Compositions, methods of making the same, and cosmetics

Abstract

The present application aims to provide a composition (particularly, a cosmetic raw material composition) that imparts excellent emulsion stability and dispersion stability. The aforementioned object can be achieved by the composition described in the specification, which is characterized by containing: component A; and one or more components selected from the group consisting of component B, component C, component D, and component E (wherein the case of only the aforementioned component C or only the aforementioned component D is excluded).

Description

Technical Field

[0001] This invention relates to compositions (particularly fragrance and cosmetic raw material compositions), methods of manufacturing the same, and cosmetics. Background Technology

[0002] Acyl-containing amino acid derivatives have gained particular attention in recent years because, even when added in trace amounts, they provide excellent stability, emulsification, and dispersibility in weakly acidic formulations, especially those with a pH close to that of hair and skin. For example, Patent Document 1 discloses a composition containing an acyl-containing amino acid derivative that exhibits excellent stability and user experience. Furthermore, Patent Document 2 discloses a technique that improves the stability, preservative effect, and low irritation of cosmetic formulations through the compounding of acyl-containing amino acid derivatives.

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: Japanese Patent No. 4070768

[0006] Patent Document 2: Japanese Patent Application Publication No. 2006-160686 Summary of the Invention

[0007] The problem the invention aims to solve

[0008] For fragrance formulations, especially in skincare and haircare applications, there is a high demand for emulsifying and dispersing abilities. However, even conventional fragrance formulations as described in Patent Documents 1 and 2 still struggle to achieve high emulsification and dispersing stability.

[0009] Therefore, the object of the present invention is to provide compositions (especially cosmetic raw material compositions) that impart excellent emulsification stability and dispersion stability.

[0010] In other words, the inventors conducted repeated and in-depth research in order to achieve the above-mentioned objectives, and as a result, they discovered that by combining amino acid derivatives containing acyl groups with specific structures with various components, compositions that impart excellent emulsification stability and dispersion stability can be provided.

[0011] That is, the present invention is as follows.

[0012] [1] A composition characterized in that it comprises:

[0013] The following component A; and

[0014] Choose one or more components from the group consisting of component B, component C, component D, and component E (excluding cases where only component C or only component D is listed).

[0015] • Component A: An acyl-containing amino acid derivative or its salt as shown in the following general formula (A).

[0016]

[0017] (In formula (A),

[0018] R1 and R2 are each independently a saturated or unsaturated straight-chain or branched hydrocarbon group.

[0019] M1, M2, and M3 are each independently a hydrogen atom, an alkali metal, an alkaline earth metal, an organic or inorganic amine, a basic amino acid, choline, aluminum, or zinc.

[0020] n1 and n2 are 0 and 2, or 2 and 0.

[0021] n3 and n4 are 0 and 2, or 2 and 0.

[0022] • Component B: N-acylpyrrolidone carboxylic acid or a salt thereof, represented by the following general formula (B).

[0023]

[0024] (In formula (B),

[0025] R3 is a saturated or unsaturated straight-chain or branched hydrocarbon group.

[0026] M4 can be hydrogen, alkali metal, alkaline earth metal, organic or inorganic amine, basic amino acid, choline, aluminum or zinc.

[0027] • Component C: Acylglutamic acid or its salt represented by the following general formula (C),

[0028]

[0029] (In formula (C),)

[0030] R4 is a saturated or unsaturated straight-chain or branched hydrocarbon group.

[0031] M5 and M6 are each independently hydrogen atoms, alkali metals, alkaline earth metals, organic or inorganic amines, basic amino acids, choline, aluminum or zinc.

[0032] • Component D: Fatty acid or its salt represented by the following general formula (D).

[0033]

[0034] (In formula (D),)

[0035] R5 is a saturated or unsaturated straight-chain or branched hydrocarbon group.

[0036] M7 represents hydrogen atoms, alkali metals, alkaline earth metals, organic or inorganic amines, basic amino acids, choline, aluminum, or zinc.

[0037] • Component E: A fatty acid amide represented by the following general formula (E),

[0038]

[0039] (In formula (E),

[0040] R6 is a saturated or unsaturated straight-chain or branched hydrocarbon group.

[0041] [2] The composition according to [1] contains the aforementioned component A and the aforementioned component B.

[0042] [3] The composition according to [1] contains the aforementioned component A and the aforementioned component E.

[0043] [4] The composition according to [1] contains the aforementioned component A, the aforementioned component B and the aforementioned component E.

[0044] [5] The composition according to any one of [1] to [4], wherein R1 to R6 in the aforementioned general formulas (A) to (E) are each independently a hydrocarbon group having 1 to 29 carbon atoms.

[0045] [6] The composition according to any one of [1] to [5], wherein M1 to M7 in the aforementioned general formulas (A) to (D) are each independently Na, K, triethanolamine, Mg, Ca, Al, Zn, arginine or H.

[0046] [7] The composition according to any one of [1], [2], [4], [5] and [6], wherein the ratio of the aforementioned component B to the aforementioned component A is 0.004% or more.

[0047] [8] The composition according to any one of [1] and [5] to [7], wherein the total mass of the aforementioned component A and the aforementioned component C is used as a basis, and the amount of the aforementioned component C is 0.8% by mass or more.

[0048] The total mass of the aforementioned components A and D is used as a benchmark, and the amount of the aforementioned component D is 0.06% by mass or more.

[0049] [9] The composition according to any one of [1] and [3] to [8], wherein the mass of the aforementioned component A is used as a basis and the amount of the aforementioned component E is 0.005% by mass or more.

[0050] A method for manufacturing the composition according to any one of

[10] [1], [2] and [4] to [9], comprising the following steps:

[0051] Step 1) In a mixed solvent containing water and organic solvent, glutamic acid or its salt is reacted with fatty acyl chloride to obtain a reaction solution containing N-acylglutamic acid or its salt. The pH of the reaction solution is adjusted to 1-6 using acid, and the solution is separated into an organic layer and an aqueous layer at a temperature of 25-80°C.

[0052] Step 2) The aforementioned organic layer is concentrated and dried under acidic conditions to convert a portion of the aforementioned N-acylglutamic acid or its salt into N-acylpyrrolidone carboxylic acid or its salt;

[0053] Step 3) React the aforementioned N-acylglutamic acid or its salt with an acid anhydride to obtain N-acylglutamic acid anhydride; and

[0054] Step 4) React the aforementioned N-acylglutamic anhydride with lysine or its salt to obtain an amino acid derivative or its salt containing an acyl group.

[0055]

[11] According to the manufacturing method described in

[10] , in the aforementioned step 2), the aforementioned organic layer is concentrated and dried until the weight loss during drying is less than 10% by mass.

[0056]

[12] According to the manufacturing method described in

[10] or

[11] , wherein the concentration drying in the aforementioned step 2) is carried out under reduced pressure and at a temperature of 50°C or higher.

[0057]

[13] The composition according to any one of [1] to [9] is a cosmetic raw material composition.

[0058] The use of any one of the compositions described in

[14] [1] to [9] as a raw material for cosmetics.

[0059]

[15] A cosmetic product comprising any one of the compositions described in [1] to [9].

[0060]

[16] The cosmetic described in

[15] has a pH of 4 or higher.

[0061] The effects of the invention

[0062] According to the present invention, compositions (especially cosmetic raw material compositions) that impart excellent emulsification stability and dispersion stability can be provided. Detailed Implementation

[0063] The following provides a detailed description of the methods for implementing the present invention (hereinafter referred to simply as "this embodiment"). This embodiment is merely an example for illustrating the present invention and is not intended to limit the invention to its contents. The present invention can be implemented with appropriate modifications within its scope.

[0064] [Composition]

[0065] This embodiment relates to compositions (particularly fragrance and cosmetic ingredient compositions) and cosmetics formulated with them, the composition containing: ingredient A; and one or more ingredients selected from the group consisting of ingredients B, C, D, and E (excluding cases where only ingredient C or only ingredient D is used). Examples of combinations of ingredients include A+B, A+E, A+B+C, A+B+D, A+B+E, A+C+D, A+C+E, A+B+C+D, A+B+C+E, and A+C+D+E.

[0066] Component A is an amino acid derivative containing an acyl group or a salt thereof, as shown in the following general formula (A).

[0067]

[0068] (In formula (A),

[0069] R1 and R2 are each independently a saturated or unsaturated straight-chain or branched hydrocarbon group.

[0070] M1, M2, and M3 are each independently a hydrogen atom, an alkali metal, an alkaline earth metal, an organic or inorganic amine, a basic amino acid, or choline.

[0071] n1 and n2 are 0 and 2, or 2 and 0.

[0072] n3 and n4 are 0 and 2, or 2 and 0.

[0073] Component B is an N-acylpyrrolidone carboxylic acid or a salt thereof, as shown in the following general formula (B). It should be noted that, in this specification, component B is also referred to as "acylPCA".

[0074]

[0075] (In formula (B),

[0076] R3 is a saturated or unsaturated straight-chain or branched hydrocarbon group.

[0077] M4 can be a hydrogen atom, an alkali metal, an alkaline earth metal, an organic or inorganic amine, a basic amino acid, or choline.

[0078] Component C is acylglutamic acid or its salt as shown in the following general formula (C).

[0079]

[0080] (In formula (C),)

[0081] R4 is a saturated or unsaturated straight-chain or branched hydrocarbon group.

[0082] M5 and M6 are each independently hydrogen atoms, alkali metals, alkaline earth metals, organic or inorganic amines, basic amino acids, or choline.

[0083] Component D is a fatty acid or its salt represented by the following general formula (D).

[0084]

[0085] (In formula (D),)

[0086] R5 is a saturated or unsaturated straight-chain or branched hydrocarbon group.

[0087] M7 can be a hydrogen atom, alkali metal, alkaline earth metal, organic or inorganic amine, basic amino acid, or choline.

[0088] Component E is a fatty acid amide represented by the following general formula (E).

[0089]

[0090] (In formula (E),

[0091] R6 is a saturated or unsaturated straight-chain or branched hydrocarbon group.

[0092] The fragrance raw material composition of this embodiment imparts high initial emulsification stability and dispersion stability to fragrance formulations, and also provides a good user experience.

[0093] In general formula (A), R1 and R2, if they are hydrocarbon groups, are not limited to saturated, unsaturated, straight-chain, or branched types; all can be used. For example, R1 and R2 can each independently be a hydrocarbon group with 9 carbons, 11 carbons, 13 carbons, 15 carbons, 17 carbons, 19 carbons, or 21 carbons. In particular, hexanoyl, undecenoyl, lauroyl, myristoyl, isomistioyl, palmitoyl, isopalmitoyl, stearyl, isostearyl, oleyl, linoleyl, linolenic acid, eicosyl, docosyl, and other commonly available hydrocarbon groups can be used as R1-C(=O)- and R2-C(=O)- structures. Mixed hydrocarbon groups derived from compositions of palm oil, palm kernel oil, and coconut oil can also be used. For example, hydrocarbon groups with 1 to 29 carbon atoms are preferred. Hydrocarbon groups with 7 to 23 carbon atoms are preferred. Hydrocarbon groups with 7 to 17 carbon atoms are more preferred. Saturated hydrocarbon groups that are easy to manage and prevent oxidation by air are especially preferred. From an economic point of view, it is even more preferable that the R1-C(=O)- and R2-C(=O)- structures are lauroyl and / or myristoyl.

[0094] The three carboxylic acid groups of the amino acid derivative containing the acyl group shown in general formula (A) can all be free carboxylic acids, all be carboxylates, or be a combination of free carboxylic acids and carboxylates.

[0095] The carboxylates (COOM1, COOM2, COOM3) in general formula (A) are not particularly limited, and can include, for example, alkali metal salts or alkaline earth metal salts such as sodium salts, potassium salts, lithium salts, magnesium salts, and calcium salts; amine salts (organic or inorganic ammonium salts) such as ammonium salts, alkylamine salts, monoethanolamine salts, diethanolamine salts, triethanolamine salts, and aminomethylpropanol salts; basic amino acid salts such as lysine salts and arginine salts; choline salts; aluminum salts; zinc salts, etc., either individually or in mixtures. From the viewpoint of performance and ease of acquisition, sodium salts, potassium salts, magnesium salts, triethanolamine salts, and arginine salts are preferred, and sodium salts are more preferred.

[0096] Based on the mass of the cosmetic raw material composition, the content of component A is preferably 0.003 to 3% by mass, more preferably 0.01 to 2% by mass, and even more preferably 0.02 to 0.5% by mass.

[0097] In general formula (B), R3, if it is a hydrocarbon group, is not limited to saturated, unsaturated, straight-chain, or branched types; all can be used. For example, R3 can be a hydrocarbon group with 9, 11, 13, 15, 17, 19, or 21 carbons. In particular, as an R3-C(=O)- structure, commonly used hydrocarbon groups such as hexanoyl, undecenoyl, lauroyl, myristoyl, isomistioyl, palmitoyl, isopalmitoyl, stearyl, isostearyl, oleyl, linoleyl, linolenic acid, eicosyl, and docosyl can all be used, as well as mixed hydrocarbon groups derived from compositions of palm oil, palm kernel oil, and coconut oil. Preferably, it is a hydrocarbon group with 7 to 23 carbons. For example, it is a hydrocarbon group with 1 to 29 carbons. More preferably, it is a hydrocarbon group with 7 to 17 carbons. It is particularly preferred to use saturated hydrocarbon groups in the hydrocarbon group that are easy to manage and prevent oxidation by air. From an economic point of view, it is even more preferred that the R3-C(=O)- structure is lauroyl and / or myristoyl.

[0098] The carboxylate (COOM4) in general formula (B) is not particularly limited, and examples include alkali metal salts or alkaline earth metal salts such as sodium salts, potassium salts, lithium salts, magnesium salts, and calcium salts; amine salts (organic or inorganic ammonium salts) such as ammonium salts, alkylamine salts, monoethanolamine salts, diethanolamine salts, triethanolamine salts, and aminomethylpropanol salts; basic amino acid salts such as lysine salts and arginine salts; choline salts; aluminum salts; zinc salts, etc., either individually or in mixtures. From the viewpoint of performance and ease of acquisition, sodium salts, potassium salts, magnesium salts, triethanolamine salts, and arginine salts are preferred, and sodium salts are more preferred.

[0099] From the viewpoint of imparting high initial emulsification stability, dispersion stability, and economy to the fragrance and cosmetic formulation, the ratio of component A to component B is preferably 0.004% or more and 7.0% or less, more preferably 0.01% or more and 3.5% or less, and even more preferably 0.02% or more and 2.0% or less. If the content of component B is 0.004% or more, the emulsification and emulsification stability of the formulation system are further improved; furthermore, if component B is 7.0% or less, the solubility stability of the formulation system is further improved. The aforementioned ratios can be determined by the HPLC analysis method described in the following examples.

[0100] Using the mass of the cosmetic raw material composition as a benchmark, the content of component B is preferably 0.00003 to 0.03% by mass, more preferably 0.0001 to 0.02% by mass, and even more preferably 0.0002 to 0.005% by mass.

[0101] In general formula (C), R4, if it is a hydrocarbon group, is not limited to saturated, unsaturated, straight-chain, or branched types; all can be used. For example, R4 can be a hydrocarbon group with 9, 11, 13, 15, 17, 19, or 21 carbons. In particular, as an R4-C(=O)- structure, commonly used hydrocarbon groups such as hexanoyl, undecenoyl, lauroyl, myristoyl, isomistioyl, palmitoyl, isopalmitoyl, stearyl, isostearyl, oleyl, linoleyl, linolenic acid, eicosyl, and docosyl can all be used, as well as mixed hydrocarbon groups derived from compositions of palm oil, palm kernel oil, and coconut oil. For example, hydrocarbon groups with 1 to 29 carbons are used. Preferably, hydrocarbon groups with 7 to 23 carbons are used. More preferably, hydrocarbon groups with 7 to 17 carbons are used. It is particularly preferred to use saturated hydrocarbon groups in the hydrocarbon group that are easy to manage and prevent oxidation by air. From an economic point of view, it is even more preferred that the R4-C(=O)- structure is lauroyl and / or myristoyl.

[0102] The carboxylates (COOM5, COOM6) in general formula (C) are not particularly limited, and examples include alkali metal salts or alkaline earth metal salts such as sodium salts, potassium salts, lithium salts, magnesium salts, and calcium salts; amine salts (organic or inorganic ammonium salts) such as ammonium salts, alkylamine salts, monoethanolamine salts, diethanolamine salts, triethanolamine salts, and aminomethylpropanol salts; basic amino acid salts such as lysine salts and arginine salts; choline salts; aluminum salts; zinc salts, etc., either individually or in mixtures. From the viewpoint of performance and ease of acquisition, sodium salts, potassium salts, magnesium salts, triethanolamine salts, and arginine salts are preferred, and sodium salts are more preferred.

[0103] Using the total mass of components A and C as a benchmark, the content (%) of component C is preferably 0.8% by mass or more, more preferably 0.8% by mass or more and 8.0% by mass or less, even more preferably 1.1% by mass or more and 8.0% by mass or less, and particularly preferably 1.5% by mass or more and 6.0% by mass or less. The above ratios can be determined by the methods described in the examples below.

[0104] In general formula (D), R5, if it is a hydrocarbon group, is not limited to saturated, unsaturated, straight-chain, or branched types; all can be used. For example, R5 can be a hydrocarbon group with 9, 11, 13, 15, 17, 19, or 21 carbons. In particular, as an R5-C(=O)- structure, commonly used hydrocarbon groups such as hexanoyl, undecenoyl, lauroyl, myristoyl, isomistioyl, palmitoyl, isopalmitoyl, stearyl, isostearyl, oleyl, linoleyl, linolenic acid, eicosyl, and docosyl can all be used, as well as mixed hydrocarbon groups derived from compositions of palm oil, palm kernel oil, and coconut oil. For example, it can be a hydrocarbon group with 1 to 29 carbons. Preferably, it is a hydrocarbon group with 7 to 23 carbons. More preferably, it is a hydrocarbon group with 7 to 17 carbons. It is particularly preferred to use saturated hydrocarbon groups in the hydrocarbon group that are easy to manage and prevent oxidation by air. From an economic point of view, it is even more preferred that the R5-C(=O)- structure is lauroyl and / or myristoyl.

[0105] The carboxylate (COOM7) in general formula (D) is not particularly limited, and examples include alkali metal salts or alkaline earth metal salts such as sodium salts, potassium salts, lithium salts, magnesium salts, and calcium salts; amine salts (organic or inorganic ammonium salts) such as ammonium salts, alkylamine salts, monoethanolamine salts, diethanolamine salts, triethanolamine salts, and aminomethylpropanol salts; basic amino acid salts such as lysine salts and arginine salts; choline salts, aluminum salts, and zinc salts, either individually or in mixtures. From the viewpoint of performance and ease of acquisition, sodium salts, potassium salts, magnesium salts, triethanolamine salts, and arginine salts are preferred, and sodium salts are more preferred.

[0106] Using the total mass of components A and D as a reference, the content (%) of component D is preferably 0.06% by mass or more, more preferably 0.06% by mass or more and 3.0% by mass or less, even more preferably 0.11% by mass or more and 3.0% by mass or less, and particularly preferably 0.14% by mass or more and 0.55% by mass or less. The above ratios can be determined by the methods described in the examples below.

[0107] In general formula (E), R6, if it is a hydrocarbon group, is not limited to saturated, unsaturated, straight-chain, or branched types; all can be used. For example, R6 can be a hydrocarbon group with 9, 11, 13, 15, 17, 19, or 21 carbons. In particular, as an R6-C(=O)- structure, commonly used hydrocarbon groups such as hexanoyl, undecenoyl, lauroyl, myristoyl, isomistioyl, palmitoyl, isopalmitoyl, stearyl, isostearyl, oleyl, linoleyl, linolenic acid, eicosyl, and docosyl can all be used, as well as mixed hydrocarbon groups derived from compositions of palm oil, palm kernel oil, and coconut oil. For example, it can be a hydrocarbon group with 1 to 29 carbons. Preferably, it is a hydrocarbon group with 7 to 23 carbons. More preferably, it is a hydrocarbon group with 7 to 17 carbons. It is particularly preferred to use saturated hydrocarbon groups in the hydrocarbon group that are easy to manage and prevent oxidation by air. From an economic point of view, it is even more preferred that the R6-C(=O)- structure is lauroyl and / or myristoyl.

[0108] From the viewpoint of imparting high initial emulsification stability, dispersion stability, and productivity to fragrance and cosmetic formulations, the ratio of component A to component E (component A / component E) is preferably 0.005% by mass or more and 5.00% by mass or less, more preferably 0.02% by mass or more and 3.00% by mass or less, and even more preferably 0.08% by mass or more and 0.6% by mass or less. The aforementioned ratio can be determined by the method described in the examples below.

[0109] The pH of the fragrance raw material composition and the cosmetics containing it in this embodiment is not particularly limited, but is preferably 4.0 to 9.0, more preferably 4.5 to 8.5, and even more preferably 5.0 to 8.0.

[0110] In formulas (A) to (D), M1 to M7 are preferably each independently selected from the group consisting of hydrogen atoms, sodium, lithium, potassium, magnesium, ammonium, triethanolamine and arginine.

[0111] M1 to M7 are more preferably each independently selected from the group consisting of hydrogen atoms, sodium, lithium, potassium, magnesium, ammonium, triethanolamine and arginine, wherein at least one of M1 to M7 is hydrogen, and at least one of M1 to M7 is selected from the group consisting of sodium, lithium, potassium, magnesium, ammonium, triethanolamine and arginine.

[0112] M1 to M7 are further preferably each independently hydrogen or sodium, with at least one of M1 to M7 being hydrogen and at least one of M1 to M7 being sodium.

[0113] [Method for manufacturing the composition]

[0114] The method for manufacturing the composition (especially the fragrance and cosmetic raw material composition) of this embodiment includes the following steps.

[0115] 1) [First step] In a mixed solvent containing water and organic solvent, glutamic acid or its salt is reacted with fatty acyl chloride to obtain a reaction solution containing N-acylglutamic acid or its salt. The pH of the aforementioned reaction solution is adjusted to 1 to 6 using acid, and the solution is separated into an organic layer and an aqueous layer at a temperature of 25 to 80°C.

[0116] 2) [Second step] The process of concentrating and drying the aforementioned organic layer under acidic conditions to convert a portion of the aforementioned N-acylglutamic acid or its salt into N-acylpyrrolidone carboxylic acid or its salt (component B).

[0117] 3) [Third step] The process of reacting the aforementioned N-acylglutamic acid or its salt with an acid anhydride to obtain N-acylglutamic acid anhydride.

[0118] 4) [Fourth step] The step of reacting the aforementioned N-acylglutamic anhydride with lysine or its salt to obtain an amino acid derivative or its salt containing an acyl group (component A).

[0119] [First Process]

[0120] The acylation reaction step in this embodiment is a step in which glutamic acid and fatty acyl chloride undergo a condensation reaction in a mixed solvent of water and organic solvents such as tert-butanol, acetone, methyl ethyl ketone, and isopropanol in the presence of an alkaline compound, thereby generating crude N-acylglutamic acid through the acylation reaction.

[0121] In the acylation reaction step, the molar ratio of fatty acyl chloride to glutamic acid is preferably 1.05 or less, more preferably 1.0 or less, and even more preferably 0.98 or less. By using a molar ratio of fatty acyl chloride to glutamic acid of 1.05 or less, there is a tendency to easily reduce the amount of free fatty acids generated.

[0122] In the acylation reaction step, the volume ratio of water to organic solvent in the mixed solvent is preferably in the range of 90 / 10 to 20 / 80, more preferably in the range of 85 / 15 to 50 / 50. By being in the range of 90 / 10 to 20 / 80, glutamic acid, fatty acyl chloride, and basic compound are easily compatible, which can improve the reaction rate.

[0123] There is no particular limitation on the concentration of glutamic acid in the acylation reaction process. The viscosity of the reaction solution increases over time during the reaction, so it is preferable to adjust the concentration to a level that allows for stirring and mixing near the end of the reaction.

[0124] The reaction temperature of the acylation reaction process is not particularly limited. From the viewpoint of promoting the main reaction and inhibiting the side reaction, it is preferred to be in the range of -10 to 70°C, more preferably in the range of -10 to 20°C, and even more preferably in the range of -5 to 10°C.

[0125] There are no particular restrictions on the basic compounds used in the acylation reaction process; examples include inorganic bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide, and barium hydroxide.

[0126] From the viewpoint of promoting the main reaction and inhibiting the side reaction, the pH in the acylation reaction process is preferably maintained in the range of 9 to 13.5, more preferably in the range of 10 to 13.

[0127] The acylation reaction solution is prepared at pH 1-6 using an acid such as hydrochloric acid or sulfuric acid (preferably an inorganic acid), and then separated into an organic layer and an aqueous layer to obtain the organic layer. In the acylation reaction solution, the generated N-acylglutamic acid exists as a basic salt. By adding acid, some or all of the carboxyl groups in the N-acylglutamic acid are converted into free acid, thereby separating the solution into an organic layer and an aqueous layer (acid precipitation step). Depending on the pH during acid precipitation, the dissociation state of the carboxyl groups changes, and the separation state, i.e., the mass ratio of the organic layer to the aqueous layer, and the removal efficiency of inorganic salts slightly change. Therefore, it is preferable to carry out the process at pH 1-3, and more preferably at pH 1-2.5.

[0128] The preferred temperature for the acid precipitation process is 25–80°C. More preferably, it is 40–70°C. Temperatures of 25°C or higher tend to shorten the time required to reach stratification equilibrium and reduce the residual amount of inorganic salts in the organic layer upon reaching equilibrium.

[0129] [Second Process]

[0130] The second step of this invention involves concentrating and drying the organic layer obtained in the first step under acidic conditions, converting a portion of the N-acylglutamic acid into N-acylpyrrolidone carboxylic acid (component B). Concentration and drying are preferably carried out under heating, atmospheric pressure, or reduced pressure. Concentration and drying are continued until the weight loss is preferably less than 10% by mass, more preferably less than 3% by mass, and even more preferably less than 1% by mass. In the next step, the acylglutamic acid is anhydrinated; therefore, to reduce moisture content, minimal weight loss is preferred.

[0131] In this specification, "loss on drying" refers to the percentage of mass lost through drying. Specifically, it is the percentage of mass lost when 1 g of a sample is dried at 105°C for 3 hours, calculated using the following formula.

[0132] Loss on drying (%) = [{initial sample mass (g) - dried sample mass (g)} / initial sample mass (g)] × 100

[0133] Concentration and drying are preferably carried out under normal or reduced pressure, initially at a temperature near the boiling point of the organic solvent or near the azeotropic point of the organic solvent and water, to remove the organic solvent and water by distillation. If the organic solvent is substantially less than 3% by mass relative to water, the coexisting acylglutamic acid is prone to foaming, so extra care must be taken to control the reduced pressure while heating. Even if the organic solvent is largely distilled off, water may still remain. As a practical operation, the reduced pressure can be continued near the boiling point of water. Compared to freeze-drying methods that involve continuous standing at a set temperature, the above operation requires controlled foaming, i.e., slow stirring adapted to the foaming condition. However, at temperatures below approximately 10% by mass and above 85°C, acylglutamic acid generates a suitable amount of acyl PCA, which can be used for emulsification and dispersibility in formulation systems.

[0134] In this process, for example, freeze-drying is used. Almost no foaming occurs during the process, and the drying operation involves no human intervention, making it simple; however, no acyl PCA was found.

[0135] If the acylglutamic acid exhibits reduced drying weight loss relative to the bulk organic matter, foaming and shrinkage will occur. When a pressure of 200 kPa is reached and the temperature of 85°C or higher is maintained for more than 20 minutes, the drying weight loss is less than 10% by mass.

[0136] To more effectively reduce drying weight loss, the pressure reduction achieved is preferably 50 kPa or less, more preferably 20 kPa or less. While the temperature also depends on the melting point of acylglutamic acid and the pressure reduction, it is preferably 70°C or higher, more preferably 95°C or higher, and even more preferably 105°C or higher.

[0137] By achieving a drying loss of less than 10% by mass, acylglutamic acid byproduct B (acyl PCA) can be generated.

[0138] [Third Process]

[0139] The solid acylglutamic acid matrix obtained in the second step is reacted with carboxylic anhydrides such as acetic anhydride. The resulting reaction solution is then filtered / dried to obtain crude crystals of the acylglutamic acid anhydride matrix.

[0140] Here, a carboxylic anhydride such as acetic anhydride is preferred as a dehydrating agent, and acetic anhydride is preferred from both economic and environmental perspectives. After the acylglutamic acid undergoes anhydridation, excess acetic anhydride and acetic acid are removed by filtration. To improve the purity of the acylglutamic acid anhydride, it is washed with diethyl ether, followed by petroleum ether, and then dried to obtain a solid product containing the acylglutamic acid anhydride.

[0141] [Fourth Process]

[0142] The solid of the acylglutamic anhydride main body obtained in the third step is reacted in accordance with Japanese Patent Publication No. 4070768 in such a way that, relative to 2 molar equivalents of acylglutamic anhydride, lysine is 1 molar equivalent, whereby an aqueous solution having as the main component an acyl-containing amino acid derivative represented by the general formula (A) as shown below can be prepared.

[0143] The cosmetic (in Japanese: 香粧品) in the present invention refers to the general term for quasi-drugs and cosmetics as defined in the Pharmaceutical Affairs Law. Specifically, as quasi-drugs, oral cooling agents, axillary odor preventives, talc products, hair tonics, depilatories, hair dyes, agents for electric hair curling, bath agents, medicinal cosmetics, medicinal toothpastes, etc. can be cited; as cosmetics, toilet soaps, facial cleansers (cream / paste type, liquid / gel type, granule / powder type, aerosol use, etc.), hair shampoos, hair conditioners, etc. for cleansing; hair dyes, hair treatment creams (including substances in cream, mist, oil, gel and other forms and hair split-end coating agents), hair styling agents (hair oils, styling lotions, curling iron lotions, pomades, hair waxes, sideburn oils, hair sprays, hair mists, hair setting lotions, hair foams, hair gels, water-based greases) and other hair cosmetics; general creams, emulsions (cleansing creams, cold creams, vanishing creams, hand creams, etc.), shaving creams (aftershave creams, shaving creams, etc.), lotions (hand lotions, general lotions, etc.), colognes, shaving milks (aftershave milks, shaving milks, etc.), makeup oils, emollients and other base cosmetics; face powders (cream face powders, solid face powders, face powders, talcum powders, face powder creams, baby powders, body powders, face paints, etc.), powders, foundations (cream, liquid, solid, etc.), rouges, eyebrow pencils, eye creams, eye shadows, mascaras and other makeup cosmetics; general perfumes, perfume creams, powder perfumes and other perfume products; gel type, liquid type, pottery type and other fragrances, deodorants, odor eliminators; tanning / sunscreen creams, tanning / sunscreen lotions, tanning / sunscreen oils and other tanning / sunscreen cosmetics; nail polishes, enamels, enamel removers and other nail cosmetics; eye makeup cosmetics; lipsticks, lip balms and other lip cosmetics; toothpastes and other oral cosmetics; bath salts, bath oils, foam baths and other bath cosmetics, etc.

[0144] In the cosmetic raw material composition of the present embodiment, in addition to Component A and Components B to E, various base materials can be used in combination according to the use and purpose as long as the object of the present invention is not impaired.

[0145] Specifically, it may contain natural rubbers such as gum arabic and tragacanth, glucosides such as saponins, cellulose derivatives such as methylcellulose, carboxycellulose, and hydroxymethylcellulose, natural polymers such as lignin sulfonates and shellac, dispersants such as polyacrylates, salts of styrene-acrylic acid copolymers, salts of vinylnaphthalene-maleic acid copolymers, sodium salts of β-naphthalenesulfonic acid formaldehyde condensate, phosphates, and other anionic polymers, as well as nonionic polymers such as polyvinyl alcohol, polyvinylpyrrolidone, and polyethylene glycol.

[0146] Higher fatty acid salts (soaps), salts of higher fatty acids with 8 to 20 carbon atoms in the hydrophobic group, and N-acyl amino acid type anionic surfactants: Acyl groups can be listed as those with 8 to 20 carbon atoms, and amino acids such as glutamic acid, aspartic acid, glycine, alanine, valine, leucine, isoleucine, proline, methionine, cysteine, tryptophan, tyrosine, phenylalanine, asparagine, glutamine, serine, threonine, hydroxyproline, β-aminopropionic acid, γ-aminobutyric acid, anthranilic acid, m-aminobenzoic acid, p-aminobenzoic acid, etc.; alkyl ether carboxylates, amide ether carboxylates, alkyl sulfates (AS), and polyoxyethylene alkyl groups. Anionic surfactants including ether sulfates (AES), alkyl ether sulfates, sulfates of higher fatty acid esters, sulfates of higher fatty acid alkanolamides, sulfated oils and fats, polyoxyethylene styrene phenyl ether sulfates, α-olefin sulfonates (AOS), alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfonates (SAS), dialkyl sulfosuccinates, α-sulfonated fatty acid salts, alkane sulfonates, sulfonates of higher fatty acid esters, α-sulfonated fatty acid salts, sulfonates of higher fatty acid amides, N-acyl-N-alkyl taurine, N-acyl-N-methyl taurine, alkyl phosphates, alkyl ether phosphates, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkylphenyl ether phosphates, and naphthalene sulfonate formaldehyde condensates;

[0147] Alkyl betaine, alkyl amide betaine, alkyl sulfonyl betaine, imidazoline betaine, acetate betaine, lecithin and other amphoteric surfactants;

[0148] Polyoxyethylene alkyl ethers (AE), polyoxyethylene alkylphenyl ethers, polyoxyethylene polystyrene phenyl ethers, polyoxyethylene polyoxypropylene glycol, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene fatty acid esters, polyoxyethylene alkyl dehydrated sorbitol fatty acid esters, polyoxyethylene fatty acid alkanolamides, polyoxyethylene alkyl glucosides, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamines, polyoxyethylene alkylphenyl ethers, etc., ethylene oxide condensation type, polyol fatty acid esters, polyoxyethylene polyol fatty acid esters, polyoxyethylene fatty acid esters, (poly)glycerol fatty acid esters, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamines, triethanolamine fatty acid esters, alkyl polyglucosides, propylene glycol fatty acid esters, dehydrated sorbitol fatty acid esters, sucrose fatty acid esters, etc., polyol esters, fatty acid alkanolamides, glycosaminoglycans, triethanolamine fatty acid esters, fatty acid alkanolamides, alkyl amine oxides, etc., are nonionic surfactants.

[0149] Cationic surfactants including primary to tertiary fatty acid amine salts, alkyl ammonium chloride salts, tetraalkyl ammonium salts, trialkyl benzyl ammonium salts, alkylpyridinium salts, alkyl hydroxyethyl imidazolineium salts, dialkylmorpholineium salts, alkyl isoquinolineium salts, phenylethylammonium salts, and benzylalkylammonium salts;

[0150] High molecular weight surfactants such as sodium alginate, starch derivatives, and tragacanth gum;

[0151] Phospholipids, lecithin, lanolin, cholesterol, saponins and other natural surfactants;

[0152] Avocado oil, turtle oil, corn oil, almond oil, olive oil, cocoa seed oil, sesame oil, safflower oil, soybean oil, camellia seed oil, peach kernel oil, castor oil, grape seed oil, macadamia nut oil, mink oil, cottonseed oil, wood wax, coconut oil, egg yolk oil, palm oil, palm kernel oil, triisocaprylic acid glyceride, tri-2-ethylhexanoic acid glyceryl cholesterol fatty acid ester, wheat germ oil, camellia seed oil, flaxseed oil, evening primrose oil, perilla seed oil, peanut oil, tea seed oil, torreya seed oil, rice bran oil, mustard oil, Japanese tung oil, jojoba oil, germ oil, tricaprylic acid glyceride, triisopalmitic acid glyceride, horse oil, hydrogenated coconut oil, beef tallow, beef foot tallow, mutton tallow, hydrogenated beef tallow, pork fat, beef bone fat, wood wax kernel oil, hydrogenated oil, wood wax, hydrogenated castor oil, and other oils;

[0153] Liquid paraffin, petrolatum, cereusin, microcrystalline wax, isoparaffins, oxorite, squalene, pterosaurane, squalane and other hydrocarbons;

[0154] Waxes including beeswax, whale wax, lanolin, carnauba wax, candelilla wax, cotton wax, bayberry wax, insect wax, lignite wax, rice bran wax, lanolin, kapok wax, acetylated lanolin, liquid lanolin, sugarcane wax, isopropyl lanolinate, hexyl laurate, reduced lanolin, jojoba wax, hard lanolin, shellac wax, polyoxyethylene lanolin alcohol ether, polyoxyethylene lanolin alcohol acetate, polyethylene glycol lanolin acid, polyoxyethylene hydrogenated lanolin alcohol ether and its derivatives.

[0155] Fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, docosanoic acid, undecenoic acid, lanolinic acid, hard lanolinic acid, soft lanolinic acid, linoleic acid, linolenic acid, eicosapentaenoic acid, and 12-hydroxystearic acid.

[0156] higher alcohols such as lauryl alcohol, cetyl alcohol, a mixture of hexadecyl alcohol and octadecyl alcohol, stearyl alcohol, oleyl alcohol, behenyl alcohol, lanolin alcohol, hydrogenated lanolin alcohol, hexyldecyl alcohol, and octyldodecyl alcohol;

[0157] Sterols such as cholesterol and phytosterols;

[0158] Isopropyl myristate, butyl stearate, cetyl octanoate, octyl dodecyl myristate, isopropyl palmitate, hexyl laurate, myristyl myristate, decyl oleate, hexyl decyl dimethyl octanoate, cetyl lactate, myristyl lactate, acetylated lanolin, isocetyl stearate, isocetyl isostearate, 12-hydroxystearic acid cholesterol ester, ethylene glycol di-2-ethylhexyl acid, dipentaerythritol fatty acid ester, N-alkyl diol monoisostearate, neopentyl glycol didecanoate, diisostearate malate, glyceryl di-2-heptyl undecanoate, trimethylolpropane tri-2-ethylhexyl acid, trimethylolpropane triisostearate, pentaerythritol tetra-2-ethylhexyl acid, glyceryl tri-2-ethylhexyl acid, ... Trimethylolpropane stearate, cetyl-2-ethylhexanoate, 2-ethylhexyl palmitate, trimyridine glyceryl, tri-2-heptylundecanoate glyceryl, castor oil fatty acid methyl ester, oleic acid ester, hexadecyl alcohol mixture, acetylglycine ester, 2-heptylundecyl palmitate, diisopropyl adipate, N-lauroyl-L-glutamic acid-2-octyldodecyl ester, di-2-heptylundecyl adipate, ethyl laurate, di-2-ethylhexyl sebacate, 2-hexyldecyl myristate, 2-hexyldecyl palmitate, di-2-hexyldecyl adipate, diisopropyl sebacate, 2-ethylhexyl succinate, ethyl acetate, butyl acetate, amyl acetate, triethyl citrate, etc.

[0159] Dimethyl polysiloxane, polyether-modified siloxane, alcohol-modified siloxane, methylphenyl polysiloxane, epoxy-modified siloxane, fluorine-modified siloxane, alkyl-modified siloxane, alkoxy-modified siloxane, amino-modified siloxane, polymeric siloxane, volatile siloxane, cyclic siloxane, and other volatile and non-volatile siloxanes.

[0160] Polyols such as glycerol, diglycerol, polyglycerol, 1,3-butanediol, propylene glycol, and polyethylene glycol;

[0161] Alkyl glycines such as N-methylglycine, N,N-dimethylglycine, N,N,N-trimethylglycine, N-ethylglycine, and glycyl betaine; sorbitol, metriose, pyrrolidone carboxylates, lactates, hyaluronic acid salts, ceramides, trehalose, xylobiose, maltose, sucrose, glucose, plant-based polysaccharides and their derivatives; water-soluble chitin, chitosan, pectin, chondroitin sulfate and its salts, glycosaminoglycans and their salts; amino acids such as glycine, serine, threonine, alanine, aspartic acid, tyrosine, valine, leucine, arginine, glutamine, and proline and their salts; amino acid compounds such as amino carbonyl reactants; plant extracts such as aloe vera and horse chestnut; urea, uric acid, ammonia, glucosamine, creatine, DNA, RNA, and other nucleic acid-related substances; and other moisturizers.

[0162] Hydroxyethyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose hydroxypropyltrimethylammonium chloride ether, methyl cellulose, ethyl cellulose, hydroxypropyl cellulose, methyl hydroxypropyl cellulose, soluble starch, carboxymethyl starch, methyl starch, propylene glycol alginate, polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl methyl ether, carboxyvinyl polymer, polyacrylate, guar gum, locust bean gum, quince seed, carrageenan, galactan, gum arabic, pectin, mannan, starch, xanthan gum, dextran, succinyl polysaccharide, gel polysaccharide, hyaluronic acid, gelatin, casein, albumin, collagen, methoxyethylene maleic anhydride copolymer, amphoteric methacrylate copolymer, polydimethylmethylene piperidinium chloride, polyacrylate copolymer, polyvinyl acetate, nitrocellulose, silicone resins, and other water-soluble and oil-soluble polymers;

[0163] Cationic cellulose derivatives, cationic starch, cationic guar gum derivatives, diallyl quaternary ammonium salt / acrylamide copolymers, quaternized polyvinylpyrrolidone derivatives, quaternized ethylene pyrrolidone / vinyl imidazole polymers, polyethylene glycol / amine condensates, quaternized collagen peptides, polyethyleneimine, cationic siloxane polymers, adipic acid / dimethylaminohydroxypropyl diethylenetriamine copolymers, polyamino polyamides, cationic chitin derivatives, quaternized polymers, and other cationic high molecular weight polyethylene glycol fatty acid esters, polyoxyethylene fatty acid ester methyl glucoside, tetradecene sulfonate, and other thickening and foaming ingredients;

[0164] Oil gelling agents such as dextrin fatty acid esters, glycerol fatty acid esters, and hydroxystearic acid;

[0165] Metal ion chelating agents such as ethylenediaminetetraacetic acid and its salts, hydroxyethylenediaminetetraacetic acid and its salts, phosphoric acid, ascorbic acid, succinic acid, gluconic acid, polyphosphates, metaphosphates, and juniper oil phenols;

[0166] Parabens, benzoic acid and its salts, phenoxyethanol, physalin, salicylic acid and its salts, sorbic acid and its salts, dehydroacetic acid and its salts, p-chloro-m-cresol, hexachlorophenol, boric acid, resorcinol, tribromosalinomyline, o-phenylphenol, sulfide, photosensitive agent 201, halocarban, trichlorocarbonyl aniline, tocopheryl acetate, zinc oxychloride, phenol, isopropyl methylphenol, 2,4,4-trichloro-2-hydroxyphenol, hexachlorophenol, chlorhexidine, benzyl chloride, benzalkonium chloride, hexadecylpyridine chloride, dequinoline chloride, stearyl dimethyl ammonium chloride, stearyl trimethyl ammonium chloride, cetyl trimethyl ammonium chloride, methylbenzyl chloride, lauryl trimethyl ammonium chloride, lapiroxamine, triclosan, and other preservatives / antibacterial agents;

[0167] pH adjusters such as citric acid, malic acid, adipic acid, glutamic acid, and aspartic acid;

[0168] Other scalp / itch prevention agents include trichloroaniline, salicylic acid, zinc sulfate, and isopropyl methylphenol;

[0169] Benzophenone derivatives, p-aminobenzoic acid derivatives, p-methoxycinnamic acid derivatives, salicylic acid derivatives, and other ultraviolet absorbers;

[0170] Ascorbic acid and its salts (sodium, potassium, magnesium, calcium, and other alkali metal or alkaline earth metal salts, as well as ammonium salts, amino acid salts, etc.), ascorbic acid derivatives (L-ascorbic acid alkyl esters, L-ascorbic acid phosphate esters and their salts, L-ascorbic acid-2-sulfate esters and their salts, L-ascorbic acid glucoside, etc.), alkoxysalicylic acid and its salts (as alkoxy groups, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, etc.), hydroquinone glycosides and their derivatives (arbutin, etc.). Whitening agents including kojic acid and its derivatives, ellagic acid, chamomile extract, marshmallow extract, licorice extract, mulberry bark extract, raspberry extract, apple flavonoids, bran extract, vitamin E and its derivatives, pyrrolidone, placental extract, 4-n-butylresorcinol (Rucinol), chamomile ET, glutathione, clove extract, tea extract, astaxanthin, bovine placental extract, tranexamic acid and its derivatives, resorcinol derivatives, chamomile ring, and γ-hydroxybutyric acid;

[0171] Blood circulation promoters include swert extract, swertinoin, vitamin E and its derivatives, and γ-oryzanol.

[0172] Topical irritants such as capsicum tincture, turmeric root tincture, cantharides tincture, and benzyl nicotinate;

[0173] Various vitamins, amino acids and other nutritional supplements;

[0174] Female hormone preparations;

[0175] Hair root activator;

[0176] Anti-inflammatory agents such as glycyrrhetinic acid, glycyrrhizic acid derivatives, allantoin, chamomile, aminocaproic acid, and hydrocortisone;

[0177] Astringents such as zinc oxide, zinc sulfate, allantoin aluminum hydroxide, aluminum chloride, aluminum sulfate, zinc phenolsulfonate, tannic acid, citric acid, and lactic acid;

[0178] Cooling agents such as menthol and camphor solution;

[0179] Antihistamines such as diphenhydramine hydrochloride, clotriphene maleate, and glycyrrhizic acid derivatives;

[0180] Antioxidants such as tocopherols, BHA, BHT, gallic acid, and NDGA;

[0181] Sebum inhibitors such as estradiol, estrone, and ethinylestradiol;

[0182] Sulfur, salicylic acid, resorcinol, and other keratolytic / dissolving agents;

[0183] Alpha-hydroxy acids such as glycolic acid, lactic acid, malic acid, tartaric acid, and citric acid;

[0184] Salicylic acid and other β-hydroxy acids;

[0185] Talc, kaolin, sericite, calcium carbonate, zinc oxide, aluminum oxide, magnesium oxide, zirconium oxide, magnesium carbonate, calcium carbonate, barium sulfate, chromium oxide, chromium hydroxide, tar-based pigments, mica, (synthetic) sericite, silicon carbide, boron nitride, titanium dioxide, black titanium oxide, ferric ammonium ferrocyanide, iron oxide red, iron oxide black, iron oxide yellow, ultramarine, titanium-coated mica, bismuth oxychloride, red iron oxide, binder pigments, ultramarine pink, ultramarine violet, chromium hydroxide, mica titanium, chromium oxide, cobalt aluminum oxide, carbon black, silicon dioxide, magnesium silicate, bentonite, (synthetic) mica, zirconium oxide, magnesium aluminosilicate (meta)silicate, calcium aluminosilicate, polyethylene powder, nylon powder, polymethyl methacrylate, poly(ethylene ether)sulfide, etc. Polyethylene phthalate-polymethyl methacrylate laminated powder, acrylonitrile-methacrylic acid copolymer powder, vinylidene chloride-methacrylic acid copolymer powder, wool powder, silk powder, crystalline cellulose, N-acyl lysine, polymethyl silsesquioxane powder, substances made by powdering plant fruits and peels, bismuth oxychloride, mica titanium, iron oxide coated mica, iron oxide mica titanium, organic pigment treated mica titanium, aluminum powder, fine-particle titanium oxide, fine-particle zinc oxide, fine-particle titanium oxide covered with mica titanium, fine-particle zinc oxide covered with mica titanium, barium sulfate covered mica titanium, magenta, β-carotene, metallic soap, chlorophyll, sunset yellow FCF, Ponceau No. 4 (Ponceau No. 4) sx), Eosin YS, Tetrabromofluorescein, Rhodamine B, Quinoline Yellow SS, Quinoline Yellow WS, Alizarine Cyanine Green, Solvent Green, Lithorubin B, Lithorubin BCA, Permaton Red, Helindone Pink CN, Phthalocyanine Blue, β-Apocarotene, Capsanthin, Lycopene, Natto Orange, Crocin, Canthaxanthin, Perilla, Radix Radix, Grape Cortexin, Safflowerin, Safflower Yellow, Rutin, Quercetin, Cocoa Pigment, Riboflavin, Lacic Acid, Carmine Acid, Carmine Ketone, Alizarin, Shikonin, Alkhanin, Echinocyanin, Hemoglobin, Curcumin, Betaine, and other cosmetic pigments:

[0186] Purified water, other firethorn fruit extracts, N-methyl-L-serine, whey, nicotinamide, diisopropylamine dichloroacetic acid, mevalonic acid, γ-aminobutyric acid (containing γ-amino-β-hydroxybutyric acid), marshmallow extract, aloe extract, apricot seed extract, turmeric extract, oolong tea extract, seawater dried matter, hydrolyzed wheat flour, hydrolyzed silk, carrot extract, cucumber extract, gentian extract, yeast extract, rice germ oil, daisy extract, soapwort extract, rehmannia extract, lithospermum root extract, birch extract, peppermint extract, swert extract, bisabolol, propolis, loofah extract, linden extract, hops extract, horse chestnut extract, soapberry extract, bee flower extract, eucalyptus extract, saxifrage extract, rosemary extract, chamomile extract, royal jelly extract, seaweed, rice bran, licorice, tangerine peel, angelica, peach leaf powder, sphingolipids, guaiac, vitamin C, etc.

[0187] Example

[0188] The present invention will be described in more detail below using examples and comparative examples, but the technical scope of the present invention is not limited thereto.

[0189] It should be noted that the various values ​​in the embodiments can be preferred lower or upper limits in the embodiments of the present invention, or they can be appropriately combined with the same type of values ​​(including the lower and upper limits of the numerical range) in the embodiments of the present invention to form a preferred numerical range. In addition, two values ​​of the same type in the embodiments can also be appropriately combined to form a preferred numerical range.

[0190] [Manufacturing Example 1]

[0191] Add 93.2 g of 87% tert-butanol aqueous solution to a mixed solution of 104 g (0.56 mol) of L-glutamic acid monohydrate, 265.2 g of pure water, and 69.6 g of 32% sodium hydroxide aqueous solution (as sodium hydroxide 0.56 mol). Maintain the solution at 3°C, and while adjusting the pH to 12 with 32% sodium hydroxide, add 117.8 g (0.54 mol) of lauroyl chloride dropwise with stirring.

[0192] Next, add 75% sulfuric acid to adjust the pH of the liquid to 2, and adjust the temperature of the liquid to 65°C. After standing for 1 hour, the liquid separates into an organic layer and an aqueous layer, and then the organic layer is separated.

[0193] At this point, the weight ratio of lauroyl glutamic acid as the main solid component in the organic layer to tert-butanol to water is 62 / 24 / 14.

[0194] [Manufacturing Example 2]

[0195] 126 g of acetone was added to a mixed solution of 104 g (0.56 mol) of L-glutamic acid monosodium hydrate, 145.8 g of pure water, and 69.6 g of 32% sodium hydroxide aqueous solution (as sodium hydroxide 0.56 mol). The solution was maintained at 3°C, and lauroyl chloride 117.8 g (0.54 mol) was added dropwise with stirring while adjusting the pH to 12 using 32% sodium hydroxide.

[0196] Next, add 75% sulfuric acid to adjust the pH of the liquid to 2, and adjust the temperature of the liquid to 50°C. After standing for 1 hour, the liquid separates into an organic layer and an aqueous layer, and then the organic layer is separated.

[0197] At this point, the weight ratio of lauroyl glutamic acid, the main solid component, to acetone to water in the organic layer is 55 / 30 / 15.

[0198] [Manufacturing Example 3]

[0199] Add 93.2 g of 87% tert-butanol aqueous solution to a mixed solution of 104 g (0.56 mol) of L-glutamic acid monohydrate, 265.2 g of pure water, and 69.6 g of 32% sodium hydroxide aqueous solution (as sodium hydroxide 0.56 mol). Maintain the solution at 3°C, and while adjusting the pH to 12 using 32% sodium hydroxide, add 26.6 g (0.11 mol) of myristoyl chloride dropwise with stirring, followed by 94.2 g (0.43 mol) of lauroyl chloride dropwise with stirring.

[0200] Next, add 75% sulfuric acid to adjust the pH of the liquid to 2, and adjust the temperature of the liquid to 65°C. After standing for 1 hour, the liquid separates into an organic layer and an aqueous layer, and then the organic layer is separated.

[0201] At this point, the weight ratio of the solid component (lauroyl glutamic acid and myristoyl glutamic acid) in the organic layer to tert-butanol to water is 62 / 27 / 11.

[0202] <HPLC Analysis>

[0203] In the examples and comparative examples containing component B, components A and B were determined by peak areas obtained through analysis using the HPLC described below.

[0204] Detector: UV detector (205nm)

[0205] As measuring instruments, for example, Shimadzu Corporation's SPD-10Avp, SPD-10AVvp, SPD-20A, and SPD-20AV can be used.

[0206] Separation tube: A stainless steel tube with an inner diameter of 6 mm and a length of 150 mm is filled with octadecylsilyl silica modified with silica gel with a particle size of 5 μm and a pore size of 12 nm.

[0207] Separator temperature: a constant temperature around 60℃

[0208] Mobile phase: Methanol / Water / Phosphoric acid = 2000 / 400 / 0.31

[0209] Flow rate: a constant rate of approximately 0.8 mL per minute.

[0210] More specifically, the component ratio is calculated from the peak areas of the detected substances, such as component A and component B, obtained through HPLC analysis. The loss on drying is first subtracted from the total component ratio of 100%, and this subtracted value is then allocated using the peak area ratio obtained through HPLC analysis. Furthermore, the component B ratio (%) is calculated using the following formula. This corresponds to "Component B Ratio (%)" in the table below.

[0211] Component B percentage (%) = [Peak area of ​​component B / Peak area of ​​component A] × 100

[0212] If UV detection is used as described above, the peak sensitivity of acyl PCA (component B) is higher than that of other substances, so high determination sensitivity can be maintained even for the percentage of component B.

[0213] [Example 1]

[0214] While stirring slowly, 100g of the organic layer (62 / 24 / 14 weight ratio of lauroyl glutamic acid and other solid components / tert-butanol / water obtained in Example 1) was heated under normal pressure until the liquid temperature reached 90°C. Then, the pressure was slowly reduced while the temperature was increased, gradually raising the pressure to avoid excessive foaming, reaching a pressure of 20 kPa and maintaining it for 20 minutes to reach a temperature of 105°C. The pressure was then slowly restored to normal, and the melt in the reactor was recovered. The resulting solid was placed in a cold storage overnight and then pulverized in a juicer blender, yielding 56.6g of solid. The loss on drying of this solid was 0.25%. HPLC analysis showed that lauroyl glutamic acid was 94.9%, lauroyl PCA was 3.7%, and lauric acid was 0.44%. No significant impurities were detected.

[0215] 54.0 g of the solid was dissolved in 36.4 g of acetic anhydride at 50 °C, followed by the addition of 18.2 g of acetic anhydride, and the reaction was carried out directly at 50 °C for 3 hours. The mixture was then cooled to room temperature, and the product was filtered from the reaction solution to obtain crude crystals with N-lauroyl-L-glutamic anhydride as the main component. These crystals were washed / dried with 80 ml of diethyl ether followed by 15 ml of petroleum ether to obtain 34.0 g of solid. The loss on drying of this solid was 0.24%. HPLC analysis showed that the content of lauroyl glutamic anhydride was 95.2%, lauroyl PCA was 2.3%, and lauroyl glutamic acid was 2.2%, with no lauric acid detected. No other significant impurities were detected.

[0216] 9.1 g (0.05 mol) of L-lysine hydrochloride and 57 g of water were mixed. While adjusting the pH of the liquid to 10–11 using a 25% sodium hydroxide aqueous solution, and maintaining the reaction temperature at 5°C, 31.1 g of the previously washed / dried solid was added over 2 hours with stirring. After stirring continuously for 30 minutes, tert-butanol was added at a concentration of 20% by mass, followed by dropwise addition of 75% sulfuric acid to adjust the pH to 2 and the temperature to 65°C. After the addition was complete, stirring was stopped, and the mixture was allowed to stand at 65°C for 20 minutes, resulting in the separation of an organic layer and an aqueous layer. The organic layer was then separated. Almost all unreacted lysine was recovered from the aqueous layer. The organic layer was then washed repeatedly with water, the solvent was removed, and neutralized with a sodium hydroxide aqueous solution at a solid content of 30% by mass and a pH of 7 (25°C). Water was then added and vacuum distilled simultaneously. Vacuum distillation was continued at a pressure of 13–22 kPa and a liquid temperature of 45–60 °C until the concentration of tert-butanol in the liquid was below 10 ppm by mass. The final product was a 32% by weight aqueous solution at pH 7 (25 °C) containing the acyl compound shown in formula (A) as the main component. Component A was 96.9%, acyl PCA in component B was 0.031%, and lauroyl glutamic acid was 2.98%. No significant impurities were detected. The acyl PCA percentage obtained by the aforementioned HPLC analysis was 0.032%.

[0217] [Comparative Example 1]

[0218] 100g of the organic layer obtained in Manufacturing Example 1, which has a solid component such as lauroyl glutamic acid, a component weight ratio of tert-butanol, and water of 62 / 24 / 14, was freeze-dried.

[0219] As a pre-freezing process, the rack circulation temperature was set to -60°C, and the sample temperature was lowered to -40°C and cooled for 2 hours. The rack circulation temperature was then set to -40°C, and after 2 hours of drying, it was set to -10°C and dried at approximately 5 Pa. The set temperature was then increased to 0°C, 10°C, and 30°C.

[0220] After confirming that the product temperature is 27.5℃ and the vacuum degree is below 1 Pa, the vacuum is released using dry nitrogen. The above drying process takes 40 hours to complete.

[0221] The obtained solid was in plate form and was pulverized in a juicer blender to obtain 57.1 g of solid. The loss on drying of the solid was 1.2%. HPLC analysis showed that lauroyl glutamic acid was 98.1%, lauroyl PCA was not detected, and lauric acid was 0.40%. No other significant impurities were detected.

[0222] 54.0 g of the solid was dissolved in 36.4 g of acetic anhydride at 50 °C, followed by the addition of 18.2 g of acetic anhydride, and the reaction was carried out directly at 50 °C for 3 hours. The mixture was then cooled to room temperature, and the product was filtered from the reaction solution to obtain crude crystals of N-lauroyl-L-glutamic acid anhydride. These crystals were washed / dried with 80 ml of diethyl ether followed by 15 ml of petroleum ether to obtain 34.3 g of solid. The weight loss on drying was 1.2%. HPLC analysis showed that the content of lauroyl glutamic acid anhydride was 96.6%, lauroyl glutamic acid was 2.1%, and lauroyl PCA and lauric acid were not detected. No other significant impurities were detected.

[0223] Then, 9.1 g (0.05 mol) of L-lysine hydrochloride and 57 g of water were mixed, and the preparation of component A was continued using the same method as in Example 1. As a result, a 32% by weight aqueous solution at pH 7 (25°C) containing component A as the main component was obtained. At this point, component A was 97.1%, and lauroyl glutamic acid was 2.62%. Lauroyl PCA and lauric acid were not detected, and no significant impurities were detected. The acyl PCA percentage obtained by HPLC analysis was 0%.

[0224] [Example 2]

[0225] While stirring slowly, 115.0 g of the organic layer (with a weight ratio of lauroyl glutamic acid and other solid components, acetone, and water of 55 / 30 / 15 obtained in Preparation Example 2) was heated under normal pressure until the liquid temperature reached 50°C. Then, the pressure was slowly reduced while the temperature was increased, gradually raising the pressure to avoid excessive foaming, reaching a final temperature of 105°C at a pressure of 20 kPa. This final temperature of 105°C was maintained at a pressure of 20 kPa for 80 minutes. The pressure was then slowly reduced back to normal, and the melt in the reactor was recovered. The entire concentration process took 10 hours from start to finish. The obtained solid was placed in a cold storage overnight and then pulverized in a juicer blender, yielding 58.9 g of solid. The loss on drying of this solid was 0.21%. HPLC analysis showed that lauroyl glutamic acid was 83.5%, lauroyl PCA was 15.6%, and lauric acid was 0.14%. No significant impurities were detected.

[0226] 54.0 g of the solid was dissolved in 36.4 g of acetic anhydride at 50 °C, followed by the addition of 18.2 g of acetic anhydride. The reaction was carried out directly at 50 °C for 3 hours. The mixture was then cooled to room temperature, and the product was filtered from the reaction solution to obtain crude crystals of N-lauroyl-L-glutamic acid anhydride. These crystals were washed / dried with 80 ml of diethyl ether followed by 15 ml of petroleum ether to obtain 34.2 g of solid. The loss on drying was 0.21%. HPLC analysis showed that the solid contained 83.7% lauroyl glutamic acid anhydride, 1.9% lauroyl glutamic acid, and 13.4% lauroyl PCA. Lauric acid was not detected. No other significant impurities were detected.

[0227] Then, 9.1 g (0.05 mol) of L-lysine hydrochloride and 57 g of water were mixed. The preparation of component A was then continued using the same method as in Example 1, resulting in a 32% by weight aqueous solution at pH 7 (25°C) containing component A as the main component. At this point, component A was 95.3%, acyl PCA of component B was 1.27%, and lauroyl glutamic acid was 3.33%. No significant impurities were detected. The acyl PCA percentage obtained by the aforementioned HPLC analysis was 1.33%.

[0228] [Comparative Example 2]

[0229] 115.0 g of the organic layer obtained in Manufacturing Example 2, which has a solid component ratio of lauroyl glutamic acid, acetone, and water of 55 / 30 / 15, was freeze-dried.

[0230] As a pre-freezing process, the rack circulation temperature was set to -60°C, and the sample temperature was lowered to -40°C and cooled for 2 hours. The rack circulation temperature was then set to -40°C, and after drying for 2 hours, it was set to -10°C and dried at approximately 12 Pa. The set temperature was then increased to 0°C, 15°C, and 30°C.

[0231] After confirming that the product temperature is 27.5℃ and the vacuum degree is below 1 Pa, the vacuum is released using dry nitrogen. The above drying process takes 70 hours to complete.

[0232] The obtained solid was in plate form and was pulverized in a juicer blender to obtain 59.5 g of solid. The loss on drying of the solid was 0.51%. HPLC analysis showed that lauroyl glutamic acid was 98.9%, and lauroyl PCA and lauric acid were not detected. No other significant impurities were detected.

[0233] 54.0 g of the solid was dissolved in 36.4 g of acetic anhydride at 50 °C, followed by the addition of 18.2 g of acetic anhydride. The reaction was carried out directly at 50 °C for 3 hours. The mixture was then cooled to room temperature, and the product was filtered from the reaction solution to obtain crude crystals of N-lauroyl-L-glutamic acid anhydride. These crystals were washed / dried with 80 ml of diethyl ether followed by 15 ml of petroleum ether to obtain 34.2 g of solid. The loss on drying was 1.2%. HPLC analysis showed that the content of lauroyl glutamic acid anhydride was 96.0%, lauroyl glutamic acid was 2.4%, and lauroyl PCA and lauric acid were not detected. No other significant impurities were detected.

[0234] Then, 9.1 g (0.05 mol) of L-lysine hydrochloride and 57 g of water were mixed, and the preparation of component A was continued using the same method as in Example 1. As a result, a 32% by weight aqueous solution at pH 7 (25°C) containing component A as the main component was obtained. At this point, component A was 96.3% and lauroyl glutamic acid was 3.30%. Lauroyl PCA and lauric acid were not detected, and no significant impurities were detected. The acyl PCA percentage obtained by HPLC analysis was 0%.

[0235] [Example 3]

[0236] While stirring slowly, 100.0 g of the organic layer with a weight ratio of acylglutamic acid / tert-butanol / water of 62 / 27 / 11 obtained in Preparation Example 3 was heated under normal pressure until the liquid temperature reached 70°C. Then, the pressure was slowly reduced while the temperature was increased, gradually raising the pressure to avoid excessive foaming, reaching a pressure of 20 kPa and a temperature of 115°C, which was maintained for 20 minutes. The pressure was then slowly restored to normal, and the melt in the reactor was recovered. The resulting solid was placed in a cold storage overnight and then pulverized in a juicer blender, yielding 55.5 g of solid. The loss on drying of this solid was 0.14%. HPLC analysis showed that the acylglutamic acid content was 90.9%, the acyl PCA content was 7.7%, and the free fatty acids (lauric acid and myristic acid total) were 0.74%. No significant impurities were detected.

[0237] 54.0 g of the solid was dissolved in 36.4 g of acetic anhydride at 50 °C, followed by the addition of 18.2 g of acetic anhydride. The reaction was carried out directly at 50 °C for 3 hours. The mixture was then cooled to room temperature, and the product was filtered from the reaction solution to obtain crude crystals of N-acyl-L-glutamic acid anhydride. These crystals were washed / dried with 80 ml of diethyl ether followed by 15 ml of petroleum ether to obtain 33.7 g of solid. The loss on drying was 0.20%. HPLC analysis showed that the solid contained 91.6% acylglutamic acid anhydride, 1.7% acylglutamic acid, and 6.1% acyl PCA, with no detectable free fatty acids. No significant impurities were also detected.

[0238] Then, 9.1 g (0.05 mol) of L-lysine hydrochloride and 57 g of water were mixed, and the preparation of component A was continued using the same method as in Example 1. As a result, a 32% by weight aqueous solution at pH 7 (25°C) containing component A as the main component was obtained. At this point, component A was 96.2%, acyl PCA of component B was 0.293%, and acyl glutamic acid was 2.61%. No free fatty acids were detected. In addition, no significant impurities were detected. The acyl PCA (%) ratio obtained by the aforementioned HPLC analysis method was 0.312%.

[0239] [Comparative Example 3]

[0240] 100g of the organic layer obtained in Manufacturing Example 3, which has a component weight ratio of acylglutamic acid and other solid components / tert-butanol / water of 62 / 27 / 11, was freeze-dried.

[0241] As a pre-freezing process, the rack circulation temperature was set to -60°C, and the sample temperature was lowered to -40°C and cooled for 2 hours. The rack circulation temperature was then set to -40°C, and after 2 hours of drying, it was set to -10°C and dried at approximately 5 Pa. The set temperature was then increased to 0°C, 20°C, and 30°C.

[0242] After confirming that the product temperature is 27.5℃ and the vacuum degree is below 1 Pa, the vacuum is released using dry nitrogen. The above drying process takes 55 hours to complete.

[0243] The obtained solid was in plate form and was pulverized in a juicer blender to obtain 57.2 g of solid. The weight loss on drying of the solid was 0.61%. HPLC analysis showed that acylglutamic acid was 98.6%, acyl PCA was not detected, and free fatty acids were 0.54%. No other significant impurities were detected.

[0244] 54.0 g of the solid was dissolved in 36.4 g of acetic anhydride at 50 °C, followed by the addition of 18.2 g of acetic anhydride. The reaction was carried out directly at 50 °C for 3 hours. The mixture was then cooled to room temperature, and the product was filtered from the reaction solution to obtain crude crystals of N-acyl-L-glutamic acid anhydride. These crystals were washed / dried with 80 ml of diethyl ether followed by 15 ml of petroleum ether to obtain 32.8 g of solid. The weight loss on drying was 1.5%. HPLC analysis showed that the acylglutamic acid anhydride content was 96.0%, the acylglutamic acid content was 2.1%, and no acyl PCA or free fatty acids were detected. No significant impurities were also detected.

[0245] Then, 9.1 g (0.05 mol) of L-lysine hydrochloride and 57 g of water were mixed, and the preparation of component A was continued using the same method as in Example 1. As a result, a 32% by weight aqueous solution at pH 7 (25°C) containing component A as the main component was obtained. At this point, component A was 96.6%, and acylglutamic acid was 3.15%. Acyl PCA and free fatty acids were not detected, and no significant impurities were detected. The acyl PCA percentage obtained by HPLC analysis was 0%.

[0246] [Example 4]

[0247] The same procedure as in Example 1 was repeated to obtain an organic layer with a solid component / tert-butanol / water weight ratio of 64 / 25 / 11. While stirring slowly, 125g of this organic layer was heated under normal pressure until the liquid temperature reached 90°C. Then, the pressure was slowly reduced while the temperature was increased, gradually raising the pressure to avoid excessive foaming, reaching a pressure of 40kPa and maintaining it for 120 minutes to reach a temperature of 105°C. The pressure was then slowly restored to normal, and the melt in the reactor was recovered. The obtained solid was placed in a cold storage overnight and then pulverized in a juicer, yielding 70.6g of solid. The loss on drying of this solid was 0.20%. HPLC analysis showed that lauroylglutamic acid was 80.7%, lauroyl PCA was 14.1%, and lauric acid was 4.7%. No significant impurities were detected.

[0248] 54.0 g of the solid was dissolved in 36.4 g of acetic anhydride at 50 °C, followed by the addition of 18.2 g of acetic anhydride. The reaction was carried out directly at 50 °C for 3 hours. The mixture was then cooled to room temperature, and the product was filtered from the reaction solution to obtain crude crystals with N-lauroyl-L-glutamic anhydride as the main component. The crystals were washed / dried with 80 ml of diethyl ether, followed by another 80 ml of diethyl ether, to obtain 32.7 g of solid. The weight loss on drying was 0.19%. HPLC analysis showed that lauroyl glutamic anhydride was 84.5%, lauroyl PCA was 13.0%, lauroyl glutamic acid was 1.9%, and lauric acid was not detected. No other significant impurities were detected.

[0249] 9.1 g (0.05 mol) of L-lysine hydrochloride and 57 g of water were mixed. The pH of the liquid was adjusted to 10–11 using a 25% sodium hydroxide aqueous solution, and the reaction temperature was maintained at 5°C. 32.7 g of the previously washed / dried solid was added over 2 hours with stirring. After stirring continuously for 30 minutes, tert-butanol was added at a concentration of 20% by mass, followed by dropwise addition of 75% sulfuric acid to adjust the pH to 2 and the temperature to 65°C. After the addition was complete, stirring was stopped, and the mixture was allowed to stand at 65°C for 20 minutes, resulting in the separation of an organic layer and an aqueous layer. The organic layer was then separated. Almost all unreacted lysine was recovered from the aqueous layer. The organic layer was then washed repeatedly with water, the solvent was removed, and neutralized with a sodium hydroxide aqueous solution at a solid content of 30% by mass and a pH of 7 (25°C). Water was then added and vacuum distilled simultaneously. Vacuum distillation was continued at a pressure of 13–22 kPa and a liquid temperature of 45–60 °C until the concentration of tert-butanol in the liquid was below 10 ppm by mass. The final product was a 32% by weight aqueous solution at pH 7 (25 °C) containing the acyl compound shown in formula (A) as the main component. Component A accounted for 91.2%, acyl PCA in component B accounted for 6.25%, and lauroyl glutamic acid accounted for 2.32%. No significant impurities were detected. The acyl PCA percentage obtained by the aforementioned HPLC analysis was 6.85%.

[0250] <HPLC Analysis and Solid Composition Determination>

[0251] When calculating the ratio of components C and D relative to component A, the purity is calculated from the peak area obtained by using the HPLC analysis described below.

[0252] Detector: RI detector

[0253] Separation tube: A stainless steel tube with an inner diameter of 6 mm and a length of 150 mm is filled with octadecylsilyl silica modified with silica gel with a particle size of 5 μm and a pore size of 12 nm.

[0254] Separator temperature: a constant temperature around 60℃

[0255] Mobile phase: Methanol / Water / Phosphoric acid = 2000 / 400 / 0.31

[0256] Flow rate: 0.8 mL per minute

[0257] Next, component C / component A+C and component D / component A+D are expressed by the following formulas, which are equivalent to "mass of component C (%)" and "mass of component D (%)" in the table below.

[0258] Component C / Component A + C = [Purity of Component C (g) / Purity of Component A (g) + Purity of Component C (g)] × 100 (%)

[0259] Component D / Component A + D = [Purity of Component D (g) / Purity of Component A (g) + Purity of Component D (g)] × 100 (%)

[0260] <Production of High-Purity Component A>

[0261] Using the freeze-dried product (2.0% moisture) of PELLICER L-30 manufactured by ASAHI KASEI FINECHEM CO.,LTD., or the freeze-dried product of PELLICER L-30 prepared by changing the acyl chloride in Example 1 as raw material, the following operation was performed. The above freeze-dried product, distilled water, and tert-butanol were stirred at 60°C in a weight ratio of 45 / 33 / 22. After reaching 60°C, sulfuric acid was slowly added, and the addition of sulfuric acid continued at 65°C until the pH reached 2. After 30 minutes, stirring was stopped, and the mixture was allowed to stand. After standing for 30 minutes, the lower layer (aqueous layer) was removed. The lower layer (aqueous layer) was weighed, and an equal weight of a 20% by weight aqueous solution of tert-butanol (tert-butanol / distilled water weight ratio of 2 / 8) was added to the upper layer. The mixture was stirred at 60°C. After 30 minutes, stirring was stopped, and the mixture was allowed to stand for 30 minutes. The lower layer was removed again. After injecting a 20% by weight aqueous solution of tert-butanol of the same weight as the aforementioned lower layer, stir, let stand, and remove the lower layer. This is considered as step 1 (water washing and desalting step). This step is repeated 2 more times, for a total of 3 times. The organic layer that has completed the water washing and desalting step is then freeze-dried.

[0262] The dried sample was washed / dried at room temperature with 100 ml of diethyl ether, followed by 50 ml of petroleum ether. This process was repeated to obtain component A. Analysis of component A using the aforementioned HPLC method revealed no other components with a peak ratio greater than 0.1%.

[0263] <Production of High-Purity Component B>

[0264] Under a nitrogen atmosphere at 10°C, 90 mmol of pyroglutamic acid, 180 mmol of triethylamine, and 150 mL of acetonitrile were mixed in a flask with stirring. Then, a solution of 90 mmol of various acyl chlorides was added to 60 mL of acetonitrile. The mixture was removed from an ice bath and stirred at room temperature for 2 hours. The reaction mixture was filtered through a glass filter and concentrated under reduced pressure using an evaporator. After adding 150 mL of water and 120 mL of 1M hydrochloric acid, the residue was extracted four times with 100 mL of ethyl acetate. The combined organic layers were dried over magnesium sulfate and concentrated under vacuum. The residue was recrystallized from heptane / ethyl acetate in a 5:4 ratio (90 mL) to obtain acylpyroglutamic acid with a purity of over 95%.

[0265] <Production of High-Purity Component C>

[0266] The composition of Aminosurfact ALMS-P1 produced by ASAHI KASEI FINECHEM CO.,LTD., or a modified acyl chloride produced using the same method as in Manufacturing Example 1, was washed twice with water. The solvent was removed from the resulting organic layer, and the mixture was neutralized with sodium hydroxide to form an aqueous solution with a solid content of 30% by weight and a pH of 7 (25°C). The mixture was then dried to obtain the final composition. This composition was used as a raw material for the following operations. The above product, distilled water, and tert-butanol were stirred at 60°C in a weight ratio of 45 / 33 / 22. After reaching 60°C, sulfuric acid was slowly added, and the addition continued at 65°C until the pH reached 2. Stirring was stopped after 30 minutes, and the mixture was allowed to stand. After standing for 30 minutes, the lower layer (aqueous layer) was removed. The lower layer (aqueous layer) was weighed, and an equal weight of a 20% by weight aqueous solution of tert-butanol (tert-butanol / distilled water weight ratio of 2 / 8) was added to the upper layer. The mixture was stirred at 60°C. Stirring was stopped after 30 minutes, and the mixture was allowed to stand for 30 minutes. Remove the lower layer again. After injecting the same weight of 20% tert-butanol aqueous solution as the aforementioned lower layer, stir, let stand, and remove the lower layer. This is considered as step 1 (water washing and desalting step). Repeat this step 2 more times, for a total of 3 times. Freeze-dry the organic layer that has completed the water washing and desalting step.

[0267] The dried sample was washed / dried at room temperature with 120 ml of diethyl ether, followed by 60 ml of petroleum ether. This process was repeated to obtain component C. Analysis of component C using the aforementioned HPLC method revealed no other components with a peak ratio greater than 0.1%.

[0268] <Obtaining high-purity component D>

[0269] The following ingredients were obtained from Tokyo Chemical Industry Co., Ltd.: caprylic acid (O0027), lauric acid (L0011), myristic acid (M0476), palmitic acid (P1145), stearic acid (S0163), and docosanoic acid (B1248).

[0270] <Obtaining high-purity component E>

[0271] Octylamide (O237203), laurylamide (516472), myristylamide (B22610), palmitamide (QE-1627), stearamide (192-04015), and docosanoamide (B131150) were obtained from FUJIFILMWako Pure Chemical Corporation.

[0272] <LC-MS Analysis Method>

[0273] In the examples and comparative examples, the purity of component E was confirmed by the following LC-MS analysis.

[0274] (LC-MS device)

[0275] Separation tube: A stainless steel tube with an inner diameter of 2 mm and a length of 30 mm is filled with a substance modified with phenyl particles with a particle size of 3 μm.

[0276] Separator temperature: a constant temperature around 40℃

[0277] Mobile phase: Gradient elution method using 10 mM ammonium acetate aqueous solution and acetonitrile.

[0278] Flow rate: a constant rate of approximately 0.3 mL per minute.

[0279] As a measuring instrument, for example, the LCMS-9030 from Shimadzu Corporation can be used.

[0280] Ionization: ESI+

[0281] Scan range: m / z 50~1200

[0282] M+H: 200.203

[0283] <HPLC Analysis>

[0284] In the examples and comparative examples, the purity was confirmed by using the following HPLC analysis when calculating the ratio of component E to component A.

[0285] Detector: UV detector (205nm)

[0286] As measuring instruments, for example, Shimadzu Corporation's SPD-10Avp, SPD-10AVvp, SPD-20A, and SPD-20AV can be used.

[0287] Separation tube: A stainless steel tube with an inner diameter of 6 mm and a length of 150 mm is filled with octadecylsilyl silica modified with silica gel with a particle size of 5 μm and a pore size of 12 nm.

[0288] Separator temperature: a constant temperature around 60℃

[0289] Mobile phase: Methanol / Water / Phosphoric acid = 2000 / 400 / 0.31

[0290] Flow rate: a constant rate of approximately 0.8 mL per minute.

[0291] More specifically, component E / component A is expressed by the following formula, which is equivalent to "component E mass (%)" in the table below.

[0292] Component E / Component A = [Purity of Component E (g) / Purity of Component A (g)] × 100 (%)

[0293] The cocoamide MEA used in the examples and comparative examples was AMISL CME from Kawaken Fine Chemicals Co., Ltd., and the laurylamide MEA was AMISL LME from Kawaken Fine Chemicals Co., Ltd.

[0294] Examples 27, 30, 33, 36, 42, 45, 48, 51, 54, 57, 60, 63, 66, 69, 72, 75, 78, 81, 84, and 87 involve mixing a 32% aqueous solution of Example 1 with the aforementioned high-purity components A, C, D, and E. Examples 28, 31, 34, 37, 43, 46, 49, 52, 55, 58, 61, 64, 67, 70, 73, 76, 79, 82, and 85... 88. A 32% aqueous solution of Example 2 was mixed with the high-purity components A, C, D, and E described above. Examples 29, 32, 35, 38, 44, 47, 50, 53, 56, 59, 62, 65, 68, 71, 74, 77, 80, 83, 86, and 89 were prepared by mixing a 32% aqueous solution of Example 4 with the high-purity components A, C, D, and E described above, in a manner to form the countersalt / pH described in the table. Other examples / comparative examples involved correctly weighing high-purity components A, C through E, and mixing sodium hydroxide, potassium hydroxide, triethanolamine, or arginine, capable of forming countersalts, with the resulting solid powder in calculated amounts to prepare aqueous solutions with adjusted pH and solid content. These aqueous solutions were then finally adjusted to the specified pH and solid content of 32%. Comparative Examples 7-9, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, and 30, in which component A was replaced with the same amount of polysorbate 60, and the ratios of components B to E were recorded as the ratios when polysorbate 60 was component A. In Example 9, 1% stearoylglutamic acid (Na) was added by replacing it with purified water. In Example 10, 3% myristic acid and 2% palmitic acid were added by replacing them with purified water.

[0295] <Emulsion Stability Confirmation Test 1>

[0296] Prepare the following components.

[0297]

[0298] The above components are produced using the following order of 1 to 4.

[0299] 1. Dissolve carbomer in purified water.

[0300] 2. Adjust the pH of the carbomer aqueous solution to the specified pH using KOH, triethanolamine, arginine, or NaOH aqueous solution.

[0301] 3. Add the 32% aqueous solution of the example or comparative example and each oil.

[0302] 4. Emulsify for 5 minutes at room temperature using a homogeneous mixer (6000 rpm).

[0303] Visually confirm the presence of the above components after storing them at 55°C for 2 months, 2.5 months, and 3.0 months.

[0304] Evaluation Criteria

[0305] 5: Complete emulsification of the liquid depth

[0306] 4: Emulsification of more than 90% of the liquid depth

[0307] 3: Emulsification of more than 80% of the liquid depth

[0308] 2: Emulsification of more than 70% of the liquid depth

[0309] 1: The emulsion depth is less than 70%.

[0310] <Emulsion Stability Confirmation Test 2>

[0311] Prepare the following components.

[0312]

[0313] The above components are produced using the following order of 1 to 4.

[0314] 1. Dissolve carbomer in purified water, and adjust the carbomer aqueous solution to the specified pH using KOH, triethanolamine, arginine, or NaOH aqueous solution.

[0315] 2. Add a 32% aqueous solution of the example or comparative example and purified water to form an aqueous phase. Heat it to 70°C.

[0316] 3. Use mineral oil and solid oil as the oil phase and heat to 70°C.

[0317] 4. Mix the aqueous phase and oil phase, and heat to 80°C using a homogeneous mixer at 3000 rpm.

[0318] 5. Emulsify for 5 minutes using a homogeneous mixer at 6000 rpm.

[0319] 6. Stir using a homogeneous mixer at 3000 rpm and cool to 25°C.

[0320] 7. Perform degassing.

[0321] Store the above composition at 55°C and visually confirm emulsification after standing for 2 months, 2.5 months, and 3.0 months.

[0322] Evaluation Criteria

[0323] 5: Complete emulsification of the liquid depth

[0324] 4: Emulsification of more than 90% of the liquid depth

[0325] 3: Emulsification of more than 80% of the liquid depth

[0326] 2: Emulsification of more than 70% of the liquid depth

[0327] 1: The emulsion depth is less than 70% of the total liquid depth.

[0328] <Dispersion Stability Confirmation Test>

[0329] Titanium oxide was added to the 0.0075% aqueous solution of the solid component of each of the Examples and Comparative Examples to achieve a 1% concentration, and KOH, triethanolamine, arginine, or NaOH aqueous solution was added to achieve the specified pH. Then, ultrasonic treatment was performed for 30 seconds, homogenization was carried out (10000 rpm, 2 minutes), and the absorbance of the supernatant after standing at 50°C was measured (wavelength 300 nm) to confirm the dispersibility in water.

[0330] The initial absorbance value was approximately 1.8. The following evaluation was conducted by measuring the absorbance after 200 hours, 224 hours, and 248 hours.

[0331] Evaluation Criteria

[0332] 5: Absorbance of 1.7 or higher

[0333] 4: Absorbance is 1.5 or higher and less than 1.7.

[0334] 3: Absorbance is 1.3 or higher and less than 1.5.

[0335] 2: Absorbance is 1.0 or higher and less than 1.3.

[0336] 1: Absorbance less than 1.0

[0337] <User Experience Review>

[0338] The formulation of polydimethylsiloxane manufactured in Emulsion Stability Confirmation Test 1 was evaluated as follows. Functional evaluation was conducted by five experts, and the average value was used as the evaluation score.

[0339] (Evaluation item: the delicate feeling during the fusion process)

[0340] Very delicate 5

[0341] It has a delicate feel 4

[0342] Slightly delicate 3

[0343] Almost no delicate feeling 2

[0344] No delicate feeling 1

[0345] (Evaluation item: Presence or absence of a sticky feeling after blending)

[0346] No stickiness 5

[0347] Almost no stickiness 4

[0348] Slightly sticky 3

[0349] Sticky 2

[0350] Extra sticky 1

[0351] (Evaluation item: Thickness of the coating)

[0352] It feels very solid.

[0353] It has a solid feel 4

[0354] Slightly thick 3

[0355] Almost no sense of solidity 2

[0356] Lacks a sense of solidity 1

[0357] (Evaluation item: the degree of uniformity of coating during the blending process)

[0358] Excellent coating uniformity 5

[0359] Good coating uniformity 4

[0360] The coating is slightly good.

[0361] The coating is not very even.

[0362] Poor even application 1

[0363] (Evaluation item: Smoothness after fusion)

[0364] Very smooth 5

[0365] Smooth 4

[0366] Slightly smooth 3

[0367] Not very smooth 2

[0368] Unsmooth 1

[0369] The four tests / evaluations described above—emulsion stability confirmation test 1, emulsion stability confirmation test 2, dispersibility stability confirmation test, and user experience evaluation—were conducted using the compositions from the examples and comparative examples, respectively. The results are shown in Tables 1 to 5.

[0370] It should be noted that, as mentioned above, the "component B ratio (%)" in the table is relative to component A, the "component C mass (%)" is relative to the total of components A and C, the "component D mass (%)" is relative to the total of components A and D, and the "component E mass (%)" is relative to component A.

[0371] [Table 1-1]

[0372]

[0373] [Table 1-2]

[0374]

[0375] [Table 2-1]

[0376]

[0377] [Table 2-2]

[0378]

[0379] [Table 3-1]

[0380]

[0381] [Table 3-2]

[0382]

[0383] [Table 3-3]

[0384]

[0385] [Table 4-1]

[0386]

[0387] [Table 4-2]

[0388]

[0389] [Table 5-1]

[0390]

[0391] [Table 5-2]

[0392]

[0393] [Table 5-3]

[0394]

[0395] The compositions of the examples contain at least ingredients A and B, ingredients A, C and D, or ingredients A and E, and therefore exhibit good emulsification stability, dispersion stability, and user experience. On the other hand, the comparative examples are compositions that do not conform to the invention, and therefore exhibit worse emulsification stability and dispersion stability than the examples.

[0396] Industrial availability

[0397] The fragrance and cosmetic raw material composition according to the present invention can provide excellent fragrance and cosmetic formulations, such as good initial emulsification and dispersion properties, and good long-term emulsification stability and dispersion.

Claims

1. A fragrance cosmetic raw material composition, characterized in that, It contains: The following component A; and The following components B and / or the following components E, • Component A: An acyl-containing amino acid derivative or its salt as shown in the following general formula (A). In formula (A), R1 and R2 are each independently a saturated or unsaturated straight-chain or branched hydrocarbon group. M1, M2, and M3 are each independently a hydrogen atom, an alkali metal, an alkaline earth metal, an organic or inorganic amine, a basic amino acid, choline, aluminum, or zinc. n1 and n2 are 0 and 2, or 2 and 0. n3 and n4 are 0 and 2, or 2 and 0. • Component B: N-acylpyrrolidone carboxylic acid or a salt thereof, represented by the following general formula (B). In formula (B), R3 is a saturated or unsaturated straight-chain or branched hydrocarbon group. M4 can be a hydrogen atom, an alkali metal, an alkaline earth metal, an organic or inorganic amine, a basic amino acid, choline, aluminum, or zinc. • Component E: A fatty acid amide represented by the following general formula (E), In formula (E), R6 is a saturated or unsaturated straight-chain or branched hydrocarbon group.

2. The fragrance and cosmetic raw material composition according to claim 1, wherein, In the general formulas (A), (B), and (E), R1 to R3 and R6 are each independently a hydrocarbon group having 1 to 29 carbon atoms.

3. The fragrance and cosmetic raw material composition according to claim 1 or 2, wherein, In the general formulas (A), (B), and (E), R1 to R3 and R6 are each independently a hydrocarbon group with 7 to 23 carbon atoms.

4. The fragrance and cosmetic raw material composition according to claim 1 or 2, wherein, In the general formulas (A), (B), and (E), R1 to R3 and R6 are each a hydrocarbon group with 7 to 17 carbon atoms.

5. The fragrance and cosmetic raw material composition according to claim 1 or 2, wherein, In the general formulas (A) and (B), M1 to M4 are each independently Na, K, triethanolamine, Mg, Ca, Al, Zn, arginine, or H.

6. The fragrance and cosmetic raw material composition according to claim 1 or 2, wherein, The ratio of component B to component A is 0.004% or more.

7. The fragrance and cosmetic raw material composition according to claim 1 or 2, wherein, The ratio of component B to component A is 0.004% or more and 7.0% or less.

8. The fragrance and cosmetic raw material composition according to claim 1 or 2, wherein, The ratio of component B to component A is more than 0.01% and less than 3.5%.

9. The fragrance and cosmetic raw material composition according to claim 1 or 2, wherein, The ratio of component B to component A is 0.02% or more and 2.0% or less.

10. The fragrance and cosmetic raw material composition according to claim 1 or 2, wherein, Using the mass of component A as a reference, the amount of component E is 0.005% by mass or more.

11. The fragrance and cosmetic raw material composition according to claim 1 or 2, wherein, Using the mass of component A as a benchmark, the amount of component E is 0.005% by mass or more and 5.00% by mass or less.

12. The fragrance and cosmetic raw material composition according to claim 1 or 2, wherein, Using the mass of component A as a benchmark, the amount of component E is 0.02% by mass or more and 3.00% by mass or less.

13. The fragrance and cosmetic raw material composition according to claim 1 or 2, wherein, Using the mass of component A as a benchmark, the amount of component E is 0.08% by mass or more and 0.6% by mass or less.

14. The fragrance and cosmetic raw material composition according to claim 1 or 2, wherein, It contains the following components C and / or D. • Component C: Acylglutamic acid or its salt represented by the following general formula (C), In formula (C), R4 is a saturated or unsaturated straight-chain or branched hydrocarbon group. M5 and M6 are each independently hydrogen atoms, alkali metals, alkaline earth metals, organic or inorganic amines, basic amino acids, choline, aluminum, or zinc. • Component D: Fatty acid or its salt represented by the following general formula (D). In formula (D), R5 is a saturated or unsaturated straight-chain or branched hydrocarbon group. M7 can be hydrogen, alkali metal, alkaline earth metal, organic or inorganic amine, basic amino acid, choline, aluminum or zinc.

15. The fragrance and cosmetic raw material composition according to claim 14, wherein, In the general formulas (C) and (D), R4 and R5 are each independently a hydrocarbon group having 7 to 17 carbon atoms. In the general formulas (C) and (D), M5 to M7 are each independently Na, K, triethanolamine, Mg, Ca, Al, Zn, arginine, or H.

16. The fragrance and cosmetic raw material composition according to claim 14, wherein, Using the total mass of component A and component C as a benchmark, the amount of component C is 0.8% by mass or more and 8.0% by mass or less, and / or, The total mass of component A and component D is used as a reference, wherein the amount of component D is more than 0.06% by mass and less than 3.0% by mass.

17. A method for manufacturing the fragrance and cosmetic raw material composition according to any one of claims 1 to 16, comprising the following steps: Step 1) In a mixed solvent containing water and organic solvent, glutamic acid or its salt is reacted with fatty acyl chloride to obtain a reaction solution containing N-acylglutamic acid or its salt. The pH of the reaction solution is adjusted to 1-6 using acid, and the solution is separated into an organic layer and an aqueous layer at a temperature of 25-80°C. Step 2) The organic layer is concentrated and dried under acidic conditions to convert a portion of the N-acylglutamic acid or its salt into N-acylpyrrolidone carboxylic acid or its salt. Step 3) React the N-acylglutamic acid or its salt with an acid anhydride to obtain N-acylglutamic acid anhydride; and Step 4) React the N-acylglutamic anhydride with lysine or its salt to obtain an acyl amino acid derivative or its salt.

18. The manufacturing method according to claim 17, wherein, In step 1), the molar ratio of fatty acyl chloride to glutamic acid or its salt is 1.05 or less.

19. The manufacturing method according to claim 17 or 18, wherein, In step 1), the molar ratio of fatty acyl chloride to glutamic acid or its salt is less than 0.

98.

20. The manufacturing method according to claim 17 or 18, wherein, In step 1), the volume ratio of water to organic solvent is in the range of 90 / 10 to 20 / 80.

21. The manufacturing method according to claim 17 or 18, wherein, In step 1), the volume ratio of water to organic solvent is in the range of 85 / 15 to 50 / 50.

22. The manufacturing method according to claim 17 or 18, wherein, In step 1), the reaction temperature of glutamic acid or its salt with fatty acyl chloride is in the range of -10 to 70°C.

23. The manufacturing method according to claim 17 or 18, wherein, In step 1), the reaction temperature of glutamic acid or its salt with fatty acyl chloride is in the range of -5 to 10°C.

24. The manufacturing method according to claim 17 or 18, wherein, In step 1), the pH of the reaction between glutamic acid or its salt and fatty acyl chloride is maintained in the range of 9 to 13.

5.

25. The manufacturing method according to claim 17 or 18, wherein, In step 1), the pH of the reaction between glutamic acid or its salt and fatty acyl chloride is maintained in the range of 10 to 13.

26. The manufacturing method according to claim 17 or 18, wherein, In step 2), the organic layer is concentrated and dried until the weight loss during drying is less than 10% by mass.

27. The manufacturing method according to claim 17 or 18, wherein, In step 2), the organic layer is concentrated and dried until the weight loss is less than 3% by mass.

28. The manufacturing method according to claim 17 or 18, wherein, In step 2), the organic layer is concentrated and dried until the weight loss is less than 1% by mass.

29. The manufacturing method according to claim 17 or 18, wherein, The concentration and drying in step 2) are carried out under reduced pressure and at a temperature above 50°C.

30. A cosmetic product comprising the fragrance ingredient composition according to any one of claims 1 to 16.

31. The cosmetic according to claim 30, wherein the pH is 4 or higher.

32. The cosmetic according to claim 31, wherein the pH is 5.0 to 8.0.

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