JP2011084489A - Cosmetic - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cosmetic that imparts excellent moist feeling, smoothness and good combing property to the hair, imparts smoothness and moist feeling free from greasiness to the skin and is excellent in shelf stability without undergoing clouding or phase separation, even when used together with an active ingredient rich in ionic groups. <P>SOLUTION: The cosmetic contains a glyceryl derivative of a protein hydrolysate wherein glyceryl groups are bound to a portion of amino groups containing amino groups on amino acid side chains and a portion of carboxy groups containing carboxy groups on the amino acid side chains in the protein hydrolysate. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a cosmetic comprising a protein hydrolyzate glyceryl derivative (N-glyceryl protein hydrolyzed-O-glycerin ester derivative) in which a glyceryl group is added to the amino group and carboxy group of a protein hydrolyzate. It has excellent moisturizing properties, gives skin a smooth and moist feeling, gives hair a moist feeling, smoothness and good combing properties, and has a large amount of ionic groups The present invention relates to a cosmetic that is excellent in storage stability without generating insoluble matter or phase separation even when used in combination with ingredients.

  Conventionally, protein hydrolysates (also referred to as hydrolyzed peptides or hydrolyzed proteins) obtained by hydrolyzing naturally-derived proteins and derivatives thereof have been widely used in hair cosmetics and skin cosmetics. This is because the protein hydrolyzate and its derivatives are compatible with the skin and hair, and since they are derived from natural proteins, they are less irritating to the hair and skin, are highly safe, and are excellent in biodegradability. . In particular, protein hydrolyzate has good sorption to hair, prevents hair damage, recovers damaged hair, and smoothes hair to improve combability, so It is widely used to be included in the material. In skin cosmetics, amino acids are sometimes referred to as NMF (natural moisturizing factor) components of the skin, and protein hydrolysates are added as components that impart moisture retention and gloss.

  Polyhydric alcohols such as glycerin and 1,3-butylene glycol are generally used as moisturizing ingredients in cosmetics, but polyhydric alcohols have no sorption property on hair and skin, The effect cannot be fully exhibited. Therefore, an N-glyceryl derivative of an amino acid in which a glyceryl group is added to the amino group of the amino acid is also used (Patent Document 1). However, amino acids have a weak sorbing ability on hair and skin, and the effect of imparting moisture retention is not fully satisfactory. Therefore, the present inventors have proposed an N-glyceryl derivative of a protein hydrolyzate in which a glyceryl group is introduced into the amino group of the protein hydrolyzate (Patent Document 2).

  Conventionally, animal-derived proteins such as collagen and keratin have been mainly used as protein sources of protein hydrolysates. Recently, however, plant-derived proteins are often used due to the occurrence of propagating bovine spongiform encephalopathy and the trend of animal welfare.

  Plant-derived proteins contain many acidic amino acids and amino acids having hydroxyl groups as constituent amino acids, and hydrolysates of plant proteins, which are hydrolysates thereof, contain many acidic amino acids and amino acids having hydroxyl groups as constituent amino acids. It is said to be excellent in feeling and moist feeling. However, since the hydrolyzate of plant-derived protein contains a lot of acidic amino acids, the sorption power to hair and skin, which is weakly acidic, is inferior to animal protein hydrolysates such as collagen and keratin, and a small amount is incorporated. Then, there was a problem that the effect was difficult to be demonstrated. In addition, O / W emulsified cosmetics that contain a large amount of cationic substances such as hair rinses and hair treatment products may cause phase separation during storage or may contain cationic substances if they are combined with protein hydrolysates that contain a large amount of acidic amino acids. There is a possibility that an insoluble matter may be formed in association with the amount of the protein, and there is a problem that it is impossible to add an amount sufficient to exert the effect of the protein hydrolyzate.

Japanese Patent Laid-Open No. 2004-083552 JP 2009-120523 A

  Therefore, the present invention solves the above-mentioned problems and imparts an excellent moisturizing feeling (moisturizing feeling) and smoothness to the hair and skin. In particular, when applied to hair, the present invention improves the combing property of the hair. And it aims at providing the cosmetics which can finish hair in a supple touch and are excellent in the storage stability which can be used together with a large amount of ionic substances.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a part of the amino group including the amino group of the amino acid side chain and the carboxy group including the carboxy group of the amino acid side chain of the protein hydrolyzate. In part, the following formula (I)

In the cosmetics containing a glyceryl derivative of a protein hydrolyzate formed by bonding a glyceryl group represented by the formula, it gives an excellent moisturizing feeling and smoothness to the hair and skin, especially when applied to the hair. It is possible to improve the passability and finish the hair with a supple feel, making it a hair cosmetic with excellent ease of uniting (hair-styling) and excellent storage stability even for cosmetics rich in ionic substances. As a result, the present invention has been completed.

  That is, in the present invention, the glyceryl group represented by the above formula (I) is added to a part of the amino group including the amino group of the amino acid side chain of the protein hydrolyzate and a part of the carboxy group including the carboxy group of the amino acid side chain. A cosmetic comprising a bound protein hydrolyzate glyceryl derivative (claim 1).

  The protein hydrolyzate glyceryl derivative contained in the cosmetic of the present invention has a glyceryl group bonded to a part of the carboxy group and part of the amino group of the protein hydrolyzate, and the ionicity of the protein hydrolyzate is weakened. Because it has a strong moisturizing effect derived from the functional group (glyceryl group) represented by the formula (I), when it is added to a hair cosmetic, it has a good moisturizing feeling and smoothness. It is possible to improve the combing property of the hair. Moreover, when it mix | blends with skin cosmetics, a moist feeling is provided to skin.

〔式中、Ａは水素原子または上記式（Ｉ）で示されるグリセリル基を表すが、Ａの一部は上記式（Ｉ）で示されるグリセリル基であり、Ｂは水素原子、上記式（Ｉ）で示されるグリセリル基またはアルカリ金属、アルカリ土類金属あるいはマグネシウムを表すが、Ｂの一部は上記式（Ｉ）で示されるグリセリル基である。Ｒ^１は側鎖の末端にアミノ基を有する塩基性アミノ酸の側鎖のアミノ基を除く残基を表し、Ｒ^２は側鎖の末端にカルボキシ基を有する酸性アミノ酸の末端カルボキシ基を除く残基を表し、Ｒ^３は中性アミノ酸の側鎖を表す。ａ、ｂおよびｃは、タンパク質加水分解物１分子内の塩基性アミノ酸単位の数、酸性アミノ酸単位の数および中性アミノ酸単位の数を示し、ａは０〜１００、ｂは０〜１００、ｃは０〜１００で、ａ＋ｂ＋ｃは２〜２００を表す（但し、ａ、ｂおよびｃはアミノ酸の数を示すのみで、配列の順序を示すものではない）〕で表されるものである請求項１に記載の化粧料である。 In the invention of claim 2, the protein hydrolyzate glyceryl derivative is represented by the following general formula (II):

[Wherein, A represents a hydrogen atom or a glyceryl group represented by the above formula (I), part of A is a glyceryl group represented by the above formula (I), B represents a hydrogen atom, and the above formula (I ) Represents a glyceryl group or an alkali metal, an alkaline earth metal or magnesium, and a part of B is a glyceryl group represented by the above formula (I). R ¹ represents a residue excluding the amino group of the side chain of a basic amino acid having an amino group at the end of the side chain, and R ² is a residue excluding the terminal carboxy group of an acidic amino acid having a carboxy group at the end of the side chain R ³ represents a side chain of a neutral amino acid. a, b and c represent the number of basic amino acid units, the number of acidic amino acid units and the number of neutral amino acid units in one molecule of the protein hydrolyzate, where a is 0 to 100, b is 0 to 100, c 0 to 100, a + b + c represents 2 to 200 (provided that a, b and c only indicate the number of amino acids, not the sequence order)] It is a cosmetic described in 1.

  In addition, although the name of the glyceryl derivative of the protein hydrolyzate represented by the general formula (II) is specifically an N-glyceryl protein hydrolyzate-O-glycerin ester derivative, in this specification, It is referred to as a protein hydrolyzate glyceryl derivative.

  Here, the protein hydrolyzate can be obtained by partially hydrolyzing a protein with an acid, an alkali, an enzyme, or a combination thereof. Therefore, it is composed of an amino acid or a peptide in which a plurality of amino acid units are bonded, and has an amino group and a carboxy group at its terminal. The amino acid unit constituting the protein hydrolyzate can include a neutral amino acid unit, a basic amino acid unit having an amino group in the side chain, and an acidic amino acid unit having a carboxy group in the side chain. That is, when a basic amino acid unit and / or an acidic amino acid unit is contained, the protein hydrolyzate has an amino group and / or carboxy group in the side chain in addition to the amino group and carboxy group at the terminal. .

This protein hydrolyzate can be represented by the following general formula (III).

In the formula, R ¹ represents a residue other than the terminal amino group of the side chain of the basic amino acid unit, R ² represents a residue other than the terminal carboxy group of the side chain of the acidic amino acid unit, and R ³ represents a neutral amino acid. The side chain of a unit is represented, and a, b, and b respectively show the number of basic amino acid units, the number of acidic amino acid units, and the number of neutral amino acid units in one protein hydrolyzate molecule. Therefore, a + b + c represents the number of amino acid units in one molecule of protein hydrolyzate, that is, the degree of amino acid polymerization. In addition, a, b, and c show only the number of amino acid units, and do not show the order of amino acid sequences.

  The values of a, b and c are theoretically 0 or a positive integer, but in practice, protein hydrolysates are actually expressed as they are a mixture of amino acids or molecules with different degrees of amino acid polymerization. The value is an average value, and is not necessarily 0 or a positive integer. Since the protein hydrolyzate contains at least one or more amino acid units, a + b + c is greater than 1.

  In the invention of claim 3, the glyceryl derivative of the protein hydrolyzate has a glyceryl group represented by the formula (I) bonded to 50% or more of all carboxy groups and all amino groups of the protein hydrolyzate portion. The cosmetic according to claim 1 or 2, wherein

  The ratio of the carboxy group and amino group glycerylated by the glyceryl group represented by the formula (I) decreases the ionicity of the protein hydrolyzate, improves the storage stability, and maintains the moisture retention property on the hair and skin. In order to exert the imparting effect, 50% or more of each of all carboxy groups and all amino groups is preferable.

  In the protein hydrolyzate constituting the protein hydrolyzate glyceryl derivative, when the amino acid unit constituting the protein hydrolyzate contains an acidic amino acid unit, derivatization is performed with the glyceryl group represented by the formula (I). The carboxy group includes not only the carboxy group at the end of the main chain but also the carboxy group at the end of the side chain of the acidic amino acid unit. The term “total carboxy group” means that this side chain carboxy group is also included. In addition, the calculation method of all the carboxy groups is mentioned later.

  Similarly, in the protein hydrolyzate constituting the protein hydrolyzate glyceryl derivative, when the amino acid unit constituting the protein hydrolyzate contains a basic amino acid unit, the glyceryl group represented by the formula (I) The amino group to be derivatized includes not only the amino group at the end of the main chain but also the amino group at the end of the side chain of the basic amino acid unit. The term “total amino group” means that this side chain amino group is also included. Further, the amount of all amino groups is specifically a value obtained from the amount of amino nitrogen.

  Invention of Claim 4 is cosmetics in any one of Claim 1 thru | or 3 whose amino acid polymerization degree of the said protein hydrolyzate is 3-30. The degree of amino acid polymerization of the protein hydrolyzate constituting the protein hydrolyzate glyceryl derivative is preferably 2 to 50, preferably 3 to 30 from the viewpoint of sorption to hair and skin and stability when blended in cosmetics. More preferred.

  As described above, the degree of amino acid polymerization is the number of amino acid units contained in one molecule of the protein hydrolyzate, and is represented by a, b and c in general formula (II) [and general formula (III)]. It corresponds to the sum, that is, a + b + c. Although the degree of amino acid polymerization is theoretically an integer, in practice, protein hydrolyzate is a mixture of molecules having different degrees of amino acid polymerization, so the actual degree of amino acid polymerization expressed is the number average value. , Not necessarily an integer.

  Invention of Claim 5 is cosmetics in any one of Claim 1 thru | or 4 whose protein hydrolyzate part of the said protein hydrolyzate glyceryl derivative is plant protein hydrolyzate. Since plant proteins contain a lot of acidic amino acids, they are highly anionic and not only weakly absorbed by weakly acidic hair and skin, but also associate with cationic substances in cosmetics to remove insoluble materials. The emulsion cosmetic tends to cause phase separation and deteriorate storage stability. Therefore, by reducing the acidity by converting the protein hydrolyzate to a glyceryl derivative, the sorption property to the hair and skin is improved, giving the hair and skin an excellent moisture feeling and smoothness, and combing properties of the hair. The effect which improves is come to be exhibited more. Further, by glycerylating the ionic group in the protein hydrolyzate, even if it is blended in a cosmetic containing a large amount of an ionic substance, the stability of the cosmetic is not impaired.

  Invention of Claim 6 is cosmetics in any one of Claim 1 thru | or 5 whose content of a protein hydrolyzate glyceryl derivative is 0.05-30 mass%. The preferred range of the content of the protein hydrolyzate glyceryl derivative in cosmetics varies depending on the type of cosmetics, the mode of use, the type of protein in the protein hydrolysate and the molecular weight, etc., but it is excellent for hair and skin. In order to impart a smoothness or moist feeling, it is usually preferably 0.05 to 30% by mass, more preferably 0.1 to 25% by mass with respect to the total weight of the cosmetic.

  When the content of the protein hydrolyzate glyceryl derivative is not more than the above range, there is a possibility that the hair and skin have an excellent smoothness and moisturizing effect, and the effect of improving the combing property of the hair may not be exhibited. When the content of the degradation product glyceryl derivative is not less than the above range, not only the improvement of the effect commensurate with the blending amount is not observed, but also there is a possibility of giving the hair and skin a sticky feeling.

  Examples of the cosmetics of the present invention include hair setting agents, hair styling agents, permanent wave agents, shampoos, hair rinses, hair conditioners, hair dyes, hair dyes, hair nourishing agents, etc., moisture creams, hand creams, emollient creams, etc. Skin cosmetics such as creams, lotions, emulsions, face wash, body shampoos, various soaps, makeup products, sunscreen products.

  The cosmetic of the present invention is excellent in the effect of imparting an excellent moisturizing feeling (moisturizing feeling), smoothness and good combing property to the hair, and has a smooth, moist feeling without stickiness on the skin. (Moisturizing feeling) is imparted, and even when used in combination with an active ingredient containing a large amount of ionic groups, it does not cause turbidity or phase separation and is excellent in storage stability.

  The protein hydrolyzate glyceryl derivative represented by the above general formula (II) contained in the cosmetic of the present invention includes a carboxy terminus of the protein hydrolyzate and a carboxy group of an acidic amino acid side chain, and an amino terminus and a basic amino acid. The glyceryl group represented by the above formula (I) is bonded to the side chain amino group. Hereinafter, the protein hydrolyzate, the protein hydrolyzate glyceryl derivative production method, and the cosmetics containing the same explain in detail.

[Protein hydrolyzate]
The protein hydrolyzate constituting the glyceryl derivative of the protein hydrolyzate to be contained in the cosmetic of the present invention is obtained by subjecting a protein source (naturally-derived protein, etc.) to a part by a known method by acid, alkali, enzyme, or a combination thereof. Obtained by hydrolysis.

  The protein source of protein hydrolyzate is derived from animals such as collagen (including gelatin, which is a modified product thereof), keratin, fibroin, sericin, casein, conchiolin, elastin, chicken, egg yolk protein, egg white protein, etc. , Soy, peas, wheat, rice (rice bran), sesame, corn, potato proteins, seaweeds such as Amanori, Kombu, Spirulina, Saccharomyces, Candida, Endomycopsis Examples include yeast proteins, yeast proteins isolated from yeasts so-called beer yeasts and sake yeasts, mushrooms (basidiomycetes) and microorganisms isolated from chlorella.

  Among these protein sources, plant-derived proteins contain a lot of acidic amino acids, so the protein hydrolyzate also has a problem that it is difficult to sorb to weakly acidic hair and skin due to repulsion between carboxy groups, It was difficult to fully exhibit the properties of plant protein hydrolyzate in hair and skin cosmetics. However, glycerin ester derivatization at the carboxy terminus reduces acidity and improves sorption to hair and skin. At the same time, even when formulated into cosmetics containing cationic substances, the stability of the cosmetics is improved. Since there is no damage, the effect of derivatizing the protein hydrolyzate glycerin ester is particularly remarkable when the protein hydrolyzate is a plant-derived protein hydrolyzate.

  The range of the degree of amino acid polymerization of the protein hydrolyzate portion, that is, the range of a + b + c in the above general formula (III) [and general formula (II)] is the type of cosmetic to be blended. However, it is usually selected from the range of 2 or more and 200 or less from the viewpoint of the stability of the cosmetic when blended into the cosmetic. Furthermore, 3-30 are preferable from the surface of the sorption property and permeability to hair and skin.

  When the amino acid polymerization degree (a + b + c) of the protein hydrolyzate exceeds the upper limit of the above range, the sorption property of the protein hydrolyzate glycerin derivative composed of this protein hydrolyzate to the hair or skin is within the above range. It is not preferable because it tends to decrease compared to the above. Furthermore, it tends to agglomerate during storage, resulting in poor cosmetic stability. Further, when applied to the skin or hair, there is a risk of a feeling of tension.

  On the other hand, even when the amino acid polymerization degree (a + b + c) of the protein hydrolyzate is less than 2, the sorption action on the hair may be reduced, and the effect may not be fully exhibited. The amino acid polymerization degree (a + b + c) of the protein hydrolyzate can be easily adjusted by adjusting the conditions for partial hydrolysis of the protein source, for example, the concentration of acid, alkali, enzyme, etc. in the reaction system, reaction temperature, and reaction time. Can be adjusted.

  The ratio of basic amino acid units having an amino group at the end of the side chain, acidic amino acid units having a carboxy group at the end of the side chain, and other amino acid units in the amino acid units constituting the protein hydrolyzate is usually It almost depends on the protein (protein source) that is the raw material of the protein hydrolyzate. The presence of basic amino acid units, acidic amino acid units, and other amino acid units affects the properties of protein hydrolyzate glyceryl derivatives. Although it is difficult to define an optimal numerical range, the higher the ratio of basic amino acid units and acidic amino acid units, the more glyceryl groups that bind to the peptide, and thus the moisture retention improves.

  In addition, although said a, b, c, and a + b + c are integers theoretically, since a protein hydrolyzate is obtained as a mixture of things from which molecular weight differs, a measured value becomes an average value. In addition, basic amino acid units are close to 70 mol% in some animal proteins, but generally more than 40 mol% is rare, and acidic amino acid units are contained in large amounts in plant-derived proteins. However, it is rare that it exceeds 50 mol%. Therefore, as a protein source of the protein hydrolyzate, in general, when a + b + c is in the range of 3-50, a is 0-30, b is 0-30, and c is in the range of 0-40. .

[Glyceryl derivatization of protein hydrolyzate]
The protein hydrolyzate glycerin derivative to be contained in the cosmetic of the present invention is obtained by introducing a glyceryl group into the amino group and carboxy group of the protein hydrolyzate. First, a glyceryl group is added to the amino group of the protein hydrolyzate. Is converted to an N-glyceryl protein hydrolyzate, and then the carboxy group is glycerylated.

  As a method for introducing a glyceryl group into an amino group of a protein hydrolyzate, for example, a method described in JP-A-2005-306799 can be employed. That is, the following general formula (III)

〔式中、Ｒ^１は塩基性アミノ酸単位の側鎖の末端アミノ基を除く残基を示し、Ｒ^２は酸性アミノ酸単位の側鎖の末端カルボキシ基を除く残基を示し、Ｒ^３は中性アミノ酸単位の側鎖を示す。ａは０〜１００、ｂは０〜１００、ｃは０〜１００で、ａ＋ｂ＋ｃは２〜２００を表す（但し、ａ、ｂおよびｃはアミノ酸の数を示すのみで、配列の順序を示すものではない）〕で表されるタンパク質加水分解物と、例えば、式（ＩＶ）

[Wherein R ¹ represents a residue other than the terminal amino group of the side chain of the basic amino acid unit, R ² represents a residue other than the terminal carboxy group of the side chain of the acidic amino acid unit, and R ³ represents neutrality. The side chain of an amino acid unit is shown. a is 0 to 100, b is 0 to 100, c is 0 to 100, and a + b + c represents 2 to 200 (provided that a, b, and c only indicate the number of amino acids and do not indicate the sequence order) A protein hydrolyzate represented by formula (IV)

で表されるグリシドール（２，３−エポキシ−１−プロパノール）、あるいは、式（Ｖ)

Or glycidol (2,3-epoxy-1-propanol) represented by formula (V)

（式中、Ｍはハロゲン原子を表す）
で表される３−ハロ−１，２−プロパンジオールなどを反応させる。

(Wherein M represents a halogen atom)
And a 3-halo-1,2-propanediol represented by

  Specifically, glycidol or 3-halo-1,2-propanediol is dropped into a 10 to 50% by mass aqueous solution of the protein hydrolyzate with stirring, and both are brought into contact with each other. The dropping time of glycidol or 3-halo-1,2-propanediol varies depending on the amount and molecular weight of the protein hydrolyzate and the introduction rate of glyceryl group, but is preferably about 30 minutes to 5 hours. After completion of the dropwise addition of 1,2-propanediol, stirring is preferably continued for about 1 to 5 hours to complete the reaction.

  Since the reaction proceeds on the basic side, the aqueous protein hydrolyzate solution needs to be adjusted to pH 8 to 11, particularly pH 9 to 10, by adding an alkaline solution such as an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution. In addition, when 3-halo-1,2-propanediol is used for the reaction, the pH of the reaction solution decreases with the progress of the reaction. -10 should be maintained.

  As the reaction temperature increases, the reaction rate increases. However, if the temperature increases at a high pH, the protein hydrolyzate may be further decomposed or a colored substance may be produced. When using the glycidol, the glycidol may be polymerized before the epoxy ring rapidly opens and reacts with the amino group of the protein hydrolyzate. Therefore, the reaction is preferably performed at 100 ° C. or less, more preferably 50 to 70 ° C.

  The progress and completion of the reaction can be confirmed by measuring the amount of amino nitrogen of the protein hydrolyzate during or after the reaction, such as by the van Slyke method.

  The rate of introduction of the glyceryl group into the amino group of the protein hydrolyzate varies depending on the molecular weight of the protein hydrolyzate and the intended use of the protein hydrolyzate glyceryl derivative. That is, when a glyceryl group is added to a protein hydrolyzate having a low molecular weight or a protein hydrolyzate containing a large amount of basic amino acids at a high introduction rate, the resulting glyceryl derivative of the protein hydrolyzate has a high moisturizing effect and in an aqueous solution. The stability of the is further increased. Therefore, in order to expect a moisturizing effect or to be formulated in a prescription containing a large amount of anionic substances, it is preferable that glyceryl groups are introduced into 50% or more of all amino groups of the protein hydrolyzate. .

  In order to introduce a glyceryl group to 50% or more of the total amino groups, although it depends on the amino acid polymerization degree of the protein hydrolyzate and the type of protein, the molar ratio is usually based on the total amino groups of the protein hydrolyzate. 0.7 to 2.0 equivalents of glycidol and 3-halo-1,2-propanediol are used. However, some protein hydrolysates are difficult to react due to steric hindrance or the like, and a larger amount of glycidol or 3-halo-1,2-propanediol may need to be used.

  The product obtained by reacting the protein hydrolyzate with 3-halo-1,2-propanediol is one in which the glyceryl group represented by the above formula (I) is bonded to the amino group of the protein hydrolyzate. When glycidol is used for the reaction, a glyceryl group represented by the above formula (I) is bonded as a main component, and as a side reaction product, the following formula (VI)

で表されるグリセリル基が、タンパク質加水分解物のアミノ基に結合した化合物も生成する可能性がある。この式（ＶＩ）で表されるグリセリル基が付加したタンパク質加水分解物グリセリル誘導体も、本発明のタンパク質加水分解物グリセリル誘導体に含まれる。

There is also a possibility that a compound in which the glyceryl group represented by the above formula is bonded to the amino group of the protein hydrolyzate is also produced. The protein hydrolyzate glyceryl derivative to which the glyceryl group represented by the formula (VI) is added is also included in the protein hydrolyzate glyceryl derivative of the present invention.

  Next, a glyceryl group is introduced into the carboxy group of the N-glyceryl protein hydrolyzate obtained as described above, but the reaction is carried out using an aqueous solution of the N-glyceryl protein hydrolyzate at pH 1 to 5 using an acid agent. In this case, preferably, the pH is adjusted to 2 to 4.5, and the glycidol of the above formula (IV) is dropped and reacted with stirring to obtain an O-glycerin ester derivative of N-glyceryl protein hydrolyzate.

  Examples of the acid agent that adjusts the aqueous solution of N-glyceryl protein hydrolyzate to acid include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid. However, when hydrochloric acid is used as the acid agent, harmful chlorohydrin is generated as a by-product, so that a removal operation is required after the reaction, and the production becomes complicated. Therefore, it is preferable to use sulfuric acid or phosphoric acid as the acid agent.

  When the pH during the glycerin esterification reaction is less than the above range or exceeds the above range, the reactivity is extremely lowered. In particular, when the pH is on the basic side, the glycerin ester may be cleaved, and management of the pH during the reaction is important.

  The reaction temperature is preferably in the range of room temperature to 80 ° C, more preferably 40 to 70 ° C. That is, when the reaction temperature is lower than the above range, the reaction rate becomes slow, and even when the reaction temperature is 80 ° C. or higher, no increase in the reaction rate is observed, and the protein hydrolyzate causes coloration or odor and quality. May decrease.

  Although the glycidol dripping time during the reaction varies depending on the amount of glycidol and the reaction temperature, it is generally 30 minutes to 3 hours. After completion of the dripping, the temperature is 1 to 5 while heating to 40 to 80 ° C. to complete the reaction. It is preferable to continue stirring for about an hour.

  As described above, the ratio of the esterified product in all the carboxyl groups of the protein hydrolyzate, that is, the esterification rate, is preferably 50% or more. Although it varies depending on the type and molecular weight of the protein hydrolyzate, the effect of glycerin esterification may not be sufficiently exhibited if the esterification rate is less than 50%. It is preferable to adjust the reaction ratio.

  The esterification rate can be adjusted by the reaction ratio of glycidol to the total carboxy group. The reaction ratio necessary for setting the esterification rate to 50% or more is usually a molar ratio of the carboxyl group of the protein hydrolyzate: glycidol = 1: 0.7 to 1: 3. Depending on the type and molecular weight of the product, the reactivity may be lowered due to steric hindrance or the like, and the glycidol reaction ratio may need to be further increased. In addition, the number of moles of the carboxy group of the protein hydrolyzate can be obtained from the measurement of the amount of amino nitrogen by the Van Slick method and the proportion of acidic amino acids in the protein hydrolyzate by amino acid analysis. The progress and termination of the esterification reaction can be confirmed by determining the esterification rate according to the ester value measurement method described later.

  After completion of the reaction, the reaction solution is neutralized, concentrated as appropriate, purified by ion exchange resin, dialysis membrane, electrodialysis, gel filtration, ultrafiltration, etc., adjusted to a pH suitable for various cosmetics and hair cosmetics Or in skin cosmetics. Further, the pH-adjusted solution can be pulverized by spray drying or the like and blended into the cosmetic as a solid component. However, in the method for producing a glyceryl derivative of the protein hydrolyzate of the present invention, the by-product when glycidol is used for glycerylation is glycerin, and since glycerin is a component that is widely blended in cosmetics, It can be blended into hair cosmetics and skin cosmetics only by adjusting the concentration and pH without any particular purification.

  The glycerylation of the amino group and carboxy group of the protein hydrolyzate is contrary to the above description. First, a glyceryl group is introduced into the carboxy group of the protein hydrolyzate under acidic conditions, and then the glycerin ester of the protein hydrolyzate. It is also possible to obtain a glycerin ester derivative of N-glyceryl protein hydrolyzate by introducing a glyceryl group into the amino group by making the pH basic and then introducing glycerin group into the amino group. When the pH of the ester derivative solution is made basic, the ester bond is cleaved, and there is a high possibility of becoming a glyceryl derivative of a protein hydrolyzate having a low introduction rate of glyceryl groups into carboxy groups. Therefore, the order of glycerylation is preferably such that the glyceryl group is first introduced into the amino group and then the glyceryl group is introduced into the carboxy group as described above.

[Cosmetics]
Examples of the cosmetic of the present invention include shampoo, hair rinse, hair conditioner, split hair coat, hair cream, first and second agents for permanent wave, set lotion, hair dye, hair dye, liquid hair conditioner, nutrition Hair cosmetics such as hair and hair restorer, lotion, cleansing cream, emollient cream, hand cream, after shave lotion, shaving foam, face wash, face wash, body shampoo, various soaps, hair remover, face pack, milky lotion, makeup Skin cosmetics such as products and sunscreen products.

  And although the quantity of the protein hydrolyzate glyceryl derivative contained in the cosmetics of this invention changes also with the kind and intended purpose of cosmetics, it is generally 0.05-30 mass% in cosmetics, Preferably it is 0.1-25 mass It is good to be about%. That is, when the content in the cosmetic is less than the above range, the effect of imparting a moisturizing feeling to the hair and skin, the imparting a moist feeling and smoothness to the hair, or the comb of the hair There is a possibility that the effect of improving the passability and finishing the hair with a supple feel will not be sufficiently exhibited. On the other hand, even if the blending amount exceeds the above range, the effect corresponding to that is not improved, but rather the protein hydrolyzate glyceryl derivative sorbs excessively on the hair and skin, causing stickiness or ionic groups. When used in combination with an active ingredient, turbidity or phase separation may occur.

  The cosmetic of the present invention is constituted by containing the protein hydrolyzate glyceryl derivative represented by the above general formula (I) as an essential component, but as a component that can be combined with the protein hydrolyzate glyceryl derivative. Are, for example, anionic surfactants, nonionic surfactants, amphoteric surfactants, cationic surfactants, cationic polymers, amphoteric polymers, synthetic polymers such as anionic polymers, semi-synthetic polymers, animal and vegetable oils, Oils such as hydrocarbons, ester oils, higher alcohols, silicone oils, natural polysaccharides, humectants, lower alcohols, amino acids, thickeners, animal and plant extracts, silicones, preservatives, fragrances, animal and plant origin and Hydrolyzed proteins obtained by hydrolyzing microorganism-derived proteins and their quaternary ammonium derivatives, acylation induction And its salts, such as silylated derivatives, can also be added as appropriate other components within a range not to impair the characteristics of the cosmetic base material of the present invention in addition to those.

  EXAMPLES Next, although an Example is given and this invention is demonstrated concretely, this invention is not limited only to those Examples. In addition, prior to the examples, production examples of the protein hydrolyzate glyceryl derivatives used in the examples are shown. First, a method for measuring the amount of nitrogen used in the production examples, a method for calculating the number of moles of carboxy groups, And a method for measuring the esterification rate.

[Measurement method of nitrogen content and number of moles of amino group]
The amount of amino nitrogen in the examples was measured by the Van Slick method, and the number of moles of amino groups was calculated based on the numerical value. Further, the total nitrogen amount in the examples was measured by an improved Dumas method.

[Calculation method for the number of moles of carboxy group]
It is assumed that the number of moles of the terminal carboxy group is the same as the number of moles obtained from the amount of amino nitrogen obtained by the Van Slick method, and the number of moles of acidic amino acid obtained from amino acid analysis is the amino acid side of the protein hydrolyzate. The number of moles of carboxy groups in the chain was taken as the sum of the number of moles of these terminal carboxy groups and the number of moles of carboxy groups in the amino acid side chain as the number of moles of all carboxy groups in the protein hydrolyzate.

[Measurement method of esterification rate]
1) First, in accordance with the ester value measurement method described in the commentary on the cosmetic raw material standard 2nd edition, the mg number (= ester value) of potassium hydroxide required to saponify (saponify) the ester in 1 g of the sample is calculated. . Specifically, 2 to 3 g of a sample is precisely weighed, put into a 200 ml flask, added with a few drops of 10 ml of ethanol and 1% phenolphthalein ethanol solution, and neutralized with a 0.1 mol / l aqueous potassium hydroxide solution. Next, 25 ml of 0.5 mol / l potassium hydroxide ethanol solution (a solution in which 35 g of potassium hydroxide was dissolved in 20 ml of water and ethanol was added to make 1000 ml) was accurately added, and the mixture was refluxed for 1 hour on a water bath. Boil gently. After boiling, the mixture is cooled, and an excessive amount of potassium hydroxide is titrated with a 0.5 mol / l hydrochloric acid aqueous solution. The consumption (ml) of the 0.5 mol / l hydrochloric acid aqueous solution at this time is defined as p.

  Except not using a sample (blank test), the consumption amount of 0.5 mol / l hydrochloric acid aqueous solution is calculated | required, and this consumption amount (ml) is set to q. The ester value is calculated from p and q thus obtained and the following formula. In the following formula, 28.053 is the number of milligrams of potassium hydroxide necessary for neutralizing 1 ml of 0.5 mol / l hydrochloric acid aqueous solution.

2) Next, by dividing the ester value obtained above by the molecular weight of potassium hydroxide, the number of moles r of potassium hydroxide required to saponify the ester in 1 g of the sample was calculated. The esterification rate is calculated from the number of moles s of carboxy groups contained in 1 g. That is, the esterification rate is obtained from the following formula.

  Esterification rate (%) = (r / s) × 100

  In addition, each protein hydrolyzate used by the manufacture example is what hydrolyzed each protein source by the well-known method using the acid, the alkali, or the enzyme (in combination with them depending on the case). Further, the degree of amino acid polymerization [a + b + c in the general formula (I)] was calculated from the ratio of the total nitrogen amount and the amino nitrogen amount. Moreover, a: b: c was calculated | required by the amino acid analysis using the Hitachi amino acid automatic analyzer, and each value of a, b, and c was calculated | required from the amino acid polymerization degree.

Production Example 1: Soy protein hydrolyzate glyceryl derivative [N-glycerylation reaction]
Hydrolyzate of soybean protein [a (basic amino acid) in general formula (III) is 0.4, b (acidic amino acid) is 1.2, c (neutral amino acid) is 2.4, a + b + c is 4] (The number of moles of amino groups in this sample is 0.26 moles, the number of moles of carboxy groups is 0.48 moles. The value obtained by the method for calculating the number of moles is the same in the following production examples), and 20% aqueous sodium hydroxide solution was added to adjust the pH to 9. While this solution was stirred at 55 ° C., 19.2 g of glycidol (1 equivalent to the amino group of soybean protein hydrolyzate) was dropped into the solution over about 30 minutes to cause a reaction. After completion of the dropwise addition, the liquid temperature was raised to 60 ° C., and stirring was continued for 3.5 hours to complete the reaction. The N-glycerylation rate determined from the amount of amino nitrogen was 70%.

[O-glycerin esterification reaction]
Dilute sulfuric acid was added to the aqueous solution of N-glyceryl soy protein hydrolyzate obtained above to adjust the pH to 4.5. While stirring this solution at 55 ° C., 35.5 g of glycidol (1 equivalent to the carboxyl group of the soy protein hydrolyzate) was added dropwise over 1 hour. After completion of the dropwise addition, the liquid temperature was raised to 60 ° C., and stirring was further continued for 3 hours to complete the reaction. After the esterification reaction is completed, the reaction solution is neutralized with a 20% aqueous sodium hydroxide solution, placed in a dialysis tube with a molecular weight cut off of 3500, and dialyzed overnight against water to produce glycerin as a by-product and the resulting salts. Was removed. After the dialysis treatment, the solution was concentrated and the pH was adjusted to 6.0 to obtain 302 g of a 30% aqueous solution of a glycerin ester derivative of N-glyceryl soybean protein hydrolyzate. When the esterification rate of the glycerin ester was determined by the method for measuring the esterification rate, it was 74%.

Production Example 2: Production of glycerin ester of wheat protein hydrolyzate [N-glycerylation reaction]
250 g of 40% aqueous solution of wheat protein hydrolyzate [a in general formula (III): 0.3, b: 3.2, c: 3.0, a + b + c = 7] (moles of amino groups in this sample) The number was 0.13 mol, and the number of carboxy groups was 0.86 mol). While this solution was stirred at 55 ° C., 9.6 g of glycidol (1 equivalent with respect to the amino group of the wheat protein hydrolyzate) was added dropwise thereto over about 30 minutes to cause a reaction. After completion of the dropwise addition, the liquid temperature was raised to 60 ° C., and stirring was continued for 3.5 hours to complete the reaction. The N-glycerylation rate determined from the amount of amino nitrogen was 65%.

[O-glycerin esterification reaction]
Dilute sulfuric acid was added to the aqueous solution of N-glyceryl wheat protein hydrolyzate obtained above to adjust the pH to 4.5. While this solution was stirred at 55 ° C., 63.6 g of glycidol (1 equivalent to the carboxyl group of the wheat protein hydrolyzate) was added dropwise over 1 hour. After completion of the dropwise addition, the liquid temperature was raised to 60 ° C., and stirring was further continued for 3 hours to complete the reaction. After the esterification reaction is completed, the reaction solution is neutralized with a 20% aqueous sodium hydroxide solution, placed in a dialysis tube with a molecular weight cut off of 3500, and dialyzed overnight against water to produce glycerin as a by-product and the resulting salts. Was removed. After the dialysis treatment, the solution was concentrated and the pH was adjusted to 6.0 to obtain 313 g of a 30% aqueous solution of a glycerin ester derivative of N-glyceryl wheat protein hydrolyzate. When the esterification rate of the glycerin ester derivative was determined by the above-described method for measuring the esterification rate, the esterification rate was 68%.

Production Example 3: Rice protein hydrolyzate glyceryl derivative [N-glycerylation reaction]
250 g of 40% aqueous solution of rice protein hydrolyzate [a in general formula (III) is 0.3, b is 0.9, c is 2.3, a + b + c = 3.5] (amino group in this sample) Was adjusted to pH 9 by adding a 20% aqueous sodium hydroxide solution to 0.16 mol and 0.23 mol of carboxy group. While stirring this solution at 55 ° C., 14.2 g of glycidol (1.2 equivalents relative to the amino group of the rice protein hydrolyzate) was added dropwise thereto over about 30 minutes to cause a reaction. After completion of the dropwise addition, the liquid temperature was raised to 60 ° C., and stirring was continued for 3.5 hours to complete the reaction. The N-glycerylation rate determined from the amount of amino nitrogen was 88%.

[O-glycerin esterification reaction]
Dilute sulfuric acid was added to the aqueous solution of N-glyceryl rice protein hydrolyzate obtained above to adjust the pH to 4.5. While this solution was stirred at 55 ° C., 17.0 g of glycidol (1 equivalent with respect to the carboxyl group of the rice protein hydrolyzate) was added dropwise over 1 hour. After completion of the dropwise addition, the liquid temperature was raised to 60 ° C. and stirring was further continued for 3 hours to complete the reaction. After completion of the esterification reaction, the reaction solution was adjusted to pH 6 with a 20% aqueous sodium hydroxide solution and the concentration was adjusted to obtain 300 g of a 30% aqueous solution of a glycerin ester derivative of N-glyceryl rice protein hydrolyzate. When the esterification rate of the glycerin ester derivative was calculated | required by the measuring method of the said esterification rate, the esterification rate was 64%.

Production Example 4: Glyceryl derivative of pea protein hydrolyzate [N-glycerylation reaction]
Pea protein hydrolyzate [a in general formula (III) is 0.6, b is 2.0, c is 3.2, and a + b + c = 5.8. ] Was adjusted to pH 9 by adding a 20% aqueous sodium hydroxide solution to 250 g of an aqueous solution of 40% (the number of moles of amino groups in this sample was 0.22 moles and the number of moles of carboxy groups was 0.36 moles). While this solution was stirred at 55 ° C., 16.3 g of glycidol (1 equivalent with respect to the amino group of the pea protein hydrolyzate) was added dropwise thereto over about 30 minutes to cause a reaction. After completion of the dropwise addition, the liquid temperature was raised to 60 ° C., and stirring was continued for 3.5 hours to complete the reaction. The N-glycerylation rate determined from the amount of amino nitrogen was 65%.

[O-glycerin esterification reaction]
Dilute sulfuric acid was added to the aqueous solution of the N-glyceryl pea protein hydrolyzate obtained above to adjust the pH to 4.5. While this solution was stirred at 55 ° C., 26.6 g of glycidol (1 equivalent to the carboxyl group of the pea protein hydrolyzate) was added dropwise over 1 hour. After completion of the dropwise addition, the liquid temperature was raised to 60 ° C. and stirring was further continued for 3 hours to complete the reaction. After completion of the esterification reaction, the reaction solution is neutralized with a 20% aqueous sodium hydroxide solution, desalted and purified with an electrodialyzer, the solution is concentrated, the pH is adjusted to 6.0, and N-glyceryl pea protein hydrolysate is added. 342 g of a 30% aqueous solution of the glycerin ester derivative of the decomposition product was obtained. When the esterification rate of the glycerin ester derivative was calculated | required by the measuring method of the said esterification rate, the esterification rate was 61%.

Production Example 5: Silk hydrolyzate glyceryl derivative [N-glycerylation reaction]
250 g of 40% aqueous solution of hydrolyzate of silk [a in general formula (III) is 0.1, b is 0.3, c is 10.6, a + b + c = 11] (number of moles of amino groups in this sample) Was adjusted to pH 9 by adding a 20% aqueous sodium hydroxide solution to 0.06 mol and the number of moles of carboxy groups was 0.08 mol). While stirring this solution at 55 ° C., 4.4 g of glycidol (1 equivalent with respect to the amino group of the silk hydrolyzate) was added dropwise thereto over about 30 minutes to cause a reaction. After completion of the dropwise addition, the liquid temperature was raised to 60 ° C., and stirring was continued for 3.5 hours to complete the reaction. The N-glycerylation rate determined from the amount of amino nitrogen was 71%.

[O-glycerin esterification reaction]
Dilute sulfuric acid was added to the aqueous solution of the N-glyceryl silk protein hydrolyzate obtained above to adjust the pH to 4.5. While this solution was stirred at 55 ° C., 8.9 g of glycidol (1.5 equivalent to the carboxyl group of the silk hydrolyzate) was added dropwise over 1 hour. After completion of the dropwise addition, the liquid temperature was raised to 60 ° C. and stirring was further continued for 3 hours to complete the reaction. After completion of the esterification reaction, the reaction solution was adjusted to pH 6.0 with a 20% aqueous sodium hydroxide solution, desalted and purified with an electrodialyzer, the solution was concentrated, the pH was adjusted to 6.0, N -350 g of a 30% aqueous solution of a glycerin ester derivative of glyceryl silk hydrolyzate was obtained. When the esterification rate of the glycerin ester derivative was determined by the above-described method for measuring the esterification rate, the esterification rate was 66%.

Production Example 6: Production of fish skin-derived collagen hydrolyzate glycerin ester [N-glycerylation reaction]
250 g of 40% aqueous solution of collagen derived from fish skin [a in the general formula (III) is 1.4, b is 2.3, c is 15.3, a + b + c = 19] The pH was adjusted to 9 by adding a 20% aqueous sodium hydroxide solution to 0.04 mol and 0.06 mol of carboxy group. While stirring this solution at 55 ° C., 3.3 g of glycidol (1.1 equivalents with respect to the amino group of the collagen hydrolyzate) was dropped into the solution over about 30 minutes to react. After completion of the dropwise addition, the liquid temperature was raised to 60 ° C., and stirring was continued for 3.5 hours to complete the reaction. The N-glycerylation rate determined from the amount of amino nitrogen was 79%.

[O-glycerin esterification reaction]
Dilute sulfuric acid was added to the aqueous solution of N-glyceryl collagen hydrolyzate obtained above to adjust the pH to 4.5. While stirring this solution at 55 ° C., 4.4 g of glycidol (1 equivalent to the carboxyl group of the collagen hydrolyzate) was added dropwise over 1 hour. After completion of the dropwise addition, the liquid temperature was raised to 60 ° C. and stirring was further continued for 3 hours to complete the reaction. After completion of the esterification reaction, the reaction solution was adjusted to pH 6.0 with a 20% aqueous sodium hydroxide solution to obtain 329 g of a 30% aqueous solution of a glycerin ester derivative of N-glyceryl collagen hydrolyzate. When the esterification rate of the glycerin ester derivative was calculated | required by the measuring method of the said esterification rate, the esterification rate was 62%.

Production Example 7: Production of keratin hydrolyzate glycerin ester [N-glycerylation reaction]
250 g of 40% aqueous solution of keratin hydrolyzate [a in general formula (III), b is 8, c is 15, a + b + c = 25] (the number of amino groups in this sample is 0.03 mol, carboxy The group was adjusted to pH 9 by adding a 20% aqueous sodium hydroxide solution to 0.08 mol). While stirring this solution at 55 ° C., 2.2 g of glycidol (1 equivalent with respect to the amino group of the keratin hydrolyzate) was dropped into this solution over about 30 minutes to react. After completion of the dropwise addition, the liquid temperature was raised to 60 ° C., and stirring was continued for 3.5 hours to complete the reaction. The N-glycerylation rate determined from the amount of amino nitrogen was 68%.

[O-glycerin esterification reaction]
Dilute sulfuric acid was added to the aqueous solution of N-glyceryl keratin hydrolyzate obtained above to adjust the pH to 4.5. While stirring this solution at 55 ° C., 5.9 g of glycidol (1 equivalent to the carboxyl group of the keratin hydrolyzate) was added dropwise over 1 hour. After completion of the dropwise addition, the liquid temperature was raised to 60 ° C. and stirring was further continued for 3 hours to complete the reaction. After completion of the esterification reaction, the reaction solution was adjusted to pH 6.0 with a 20% aqueous sodium hydroxide solution to obtain 305 g of a 30% aqueous solution of a glycerol ester derivative of N-glyceryl keratin hydrolyzate. When the esterification rate of the glycerol ester derivative was determined by the above-described method for measuring the esterification rate, it was 61%.

Examples 1 to 7 and Comparative Examples 1 to 7: Formulation test for O / W emulsified hair treatment W / O emulsified types having the compositions shown in Table 1 using the protein hydrolyzate glyceryl derivatives of Production Examples 1 to 7 Hair treatments were prepared as Examples 1-7. Moreover, it replaced with protein hydrolyzate glyceryl derivative, the protein hydrolyzate used as a raw material of the protein hydrolyzate glyceryl derivative of each manufacture example 1-7, and N-glyceryl protein hydrolysis in the middle of manufacture of each manufacture example 1-7 Similar W / O emulsified hair treatments using the degradation products (state before O-glycerin ester derivatization) were prepared as Comparative Example A and Comparative Example B. In Table 1, the compounding amount of the additive is expressed by mass%. However, the compounding amount of the glyceryl derivative, the protein hydrolyzate of the raw material, and the N-glyceryl protein hydrolyzate in the course of each production is shown in FIG. In order to make the blending amount of the degradation product portion the same, the mass of the protein hydrolyzate portion was adjusted to 1% in the O / W emulsified hair treatment formulation. Moreover, about the thing whose compounding quantity is not solid content, solid content concentration is shown in parenthesis after the component name.

The O / W emulsified hair treatments of Examples 1 to 7, Comparative Examples 1A to 7A and Comparative Examples 1B to 7B were stored in a thermostatic bath at 50 ° C. for 24 hours, and the appearance after storage was visually observed. It was evaluated according to the evaluation criteria. The results are shown in Table 2.
Evaluation standard for O / W type hair treatment Uniform emulsification state: ○
Uneven emulsification state: △
Two-layer separation state: ×

  As shown in Table 2, while Examples 1-7 using the protein hydrolyzate glyceryl derivatives of Production Examples 1-7 are all in an emulsified state, Comparative Examples 1A-7A, which are their raw materials, are used. When used, both were in a two-layer separated state or a non-uniform emulsified state. Moreover, in Comparative Examples 1B to 7B using those obtained by N-glycerylation of those raw materials, the emulsified state is slightly improved, but the emulsified state is improved particularly in the hydrolyzed protein derived from plant protein (No. 1B to 4B). It is understood that is insufficient. That is, it was clear that glycerylation of the amino group and carboxy group of the protein hydrolyzate makes it possible to stably exist in the O / W emulsified hair treatment formulation. In particular, the tendency was strongly expressed in protein hydrolysates derived from plant proteins with many acidic amino acids.

Example 8 and Comparative Examples 8A-8B
Three types of hair rinses having the compositions shown in Table 3 were prepared, and each hair rinse was used for hair washed with shampoo, and the moisture retention rate of the hair after use was measured. Sensory evaluation was performed on the street. In addition, the compounding quantity of each component in a table | surface is based on a mass part, and about the thing whose compounding quantity is not solid content, the solid content density | concentration is shown in the parenthesis after the component name. The same applies to Table 5, Table 7, Table 9, Table 11, Table 13, Table 15 and the like in the following examples.

  In Example 8, the soybean protein hydrolyzate glyceryl derivative produced in Production Example 1 was used. In Comparative Example 8A, the soybean protein hydrolyzate used as a raw material in Production Example 1 was used. In Comparative Example 8B, the carboxy group was changed to a glycerin ester. N-glyceryl soy protein hydrolyzate is used.

  Prior to the treatment with the hair rinse, three hair bundles having a length of 15 cm and a weight of 1.5 g are prepared, and an aqueous solution containing 3% hydrogen peroxide solution and 1% ammonia is used to make the hair damage constant. A bleaching treatment was performed by immersing at 30 ° C. for 30 minutes, and after washing with tap water, further rinsed with ion-exchanged water. The bleached hair bundle was washed with a commercially available shampoo containing no protein hydrolyzate or derivative thereof, and rinsed with hot water. The hair bundle after washing was treated with 2 g of each of the hair rinses of Example 8 and Comparative Examples 8A to 8B, rinsed with hot water, and dried with a hair dryer. After repeating this shampoo washing, hair rinse treatment, and dryer drying five times, each female bundle was blindly evaluated (blind) by 10 female panelists for moisture feeling, smoothness, and combability according to the following evaluation criteria. . The results are shown in Table 4 as an average of 10 people.

Moisture Evaluation Criteria 3: Moist 2: Moist but sticky 1: Sticky
Evaluation criteria for smoothness 3: Smoothness 2: Slightly smooth 1: No smoothness
Evaluation criteria of comb-through property 3: Comb street is very good 2: Comb street is slightly good 1: Comb street is bad

  As shown in Table 4, the hair treated with the hair rinse of Example 8 containing the glyceryl derivative of soy protein hydrolyzate was soy protein hydrolyzed in any of the evaluation items of hair moisturization, smoothness, and combability. The hair rinse of Comparative Example 8A containing the degradation product, the evaluation value is higher than the hair treated with the hair rinse of Comparative Example 8B containing the N-glyceryl soy protein hydrolyzate, and the soy protein hydrolyzate glyceryl derivative is moisturized to the hair, It was clear that the effect of imparting smoothness and good combing properties was high.

Example 9 and Comparative Examples 9A-9B
Three types of hair set lotions having the composition shown in Table 5 were prepared, and each hair set lotion was used for the washed hair bundle to give a moist feeling, smoothness and ease of hair uniting after treatment (hair styling properties). ) Was subjected to sensory evaluation.

  In Example 9, the wheat protein hydrolyzate glyceryl derivative produced in Production Example 2 was used, in Comparative Example 9A, the wheat protein hydrolyzate used as a raw material in Production Example 2 was used, and in Comparative Example 9B, a moisturizer was generally used for cosmetics. The glycerin used as is used. In addition, content of glycerin is an amount almost equivalent to the glyceryl group part of a wheat protein hydrolyzate glyceryl derivative.

  Prior to the treatment with the above hair set lotion, three hair bundles of 30 cm in length and 2.5 g in weight are prepared, and these hair bundles are washed with 2% aqueous solution of polyoxyethylene (3) sodium lauryl ether sulfate. Rinse in running water and air dry at room temperature. The hair bundle was wound around a curling rod having a diameter of 25 mm, and 2 g each of the hair set lotions of Example 9 and Comparative Examples 9A to 9B were applied to the hair bundle wound around the rod and dried with a hair dryer. After drying, the hair bundle is removed from the rod, and the moisturizing and smoothness of the hair is evaluated by the same evaluation criteria as in Example 8, and the ease with which the hair is organized is evaluated by 10 female panelists according to the following evaluation criteria. It was. The results are shown in Table 6 as an average of 10 people.

Evaluation criteria for ease of uniting 3: Small spread of the hem of the hair bundle 2: Slightly large spread of the hem of the hair bundle 1: Large spread of the hem of the hair bundle

  As shown in Table 6, the hair treated with the hair set lotion of Example 9 containing a wheat protein hydrolyzate glyceryl derivative is generally used in Comparative Example 9A containing a wheat protein hydrolyzate as a raw material and cosmetics. Compared to the hair treated with the hair set lotion of Comparative Example 9B containing glycerin used, the evaluation value is higher in all evaluation items of moisture feeling, smoothness, and ease of hair uniting, and the wheat protein hydrolyzate glyceryl derivative is hair It was clear that it was excellent in the action which gives a moist feeling and smoothness to the hair and suppresses the spread of the hair due to the repulsion between the hairs.

Example 10 and Comparative Examples 10A to 10B
Three types of emulsions having the compositions shown in Table 7 were prepared, and each emulsion was applied to the skin, and the sticky feeling and moist feeling of the skin after use were evaluated.

  In Example 10, the rice protein hydrolyzate glyceryl derivative produced in Production Example 3 was used, in Comparative Example 10A, the rice protein hydrolyzate used as a raw material in Production Example 2 was used, and in Comparative Example 10B, it was common for cosmetics. 1.3-butylene glycol used in the above is used. In addition, the content of 1,3-butylene glycol is an amount substantially corresponding to the glyceryl group part of the rice protein hydrolyzate glyceryl derivative.

  Evaluation of the emulsions of Example 10 and Comparative Examples 10A to 10B was performed as follows. Specifically, 1 ml of each emulsion was applied to 10 female panelists on the back of the hand, and the sticky feeling and moist feeling of the skin after drying were evaluated according to the following evaluation criteria. The results are shown in Table 8 as an average of 10 people.

Stickiness Evaluation Criteria 3: Not Sticky 2: Not Sticky 1: Sticky
Evaluation criteria for moist feeling 3: Moist 2: Moist 1: Not moist

  As shown in Table 8, the skin treated with the emulsion of Example 10 containing a glyceryl derivative of rice protein hydrolyzate has a high evaluation value for both stickiness and moist feeling, and is particularly commonly used as a moisturizing agent. In the emulsion of Comparative Example 10B containing 1,3-butylene glycol, the stickiness was strong, but the glyceryl derivative of rice protein hydrolyzate was excellent in the effect of giving a sticky or moist feel.

Example 11 and Comparative Examples 11A-11B
Three types of lotions having the compositions shown in Table 9 were prepared, and the stickiness and moist feeling when each lotion was applied to the skin were evaluated.

  In Example 11, the pea protein hydrolyzate glyceryl derivative produced in Production Example 4 was used. In Comparative Example 11A, the pea protein hydrolyzate used as a raw material in Production Example 4 was used. In Comparative Example 11B, the carboxy group was glycerin. N-glyceryl pea protein hydrolyzate not converted to an ester is used.

  The skin lotion of Example 11 and Comparative Examples 11A to 11B was evaluated as follows. That is, 10 female panelists applied each lotion to each person's forearm, and evaluated the sticky feeling and moist feeling after application according to the same evaluation criteria as in Example 10. The results are shown in Table 10 as the average value of 10 people.

  As shown in Table 10, the lotion of Example 11 containing a pea protein hydrolyzate glyceryl derivative contains the lotion of Comparative Example 11A containing a pea protein hydrolyzate and N-glyceryl pea protein hydrolyzate. As compared with the lotion of Comparative Example 11B, the evaluation value was high for both stickiness and moist feeling.

Example 12 and Comparative Examples 12A-12B
Three types of shampoos having the composition shown in Table 11 were prepared, each shampoo was used for hair, the moisture retention rate of the hair after use was measured, and the moisture feeling, smoothness, and combing properties of the hair were functional. evaluated.

  In Example 12, the silk hydrolyzate glyceryl derivative produced in Example 5 was used, in Comparative Example 12A, the silk hydrolyzate used as a raw material in Example 5 was used, and in Comparative Example 12B, the cosmetics were generally used. The glycerin used is used. The glycerin content is an amount corresponding to the glyceryl group portion of the silk hydrolyzate glyceryl derivative.

  Prior to the treatment of the hair with the shampoo described above, three hair bundles having a length of 15 cm and a weight of 1.5 g were prepared, and the same bleaching treatment as in Example 8 was performed in order to make the damage degree of the hair constant. After washing with running water, it was rinsed with ion-exchanged water. With respect to the hair bundle which performed this bleaching process 5 times, the hair bundle was washed with 2 g of each of the shampoos of Example 13 and Comparative Examples 13A to 13B, rinsed in running hot water, and dried with a hair dryer. After this washing, rinsing, and drying treatment with a hair dryer were repeated 10 times, each panel of hairs was evaluated by 10 panelists on the same evaluation criteria as in Example 8 for the moist feeling, smoothness and combability. The results are shown in Table 12.

  As shown in Table 12, the hair treated with the shampoo of Example 12 containing the silk hydrolyzate glycerin ester derivative was the hair or glycerin treated with the shampoo of Comparative Example 12A containing the silk hydrolyzate as the raw material. As compared with the hair treated with the shampoo of Comparative Example 12B containing No. 1, the evaluation values were high in all evaluation items of moisture feeling, smoothness and combability.

Example 13 and Comparative Example 13
Two types of hand creams having the compositions shown in Table 13 were prepared and evaluated for the sticky feeling, moist feeling and smoothness of the skin after continuous application to the skin.

  In Example 13, the fish-derived collagen hydrolyzate glyceryl derivative produced in Production Example 6 was used, and in Comparative Example 13, the raw fish-derived collagen and 1,3-butylene glycol were used. The content of the fish-derived collagen hydrolyzate is an amount substantially corresponding to the collagen hydrolyzate portion of the fish-derived collagen hydrolyzate glyceryl derivative, and the content of 1,3-butylene glycol is the amount of the fish-derived collagen hydrolyzate. The amount is substantially equivalent to the glyceryl group portion of the degradation product glyceryl derivative.

  For the above two types of hand creams, 10 female panelists do not know which hand cream is an example, apply it to their hands at least once daily, and use the hand cream of Comparative Example 13 for the first week. For the next week, the hand cream of Example 13 was used. After a period of use of 2 weeks (that is, after using the hand cream of Example 13 for 1 week), the stickiness, moistness and smoothness were improved or worse than when Comparative Example 13 was used. The answer was whether or not changed. The results are shown in Table 14 in terms of the number of people who answered that they improved, the number of people who answered that they got worse, and the number of people who answered that they did not change.

  As is apparent from the results shown in Table 14, the majority of panelists in any of the evaluation items of stickiness, moistness, and smoothness after using the hand cream containing the glyceryl derivative derived from a fish-derived collagen hydrolyzate The glyceryl derivative of fish-derived collagen hydrolyzate has less stickiness than the mixture of fish-derived collagen hydrolyzate and 1,3-butylene glycol, which is moist and smooth. The effect to give is high.

Example 14 and Comparative Example 14
Three types of permanent wave first agents having the compositions shown in Table 15 were prepared, and each permanent wave was permanently added to the hair bundle using the first agent for permanent waves and the second agent for permanent waves consisting of a 6% sodium bromate aqueous solution. Wave treatment was performed, and the moisture feeling, smoothness and combability of the hair were evaluated.

  In Example 14, the keratin hydrolyzate glyceryl derivative produced in Production Example 7 was used. In Comparative Example 14A, the keratin hydrolyzate used as a raw material in Production Example 7 was used. In Comparative Example 14B, the carboxy group was glycerin ester. N-glyceryl keratin hydrolyzate not used is used.

  The treatment of the hair with the first permanent wave agent was performed as follows. That is, hair with a length of 20 cm was previously washed with a 2% aqueous solution of polyoxyethylene (3) sodium lauryl ether sulfate, rinsed in running tap water, and air-dried at room temperature. They were made and wound around rods each having a length of 10 cm and a diameter of 1 cm. Apply 2 ml each of the permanent wave first agent of Example 14 and Comparative Examples 14A-14B to the hair bundle wound around the rod, cover the hair bundle with a wrap, leave it for 15 minutes, and then gently with running water Washed for 10 seconds. Then, 2 ml of the permanent wave second agent was applied, covered with wrap, allowed to stand for 15 minutes, the hair bundle was removed from the rod, and gently washed in running water for 30 seconds. Each hair bundle was dried in a hot air drier at 60 ° C., and after drying, ten panelists evaluated the hair moistness, smoothness and combability according to the same evaluation criteria as in Example 8. The results are shown in Table 16 as an average of 10 people.

As apparent from the results in Table 16, the difference between the three was not extremely large, but the hair treated with the first agent for permanent wave of Example 14 containing the keratin hydrolyzate glyceryl derivative was From the hair treated with the first agent for permanent wave of Example 14A containing keratin hydrolyzate and Comparative Example 14B containing N-glyceryl keratin hydrolyzate, any of moist feeling, smoothness, and combability The evaluation value was also high in the evaluation items. That is, it has been shown that the keratin hydrolyzate glyceryl derivative is highly effective in imparting moisturizing feeling, smoothness and good combing property to the hair.

Claims (6)

A part of the amino group including the amino group of the amino acid side chain of the protein hydrolyzate and a part of the carboxy group including the carboxy group of the amino acid side chain are represented by the following formula (I):

A cosmetic product comprising a protein hydrolyzate glyceryl derivative to which a glyceryl group represented by the formula: The protein hydrolyzate glyceryl derivative is represented by the following general formula (II)

[Wherein, A represents a hydrogen atom or a glyceryl group represented by the above formula (I), part of A is a glyceryl group represented by the above formula (I), B represents a hydrogen atom, and the above formula (I ) Represents a glyceryl group or an alkali metal, an alkaline earth metal or magnesium, and a part of B is a glyceryl group represented by the above formula (I). R ¹ represents a residue excluding the amino group of the side chain of a basic amino acid having an amino group at the end of the side chain, and R ² is a residue excluding the terminal carboxy group of an acidic amino acid having a carboxy group at the end of the side chain R ³ represents a side chain of a neutral amino acid. a, b and c represent the number of basic amino acid units, the number of acidic amino acid units and the number of neutral amino acid units in one molecule of the protein hydrolyzate, where a is 0 to 100, b is 0 to 100, c Is 0 to 100 and a + b + c represents 2 to 200 (provided that a, b and c only indicate the number of amino acids, not the sequence order)]
The cosmetic according to claim 1, which is represented by:   In the protein hydrolyzate glyceryl derivative, 50% or more of all carboxy groups and 50% or more of all amino groups of the protein hydrolyzate are glycerylated with the glyceryl group represented by the above formula (I). The cosmetic according to claim 1 or 2.   The cosmetic according to any one of claims 1 to 3, wherein the protein hydrolyzate part of the protein hydrolyzate glyceryl derivative has an amino acid polymerization degree of 3 to 50.   The cosmetic according to any one of claims 1 to 4, wherein the protein hydrolyzate portion of the protein hydrolyzate glyceryl derivative is a plant protein hydrolysate. The cosmetic according to any one of claims 1 to 5, wherein the content of the protein hydrolyzate glyceryl derivative is 0.05 to 30% by mass.