 10 women, for a total of 20 panelists. The body shampoo of Example 1 was placed on the right side of 10 panelists out of 20. Let the body shampoo of Comparative Example 1 be used on the left, and use the Comparative Example 1 on the right for the remaining 10 people.
Use the body shampoo of Example 1 on the left side, especially wash the underarms and soles with each of the above body shampoos, then do daily life including mild sports, then 6 hours Later, the body shampoo of Example 1 was added to each panelist in Comparative Example 1.
Of the body shampoo was evaluated according to the following evaluation criteria.
Table 3 shows the evaluation results of each panel.

Evaluation standard of body odor control effect Very effective 3 Effective 2 Slightly effective 1 No effect 0 The average of the evaluation values of the evaluation results of each panelist shown in Table 3 is 2.15, which indicates that the body shampoo of Example 1 has a body odor control effect as compared with the body shampoo of Comparative Example 1. Was.

Table 4 shows the results of the evaluation of the feeling of use together with the evaluation of the above-mentioned body odor control effect. The evaluation method was to evaluate how much the body shampoo of Example 1 was superior to the body shampoo of Comparative Example 1 for smoothness and moisture of the skin, and the evaluation criteria were as follows. The evaluation results in Table 4 are the average values of 20 panelists.

Usability evaluation criteria Fairly good 3 Good 2 Slightly good 1 Don't know 0 As shown in Table 4, the evaluation value of the body shampoo of Example 1 was about 2, and the feeling of use was superior to the body shampoo of Comparative Example 1.

Example 2 A body shampoo having the following composition containing the N- (3-stearyldimethylammonio-2-hydroxypropyl) keratin peptide obtained in Reference Example 2 was prepared.

N- (3-stearyldimethylammonio-2-hydroxypropyl) keratin peptide of Reference Example 2 (25%) 6.0 Hydrolyzed collagen coconut oil fatty acid condensate potassium salt (30%) (Promois ECP-C manufactured by Seiwa Chemical Co., Ltd.) 40.0) Coconut oil alkylamidopropyl acetate betaine (40%) 10.0 Sodium N-lauroyl-L-glutamate 4.0 Diethanolamide laurate 3.0 Polyethylene glycol 4000 3.0 Polyoxyethylene glycol dioleate 1000 1.5 Stearic acid 0.3 1,3-butylene glycol 5.0 Stearic acid monoethanolamide 0.8 EDTA-2Na 0.1 Mixture of paraoxybenzoic acid ester and phenoxyethanol (Secept, manufactured by Seiwa Chemical Co., Ltd.) 0.2 Fragrance Appropriate amount Sterilized ion-exchanged water Total 100.0 In addition, N- (3- Stearyl dimethylammonio-2-hi The keratin peptide used in the production of the N- (3-stearyldimethylammonio-2-hydroxypropyl) keratin peptide in Reference Example 2 in place of the (droxypropyl) keratin peptide (n =
A body shampoo having the same composition as in Example 2 was prepared except that the same amount of 10) was blended.

The body shampoos of Example 2 and Comparative Example 2 were evaluated for body odor control effect by the same method as in Example 1, and the body shampoo of Example 2 was replaced with the body shampoo of Comparative Example 2. The evaluation value was higher than that, and it had a body odor control effect. In addition, the feeling of use was evaluated by the same method as in Example 1, and the body shampoo of Example 2 had a high evaluation value and excellent feeling in use, both in terms of skin smoothness and skin moisture. Was.

Example 3 A body shampoo (bubble bath) having the following composition containing the N- (3-coconut oil alkyldimethylammonio-2-hydroxypropyl) casein peptide obtained in Reference Example 3 was prepared.

N- (3-coconut fatty acid dimethylammonio-2-hydroxypropyl) casein peptide of Reference Example 3 (30
3.0) Potassium salt of hydrolyzed collagen lauric acid condensate (30%
%) (Promoil ELP manufactured by Seiwa Kasei Co., Ltd.) 20.0 Hydrolyzed silk (6%) (Silk-100 manufactured by Seiwa Kasei Co., Ltd.)
0) 2.5 Ammonium lauryl sulfate (30%) 30.0 Sodium polyoxyethylene alkyl ether sulfosuccinate (40%) (Lionol MSC manufactured by Lion) 35.0 Flavor appropriate amount EDTA-2Na 0.1 Sterilized ion-exchange water Total 100.0 Instead of the N- (3-lauryldimethylammonio-2-hydroxypropyl) collagen peptide of Example 1, it was used in the production of the N (3-lauryldimethylammonio-2-hydroxypropyl) collagen peptide in Reference Example 1. Collagen peptide (n =
A body shampoo having the same composition as in Example 3 was prepared except that 3) was blended in the same amount, and this was designated as Comparative Example 3.

The body shampoos of Example 3 and Comparative Example 3 were evaluated for their body odor control effect by the same method as in Example 1. As a result, the body shampoo of Example 3 was compared with the body shampoo of Comparative Example 3. The evaluation value was high, and it had a body odor control effect. The feeling of use was also evaluated by the same method as in Example 1, and the body shampoo of Example 3 had a high evaluation value for the smoothness of the skin and the moisture of the skin, indicating that the feeling of use was excellent. .

Example 4 A body shampoo for a baby having the following composition containing the N- (3-lauryldimethylammonio-2-hydroxypropyl) collagen peptide obtained in Reference Example 1 was prepared.

N (3-lauryldimethylammonio-2) of Reference Example 1
-Hydroxypropyl) collagen peptide (30%) 9.0 Hydrolyzed collagen coconut oil condensate potassium salt (30%) (Promois ECP manufactured by Seiwa Kasei Co., Ltd.) 3.0 Disodium lauryl polyoxyethylene sulfosuccinate (30%) 3.0 2- Lauryl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine (30%) 18.0 Myristic acid 1.5 Sodium hydroxide 0.25 Methyl paraben 0.2 Propyl paraben 0.02 EDTA-2Na 0.1 Sterilized ion-exchange water Total 100.0 N- (3-lauryldimethylammonio-2-hydroxypropyl) collagen peptide was not blended, and its amphoteric surfactant, 2-lauryl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine (30 %), And the same composition as in Example 4 except that The use body shampoo was prepared,
This was designated as Comparative Example 4.

In order to compare the feeling of use of the baby body shampoos of Example 4 and Comparative Example 4, it was used by adult female panelists. The baby body shampoo of Example 4 was the same as the baby body shampoo of Comparative Example 4. There was less stimulus than in. However, the cleaning effect was the same for both the baby body shampoo of Example 4 and the baby body shampoo of Comparative Example 4. In addition, in the case of the baby body shampoo of Example 1, the N- (3-lauryldimethylammonio-2-hydroxypropyl) collagen peptide of Reference Example 1 has an antibacterial action, so that bacterial inflammation of the skin is caused by bacteria. The effect of preventing such problems can be expected.

Example 5 A face wash having the following composition was prepared by blending N (3-tallowalkyldimethylammonio-2-hydroxypropyl) silk peptide obtained in Reference Example 4.

N (3-tallowalkyldimethylammonio-2-hydroxypropyl) silk peptide (20%) 6.7 Hydrolyzed collagen coconut oil fatty acid condensate potassium salt (30%) (Promois ECP-C manufactured by Seiwa Kasei Co., Ltd.) 30.0 Hydrolysis Casein (30%) (Promois milk manufactured by Seiwa Kasei Co., Ltd.) 5.5 Myristic acid 3.0 Stearic acid 3.0 Isostearic acid 1.0 Glycerin 3.0 1,3-butylene glycol 5.0 Polyoxyethylene glycol monostearate (14
0) 2.5 Polyoxyethylene (120) methyl glucosidediolate 0.5 Butyl paraoxybenzoate 0.1 2-Amino-2-methylpropanol 3.5 Sterilized ion-exchange water Total 100.0 In addition, N- (3-tallow alkyl) in Reference Example 4 above was used. In place of the dimethylammonio-2-hydroxypropyl) silk peptide, the silk peptide (n = 3) used in the production of the N- (3-tallowalkyldimethylammonio-2-hydroxypropyl) silk peptide in Reference Example 4 was used.
Except that 2) was added in the same amount, a face wash having the same composition as in Example 5 was prepared, and this was designated as Comparative Example 5.

The facial cleanser of Example 5 and Comparative Example 5 was used by female panelists, and the feeling of use was compared.
The face wash of Comparative Example 5 was superior to the face wash of Comparative Example 5 in the effect of moisturizing the skin and imparting smoothness to the skin.

Example 6 A body lotion having the following composition containing the N- (3-lauryldimethylammonio-2-hydroxypropyl) collagen peptide obtained in Reference Example 1 was prepared.

N- (3-lauryl dimethyl ammonium) of Reference Example 1
2-Hydroxypropyl) collagen peptide (30%) 3.5 Magnesium aluminum silicate 0.5 Hydrolyzed collagen isostearic acid condensate 2-amino-2-methyl-1,3-propanediol salt (25%)
(Promois E-118D manufactured by Seiwa Kasei Co., Ltd.) 1.0 99% ethanol 13.5 Propylene glycol 3.0 Crosslinked polyacrylic acid (Carbopol 940, Goodrich) 0.07 Methyl parahydroxybenzoate 0.10 Propyl paraoxybenzoate 0.01 Sorbitol (70%) 3.50 2 -Amino-2-methylpropanol qs. Sterilized ion-exchanged water to a total of 100.0. In place of the N- (3-stearyldimethylammonio-2-hydroxypropyl) collagen peptide of Reference Example 5 above, A body lotion having the same composition as in Example 6 was prepared except that the same amount of the collagen peptide (n = 30) used in the production of N- (3-stearyldimethylammonio-2-hydroxypropyl) collagen peptide was blended. This was designated as Comparative Example 6.

The body lotions of Example 6 and Comparative Example 6 were used by female panelists, and their feeling of use was evaluated by the same method as in Example 1. As a result, both skin smoothness and skin moisture were evaluated. The body lotion of No. 6 had a high evaluation value and was excellent in usability. In the case of the body lotion of Example 6, the N- (2-lauryldimethylammonio-2) of Reference Example 1 having an antibacterial action was used.
(Hydroxypropyl) collagen peptide is blended, so that an antibacterial action not found in the body lotion of Comparative Example 6 can be expected.

Example 7 An antiperspirant and deodorant (roll-on type) having the following composition, which contains the N- (3-lauryldimethylammonio-2-hydroxypropyl) collagen peptide obtained in Reference Example 1, was prepared.

N- (3-lauryl dimethyl ammonium) of Reference Example 1
2-Hydroxypropyl) collagen peptide (30%) 3.5 Chlorohydroxyaluminum 20.0 Polyoxyethylene (20) Polyoxypropylene (8) Cetyl ether 2.0 Hydroxyethylcellulose 0.5 Ethanol 40.0 Perfume Appropriate amount Sterilized ion exchange water Total 100.0 Instead of the N- (3-tallow alkyldimethylammonio-2-hydroxypropyl) silk peptide of Reference Example 4, the N- (3-tallow alkyldimethylammonio-2-hydroxypropyl) silk peptide of Reference Example 4 Silk peptide (n =
Except that 2) was added in the same amount, an antiperspirant and deodorant having the same composition as in Example 7 was prepared, and this was designated as Comparative Example 7.

The antibacterial activity of the antiperspirant deodorants of Example 7 and Comparative Example 7 against Staphylococcus aureus, Bacillus subtilis, and Escherichia coli was formed in the same manner as in the case of the N-quaternary ammonium-derived peptide of Reference Examples 1 to 5. The result measured by the
It is shown in the table. However, the antiperspirant and deodorant of Example 7 and Comparative Example 7 (however, ethanol in the formulation was replaced with water) were used as the sample solution.

As shown in Table 5, the antiperspirant and deodorant of Example 7 formed an inhibition zone and had an antibacterial action. This is similar to Example 7
Is based on the fact that the N- (3-tallowalkyldimethylammonio-2-hydroxypropyl) silk peptide of Reference Example 4 blended with the antiperspirant deodorant has an antibacterial effect. The antiperspirant and deodorant of Comparative Example 7 in which the raw material silk peptide was blended in place of the (3-tallow alkyldimethylammonio-2-hydroxypropyl) silk pepti did not form any inhibition zone and had no antibacterial action. .

The antiperspirant deodorants of Example 7 and Comparative Example 7 were applied to a total of 20 panelists of 10 men and 10 women, and 10 out of 20 panelists.
The person was allowed to use the antiperspirant and deodorant of Example 7 under the right armpit (armpit), the left armpit was used with the antiperspirant and deodorant of Comparative Example 7, and the remaining 10 persons were under the right armpit. The antiperspirant and deodorant of Comparative Example 7 were used, and the antiperspirant and deodorant of Example 7 were used beneath the left armpit. After that, daily life including mild sports was performed. To what extent the antiperspirant and deodorant of Comparative Example 7 were compared with the antiperspirant and deodorant of Comparative Example 7.
The following evaluation criteria were used to determine whether the body odor had an anti-odor effect. Table 6 shows the evaluation results of each panelist.

Evaluation standard of body odor control effect Very effective 3 Effective 2 Slightly effective 1 No effect 0 The average of the evaluation values of the evaluation results of each panel shown in Table 6 was 2.6, indicating that the antiperspirant and deodorant of Example 7 had an effect of controlling body odor compared to the antiperspirant and deodorant of Comparative Example 7. Was revealed.

Example 8 Antiperspirant and deodorant having the following composition containing N- (3-tallowalkyldimethylammonio-2-hydroxypropyl) silk peptide obtained in Reference Example 4 (however, powdered by spray drying) An agent (stick type) was prepared.

N- (3-tallowalkyldimethylammonio-2-hydroxypropyl) silk peptide of Reference Example 4 1.7 Stearyl alcohol 22.3 Isopropyl palmitate 20.0 Polypropylene glycol (14) butyl ether 10.0 Hydrogenated castor oil 4.0 Polyoxyethylene (4) lauryl ether 1.0 Talc 4.0 Chlorohydroxyaluminum 20.0 Cyclic dimethylpolysiloxane 17.0 Fragrance Appropriate amount In place of N- (3-tallowalkyldimethylammonio-2-hydroxypropyl) silk pepti in Reference Example 4, the above N -Silk peptide used for producing (3-tallowalkyldimethylammonio-2-hydroxypropyl) silk peptide (n = 2)
Was prepared in the same manner as in Example 8, except that the same amount was mixed.

About the antiperspirant and deodorant of Example 8 and Comparative Example 8,
When the deodorant effect of body odor was evaluated by the same method as in Example 7, the antiperspirant and deodorant of Example 8 had a higher evaluation value than the antiperspirant and deodorant of Comparative Example 8, and the It had an anti-odor effect. Further, the antiperspirant and deodorant of Example 8 is the same as that of N- (3-tallowalkyldimethylammonio-2 in Reference Example 4.
(Hydroxypropyl) silk peptide.

Example 9 Antiperspirant and deodorant having the following composition containing N- (3-tallowalkyldimethylammonio-2-hydroxypropyl) silk peptide obtained in Reference Example 4 (however, powdered by spray drying) An agent (aerosol type) was prepared.

N- (3-tallowalkyldimethylammonio-2-hydroxypropyl) silk peptide of Reference Example 4 2.0 Palm mint oil 1.5 Ethanol 25.0 Isoprene glycol 4.5 Flavor Appropriate amount Isobutane-propane mixed gas 66.0 The above antiperspirant deodorant The preparation was carried out by previously mixing the components except for the mixed gas of isobutane and propane, placing the mixture in a closed aerosol-type container, and mixing the mixed gas with the mixed gas of isobutane and propane.

Also, in place of the N- (3-tallowalkyldimethylammonio-2-hydroxypropyl) silk peptide of the above-mentioned Reference Example 4, the above-mentioned N- (3-tallowalkyldimethylammonio-2-hydroxypropyl) was used in the reference example 4. Silk peptide used for production of silk peptide (n =
Except that 2) was added in the same amount, an antiperspirant and deodorant having the same composition as in Example 9 was prepared, and this was designated as Comparative Example 9.

About the antiperspirant and deodorant of Example 9 and Comparative Example 9,
When the deodorant effect of body odor was evaluated in the same manner as in Example 7, the antiperspirant and deodorant of Example 9 had a higher evaluation value than the antiperspirant and deodorant of Comparative Example 9, and the It had an anti-odor effect. Further, the antiperspirant and deodorant of Example 9 are the same as the N- (3-tallowalkyldimethylammonio-2) of Reference Example 4.
(Hydroxypropyl) silk peptide.

Example 10 An antiperspirant and deodorant of the following composition containing the N- (3-stearyldimethylammonio-2-hydroxypropyl) collagen peptide selected in Reference Example 5 (provided that it is spray-dried into a powder). (Powder type) was prepared.

N- (3-stearyldimethylammonio-2-hydroxypropyl) collagen peptide of Reference Example 5 0.3 cyclic dimethylpolysiloxane 5.5 isopropyl stearate 0.5 silica 0.8 talc 1.8 chlorohydroxyaluminum 7.0 mixed gas of isobutane-propane 84.1 The deodorant was prepared by mixing components except for the isobutane-propane mixed gas in advance, placing the components in an aerosol-type closed container, and mixing with the isobutane-propane mixed gas therein.

Further, instead of the N- (3-stearyldimethylammonio-2-hydroxypropyl) collagen peptide of Reference Example 5, the N- (3-stearyldimethylammonio-2-hydroxypropyl) collagen peptide of Reference Example 5 was used. An antiperspirant and deodorant having the same composition as in Example 10 was prepared, except that the same amount of the collagen peptide (n = 30) used in the production of was prepared.

For the antiperspirant deodorant of Example 10 and Comparative Example 10,
When the deodorant effect of body odor was evaluated by the same method as in Example 7, the antiperspirant and deodorant of Example 10 had a higher evaluation value than the antiperspirant and deodorant of Comparative Example 10, and the It had an anti-odor effect. Further, the antiperspirant and deodorant of Example 10 is the same as the N- (3-stearyldimethylammonio-2-
(Hydroxypropyl) collagen peptide had the same antibacterial activity.

Example 11 An after-shaving lotion having the following composition and containing the N- (3-lauryldimethylammonio-2-hydroxypropyl) collagen peptide obtained in Reference Example 1 was prepared.

N- (3-lauryl dimethyl ammonium) of Reference Example 1
2-hydroxypropyl) collagen peptide (30%) 3.5 cetyl alcohol 1.8 diisobutyl adipate 2.0 polyoxyethylene (10) polyoxypropylene (4) cetyl ether 1.0 polyoxyethylene (2) nonylphenyl ether
5 Triethanolamine 0.25 Cross-linked polyacrylic acid (Carbopol manufactured by Goodrich Corporation)
940) 0.25 ethanol 16.0 Sterile ion-exchanged water Total 100.0 Further, in place of the N- (3-lauryldimethylammonio-2-hydroxypropyl) collagen peptide of Reference Example 1, the N- (3 -Lauryl dimethyl ammonium-hydroxypropyl) keratin peptide (n =
After shaving lotion having the same composition as that of Example 11 except that 3) was added in the same amount, Comparative Example 11 was used.

Antibacterial activity of the after-shaving lotion of Example 11 and Comparative Example 11 against Staphylococcus aureus, Bacillus subtilis and Escherichia coli was determined in the same manner as in the case of the N-quaternary ammonium-derived peptide of Reference Examples 1 to 5. Table 7 shows the measurement results. However, the after-shave lotion of Example 11 and Comparative Example 11 (provided that ethanol in the formulation was replaced with water) was used as the sample solution.

As shown in Table 7, the after-shave lotion of Example 11 formed an inhibition zone and had an antibacterial action. This is based on the fact that the N- (3-lauryldimethylammonio-2-hydroxypropyl) collagen peptide of Reference Example 1 blended in the after-shaving lotion of Example 11 has an antibacterial effect. 1 of N- (3-lauryldimethylammonio-2
The after-shaving lotion of Comparative Example 11, in which the raw material collagen peptide was blended in place of the (hydroxypropyl) collagen peptide, did not form any inhibition zone and had no antibacterial effect.

In addition, the after-shave lotions of Example 11 and Comparative Example 11 were used by female panelists, and their usability was evaluated by the same method as in Example 1. ,Example
11 after-shave lotions have high evaluation values,
The feeling of use was excellent.

Example 12 A shaving cream having the following composition containing the N- (3-lauryldimethylammonio-2-hydroxypropyl) collagen peptide obtained in Reference Example 1 was prepared.

N- (3-lauryl dimethyl ammonium) of Reference Example 1
2-Hydroxypropyl) collagen peptide (30%) 3.5 Stearic acid 7.5 Coconut oil sodium alkylisethionate 3.2 Polyoxyethylene (60) hydrogenated castor oil 0.6 Hydrolyzed collagen coconut oil fatty acid condensate triethanolamine salt (Seiwa Chemical Co., Ltd.) 16.0 Triethanolamine 4.8 1,3-butylene glycol 2.5 Methyl paraben 0.2 Propyl paraben 0.02 Sterile ion-exchange water Total 100.0 In addition, N- (3-lauryldimethylammonio-2-hydroxypropyl) in Reference Example 1 above was used. ) Instead of the collagen peptide, the collagen peptide (n) used in the production of the N- (3-lauryldimethylammonio-2-hydroxypropyl) collagen peptide in Reference Example 1 was used.
= 3) was prepared in the same manner as in Example 12, except that the same amount was added.

The shaving creams of Example 12 and Comparative Example 12 were used by female panelists, and their usability was evaluated in Example 1.
When evaluated by the same method as in the case of the above, the shaving cream of Example 12 had a high evaluation value and excellent feeling in use, both in terms of skin smoothness and skin moisture.

The shaving cream of Example 12 was easier to prepare and had better storage stability than the shaving cream of Comparative Example 12.

Example 13 An acne lotion having the following composition, in which the N- (3-lauryldimethylammonio-2-hydroxypropyl) collagen peptide obtained in Reference Example 1 was blended, was prepared.

N- (3-lauryl dimethyl ammonium) of Reference Example 1
2-Hydroxypropyl) collagen peptide (30%) 1.5 Colloidal sulfur 0.3 Dipotassium glutyl litate 0.2 Ethanol 10.0 Carboxyvinyl polymer 0.2 Diisopropanolamine 0.2 Methyl paraben 0.10 Propyl paraben 0.02 Sterilized ion exchange water Total 100.0 In place of the-(3-lauryldimethylammonio-2-hydroxypropyl) collagen peptide, the collagen peptide used in the production of the N- (3-lauryldimethylammonio-2-hydroxypropyl) collagen peptide in Reference Example 1 ( n
= 3) was prepared in the same manner as in Example 13, except that the same amount was added.

The antibacterial activity of the acne lotion of Example 13 and Comparative Example 13 against Staphylococcus aureus, Bacillus subtilis and Escherichia coli was measured in the same manner as in the case of the N-quaternary ammonium-derived peptide of Reference Examples 1 to 5. Table 8 shows the measurement results. However, for the sample solution,
The acne lotion of Example 11 and Comparative Example 11 (however, ethanol in the formulation was replaced with water) was used.

As shown in Table 8, the acne lotion of Example 13 formed a zone of inhibition and had an antibacterial effect. this is,
N- of Reference Example 1 blended in the acne lotion of Example 13
The (3-lauryldimethylammonio-2-hydroxypropyl) collagen peptide is based on the fact that the collagen peptide has an antibacterial action, but the N- (3-lauryldimethylammonio-2-hydroxypropyl) collagen peptide of Reference Example 1 is used. The acne lotion of Comparative Example 13, in which the raw material collagen peptide was blended in place of the above, did not form a sufficient inhibition zone, and did not have a sufficient antibacterial action as the acne lotion. It is considered that the slight formation of the inhibition band in the acne lotion of Comparative Example 13 was due to methylparaben and propylparaben added as preservatives.

In addition, the acne lotion of Example 13 and Comparative Example 13 was used by female panelists, and their feeling of use was evaluated by the same method as in Example 1, showing that the smoothness of the skin and the moisture of the skin were The acne lotion of Example 13 had a high evaluation value and was excellent in usability.

Example 14 A vanishing cream containing the N- (3-coconut oil alkyldimethylammonio-2-hydroxypropyl) casein peptide obtained in Reference Example 3 and having the following composition was prepared.

The N- (3-coconut oil alkyldimethylammonio-2-hydroxypropyl) casein peptide of Reference Example 3 (25
%) 1.2 Isopropyl isostearate (Matte Lube I / I manufactured by Seiwa Chemical Co., Ltd.) 5.5 Glycerin isostearate (Ayakol GMIS manufactured by Seiwa Chemical Co., Ltd.) 0.5 Glyceride monostearate 2.0 Methylpolysiloxane (Silicone KF96-350cs manufactured by Toray Silicon Co., Ltd.) 0.25 Stearic acid 10.0 Butyl paraoxybenzoate 0.1 Cetanol 1.0 Jojoba oil 0.5 Polyoisethylene sol pit tetraoleate (40
EO) 1.7 Hydrolyzed silk (6%) (Promois Silk-1000 manufactured by Seiwa Chemical Co., Ltd.) 1.0 Dipotassium glycyrrhizinate 0.05 Triethanolamine 1.0 Hyaluronic acid 0.01 Disodium edetate 0.10 Fragrance Appropriate amount Sterilized ion-exchanged water Total 100.0% In addition, instead of the N- (3-coconut oil dimethylammonio-2-hydroxypropyl) casein peptide of Reference Example 3, the above N- (3-coconut oil dimethylammonio-2-hydroxypropyl) is used in Reference Example 3. A vanishing cream having the same composition as in Example 14 was prepared, except that the same amount of casein peptide (n = 7) used in the synthesis of casein peptide was used.

The burnishing creams of Example 14 and Comparative Example 14 were used by female panelists, and their feeling of use was evaluated by the same method as in Example 1. As a result, both skin smoothness and skin hydration were evaluated. The 14 burnishing creams had high evaluation values and excellent feeling in use.

Further, the burnishing cream of Example 14 was used as a comparative example.
Easy to prepare compared to 14 burnishing creams,
The storage stability was also excellent.

Example 15 A hand cream having the following composition containing the N- (3-stearyldimethylammonio-2-hydroxypropyl) collagen peptide obtained in Reference Example 5 was prepared.

The N- (3-stearyldimethylammonio-2-hydroxypropyl) collagen peptide (25
%) 0.6 Isopropyl isostearate (Matte Lube I / I manufactured by Seiwa Kasei Co., Ltd.) 3.8 Polyoxyethylene (15) lauryl ether (Ayakol PL-50 manufactured by Seiwa Kasei Co., Ltd.) 0.7 Polyoxyethylene (25) cetyl ether 0.6 methylpoly Siloxane (silicone KF96-350cs manufactured by Toray Silicon Co.) 0.2 Methyl paraoxybenzoate 0.1 Butyl paraoxybenzoate 0.1 cetyl alcohol 3.0 Emulsifier mixture (Ayakol LC-WAX manufactured by Seiwa Kasei Co., Ltd.) 5.0 Hydrolyzed keratin (25%) (Seiwa Kasei Promois
WK) 4.0 Glycerin 5.3 1,3-butylene glycol 3.1 Liquid paraffin # 70 2.5 Perfume Appropriate amount Sterile ion-exchanged water Total 100.0 In addition, N- (3-stearyldimethylammonio-2-hydroxypropyl) in Reference Example 5 above was used. ) In the same manner as in Reference Example 5 except that the same amount of the collagen peptide (n = 30) used in the production of the N- (3-stearyldimethylammonio-2-hydroxypropyl) collagen peptide in Reference Example 5 was used instead of the collagen peptide, A hand cream having the same composition as that of Example 15 was prepared, and this was designated as Comparative Example 15.

The hand creams of Example 15 and Comparative Example 15 were used by female panelists, and their feeling of use was evaluated by the same method as in Example 1. As a result, both skin smoothness and skin hydration were evaluated. The hand cream of No. 15 had a high evaluation value and was excellent in usability.

Further, the hand cream of Example 15 was easier to prepare and had better storage stability than the hand cream of Comparative Example 15.

Example 16 A face wash cream having the following composition, which contains the N- (3-lauryldimethylammonio-2-hydroxypropyl) collagen peptide obtained in Reference Example 1, was prepared.

N- (3-lauryl dimethyl ammonium) of Reference Example 1
2-hydroxypropyl) collagen peptide (30%)
1.0 Hydrolyzed collagen (30%) 1.0 Coconut oil hydrolyzed collagen potassium (Promois ECP-C manufactured by Seiwa Chemical Co., Ltd.) 40.0 Coconut oil fatty acid sodium methyltaurine (30%) 40.0 Diethanolamide laurate 3.0 Polyethylene glycol monosterate 4.5 Diolein Polyethylene glycol acid 4.0 Mixture of p-hydroxybenzoic acid ester and phenoxyethanol (Secept, Seiwa Kasei Co., Ltd.) 0.5 Perfume Appropriate amount Sterilized ion-exchanged water Adjust to a total of 100.0 Malic acid Adjusted to pH 6.0 In addition, N- (3 Instead of the -lauryldimethylammonio-2-hydroxypropyl) collagen peptide, the collagen peptide (n) used in the production of the N- (3-lauryldimethylammonio-2-hydroxypropyl) collagen peptide in Reference Example 1 was used.
= 3) was prepared in the same manner as in Example 16, except that the same amount was added.

The facial cleansing creams of Example 16 and Comparative Example 16 were used by female panelists, and their feeling of use was evaluated by the same method as in Example 1. As a result, both the smoothness of the skin and the moisture of the skin were evaluated. The face wash cream of 16 had a high evaluation value and was excellent in use feeling.

In addition, the face wash cream of Example 16 was easier to prepare and had better storage stability than the face wash cream of Comparative Example 16.

Example 17 A face pack having the following composition, which contains the N- (3-stearyldimethylammonio-2-hydroxypropyl) keratin peptide obtained in Reference Example 2, was prepared.

N- (3-stearyldimethylammonio-2-hydroxypropyl) keratin peptide of Reference Example 2 (25%) 0.2 hydrolyzed casein (30%) 1.0 coconut oil fatty acid hydrolyzed collagen potassium (Promois ECP- manufactured by Seiwa Chemical Co., Ltd.) C) 40.0 Sodium methyltaurine coconut oil fatty acid (30%) 40.0 Diethanolamide laurate 3.0 Polyethylene glycol monostearate 4.5 Polyethylene glycol dioleate 4.0 Mixture of paraoxybenzoate and phenoxyethanol (Secept, Seiwa Chemical Co., Ltd.) 0.5 Perfume Colorant Appropriate amount Sterilized ion-exchanged water Total 100.0 Citric acid pH 6.0 Further, in place of the N- (3-stearyldimethylammonio-2-hydroxypropyl) keratin peptide of Reference Example 2 above, Reference Example 2 was used. In the above, N- (3-stearyldi Chiruanmonio-2-hydroxypropyl) keratin used in the preparation of the keratin peptide peptide (n =
A face pack having the same composition as in Example 17 was prepared, except that the same amount of 7) was blended, and this was designated as Comparative Example 17.

The face packs of Example 17 and Comparative Example 17 were used by female panelists, and their feeling of use was evaluated by the same method as in Example 1. As a result, both the smoothness of the skin and the moisture of the skin were evaluated. The 17 face packs had high evaluation values and excellent usability.

The face pack of Example 17 was easier to prepare and had better storage stability than the face pack of Comparative Example 17.

〔The invention's effect〕

As described above, in the present invention, the N-quaternary ammonium-derived peptide represented by the general formula (I) has a surfactant activity by itself, and thus has antibacterial, antibacterial, sterilization, and disinfecting effects on the skin. It has an action and has anti-odor, deodorant and deodorant effects such as body odor, and has a strong affinity for the skin, has a great effect of moisturizing the skin and imparts smoothness, is less irritating, and emulsifies. Since the N-quaternary ammonium-derived peptide represented by the general formula (I) has an action and a dispersing action, it can exhibit the properties of the formulation in each skin cosmetic by blending the peptide with the skin cosmetic. Can be.

For example, a body shampoo can moisturize the skin, impart smoothness, and exert a body odor control effect. Also, in body shampoo for baby,
In addition to the above characteristics, it is possible to exhibit the characteristic of being low irritant. Antiperspirant and deodorant can exert antibacterial action and body odor deodorant action, and after shaving lotion and acne lotion etc. exert antibacterial action and moisturize skin, and exert action to smooth skin be able to. Furthermore, shaving creams, burnishing reams, hand creams, face creams, face packs, and the like can provide the skin with a moisturizing and smoothing effect, and also facilitate their preparation and storage. Good stability can be achieved.

Continuation of the front page (51) Int.Cl. ⁶ identification code FI A61K 7/15 A61K 7/15 (58) Investigation field (Int.Cl. ⁶ , DB name) A61K 7/00 A61K 7/15 A61K 7 / 32

Claims (1)

(57) [Claims] 1. The compound of the general formula (I) (Wherein at least one of R ₁ , R ₂ , and R ₃ has at least 8 carbon atoms)
22 alkyl groups or alkenyl groups having 8 to 22 carbon atoms,
The rest is an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group having 1 to 3 carbon atoms or a benzyl group. A is a hydroxyalkylene having 2 to 3 carbon atoms or an alkylene having 2 to 3 carbon atoms, R ₄ is a side chain of various amino acids constituting the peptide, and n is 1 to 50). A skin cosmetic comprising a quaternary ammonium-derived peptide.