JP2010111659A - Cosmetic base comprising quaternarized-ammoniated hydrolyzed protein or quaternarized-ammoniated amino acid glycerol ester derivative, and cosmetic including the cosmetic base - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cosmetic base good in compatibility with cationic substances, with no cause of solid/liquid separation even if compounded with an emulsified product, therefore easily compoundable in a hair conditioner such as hair rinse or hair treatment, and high in adsorptivity to the hair, and also because of being highly soluble even under acidic conditions, compoundable in weakly acidic and transparent cosmetics, and to provide a cosmetic compounded with the above cosmetic base. <P>SOLUTION: The cosmetic base comprises a hydrolyzed protein or an amino acid derivative; wherein the hydrolyzed protein is a quaternarized ammoniated hydrolyzed protein having amino group bound with quaternarized ammonium functional group and a carboxy group with glycerol ester-linkaged thereto, or a glycerol ester derivative of a quaternarized ammoniated amino acid. The cosmetic includes the above cosmetic base. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a cosmetic base material comprising a quaternary ammonium salt hydrolyzed protein or a glycerin ester derivative of a quaternary ammonium salt amino acid, and a cosmetic containing the same. Specifically, the present invention relates to a quaternary ammonium-modified hydrolyzed protein or quaternary in which a functional group containing quaternary ammonium is covalently bonded to an amino group of a hydrolyzed protein or amino acid, and a carboxy group is ester-bonded to glycerin. The present invention relates to a cosmetic base material comprising a glycerin ester derivative of an ammonium amino acid, which is easy to be blended in cosmetics, particularly hair conditioning agents such as hair rinses and hair treatments and weakly acidic cosmetics, and cosmetics containing the same.

Cosmetic base materials composed of hydrolyzed proteins, amino acids, or derivatives thereof are blended in hair conditioning agents such as hair rinses and hair treatments, and are used to impart elasticity and luster to hair. Among them, a cosmetic base material made of quaternary ammonium hydrolyzed protein or quaternary ammonium amino acid has high adsorptivity to damaged hair, and has a great effect of imparting flexibility and antistatic action to hair. It is widely used in hair cosmetics and skin cosmetics, mainly hair conditioning agents such as hair rinses and hair treatments (Patent Documents 1 and 2).

  However, when preparing emulsified cosmetics such as hair rinses and hair treatments, an emulsification method using a higher alcohol and an alkylammonium salt is generally used. However, quaternary ammonium hydrolyzed proteins and quaternary ammonium salts are used. Amino acids are not compatible with this emulsifying system, and cannot be emulsified when mixed in a large amount, causing liquid phase separation. In addition, some quaternary ammonium-modified hydrolyzed proteins and quaternary ammonium-modified amino acids have low water solubility, especially in weakly acidic regions favored by cosmetics in recent years. There were many things that produced. And these reasons have become obstacles when blending quaternary ammonium-modified hydrolyzed proteins and quaternary ammonium-modified amino acids into cosmetics.

  As derivatives of hydrolyzed proteins to be blended in cosmetics, alkylesterified hydrolyzed proteins obtained by dehydration condensation of carboxy groups of hydrolyzed proteins and alcohols are also known (Patent Document 3). However, this alkyl esterified hydrolyzed protein tends to be insoluble in water-soluble cosmetics and has a problem that it can be used only in cosmetics containing alcohol such as hair tonics and hair sprays.

In addition, a proposal has been made to use modified collagen obtained by esterifying collagen with an alkyloxyalkylene glycol derivative in cosmetics (Patent Document 4). However, esterified derivatives of this protein are not suitable for hair cosmetics because high molecular weight collagen is used. Furthermore, since the production is carried out by esterifying solid or powdered collagen in the presence of a glycol derivative and an organic solvent, the process is complicated and there is a problem that an organic solvent is used.

Japanese Patent No. 2878287 Japanese Patent Laid-Open No. 60-243010 JP-A-2-142712 JP-A-9-76631

  This invention makes it a subject to provide the cosmetic base material which solves said problem of a prior art. That is, even if it is blended in an emulsion, it does not cause liquid phase separation. Therefore, it is easy to blend in emulsified cosmetics such as hair rinses and hair treatments, and has excellent solubility even under acidic conditions. It is an object of the present invention to provide a cosmetic base material that can be blended into cosmetics and a cosmetic containing the cosmetic base material.

  As a result of intensive studies to solve the above problems, the present inventors have found that a functional group containing quaternary ammonium is bonded to an amino group of a hydrolyzed protein or amino acid, and a carboxy group is ester-bonded to glycerin. The resulting quaternary ammonium hydrolyzed protein or glycerin ester derivative of a quaternary ammonium amino acid does not cause liquid phase separation even when incorporated into an emulsion, and is excellent in solubility even under acidic conditions. As a result, the present invention has been completed.

That is, the present invention
A hydrolyzed protein or amino acid derivative,
A quaternary ammonium functional group is bonded to part of the amino group, and the following general formula (I):
It comprises a glycerin ester derivative of a quaternary ammonium salt hydrolyzed protein or a quaternary ammonium salt amino acid having a functional group represented by the formula (Claim 1).

  Even if it mix | blends with the emulsion base material of the cosmetics base material of this invention, it does not cause liquid phase separation, Therefore An emulsification system, such as a hair rinse and a hair treatment, is not broken. Therefore, it can be easily blended into many emulsified cosmetics including hair conditioning agents such as hair rinses and hair treatments. Furthermore, since it is excellent in solubility even under acidic conditions, it can be blended into weakly acidic cosmetics, and even if blended in large amounts in weakly acidic transparent cosmetics, problems such as turbidity and precipitation are unlikely to occur.

  As will be described later, the cosmetic base material of the present invention can be produced in an aqueous system without using an organic solvent. Therefore, in addition to the above effects, there is an effect that industrially easy production is possible.

  The glycerin ester derivative of the quaternary ammonium salt hydrolyzed protein or quaternary ammonium salt amino acid constituting the cosmetic base material of the present invention is a hydrolyzed protein or amino acid derivative. Hydrolyzed protein refers to a main chain in which two or more amino acid units obtained by partial hydrolysis of a protein (protein source) with acid, alkali, enzyme, or a combination thereof are peptide-bonded (—CO—NH—). It means a peptide having an amino group and a carboxy group at its end. In addition, amino acids mean amino acids obtained by fermentation using microorganisms and amino acids isolated from natural products. In addition, amino acids obtained by total degradation of proteins are amino acids that constitute the cosmetic base material of the present invention. Applicable.

  The quaternary ammonium-modified hydrolyzed protein or glycerin ester derivative of a quaternary ammonium-containing amino acid constituting the cosmetic base material of the present invention is obtained by reacting a hydrolyzed protein or amino acid with a quaternary ammonium agent in an aqueous solution. After synthesizing a functional group containing quaternary ammonium to the amino group of the hydrolyzed protein or amino acid to synthesize a quaternary ammonium hydrolyzed protein or quaternary ammonium amino acid, the carboxy group is reacted with glycidol. Can be manufactured.

  The glycerin ester derivative of the quaternary ammonium-modified hydrolyzed protein or quaternary ammonium-modified amino acid is first made into a hydrolyzed protein glycerin ester derivative or an amino acid glycerin ester derivative by reacting glycidol with the carboxy group of the hydrolyzed protein or amino acid. Then, it can also manufacture by making a quaternary ammonium agent react with the amino group of a hydrolyzed protein glycerol ester derivative or an amino acid glycerol ester derivative. However, since the reaction between the amino group of the hydrolyzed protein or amino acid and the quaternary ammonium agent is carried out on the basic side, the ester bond of the glycerin ester derivative of the hydrolyzed protein or amino acid is cleaved by hydrolysis. Therefore, in such a production method, a quaternary ammonium salt hydrolyzed protein or a glycerin ester derivative of a quaternary ammonium salt amino acid having a low esterification rate can be obtained. Therefore, the hydrolyzed protein or amino acid is converted to a quaternary ammonium salt derivative. Then, glycerin esterification is preferable.

  The invention according to claim 2 is characterized in that 50% or more of the total carboxy groups of the hydrolyzed protein or amino acid are esterified with the functional group represented by the general formula (I). This is a cosmetic base material. Here, the total carboxy group means that when the hydrolyzed protein contains an acidic amino acid unit, it includes a side chain carboxy group as well as a carboxy group at the end of the main chain. Moreover, in the case of an acidic amino acid, it is meant to include a side chain carboxy group together with a carboxy group bonded to the α-position carbon. The esterification rate of the carboxy group of the quaternary ammonium-modified hydrolyzed protein or quaternary ammonium-modified amino acid is not particularly limited, but if the esterification rate is 50% or less, the effect of glycerol esterification tends not to be sufficiently exhibited.

  In the invention according to claim 3, the quaternary ammonium functional group has the following general formula (II):

(In the formula, R ¹ , R ² , and R ³ may be the same or different, and an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, or ^{one of} R ^{1 to} R ³ or 2 represents an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms, and the remaining represents an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group having 1 to 3 carbon atoms, or a benzyl group. 4. A saturated hydrocarbon having 2 to 3 carbon atoms or a saturated hydrocarbon having a hydroxyl group having 2 to 3 carbon atoms, wherein X represents a halogen atom). The cosmetic base material according to Item. The quaternary ammonium functional group is a monovalent group that can be bonded to an amino group, and among them, a quaternary ammonium functional group represented by the general formula (II) is preferable.

  The invention according to claim 4 is characterized in that the functional group represented by the general formula (II) is bonded to 50% or more of the total amino groups of the hydrolyzed protein or amino acid. Cosmetic base material. Here, the total amino group means that when the hydrolyzed protein contains a basic amino acid unit, it includes a side chain amino group as well as an amino group at the end of the main chain. In the case of a basic amino acid, it means that the amino group in the side chain is included together with the amino group bonded to the α-position carbon.

  The preferable range of the introduction rate of the quaternary ammonium functional group to the hydrolyzed protein or amino acid varies depending on the molecular weight of the hydrolyzed protein or amino acid or the presence ratio of the amino group, but generally, the amino group of the hydrolyzed protein or amino acid is 50 It is preferable to introduce it in% or more. When the introduction rate of the quaternary ammonium functional group into the hydrolyzed protein or amino acid is not more than the above range, the effect of imparting flexibility and antistatic action to the hair caused by the quaternary ammonium functional group tends not to be sufficiently exhibited. .

  Examples of protein sources of amino acids obtained by total hydrolysis of hydrolyzed proteins and proteins include animal proteins, plant proteins, and microorganism-derived proteins. Hydrolyzed proteins and amino acids that constitute amino acids include acidic amino acids having a carboxy group in the side chain, basic amino acids having an amino group in the side chain, and neutral amino acids having no amino or carboxy group in the side chain Can be mentioned.

  Hydrolyzed proteins and amino acids containing many acidic amino acids having a carboxy group in the side chain have a problem that they are difficult to adsorb on damaged hair containing many cysteic acids having sulfonic acid groups, which are strongly acidic functional groups. In addition, the carboxy group of hydrolyzed proteins and amino acids is not compatible with O / W emulsification prepared by an emulsification method using a higher alcohol and an alkyl ammonium salt, and this problem is caused by adding a quaternary ammonium functional group to the amino group. The same applies to quaternary ammonium-modified hydrolyzed proteins and quaternary ammonium-modified amino acids. Among the protein sources, the vegetable protein contains a lot of acidic amino acids, and this problem is particularly serious in the case of a quaternary ammonium hydrolyzed vegetable protein obtained from the vegetable protein. Among amino acids, this problem is particularly serious in the case of glutamic acid and aspartic acid having two carboxy groups in one molecule.

  However, by converting the carboxy group of the hydrolyzed protein or amino acid to glycerin ester, the quaternary ammonium-modified hydrolyzed protein or quaternary ammonium-modified amino acid can be emulsified even in O / W emulsified cosmetics such as hair rinses and hair conditioners. Since it can exist without breaking, the effect of the present invention, that is, the effect of derivatization of glycerin ester of a quaternary ammonium-modified hydrolyzed protein or quaternary ammonium-modified amino acid is a hydrolyzed protein containing a large amount of acidic amino acids, such as hydrolyzed protein. The degradation protein is particularly large when the protein source is vegetable protein, or when the amino acid is glutamic acid or aspartic acid. Therefore, in the present invention, the quaternary ammonium salt hydrolyzed protein or the glycerin ester derivative of the quaternary ammonium salt amino acid is obtained from a hydrolyzate of a plant protein. A cosmetic substrate according to claim 5 is provided as claim 5.

  The invention according to claim 6 is the cosmetic base material according to any one of claims 1 to 5, wherein the hydrolyzed protein has an average amino acid polymerization degree of 2 to 50.

  The average degree of amino acid polymerization of the hydrolyzed protein portion is usually selected from the range of 1 to 400 in view of the adsorptivity and permeability to hair and skin, and the stability of cosmetics when blended in cosmetics. However, 2-50 are preferable and 3-30 are more preferable. If the average amino acid degree of polymerization of the hydrolyzed protein is not less than the above range, aggregation tends to occur during storage, and the stability of the cosmetics will deteriorate.

  The cosmetic base material comprising the quaternary ammonium salt hydrolyzed protein or the glycerin ester derivative of the quaternary ammonium salt amino acid according to the present invention does not cause liquid phase separation even when blended in an O / W emulsion, under acidic conditions However, since it has excellent characteristics such as excellent solubility, it can be easily blended into hair cosmetics and skin cosmetics, and is inherently possessed by quaternary ammonium hydrolyzed proteins and quaternary ammonium amino acids. An excellent effect, for example, a function of imparting flexibility and antistatic action to hair can be exhibited.

  In particular, when it is blended in a hair cosmetic, the function of imparting flexibility and antistatic action to the hair can be sufficiently exerted due to the feature of high adsorption performance to the hair. Among the cosmetics, the effects of the present invention are exhibited when they are contained in hair cosmetics, particularly hair conditioning agents such as hair rinses and hair treatments. As a seventh aspect of the present invention, there is also provided a cosmetic comprising the cosmetic base material according to any one of the first to sixth aspects.

  The cosmetic base material of the present invention has an excellent function of imparting flexibility and antistatic action to the hair, and does not cause liquid phase separation even when blended in an O / W emulsion, and adsorbs to the hair. It has an excellent effect that the solubility is excellent even under acidic conditions. And even if it mixes with O / W emulsion, it does not cause liquid phase separation, so it does not break the emulsifying system such as hair rinse and hair treatment. Therefore, it can be easily applied to emulsified cosmetics such as hair rinse and hair treatment. Can be blended. Moreover, since the adsorption | suction performance to hair is high, the softness | flexibility can be provided to hair and an antistatic effect can fully be exhibited. Furthermore, since it is excellent in solubility even under acidic conditions, it can be blended into weakly acidic cosmetics, and even if blended in large amounts in weakly acidic transparent cosmetics, problems such as turbidity and precipitation are unlikely to occur. Therefore, it is suitably used for cosmetics, especially hair cosmetics, and imparts flexibility to the hair and exhibits an antistatic effect.

2 is an IR spectrum of a quaternary ammonium-modified hydrolyzed pea protein used in Example 1. 2 is an IR spectrum of a quaternary ammonium-modified hydrolyzed pea protein glycerin ester derivative obtained in Example 1. It is the graph which showed the change of pH by 0.1 mol / L hydrochloric acid addition of the quaternary ammonium-ized hydrolysis pea protein glycerin ester derivative aqueous solution of Example 1, and a quaternary ammonium-ized hydrolysis pea protein aqueous solution.

  Next, the form for implementing this invention is demonstrated more concretely. A preferred form of the glycerin ester derivative of the quaternary ammonium salt hydrolyzed protein or quaternary ammonium salt amino acid constituting the cosmetic base material of the present invention is represented by the following general formula (III).

In the formula (III), R ⁴ represents a residue of a side chain excluding a terminal amino group of a basic amino acid having an amino group at the end of the side chain, and R ⁵ represents an acidic amino acid having a carboxy group at the end of the side chain. Represents a residue of a side chain excluding a terminal carboxy group, R ⁶ represents a residue of a side chain of a neutral amino acid (an amino acid having neither an amino group nor a carboxy group at the end of the side chain), a, b and c represents an integer of 0 or more independently.

R ⁷ represents hydrogen or a group represented by the formula (II), but at least a part is a group represented by the formula (II), and preferably 50% or more is a group represented by the formula (II). . R ⁸ represents hydrogen or a group represented by the formula (I), and at least a part of the group is represented by the formula (I), and preferably 50% or more is a group represented by the formula (I). is there.

  In addition, a, b, and c show only the number of amino acids, and do not show the order of amino acid sequences. Moreover, although a, b, c, and a + b + c are theoretically integers, hydrolyzed proteins are obtained as a mixture of different molecular weights, and thus the measured values are average values and are usually other than integers.

  As mentioned above, the amino acid average polymerization degree of the hydrolyzed protein is preferably in the range of 2-50. Therefore, in the general formula (III), the average degree of polymerization of amino acids is preferably 2 to 50 in a + b + c. The more preferable range of a + b + c is 3-30.

  The number of each amino acid unit constituting the quaternary ammoniumated hydrolyzed protein or glycerin ester derivative of quaternary ammoniumated amino acid, that is, quaternary ammoniumated hydrolyzed protein or glycerin ester derivative of quaternary ammoniumated amino acid A basic amino acid unit having an amino group in the side chain in the molecule (amino acid unit having a in formula (III)), an acidic amino acid unit having a carboxy group in the side chain (in formula (III), b is Amino acid units) and other amino acid units (amino acid units to which c is added in formula (III)), the preferred range of each number depends on its use, raw material circumstances, type of each amino acid unit, etc. It fluctuates and is not particularly limited. However, glycerin ester derivatives of quaternary ammonium-modified hydrolyzed proteins or quaternary ammonium-modified amino acids are often used in normal hair cosmetics, and a + b + c is 1 or more and 50 or less, and a is 0. -35 are preferable, 1-5 are more preferable, b is preferably 0-30, more preferably 1-20, and c is preferably 0-50, more preferably 1-40.

  When a is larger than the above range, the number of quaternary ammonium groups bonded to the side chain amino group increases, which may adversely affect the stability of the cosmetic. On the other hand, when b and c are larger than the above range, the ratio of the quaternary ammonium functional group to the hydrolyzed protein is lowered, the quaternary ammonium compound has a high adsorptivity to damaged hair, and the hair has flexibility. There is a tendency that the effect of imparting an antistatic effect is not sufficiently exhibited. Moreover, when b becomes larger than the above range, the glycerin part introduced into the quaternary ammonium-modified hydrolyzed protein glycerin ester derivative increases, and may give a sticky feeling when applied to hair or skin.

  Next, a hydrolyzed protein and a quaternary ammonium salt hydrolyzed protein used for the production of a quaternary ammonium salt hydrolyzed protein or a glycerin ester derivative of a quaternary ammonium salt amino acid constituting the cosmetic base material of the present invention. The quaternary ammonium amino acid will be described in detail.

[Hydrolyzed protein]
The hydrolyzed protein portion constituting the quaternary ammonium-modified hydrolyzed protein glycerin ester derivative of the present invention is obtained by hydrolyzing a protein (protein source) with acid, alkali, enzyme, or a combination thereof, and this protein. Examples of the source include animal protein, plant protein, and microorganism-derived protein. Examples of animal proteins include collagen (including gelatin, which is a modified product thereof), keratin, fibroin, sericin, casein, conchiolin, elastin, protamine, and egg yolk proteins and egg white proteins such as chicken. Examples thereof include proteins contained in soybeans, wheat, rice (rice bran), sesame, peas, corn, potatoes and the like, and proteins obtained from algae such as seaweed, kombu, wakame and spirulina. In addition, the proteins derived from microorganisms include yeasts belonging to the genus Saccharomyces, Candida and Endomycopsis, yeast proteins isolated from yeasts called beer yeast and sake yeast, proteins isolated from mushrooms (basidiomycetes) and chlorella And so on.

  The proportion of basic amino acids, acidic amino acids, and other amino acids in the hydrolyzed protein is almost dependent on the proportion of amino acids in the protein source. In hydrolysates of natural proteins, basic amino acids are rare if they are 70 mol% or more of all amino acids, and acidic amino acids are contained in large amounts in plant proteins, but those exceeding 60 mol% are rare. It is. As for the numerical values of a, b, and c in formula (III), preferred ranges can be considered as described above. However, when a natural protein that is generally used as a cosmetic raw material is used as a protein source, a that occupies a + b + c Is at most 70 mol%, and the proportion of b in a + b + c is at most 60 mol%.

[Quaternary ammonium salt hydrolyzed protein and quaternary ammonium salt amino acid]
A quaternary ammonium-modified hydrolyzed protein or a quaternary ammonium-modified amino acid can be obtained by reacting a hydrolyzed protein or amino acid with a quaternary ammonium agent under alkaline conditions. Specific examples of the quaternary ammonium agent include glycidyl ammonium salts such as glycidyl stearyl dimethyl ammonium chloride, glycidyl coconut oil alkyl dimethyl ammonium chloride, glycidyl lauryl dimethyl ammonium chloride, glycidyl trimethyl ammonium chloride, 3-chloro-2- Hydroxypropylstearyldimethylammonium chloride, 3-chloro-2-hydroxypropyl coconut oil alkyldimethylammonium chloride, 3-chloro-2-hydroxypropyllauryldimethylammonium chloride, 3-chloro-2-hydroxypropylethyldimethylammonium chloride, 3- 3-halo-2-hydroxypropyl such as chloro-2-hydroxypropyltrimethylammonium chloride Ammonium salts, 2-chloroethyl trimethyl ammonium chloride such as 2-halo - ethylammonium salt, 3-halo, such as 3-chloropropyl trimethyl ammonium chloride - such as propyl ammonium salts. The reaction of the hydrolyzed protein or amino acid with the above quaternary ammonium agent can be carried out according to the method described in JP-A-60-243010, Japanese Patent No. 2878287, or the like.

  More specifically, a hydrolyzed protein aqueous solution or amino acid aqueous solution adjusted to pH 9 to 11 is heated to 40 to 60 ° C., and a quaternary ammonium agent is dropped therein and stirred for 1 to 5 hours. By continuing the reaction, a quaternary ammonium salt hydrolyzed protein or a quaternary ammonium salt amino acid can be obtained.

[Quaternary Ammonium Hydrolyzed Protein or Glycerin Ester Derivative of Quaternary Ammonium Amino Acid]
The quaternary ammonium hydrolyzed protein or glycerin ester derivative of a quaternary ammonium amino acid of the present invention is a carboxy group of a quaternary ammonium hydrolyzed protein or quaternary ammonium amino acid obtained as described above. (Along with the carboxy group at the end of the main chain, the carboxy group of the amino acid side chain is also included.) Glycerol esterification (glyceryl esterification). A glycerin ester derivative of a quaternary ammonium hydrolyzed protein or a quaternary ammonium amino acid has the following general formula (IV):

It is carried out by reacting glycidol represented by the formula (2,3-epoxy-1-propanol) with quaternary ammonium hydrolyzed protein or quaternary ammonium amino acid under acidic conditions.

  Specifically, the pH of the aqueous solution of the quaternary ammonium-modified hydrolyzed protein or quaternary ammonium-containing amino acid is adjusted to 1 to 6, preferably 2 to 5, more preferably 3.5 to 4.5, and stirring. Glicidol is added dropwise at the bottom to react. In addition, since glycidol reacts with the amino group which quaternary ammonium-ized hydrolyzed protein or quaternary ammonium-ized amino acid remains when pH at the time of glycerol esterification reaction is high, pH is 6 or less, Preferably it is 5 or less More preferably, it is necessary to keep it at 4.5 or less.

  Examples of the acid that adjusts the aqueous solution of the quaternary ammonium-modified hydrolyzed protein or the quaternary ammonium-modified amino acid to acid include inorganic acids such as sulfuric acid, phosphoric acid, nitric acid, and hydrochloric acid, but sulfuric acid, phosphoric acid, nitric acid, etc. An acid having a low nucleophilicity is preferred. The glycerin esterification of a quaternary ammoniumated hydrolyzed protein or quaternary ammoniumated amino acid is carried out by nucleophilic reaction of the carboxy group of the quaternary ammoniumated hydrolyzed protein or quaternary ammoniumated amino acid to the epoxy group of glycidol. It is thought to occur. Therefore, when hydrochloric acid is used as the acid agent, the chloride ion of hydrochloric acid reacts with glycidol competitively with the carboxy group of the quaternary ammonium salt hydrolyzed protein or quaternary ammonium salt amino acid, and the quaternary salt. May interfere with glycerin esterification of ammonium hydrolyzed proteins or quaternary ammonium amino acids. In addition, the compound produced by the reaction of chloride ion and glycidol is chlorohydrin, and this chlorohydrin is not preferred as a cosmetic raw material. Therefore, hydrochloric acid is used for glycerin esterification reaction of quaternary ammonium-modified hydrolyzed protein or quaternary ammonium-containing amino acid. When is used, a step of removing the produced chlorohydrin is required, and therefore sulfuric acid other than hydrochloric acid, phosphoric acid, nitric acid and the like are preferable.

  The reaction temperature is preferably in the range of room temperature to 80 ° C, more preferably in the range of 40 to 70 ° C. When the reaction temperature is below the above range, the reaction rate becomes slow. On the other hand, even when the reaction temperature is 80 ° C. or higher, no increase in the reaction rate is observed, and quaternary ammonium hydrolyzed protein or quaternary ammonium ion There is a possibility that the glycerin ester derivative of an amino acid causes coloring or odor and the quality is lowered.

  The glycidol dripping time during the reaction varies depending on the amount of glycidol and the reaction temperature, but is generally from 30 minutes to 3 hours. After completion of the dripping, the mixture is heated to 40 to 75 ° C. while warming to 1 to 5 to complete the reaction. It is preferable to continue stirring for about an hour.

  Since the esterification rate of the carboxy group of the quaternary ammonium-modified hydrolyzed protein or quaternary ammonium-modified amino acid is preferably 50% or more, the reaction ratio is preferably adjusted so that the esterification rate is 50% or more. Usually, the molar ratio of the quaternary ammonium hydrolyzed protein or the quaternary ammonium amino acid carboxy group: glycidol = 1: 0.7-1: 3 and the esterification rate is 50% or more, Depending on the type of hydrolyzed protein or amino acid and the degree of amino acid polymerization, the reactivity may be reduced due to the influence of steric hindrance, and the reaction ratio of glycidol may need to be further increased.

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 can be adjusted to a pH and concentration suitable for various cosmetics and used as a cosmetic base material. Further, after neutralizing the reaction solution, it may be purified by ion exchange resin, dialysis membrane, electrodialysis, gel filtration, ultrafiltration, etc. and blended into hair cosmetics or skin cosmetics. However, in the glycerin esterification reaction of the quaternary ammonium hydrolyzed protein or quaternary ammonium amino acid of the present invention, the by-product from glycidol is glycerin, and glycerin is a component widely mixed in cosmetics. After completion of the reaction, it can be incorporated into hair cosmetics and skin cosmetics only by adjusting the concentration and pH without any particular purification.

  Next, the use of a cosmetic base material composed of a quaternary ammonium salt hydrolyzed protein or a glycerin ester derivative of a quaternary ammonium salt amino acid will be described.

  Examples of cosmetics to which a cosmetic base material composed of the quaternary ammonium-modified hydrolyzed protein of the present invention or a glycerin ester derivative of a quaternary ammonium-modified amino acid are blended include shampoo, hair rinse, hair conditioner, split coat, hair Cream, permanent wave first and second agent, set lotion, hair dye, hair dye, liquid hair conditioner, hair cosmetics such as hair nourishing and hair restorer, cleansing cream, emollient cream, hand cream, after shaving lotion Skin cosmetics such as shaving foams, facial cleansing creams, facial cleansers, body shampoos, various soaps, hair removal agents, face packs, emulsions, makeup products, sunscreen products.

  The preferable range of the blending amount of the cosmetic base material of the present invention (content in the cosmetic) varies depending on the type of cosmetic and cannot be particularly limited, but is preferably 0.1 to 30% by mass in the cosmetic. In many cases, about 1 to 20% by mass is particularly preferable. When the blending amount in the cosmetic is less than the above range, the effect of imparting flexibility and antistatic action to the hair may not be sufficiently exhibited. In addition, even if the amount of the cosmetic base composed of a quaternary ammonium-modified hydrolyzed protein or a glycerin ester derivative of a quaternary ammonium-containing amino acid exceeds the above range, the effect corresponding to the amount is not improved, but rather the hair. In some cases, excessive quaternary ammonium hydrolyzed protein or glycerin ester derivative of quaternary ammonium amino acid is adsorbed on the skin to cause stickiness.

  Ingredients that can be blended in the cosmetics together with the cosmetic base material of the present invention include, for example, anionic surfactants, nonionic surfactants, amphoteric surfactants, cationic surfactants, cationic polymers, Synthetic polymers such as amphoteric polymers and anionic polymers, semi-synthetic polymers, animal and vegetable oils, hydrocarbons, ester oils, higher alcohols, amino acids, thickeners, animal and plant extracts, silicones, preservatives, fragrances, animals and plants Examples thereof include hydrolyzed proteins obtained by hydrolyzing proteins derived from microorganisms and microorganisms, esterified derivatives of these hydrolyzed proteins, quaternary ammonium derivatives, silylated derivatives, acylated derivatives and salts thereof. In addition to these, other components can be appropriately added as long as the properties of the cosmetic base material of the present invention are not impaired.

  EXAMPLES Next, although an Example is given and this invention is demonstrated concretely, this invention is not limited only to those Examples. In addition, all% used in an Example is the mass%. First, the method for measuring the amount of amino nitrogen, the method for measuring the total amount of nitrogen, the method for estimating the number of moles of carboxy groups, and the method for measuring the esterification rate used in the examples are described.

[Measurement of amino nitrogen and total nitrogen content]
The amount of amino nitrogen in the examples was measured by the van Slyke method. The total nitrogen amount was measured by the improved Dumas method.

[Method for estimating the number of moles of carboxy group]
The number of moles of the carboxy group of the quaternary ammonium-modified hydrolyzed protein or quaternary ammonium-containing amino acid was determined as follows. In other words, it is assumed that there is a terminal carboxy group equivalent to the number of moles of amino nitrogen determined from the amount of amino nitrogen obtained by the van Slyke method, and an acidic amino acid (glutamic acid and asparagine obtained by amino acid analysis). The number of moles of acid) was the number of moles of the side chain carboxy group of the hydrolyzed protein or amino acid. And the sum of the number of moles of these terminal carboxy groups and the number of moles of side chain carboxy was estimated as the number of moles of all carboxy groups of the hydrolyzed protein or amino acid.

[Measurement method of esterification rate]
1) First,
According to the ester value measurement method described in the comment on the cosmetic raw material standard second 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 (35 ml of potassium hydroxide dissolved in 20 ml of water and 1000 ml added with ethanol) was accurately added, and attached on a water bath with a reflux condenser for 1 hour. Boil gently. After boiling, the mixture is cooled and excess potassium hydroxide is titrated with 0.5 mol / L hydrochloric acid. The consumption (mL) of 0.5 mol / L hydrochloric acid at this time is defined as p.

  Except not using a sample, it carries out similarly to the above (blank test), calculates | requires the consumption of 0.5 mol / L hydrochloric acid, and makes this consumption (mL) q. The ester value is calculated from p and q thus obtained and the following formula. 28.053 is the number of milligrams of potassium hydroxide required to neutralize 1 mL of 0.5 mol / L hydrochloric acid.

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 hydrolyzed protein used in the Examples is obtained by partially hydrolyzing each protein source by a known method using an acid or an alkali (and optionally using an enzyme). The degree of amino acid polymerization (a + b + c in the general formula (III)) 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 amino acid automatic analyzer made from Hitachi, and each value of a, b, and c was calculated | required from the amino acid polymerization degree.

Example 1: Quaternary ammonium-modified hydrolyzed pea protein glycerin ester derivative Hydrolyzed pea protein [a hydrolyzate of pea protein, a (basic amino acid) in general formula (III) is 0.4, b (acidic amino acid) ) Is 1.3, c (other amino acids) is 2.1, and a + b + c is 3.8. Note that a, b, and c are average values. The same applies to the following embodiments. ] 400 g (The number of moles of amino groups is 0.26 mol and the number of moles of carboxy groups is 0.42 mol. The number of moles of amino groups is measured by the above-mentioned measuring method of amino nitrogen and total nitrogen amount. The number of moles of carboxy groups is the value obtained by the above-described method for estimating the number of moles of carboxy groups (the same applies to the following examples)) and 20% sodium hydroxide. The pH was adjusted to 10 by adding an aqueous solution. The solution was stirred at 55 ° C., and 232.7 g of glycidyl coconut alkyldimethylammonium chloride (purity 32%) (0.8 equivalent to the amino group of the hydrolyzed pea protein) was added dropwise over 2 hours. Then, a quaternary ammonium reaction was performed on the amino group of the hydrolyzed pea protein. After completion of the dropwise addition of glycidyl coconut alkyldimethylammonium chloride, stirring is continued at 55 ° C. for 2 hours to complete the reaction to obtain an aqueous solution of quaternary ammonium hydrolyzed pea protein having a quaternary ammonium conversion rate of 51%. It was. The quaternary ammonium reaction rate is a value obtained from the following formula, where u is the total amino nitrogen content of the hydrolyzed pea protein before the quaternary ammonium reaction, and t is the total amino nitrogen content after the reaction. It is.
Quaternary ammonium conversion (%) = 1− (t / u) × 100

  Dilute sulfuric acid is added to the aqueous solution of the quaternary ammonium-modified hydrolyzed pea protein obtained above to adjust the pH to 4.5, and this adjusted solution is stirred at 55 ° C., and glycidol (Daicel Chemical Industries) 62.2 g (2.0 equivalents relative to the carboxy group of the hydrolyzed pea protein) was added dropwise over 1 hour. After completion of dropwise addition of glycidol, stirring was continued at 55 ° C. for 3 hours to complete the reaction. Since the pH of the solution increased during the reaction, the pH of the solution was maintained around 4 using dilute sulfuric acid.

  After completion of the reaction, the reaction solution was adjusted to pH 6 with a 20% aqueous sodium hydroxide solution, and water was added thereto to add 774.9 g of an aqueous solution of a quaternary ammonium hydrolyzed pea protein glycerin ester derivative having a solid content concentration of 30%. Obtained.

Infrared absorption spectrum analysis (IR analysis) of the obtained quaternary ammonium-modified hydrolyzed pea protein glycerol ester derivative and the quaternary ammonium-modified hydrolyzed pea protein before glycerol esterification was performed. The results are shown in FIG. 1 and FIG. 2, and the spectrum of the quaternary ammonium salt hydrolyzed pea protein glycerin ester derivative shown in FIG. 2 is compared with the spectrum of the quaternary ammonium salt hydrolyzed pea protein shown in FIG. 1735 cm ⁻¹ , a large absorption was observed, confirming that the carboxy group of the quaternary ammonium-modified hydrolyzed pea protein was esterified. Further, the esterification rate of the quaternary ammonium-modified hydrolyzed pea protein glycerin ester derivative obtained by the above-described method for measuring the esterification rate was found to be 69%.

Example 2: Quaternary ammonium-modified hydrolyzed soy protein glycerin ester derivative Hydrolyzed soy protein [a hydrolyzate of soy protein, a in general formula (III) is 0.3, b is 1.2, c is 1 7 and a + b + c is 3.2] in a 27% aqueous solution of 400 g (amino group mole number is 0.28 mol, carboxyl group mole number is 0.47 mol), and 20% sodium hydroxide aqueous solution is added to adjust the pH to 10. did. The solution was stirred at 55 ° C., and 250.6 g of glycidyl coconut alkyldimethylammonium chloride (purity 32%) (0.8 equivalent to the amino group of the hydrolyzed soybean protein) was dropped into the solution over 2 hours. Then, a quaternary ammonium reaction was performed on the amino group of the hydrolyzed soybean protein. After completion of the dropwise addition of glycidyl coconut alkyldimethylammonium chloride, stirring is continued at 55 ° C. for 2 hours to complete the reaction to obtain an aqueous solution of quaternary ammonium hydrolyzed soy protein having a quaternary ammonium conversion rate of 53%. It was.

  Dilute sulfuric acid is added to the aqueous solution of the quaternary ammonium hydrolyzed soy protein obtained above to adjust the pH to 4.5, and while stirring this adjusted solution at 55 ° C., glycidol (Daicel Chemical Industries) 27.8 g (0.8 equivalent to the carboxy group of hydrolyzed soy protein) was added dropwise over 1 hour. After completion of dropwise addition of glycidol, stirring was continued at 55 ° C. for 3 hours to complete the reaction. Since the pH of the solution increased during the reaction, the pH of the solution was maintained around 4 using dilute sulfuric acid.

  After completion of the reaction, the reaction solution was adjusted to pH 6 with a 20% aqueous sodium hydroxide solution, water was added, and an aqueous solution of a quaternary ammonium-modified hydrolyzed soybean protein glycerin ester derivative having a solid content concentration of 30% was 662.4. Obtained.

IR analysis of the obtained quaternary ammonium-modified hydrolyzed soybean protein glycerin ester derivative and quaternary ammonium-modified hydrolyzed soy protein before glycerol esterification was conducted, and the IR spectra of both were compared. Absorption was observed in the vicinity of 1735 cm ⁻¹ only in the spectrum of the hydrolyzed soy protein glycerin ester derivative, confirming the esterification of the carboxy group of the quaternary ammonium hydrolyzed soy protein. Moreover, the esterification rate of the quaternary ammonium-modified hydrolyzed soybean protein glycerin ester derivative by the above esterification rate measurement method was 50%.

Example 3: Quaternary ammonium-modified hydrolyzed wheat protein glycerin ester derivative Hydrolyzed wheat protein [a hydrolyzate of wheat protein, a in formula (III) is 0.1, b is 2.6, c is 3 0.0, a + b + c is 5.7] 27% aqueous solution of 400 g (amino group mole number is 0.14 mol, carboxy group mole number is 0.47 mol), and 20% aqueous sodium hydroxide solution is added to adjust pH to 10. did. The solution was stirred at 55 ° C., and 125.3 g of glycidyl coconut oil alkyldimethylammonium chloride (purity 32%) (0.8 equivalent to the amino group of the hydrolyzed wheat protein) was dropped into the solution over 2 hours. Then, a quaternary ammonium reaction was performed on the amino group of the hydrolyzed wheat protein. After completion of the dropwise addition of glycidyl coconut alkyldimethylammonium chloride, stirring is continued at 55 ° C. for 2 hours to complete the reaction to obtain an aqueous solution of quaternary ammonium hydrolyzed wheat protein having a quaternary ammonium conversion rate of 55%. It was.

  Dilute sulfuric acid is added to the aqueous solution of the quaternary ammonium hydrolyzed wheat protein obtained above to adjust the pH to 4.5, and while stirring this adjusted solution at 55 ° C., glycidol (Daicel Chemical Industries) 34.8g (1.0 equivalent with respect to the carboxy group of hydrolyzed wheat protein) was dripped over 1 hour. After completion of dropwise addition of glycidol, stirring was continued at 55 ° C. for 3 hours to complete the reaction. Since the pH of the solution increased during the reaction, the pH of the solution was maintained around 4 using dilute sulfuric acid.

  After completion of the reaction, the reaction solution was adjusted to pH 6 with a 20% aqueous sodium hydroxide solution, and water was added thereto to add 579.2 g of an aqueous solution of a quaternary ammonium-modified hydrolyzed wheat protein glycerin ester derivative having a solid content concentration of 30%. Obtained.

IR analysis of the obtained quaternary ammonium-modified hydrolyzed wheat protein glycerin ester derivative and quaternary ammonium-modified hydrolyzed wheat protein before glycerin esterification was conducted and the IR spectra of both were compared. Absorption was observed in the vicinity of 1735 cm ⁻¹ only in the spectrum of the hydrolyzed wheat protein glycerin ester derivative, confirming the esterification of the carboxy group of the quaternary ammonium-modified hydrolyzed wheat protein. Moreover, the esterification rate of the quaternary ammonium-modified hydrolyzed wheat protein glycerin ester derivative by the esterification rate measuring method was 52%.

Example 4: Quaternary ammonium-modified hydrolyzed rice protein glycerin ester derivative Hydrolyzed rice protein [A hydrolyzate of rice protein, a in general formula (III) is 0.32, b is 0.91, c is 2 27, a + b + c is 3.5], and adjusted to pH 10 by adding 20% aqueous sodium hydroxide solution to 400 g of 27% aqueous solution of 0.23 mol of amino groups and 0.33 mol of carboxy groups. did. The solution was stirred at 55 ° C., and 205.9 g of glycidyl coconut alkyldimethylammonium chloride (purity 32%) (0.8 equivalent to the amino group of the hydrolyzed rice protein) was added dropwise over 2 hours. Then, a quaternary ammonium reaction was performed on the amino group of the hydrolyzed rice protein. After completion of the dropwise addition of glycidyl coconut alkyldimethylammonium chloride, stirring is continued at 55 ° C. for 2 hours to complete the reaction to obtain an aqueous solution of quaternary ammonium hydrolyzed rice protein having a quaternary ammonium conversion rate of 54%. It was.

  Dilute sulfuric acid is added to the aqueous solution of the quaternary ammonium-modified hydrolyzed rice protein obtained above to adjust the pH to 4.5, and this adjusted solution is stirred at 55 ° C., and glycidol (Daicel Chemical Industries, Ltd.) is added thereto. 36.6 g (manufactured by Co., Ltd.) (1.5 equivalents relative to the carboxy group of the hydrolyzed rice protein) was added dropwise over 1 hour. After completion of dropwise addition of glycidol, stirring was continued at 55 ° C. for 3 hours to complete the reaction. Since the pH of the solution increased during the reaction, the pH of the solution was maintained around 4 using dilute sulfuric acid.

  After completion of the reaction, the reaction solution was adjusted to pH 6 with a 20% aqueous sodium hydroxide solution, added with water, and 652.6 g of an aqueous solution of a quaternary ammonium-modified hydrolyzed rice protein glycerin ester derivative having a solid content concentration of 30%. Obtained.

IR analysis of the resulting quaternary ammonium-modified hydrolyzed rice protein glycerin ester derivative and quaternary ammonium-modified hydrolyzed rice protein before glycerin esterification was conducted and the IR spectra of both were compared. Absorption was observed in the vicinity of 1735 cm ⁻¹ only in the spectrum of the hydrolyzed rice protein glycerin ester derivative, confirming esterification of the carboxy group of the quaternary ammonium-modified hydrolyzed rice protein. Moreover, the esterification rate of the quaternary ammonium-modified hydrolyzed rice protein glycerin ester derivative by the esterification rate measuring method was 61%.

Example 5: Quaternary ammonium-modified hydrolyzed silk glycerin ester derivative Hydrolyzed silk [silk hydrolyzate, a in formula (III) is 0.1, b is 0.3, c is 10.6 , A + b + c was 11], and the pH was adjusted to 10 by adding a 20% aqueous sodium hydroxide solution to 400 g of 27% aqueous solution (the number of moles of amino groups was 0.09 mol and the number of moles of carboxy groups was 0.12 mol). This solution was stirred at 55 ° C., and 14.6 g of glycidyltrimethylammonium chloride (purity 75%) (0.8 equivalent with respect to the amino group of the hydrolyzed silk) was dropped into the solution over 2 hours. A quaternary ammonium reaction was performed on the amino group. After completion of the dropwise addition of glycidyltrimethylammonium chloride, stirring was continued at 55 ° C. for 2 hours to complete the reaction to obtain an aqueous solution of quaternary ammonium hydrolyzed silk having a quaternary ammonium conversion rate of 58%.

  Diluted sulfuric acid was added to the aqueous solution of the quaternary ammonium hydrolyzed silk obtained above to adjust the pH to 4.5, and while stirring this adjusted liquid at 55 ° C., glycidol (Daicel Chemical Industries, Ltd.) 17.8 g (2.0 equivalents based on the carboxy group of the hydrolyzed silk) was added dropwise over 1 hour. After completion of dropwise addition of glycidol, stirring was continued at 55 ° C. for 3 hours to complete the reaction. Since the pH of the solution increased during the reaction, the pH of the solution was maintained around 4 using dilute sulfuric acid.

  After completion of the reaction, the pH of the reaction solution was adjusted to 6 with a 20% aqueous sodium hydroxide solution, and water was added to obtain 410.2 g of an aqueous solution of a quaternary ammonium hydrolyzed silk glycerol ester derivative having a solid content concentration of 30%. It was.

IR analysis of the resulting quaternary ammonium hydrolyzed silk glycerin ester derivative and quaternary ammonium hydrolyzed silk before glycerin esterification was conducted and the IR spectra of both were compared. Absorption was observed in the vicinity of 1735 cm ⁻¹ only in the spectrum of the silk glycerin ester derivative, confirming the esterification of the carboxy group of the quaternary ammonium-modified hydrolyzed silk. Moreover, the esterification rate of the quaternary ammonium-modified hydrolyzed silk glycerol ester derivative by the above-mentioned esterification rate measurement method was 71%.

Example 6: Quaternary Ammonium Hydrolyzed Collagen Glycerin Ester Derivative Hydrolyzed Collagen [Collagen hydrolyzate, a in general formula (III) is 1.4, b is 2.3, c is 15.3 , A + b + c was 19], and the pH was adjusted to 10 by adding a 20% aqueous sodium hydroxide solution to 400 g of a 27% aqueous solution (the number of moles of amino groups was 0.06 mol and the number of moles of carboxy groups was 0.09 mol). The solution was stirred at 55 ° C., and 9.7 g of glycidyltrimethylammonium chloride (purity 75%) (0.8 equivalent to the amino group of the hydrolyzed collagen) was dropped into the solution over 2 hours. A quaternary ammonium reaction was performed on the amino group. After completion of the dropwise addition of glycidyltrimethylammonium chloride, stirring was continued at 55 ° C. for 2 hours to complete the reaction, whereby an aqueous solution of quaternary ammonium hydrolyzed collagen having a quaternary ammonium conversion rate of 56% was obtained.

  Dilute sulfuric acid is added to the aqueous solution of the quaternary ammonium hydrolyzed collagen obtained above to adjust the pH to 4.5, and while stirring this adjusted solution at 55 ° C., glycidol (Daicel Chemical Industries, Ltd.) 20.0 g (manufactured by company) (3.0 equivalents relative to the carboxy group of hydrolyzed collagen) was added dropwise over 1 hour. After completion of dropwise addition of glycidol, stirring was continued at 55 ° C. for 3 hours to complete the reaction. Since the pH of the solution increased during the reaction, the pH of the solution was maintained around 4 using dilute sulfuric acid.

  After completion of the reaction, the reaction solution was adjusted to pH 6 with a 20% aqueous sodium hydroxide solution, and water was added to obtain 405.8 g of an aqueous solution of a quaternary ammonium hydrolyzed collagen glycerin ester derivative having a solid content concentration of 30%. It was.

IR analysis of the resulting quaternary ammonium hydrolyzed collagen glycerin ester derivative and quaternary ammonium hydrolyzed collagen before glycerin esterification was conducted and the IR spectra of both were compared. Absorption was observed in the vicinity of 1735 cm ⁻¹ only in the spectrum of the collagen glycerin ester derivative, and esterification of the carboxy group of the quaternary ammonium agent hydrolyzed collagen was confirmed. The esterification rate of the quaternary ammonium-modified hydrolyzed collagen glycerol ester derivative by the above esterification rate measurement method was 69%.

Example 7: Quaternary ammonium salt hydrolyzed keratin glycerin ester derivative Hydrolyzed keratin [hydrolyzate of keratin, a in formula (III) is 2, b is 8, c is 15, a + b + c is 25] The pH was adjusted to 10 by adding a 20% aqueous sodium hydroxide solution to 400 g of a 27% aqueous solution (the number of moles of amino groups was 0.04 mol and the number of moles of carboxy groups was 0.11 mol). The solution was stirred at 55 ° C., and 6.5 g of glycidyltrimethylammonium chloride (purity 75%) (0.8 equivalent with respect to the amino group of the hydrolyzed keratin) was dropped into the solution over 2 hours. A quaternary ammonium reaction was performed on the amino group. After completion of the dropwise addition of glycidyltrimethylammonium chloride, stirring was continued at 55 ° C. for 2 hours to complete the reaction to obtain an aqueous solution of quaternary ammonium hydrolyzed keratin having a quaternary ammonium conversion rate of 52%.

  Dilute sulfuric acid is added to the aqueous solution of the quaternary ammonium hydrolyzed keratin obtained above to adjust the pH to 4.5, and while stirring this adjusted solution at 55 ° C., glycidol (Daicel Chemical Industries, Ltd.) 20.4 g (manufactured by company) (2.5 equivalents relative to the carboxy group of hydrolyzed keratin) was added dropwise over 1 hour. After completion of dropwise addition of glycidol, stirring was continued at 55 ° C. for 3 hours to complete the reaction. Since the pH of the solution increased during the reaction, the pH of the solution was maintained around 4 using dilute sulfuric acid.

  After completion of the reaction, the reaction solution was adjusted to pH 6 with a 20% aqueous sodium hydroxide solution, and water was added to obtain 399.9 g of an aqueous solution of a quaternary ammonium hydrolyzed keratin glycerol ester derivative having a solid content concentration of 30%. It was.

IR analysis of the obtained quaternary ammonium salt hydrolyzed keratin glycerin ester derivative and quaternary ammonium salt hydrolyzed keratin before glycerol esterification was conducted, and the IR spectra of both were compared. Absorption was observed in the vicinity of 1735 cm ⁻¹ only in the spectrum of the keratin glycerin ester derivative, and esterification of the carboxy group of the quaternary ammonium-modified hydrolyzed keratin was confirmed. Moreover, the esterification rate of the quaternary ammonium-modified hydrolyzed keratin glycerol ester derivative by the above esterification rate measurement method was 65%.

Example 8: Quaternary Ammonium Hydrolyzed Silk Amino Acid Glycerin Ester Derivative Hydrolyzed silk amino acid obtained by total hydrolysis of silk to amino acid units [silk hydrolyzate, a in formula (III) is 0 .010, b is 0.037, c is 1.073, and a + b + c is 1.12] in 400 g of a 27% aqueous solution (the number of moles of amino groups is 0.34 mol and the number of moles of carboxy groups is 0.99 mol). The pH was adjusted to 10 by adding an aqueous sodium hydroxide solution. The solution was stirred at 55 ° C., and 55.0 g of glycidyltrimethylammonium chloride (purity 75%) (0.8 equivalent to the amino group of the hydrolyzed silk amino acid) was dropped into the solution over 2 hours. A quaternary ammonium reaction was performed on the amino group of the silk amino acid. After completion of the dropwise addition of glycidyltrimethylammonium chloride, stirring was continued at 55 ° C. for 2 hours to complete the reaction to obtain an aqueous solution of a quaternary ammonium hydrolyzed silk amino acid having a quaternary ammonium conversion rate of 71%.

  Dilute sulfuric acid is added to the aqueous solution of the quaternary ammonium-modified hydrolyzed silk amino acid obtained above to adjust the pH to 4.5, and while stirring this adjusted solution at 55 ° C., glycidol (Daicel Chemical Industries) 73.3g (1.0 equivalent with respect to the carboxy group of a hydrolyzed silk amino acid) was dripped over 1 hour. After completion of dropwise addition of glycidol, stirring was continued at 55 ° C. for 3 hours to complete the reaction. Since the pH of the solution increased during the reaction, the pH of the solution was maintained around 4 using dilute sulfuric acid.

  After completion of the reaction, the reaction solution was adjusted to pH 6 with a 20% aqueous sodium hydroxide solution, and water was added to prepare 708.9 g of an aqueous solution of a quaternary ammonium hydrolyzed silk amino acid glycerin ester derivative having a solid content concentration of 30%. Obtained.

The IR analysis of the obtained quaternary ammonium-modified hydrolyzed silk amino acid glycerin ester derivative and the quaternary ammonium-modified hydrolyzed silk amino acid before glycerol esterification was conducted and the IR spectra of both were compared. Absorption was observed in the vicinity of 1735 cm ⁻¹ only in the spectrum of the hydrolyzed silk amino acid glycerin ester derivative, confirming the esterification of the carboxy group of the quaternary ammonium-modified hydrolyzed silk amino acid. The esterification rate of the quaternary ammonium-modified hydrolyzed silk amino acid glycerin ester derivative by the above esterification rate measurement method was 66%.

Measurement Example 1 [Acidity of Glycerin Ester Derivative of Quaternary Ammonium Hydrolyzed Protein or Quaternary Ammonium Amino Acid]
The acidity of the glycerin ester derivatives of the quaternary ammoniumated hydrolyzed proteins or quaternary ammoniumated amino acids of Examples 1 to 8 was measured. First, each quaternary ammonium salt hydrolyzed protein or glycerin ester derivative of a quaternary ammonium salt amino acid is diluted with water so that the total nitrogen amount becomes 0.36 g / 100 mL, and 100 mL of this solution is adjusted to pH 7.0. The prepared solution was used as a test solution. Next, 1 mL of 0.1 mol / L hydrochloric acid was added to each test solution, and the change in pH of the test solution was examined. Moreover, it replaced with the glycerol ester derivative of the quaternary ammonium-ized hydrolyzed protein or the quaternary ammonium-ized amino acid, and the glycerol ester of the quaternary ammonium-ized hydrolyzed protein of each Example 1-8 or a quaternary ammonium-ized amino acid. The quaternary ammonium-modified hydrolyzed protein or quaternary ammonium-modified amino acid used as a raw material of the derivative was examined as a comparative example 1 to 8, respectively, and the change in pH was examined by the same method as described above. Comparison was made with changes in pH of glycerin ester derivatives of proteins or quaternary ammonium amino acids.

  FIG. 3 shows the relationship between the amount of 0.1 mol / L hydrochloric acid added and the pH change of the quaternary ammonium salt hydrolyzed pea protein glycerin ester derivative of Example 1 and the quaternary ammonium salt hydrolyzed pea protein of Comparative Example 1. . As is clear from FIG. 3, as the amount of 0.1 mol / L hydrochloric acid added increased, the pH in Comparative Example 1 gradually decreased, whereas in Example 1, the pH decreased rapidly. That is, it turned out that the quaternary ammonium-ized hydrolysis pea protein glycerin ester derivative has the effect | action which buffers the hydrogen ion of hydrochloric acid from the quaternary ammonium-ized hydrolysis pea protein. Therefore, it was confirmed that the number of carboxy groups (acidity) of the quaternary ammonium-modified hydrolyzed pea protein glycerin ester derivative was reduced as compared with the quaternary ammonium-modified hydrolyzed pea protein.

  Moreover, about the quaternary ammonium-ized hydrolyzed protein of Examples 2-8 or the glycerol ester derivative of a quaternary ammonium-ized amino acid, and the quaternary ammonium-ized hydrolyzed protein or quaternary ammonium-ized amino acid of Comparative Examples 2-8. Quaternary ammonium-modified hydrolyzed protein or glycerin ester derivative of quaternary ammonium-modified amino acid with a smaller amount of hydrochloric acid than quaternary ammonium-modified hydrolyzed protein or quaternary ammonium-modified amino acid. It was confirmed that the pH dropped rapidly.

  Table 1 shows quaternary ammonium-modified hydrolyzed proteins or glycerin ester derivatives of quaternary ammonium-modified amino acids of Examples 1 to 8 and quaternary ammonium-modified hydrolyzed proteins or quaternary ammonium-containing compounds of Comparative Examples 1 to 8. The amount of 0.1 mol / L hydrochloric acid required for bringing each aqueous solution of amino acid to pH 3.0 is shown as a guide for acidity.

  As shown in Table 1, the quaternary ammonium salt hydrolyzed protein of Examples 1 to 8 or the glycerin ester derivative of the quaternary ammonium salt amino acid is a quaternary ammonium salt hydrolyzed protein before glycerol esterification. Or, compared with quaternary ammonium amino acids, the amount of hydrochloric acid required to achieve pH 3.0 is small. Therefore, the glycerin ester derivatives of the quaternary ammonium hydrolyzed proteins or the quaternary ammonium amino acids of Examples 1 to 8 are reduced in acidity and increased in basicity as a result of carboxy group reduction by glycerin esterification. I found out.

Measurement Example 2 [Combination Test of Quaternary Ammonium Hydrolyzed Protein or Glycerin Ester Derivative of Quaternary Ammonium Amino Acid into O / W Emulsified Hair Treatment]
Using the quaternary ammonium hydrolyzed protein of Examples 1 to 8 or the glycerin ester derivative of a quaternary ammonium amino acid, an O / W emulsified hair treatment having the composition shown in Table 2 was prepared as Examples 1 to 8. did. Moreover, it replaced with the glycerol ester derivative of the quaternary ammonium-ized hydrolyzed protein or the quaternary ammonium-ized amino acid, and the glycerol ester of the quaternary ammonium-ized hydrolyzed protein of each Example 1-8 or a quaternary ammonium-ized amino acid. Comparative products 1 to 8 containing the quaternary ammonium hydrolyzed protein or quaternary ammonium amino acid used as a raw material for the derivatives were also prepared in the same manner. Furthermore, as a control product, neither quaternary ammonium hydrolyzed protein or glycerin ester derivative of quaternary ammonium amino acid, nor quaternary ammonium hydrolyzed protein or quaternary ammonium amino acid is blended. A / W emulsified hair treatment was prepared. In Table 2, the amount of additive is expressed by mass% in principle. However, quaternary ammonium-modified hydrolyzed protein or glycerin ester derivative of quaternary ammonium-modified amino acid, and quaternary ammonium-modified hydrolyzed protein. Alternatively, the amount of the quaternary ammonium amino acid is adjusted so that the amount of the hydrolyzed protein or amino acid moiety is the same so that the mass of the quaternary ammonium hydrolyzed protein or quaternary ammonium amino acid moiety is O / W. 1% in the emulsified hair treatment formulation.

Appearances of the above-mentioned Examples 1 to 8, Comparative Products 1 to 8, and Control were immediately observed. The results are shown in Table 3 with symbols based on the following evaluation criteria.
Evaluation criteria for O / W emulsified hair treatment ○: Uniform emulsification state Δ: Non-uniform emulsification state ×: Two-layer separation state (emulsification impossible)

  As is apparent from Table 3, Examples 1 to 8 containing the quaternary ammonium-modified hydrolyzed protein of Examples 1 to 8 or glycerin ester derivatives of quaternary ammonium-containing amino acids were uniformly emulsified in the same manner as the control product. In contrast, Comparative products 1 to 8 containing quaternary ammonium-modified hydrolyzed protein or quaternary ammonium-containing amino acid did not become uniform emulsions. The quaternary ammonium-modified hydrolyzed protein or quaternary ammonium-containing amino acid has a carboxy group in the molecule, and its anionic property is an alkyl chloride generally contained in an O / W emulsified hair treatment. It is thought that it forms a complex with a cationic substance such as trimethylammonium and hinders emulsification. However, quaternary ammonium-modified hydrolyzed protein with glycerin esterified carboxy group or glycerin ester derivative of quaternary ammonium amino acid does not form a complex with cationic substances such as alkyltrimethylammonium chloride. It is thought that it will not hinder. In particular, the comparative product containing a quaternary ammonium product of a plant protein having a large number of carboxy groups could not be separated into two layers and emulsified, whereas the practical product containing a glycerin derivative was uniformly emulsified. It can be said that the formation of an object shows the above theory remarkably.

Measurement Example 3 [Solubility on Acid Side of Glycerin Ester Derivative of Quaternary Ammonium Hydrolyzed Protein or Quaternary Ammonium Amino Acid]
The solubility of the glycerin ester derivatives of the quaternary ammonium-modified hydrolyzed proteins or quaternary ammonium-modified amino acids of Examples 1 to 8 in the range of pH 3.0 to 7.0 was examined. Specifically, 1 mol / L hydrochloric acid is added to each aqueous solution adjusted to a solid content concentration of 10% to adjust the pH of the aqueous solution to 3.0, 4.0, 5.0, 6.0, and 7.0. The state of the solution when adjusted was visually observed. The observation results are shown in Table 4. Moreover, also about the quaternary ammonium-ized hydrolyzed protein before glycerol esterification in Examples 1-8 or a quaternary ammonium-ized amino acid, a solubility is investigated by the method similar to the above, and as comparative examples 1-8, respectively, The observation results are shown in Table 4. The observation results are indicated by symbols according to the following evaluation criteria.

Observation result: Evaluation criteria for solubility ◎: Transparent ○: Slightly turbid △: Emulsion ×: Generation of precipitate

  As apparent from Table 4, the aqueous solution of the quaternary ammonium-modified hydrolyzed protein or glycerin ester derivative of the quaternary ammonium-containing amino acid in each example is transparent or slightly turbid under the condition of pH 5.0 to 7.0. In contrast, some of the quaternary ammonium-modified hydrolyzed proteins or quaternary ammonium-modified amino acids of Comparative Examples 1 to 8 were already cloudy at pH 7, and precipitated on the acidic side from around pH 5.0. There were many things that gave rise to. Moreover, it was shown that the glycerin ester derivative of the quaternary ammonium salt hydrolyzed protein or quaternary ammonium salt amino acid of each example had better solubility than the comparative example even in an acidic region of pH 5.0 or less. Therefore, the glycerin ester derivative of quaternary ammonium-modified hydrolyzed protein or quaternary ammonium-modified amino acid has a weak pH of about 5.0, which was impossible with quaternary ammonium-modified hydrolyzed protein or quaternary ammonium-modified amino acid. This result shows that it can be incorporated into an acidic transparent cosmetic.

Claims (7)

A hydrolyzed protein or amino acid derivative,
A quaternary ammonium functional group is bonded to part of the amino group, and the following general formula (I):
A cosmetic base material comprising a glycerin ester derivative of a quaternary ammonium salt hydrolyzed protein or a quaternary ammonium salt amino acid to which a functional group represented by   The cosmetic base material according to claim 1, wherein 50% or more of the total carboxy groups of the hydrolyzed protein or amino acid are esterified with the functional group represented by the general formula (I). The quaternary ammonium functional group has the following general formula (II):
(In the formula, R ¹ , R ² , and R ³ may be the same or different, and an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, or ^{one of} R ^{1 to} R ³ or 2 represents an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms, and the remaining represents an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group having 1 to 3 carbon atoms, or a benzyl group. (Saturated hydrocarbon having 2 to 3 carbon atoms or saturated hydrocarbon having a hydroxyl group having 2 to 3 carbon atoms, X represents a halogen atom)
The cosmetic base material according to claim 1, wherein the cosmetic base material is represented by:   The cosmetic base material according to claim 3, wherein the functional group represented by the general formula (II) is bonded to 50% or more of the total amino groups of the hydrolyzed protein or amino acid.   The cosmetic product according to any one of claims 1 to 4, wherein the hydrolyzed protein portion of the glycerin ester derivative of the quaternary ammonium-modified hydrolyzed protein is obtained from a hydrolyzate of a plant protein. Base material.   The cosmetic substrate according to any one of claims 1 to 5, wherein the hydrolyzed protein has an average amino acid polymerization degree of 2 to 50.   A cosmetic comprising the cosmetic base material according to any one of claims 1 to 6.