Cleaning agent composition, manufacturing method thereof and cleaning product containing cleaning agent composition

Abstract

The present invention relates to a cleaning agent composition containing (A) one or more substances selected from the group consisting of N-acyl alanine having an acyl group having 8-22 carbon atoms and salts thereof, (B) one or more substances selected from the group consisting of fatty acids having 8-22 carbon atoms and salts thereof, and (C) one or more substances selected from the group consisting of alanine and salts thereof, the content ratio of component (A), component (B), and component (C) [(A): (B): (C)] being 100: 45-245: 10-150 by weight ratio. According to the present invention, it is possible to provide a detergent composition containing an N-acyl neutral amino acid or a salt thereof, the detergent composition having excellent foamability, foam quality, and feeling of use, imparting a good moist feeling to the skin and hair after washing and drying, and further improving the dry feeling after washing.

Description

Technical Field

[0001] This invention relates to a cleaning agent composition containing an N-long-chain acyl neutral amino acid or its salt, a method for manufacturing the same, and a cleaning article containing the cleaning agent composition. Background Technology

[0002] Because N-long-chain acyl neutral amino acids or their salts possess excellent surface activity and antibacterial properties, and are low in irritation, they are used as cleaning agent components in various cleaning agent compositions. However, when using N-long-chain acyl neutral amino acids or their salts alone as cleaning agents, the following problems exist: insufficient foam volume or foam persistence; furthermore, the desired user experience, such as a dry or moisturized feeling on the skin or hair after washing and drying, is not adequately achieved. Therefore, various studies have been conducted to address these issues.

[0003] For example, a cleaning agent composition containing N-long-chain acyl dipeptide, N-long-chain acylglycylglycinate, N-long-chain acylβ-alanylβ-alanylate, and N-long-chain acylglycinate or N-long-chain acylβ-alanylate in a specific ratio is proposed (Patent Document 1); a cleaning agent composition containing N-long-chain acylalanylalanylate is proposed (Patent Document 2). The cleaning agent composition described in Patent Document 1 has excellent foaming properties and foam persistence, and good defoaming properties during rinsing, but leaves the hair feeling tight and lacks sufficient moisturization after washing. The cleaning agent composition described in Patent Document 2 has excellent foaming properties and foam persistence, and improves hard water resistance and dryness during use, but leaves the hair feeling insufficiently dry (smooth) after washing.

[0004] Furthermore, as a cleansing agent composition with excellent foaming properties and foam persistence, capable of imparting a dry and moisturizing feeling to skin or hair after washing and drying, a cleansing agent composition containing N-acyl neutral amino acids or their salts, N-long-chain acyl neutral amino acid dipeptides or their salts, and N-long-chain acyl neutral amino acid tripeptides or their salts in specific proportions has been proposed (Patent Document 3). In Patent Document 3, compared to the conventional Schotten-Baumann reaction using fatty acyl chlorides, as a manufacturing method to reduce environmental impact, a method of mixing long-chain fatty acids, neutral amino acids, and an alkaline substance, heating, and directly performing a dehydration condensation reaction has been proposed. However, a new problem has been discovered in the cleansing agent composition described in Patent Document 3: a dry feeling after washing.

[0005] Therefore, there is a need for a cleaning composition containing an N-acyl neutral amino acid or its salt, which has excellent foaming properties, foam quality, and user experience, and can provide a good moisturizing feeling to the skin or hair after washing and drying, thereby improving the dryness after washing.

[0006] Existing technical documents Patent documents Patent Document 1: Japanese Patent Application Publication No. 5-078693 Patent Document 2: Japanese Patent Application Publication No. 7-188694 Patent document 3: International Publication No. 2005 / 033255. Summary of the Invention

[0007] The technical problem that the invention aims to solve Therefore, the object of the present invention is to provide a cleaning composition containing an N-acyl neutral amino acid or its salt, which has excellent foaming properties and foam quality, and a pleasant user experience, and can provide a good moisturizing feeling to the skin or hair after washing and drying, thereby improving the dryness after washing.

[0008] Means for solving technical problems In order to solve the above-mentioned problems, the inventors conducted in-depth research and found that by containing a cleaning agent composition in which (A) is selected from one or more N-acylalanine and its salts having an acyl group having 8 to 22 carbon atoms, (B) is selected from one or more fatty acids and their salts having 8 to 22 carbon atoms, and (C) is selected from one or more alanine and its salts, in a weight ratio of (A):(B):(C) of 100:45 to 245:10 to 150, the foaming properties, foam quality, user experience, and moisturizing feeling after washing and drying are improved, and the dryness after washing is also improved. The present invention was completed through further research.

[0009] That is, the present invention relates to the following: [1] A cleaning agent composition, comprising: (A) Selected from one or more N-acylalanines having an acyl group having 8 to 22 carbon atoms and their salts. (B) One or more fatty acids and their salts selected from those having 8 to 22 carbon atoms, and (C) Selected from one or more of alanine and its salts. The content ratio of the above components (A), (B) and (C) [(A):(B):(C)] is 100:45~245:10~150 by weight; [2] The cleaning agent composition according to [1] further contains (D) one or more selected from N-acylalanylalanine having an acyl group having 8 to 22 carbon atoms and its salts; [3] The cleaning agent composition according to [2], wherein the content ratio of component (A) to component (D) [(A):(D)] is 100:1 to 10 by weight; [4] The cleaning composition according to any one of [1] to [3], wherein (A) is selected from one or more N-acylalanines having an acyl group having 8 to 22 carbon atoms and their salts, and contains two or more N-acylalanines having an acyl group having different carbon atoms or their salts; [5] The cleaning composition according to any one of [1] to [4], wherein (B) is selected from one or more fatty acids having 8 to 22 carbon atoms and their salts, and contains two or more fatty acids having different numbers of carbon atoms or their salts; [6] The cleaning composition according to any one of [2] to [5], wherein (D) is selected from one or more N-acylalanylalanine having an acyl group having 8 to 22 carbon atoms and its salts, and contains two or more N-acylalanylalanine having an acyl group having different carbon atoms or its salts; [7] A method for preparing a cleaning agent composition, the method comprising the step of reacting (a) a fatty acid having 8 to 22 carbon atoms, (b) alanine and (c) one or more selected from alkali metal hydroxides and amines at 147°C to 190°C; [8] According to the manufacturing method described in [7], 0.5 to 1.5 moles of (a) fatty acids with 8 to 22 carbon atoms are used relative to 1 mole of (b) alanine; [9] According to the manufacturing method described in [7] or [8], wherein, relative to 1 mole of alanine, 0.5 to 1.5 moles of (c) one or more selected from alkali metal hydroxides and amines are used;

[10] The manufacturing method according to any one of [7] to [9], wherein (a) the fatty acid having 8 to 22 carbon atoms is a mixture of two or more fatty acids with different carbon atom numbers;

[11] The manufacturing method according to any one of [7] to

[10] , wherein (b) alanine is L-alanine or DL-alanine;

[12] The manufacturing method according to any one of [7] to

[11] , wherein (c) is sodium hydroxide, which is selected from one or more hydroxides of alkali metals and amines;

[13] A cleaning article, wherein the cleaning agent composition described in any one of [1] to [6] is a cleaning agent component;

[14] The cleaning product according to

[13] , wherein the viscosity measured at 25°C using a type B viscometer is 500 mPa·s to 60000 mPa·s;

[15] A cleaning article, wherein the cleaning agent composition described in any one of [1] to [6] is used as a cleaning aid;

[16] The cleaning product according to

[15] , wherein the viscosity measured at 25°C using a type B viscometer is 500 mPa·s to 60000 mPa·s;

[17] A cleaning article, wherein the cleaning agent composition described in any one of [1] to [6] is included as a cleaning agent component, and further includes a thickener;

[18] The cleaning product according to

[17] , wherein the thickener is selected from one or more of hydroxypropyl starch phosphate, fatty acid alkanolamide, glycine-type amphoteric surfactant, aminoacetic acid betaine-type amphoteric surfactant, sulfobetaine-type amphoteric surfactant and amidoamine oxide-type amphoteric surfactant;

[19] The cleaning product according to

[17] or

[18] , wherein the content of the thickener is 1% to 5% by weight relative to the total amount of the cleaning product;

[20] The cleaning product according to any one of

[17] to

[19] , wherein the viscosity measured at 25°C using a type B viscometer is 500 mPa·s to 400000 mPa·s;

[21] A cleaning article, wherein the cleaning agent composition described in any one of [1] to [6] is used as a cleaning aid, and further contains a thickener;

[22] The cleaning product according to

[21] , wherein the thickener is selected from one or more of hydroxypropyl starch phosphate, fatty acid alkanolamide, glycine-type amphoteric surfactant, aminoacetic acid betaine-type amphoteric surfactant, sulfobetaine-type amphoteric surfactant and amide amine oxide-type amphoteric surfactant;

[23] The cleaning product according to

[21] or

[22] , wherein the content of the thickener is 1% to 5% by weight relative to the total amount of the cleaning product;

[24] The cleaning product according to any one of

[21] to

[23] , wherein the viscosity measured at 25°C using a type B viscometer is 500 mPa·s to 400000 mPa·s.

[0010] The effects of the invention According to the present invention, a cleaning agent composition can be provided that exhibits excellent foaming properties and foam quality, provides a pleasant user experience, imparts a moisturizing sensation after washing and drying, and further improves the dryness after washing. The cleaning agent composition can be used as a cleaning agent component and cleaning aid in cleaning products for skin or hair. Furthermore, according to the present invention, a method for manufacturing the cleaning agent composition can be provided, wherein the environmental impact is minimal, the reaction can be carried out under relatively mild conditions, and the reaction mixture can be used directly as a cleaning agent composition. Furthermore, according to the present invention, a cleaning product containing the above-mentioned cleaning agent composition can be provided, exhibiting excellent foaming properties and foam quality, providing a good moisturizing sensation to the skin or hair after washing and drying, improving the dryness after washing, and providing a pleasant user experience. Detailed Implementation

[0011] This invention provides a cleaning agent composition. As described below, in this specification, "cleaning agent composition" refers to a composition contained in a cleaning article for skin or hair as a cleaning agent component or cleaning aid. The cleaning agent composition of this invention contains (A) one or more N-acylalanines having an acyl group having 8 to 22 carbon atoms and their salts, (B) one or more fatty acids having 8 to 22 carbon atoms and their salts, and (C) one or more alanines and their salts.

[0012] In the cleaning agent composition of the present invention, the alanine constituting the N-acylalanine contained as component (A) is 2-aminopropionic acid, which is a neutral aliphatic amino acid, and can be any one of L-type, D-type, and DL-type, preferably L-type and DL-type.

[0013] In the cleaning agent composition of the present invention, the acyl group of N-acylalanine contained as component (A) is a long-chain acyl group with 8 to 22 carbon atoms, such as: capryloyl, 6-methylheptanoyl (isocapryloyl), 2-ethylhexanoyl, caprinoyl, dodecanoyl (lauroyl), tetradecanoyl (myristoyl), 12-methyltetrazanoyl (isomyristoyl), hexadecanoyl Palmitoyl, 14-methylpentadecanoyl (isopalmitoyl), octadecanoyl (stearoyl), 16-methylheptadecanoyl (isostearoyl), eicosanoyl (arachidoyl), docosanoyl (behenoyl), and other straight-chain or branched saturated acyl groups with 8 to 22 carbon atoms; octenyl, 6-methylheptenyl (isooctenyl), decenyl, dodecenoyl, tetradecenoyl, and 9-hexadecenoyl (palmitoyl). 9-Octadecanyl (oleoyl), 11-Octadecanyl (Vaccenoyl), cis,cis-9,12-Octadecanadienoyl (linoleoyl), 9,12,15-Octadecantrienoyl (9,12,15-linolenic acid), 6,9,12-Octadecantrienoyl (6,9,12-linolenic acid), 5,8,11,14-Eicosatetraenoyl (arachidonic acid), cis-13-docosaenoyl Straight-chain or branched unsaturated acyl groups with 8 to 22 carbon atoms can be a mixture of saturated and unsaturated acyl groups derived mainly from a mixture of fatty acids containing 8 to 18 carbon atoms, or a mixture of saturated and unsaturated acyl groups derived mainly from fatty acids from vegetable oils containing 8 to 18 carbon atoms, such as coconut oil fatty acid acyl group, palm oil fatty acid acyl group, and palm kernel oil fatty acid acyl group.

[0014] In the cleansing composition of the present invention, as component (A), a salt of the aforementioned N-acylalanine may also be used. As a salt of N-acylalanine, there are no particular limitations as long as it is a pharmaceutically acceptable salt and can be used in skin compositions; examples include acid addition salts and salts with bases. Specifically, examples include salts with inorganic bases, organic bases, inorganic acids, organic acids, and salts with amino acids. Examples of salts with inorganic bases include salts with alkali metals such as lithium, sodium, and potassium; salts with alkaline earth metals such as magnesium and calcium; and ammonium salts. Examples of salts with organic bases include salts with alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine; and salts with heterocyclic amines such as morpholine and piperidine. Examples of salts with inorganic acids include salts with hydrohalic acids (hydrochloric acid, hydrobromic acid, hydroiodic acid, etc.), sulfuric acid, nitric acid, and phosphoric acid. Examples of salts containing organic acids include: salts containing monocarboxylic acids such as formic acid, acetic acid, and propionic acid; salts containing saturated dicarboxylic acids such as oxalic acid, malonic acid, and succinic acid; salts containing unsaturated dicarboxylic acids such as maleic acid and fumaric acid; salts containing tricarboxylic acids such as citric acid; and salts containing keto acids such as α-ketoglutarate. Examples of salts containing amino acids include: salts containing aliphatic amino acids such as glycine; salts containing aromatic amino acids such as tyrosine; salts containing basic amino acids such as lysine; and salts containing acidic amino acids such as aspartic acid and glutamic acid. These salts can be hydrates (hydrated salts), and examples of hydrates include monohydrates to hexahydrates. From the viewpoints of ease of acquisition and operability, alkali metal salts such as sodium salts and potassium salts are preferred as salts containing monoethanolamine, diethanolamine, and triethanolamine, and salts containing alkaneolamines such as monoethanolamine, diethanolamine, and triethanolamine are more preferred, with sodium salts, potassium salts, and triethanolamine salts being even more preferred.

[0015] In the cleaning agent composition of the present invention, the aforementioned N-acylalanine and its salts may be used alone or in combination of two or more. For the purposes of the present invention, as component (A), it is preferable to select two or more N-acylalanines or their salts having different numbers of carbon atoms and use them in combination. In the cleaning agent composition of the present invention, regarding the inclusion of one or more N-acylalanines or their salts having acyl groups having 8 to 22 carbon atoms as component (A), it is preferable to use a mixture of N-acylalanines or their salts having straight-chain or branched saturated acyl groups having 8 to 22 carbon atoms; more preferably, a mixture of N-acylalanines or their salts having saturated acyl groups having 10 to 14 carbon atoms, such as N-caprinoyl alanine or its salt, N-dodecanoyl (lauroyl) alanine or its salt, and a mixture of N-tetradecanoyl (myristoyl) alanine or its salt. In addition, it is preferred to use N-acylalanine or its salt having an acyl group derived from a mixture of fatty acids containing saturated fatty acids with a majority of 8 to 18 carbon atoms. More preferably, it is N-coconut oil fatty acid acylalanine or its salt, N-palm oil fatty acid acylalanine or its salt, N-palm kernel oil fatty acid acylalanine or its salt, etc., or N-acylalanine or its salt having an acyl group derived from fatty acids from vegetable oils containing saturated fatty acids with a majority of 8 to 18 carbon atoms.

[0016] The aforementioned N-acylalanine and its salts can be manufactured and used by the heating dehydration condensation reaction of alanine, fatty acids with 8 to 22 carbon atoms and alkaline substances in the manufacturing method of the cleaning agent composition of the present invention described later, or by other manufacturing methods known to them. Alternatively, commercially available products provided by companies such as Ajinomoto Co., Ltd. can be used.

[0017] Examples of straight-chain or branched saturated fatty acids containing 8 to 22 carbon atoms as component (B) in the cleaning agent composition of the present invention include: caprylic acid, 2-ethylhexanoic acid, nonanoic acid, capric acid, dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), 12-methyltridecanoic acid (isomyristic acid), hexadecanoic acid (palmitic acid), 14-methylpentadecanoic acid (isopalmitic acid), stearic acid (stearic acid), 16-methylheptadecanoic acid (isostearic acid), eicosanonic acid (arachidic acid), and behenic acid; octenic acid, 6-methylheptenoic acid (isooctenic acid), decenoic acid, 10-undecenoic acid, dodecenoic acid, and tetradecenoic acid. Straight-chain or branched-chain unsaturated fatty acids such as 9-hexadecenoic acid (palmitoic acid), cis-9-octadecenoic acid (oleic acid), 11-octadecenoic acid (isooleic acid), cis,cis-9,12-octadecadienoic acid (linoleic acid), 9,12,15-octadecanetrienoic acid (9,12,15-linolenic acid), 6,9,12-octadecanetrienoic acid (6,9,12-linolenic acid), 5,8,11,14-eicosatetraenoic acid (arachidonic acid), and cis-13-docosahexaenoic acid (erucic acid) can be used. Additionally, mixtures of fatty acids primarily containing 8 to 18 carbon atoms can be used, as well as fatty acids from vegetable oils such as coconut oil, palm oil, and palm kernel oil, which primarily contain 8 to 18 carbon atoms.

[0018] In the cleansing composition of the present invention, as component (B), salts of fatty acids having 8 to 22 carbon atoms can be used. As for the salts of fatty acids having 8 to 22 carbon atoms, there are no particular limitations as long as they are pharmaceutically acceptable and usable in skin compositions; examples include salts with inorganic or organic bases. Examples of salts with inorganic bases include salts with alkali metals such as lithium, sodium, and potassium; salts with alkaline earth metals such as magnesium and calcium; and ammonium salts. Examples of salts with organic bases include salts with alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine; and salts with heterocyclic amines such as morpholine and piperidine. From the viewpoints of ease of acquisition and operability, salts of alkali metals such as sodium and potassium salts, and salts with alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine, are preferred as salts of fatty acids having 8 to 22 carbon atoms; salts of sodium, potassium, and triethanolamine salts are more preferred; and salts of sodium and potassium salts are even more preferred.

[0019] In the cleaning agent composition of the present invention, the fatty acids and their salts having a carbon number of 8 to 22 can be used alone or in combination of two or more. For the purposes of the present invention, as component (B), it is preferable to select two or more fatty acids or their salts with different carbon numbers and use them in combination. In the cleaning agent composition of the present invention, regarding the one or more fatty acids and their salts selected as component (B), preferably a mixture of straight-chain or branched saturated fatty acids or their salts having a carbon number of 8 to 22, more preferably a mixture of saturated fatty acids or their salts having a carbon number of 10 to 14, such as capric acid or its salt, lauric acid or its salt, and myristic acid or its salt. Furthermore, it is also preferable to use a mixture of fatty acids or their salts containing a majority of saturated fatty acids having a carbon number of 8 to 18, more preferably fatty acids or their salts from vegetable oils containing a majority of saturated fatty acids having a carbon number of 8 to 18, such as coconut oil fatty acids, palm oil fatty acids, palm kernel oil fatty acids, etc.

[0020] The fatty acids and their salts with 8 to 22 carbon atoms mentioned above can be extracted, refined and used from plants and animals that contain them, or they can be manufactured and used using methods known to them, or they can be commercially available products provided by various companies.

[0021] Regarding alanine, which is included as component (C) in the cleaning agent composition of the present invention, it is as described above regarding alanine constituting component (A). Examples of salts of alanine include salts identical to those described above as salts of N-acylalanine, namely salts with inorganic bases, organic bases, inorganic acids, organic acids, and salts with amino acids. In the cleaning agent composition of the present invention, alanine and its salts may be used alone or in combination of two or more. Alanine and its salts can be extracted, purified, and used from plants and animals containing them, or manufactured and used using methods known per se, or commercially available products from various companies may be used.

[0022] In the cleaning agent composition of the present invention, (A) is selected from one or more N-acylalanine having an acyl group having 8 to 22 carbon atoms and its salts, (B) is selected from one or more fatty acids having 8 to 22 carbon atoms and their salts, and (C) is selected from one or more alanine and its salts, and is contained in a weight ratio of 100:45 to 245:10 to 150 based on the content ratio [(A):(B):(C)], preferably in a weight ratio of 100:60 to 200:10 to 120, and more preferably in a weight ratio of 100:85 to 200:10 to 80. If the ratio of the content of component (B) to the content of component (A) [(B) / (A)] by weight is 0.45 to 2.45, and the ratio of the content of component (C) to the content of component (A) [(C) / (A)] by weight is 0.1 to 1.5, then the foaming properties and foam quality become good, the moisturizing feeling on the skin and hair after washing and drying is improved, and the dryness during washing is reduced.

[0023] In addition to comprising components (A) to (C) described above, the cleaning agent composition of the present invention preferably contains (D) one or more of N-acylalanylalanine having an acyl group having 8 to 22 carbon atoms and its salts. In the cleaning agent composition of the present invention, the alanylalanine constituting the N-acylalanylalanine included as component (D) can be a dipeptide based on any one of L-alanine, D-alanine, and DL-alanine, but is preferably a dipeptide based on L-alanine and DL-alanine. Regarding the acyl group having 8 to 22 carbon atoms, it is as described above regarding the acyl group having 8 to 22 carbon atoms in component (A). Regarding the salt of N-acylalanylalanine, the same salt as described above as the salt of N-acylalanine (A) can also be cited.

[0024] In the cleaning agent composition of the present invention, N-acylalanylalanine and its salt having an acyl group having 8 to 22 carbon atoms can be used alone or in combination of two or more. For the purposes of the present invention, as component (D), it is preferable to use in combination two or more N-acylalanylalanines or their salts having acyl groups having different numbers of carbon atoms. In the cleaning agent composition of the present invention, regarding the inclusion of one or more of N-acylalanylalanine and its salts having an acyl group having 8 to 22 carbon atoms as component (D), it is preferable to use a mixture of N-acylalanylalanine or its salts having a straight-chain or branched saturated acyl group having 8 to 22 carbon atoms, and more preferably a mixture of N-acylalanylalanine or its salts having a saturated acyl group having 10 to 14 carbon atoms, such as N-caprinoylalanylalanine or its salt, N-dodecanoylalanylalanylalanine or its salt, and a mixture of N-tetradecanoylalanylalanylalanine or its salt. In addition, it is preferred to use N-acylalanylalanine or its salt having an acyl group derived from a mixture of fatty acids containing saturated fatty acids with a majority of 8 to 18 carbon atoms. More preferably, it is N-coconut oil fatty acid acylalanylalanine or its salt, N-palm oil fatty acid acylalanylalanine or its salt, N-palm kernel oil fatty acid acylalanylalanine or its salt, or N-acylalanylalanine or its salt having an acyl group derived from fatty acids from vegetable oils containing saturated fatty acids with a majority of 8 to 18 carbon atoms.

[0025] N-acylalanylalanine and its salts can be manufactured and used by methods known to the public. Alternatively, they can be produced by the method for manufacturing the cleaning agent composition of the present invention described later, through a heating dehydration condensation reaction of a fatty acid with 8 to 22 carbon atoms, alanine, and an alkaline substance.

[0026] In the cleaning agent composition of the present invention, (D) is selected from one or more of N-acylalanylalanine having 8 to 22 carbon atoms and its salts, and is preferably included in a weight ratio of 100:1 to 10 relative to the content ratio of component (A):(D)], more preferably in a weight ratio of 100:1 to 3. By containing component (D), the dryness and feel of hair are improved when washing with the cleaning agent composition.

[0027] In the cleaning agent composition of the present invention, in addition to the components (A) to (D) above, solvents such as water, thickeners, pH adjusters, chelating agents, preservatives and other common additives may be added without impairing the characteristics of the present invention.

[0028] The cleaning agent composition of the present invention can be prepared by mixing the above-described components (A) to (C) or components (A) to (D), adding solvents such as water or additives as needed, and making them homogeneous. Alternatively, the reaction product obtained by the manufacturing method of the cleaning agent composition of the present invention described later can be used directly as the cleaning agent composition of the present invention. The cleaning agent composition of the present invention can be provided in various forms such as liquid, paste, gel, and solid.

[0029] The cleaning composition of the present invention has excellent foaming properties and foam quality, provides a good user experience, and can impart a moisturizing feeling after washing and drying, thereby improving the dryness after washing. It can be well used as a cleaning agent component in cleaning products for skin or hair, and can also be well used as a cleaning aid.

[0030] In addition, the present invention provides a method for manufacturing a cleaning agent composition (hereinafter also referred to as "the manufacturing method of the present invention" in this specification). The preparation method of the present invention includes the step of reacting (a) a fatty acid having 8 to 22 carbon atoms, (b) alanine, and (c) one or more selected from alkali metal hydroxides and amines at a temperature of 147°C to 190°C.

[0031] Regarding the fatty acids with 8 to 22 carbon atoms used in the manufacturing method of the present invention (a), as described above for fatty acids with 8 to 22 carbon atoms included as component (B) in the cleaning agent composition of the present invention. In the manufacturing method of the present invention, as the fatty acids with 8 to 22 carbon atoms (a), it is preferable to select two or more fatty acids with different carbon chain lengths and use them in combination; more preferably, a mixture of straight-chain or branched saturated fatty acids with 8 to 22 carbon atoms is used. Particularly preferred are mixtures of fatty acids with 10 to 14 carbon atoms, such as a mixture of capric acid, lauric acid, and myristic acid, and fatty acids from vegetable oils containing a large number of fatty acids with 8 to 18 carbon atoms, such as coconut oil fatty acids, palm oil fatty acids, and palm kernel oil fatty acids.

[0032] Regarding the alanine used in the manufacturing method of the present invention, it is as described for alanine that is included as component (A) in the cleaning agent composition of the present invention. In the manufacturing method of the present invention, L-alanine and DL-alanine are preferably used as (b) alanine.

[0033] In the manufacturing method of the present invention, one or more of (c) selected from alkali metal hydroxides and amines are used as the alkaline substance. Examples of alkali metal hydroxides include lithium hydroxide, sodium hydroxide, and potassium hydroxide; examples of amines include monoethanolamine, diethanolamine, and triethanolamine. From the viewpoint of the condensation reaction of fatty acids with 8 to 22 carbon atoms with alanine, alkali metal hydroxides are preferred as the alkaline substance, sodium hydroxide and potassium hydroxide are more preferred, and sodium hydroxide is even more preferred.

[0034] In the manufacturing method of the present invention, relative to 1 mole of (b) alanine, the amount of (a) fatty acids having 8 to 22 carbon atoms is preferably 0.5 to 1.5 moles, more preferably 0.7 to 1.2 moles, even more preferably 0.8 to 1.0 moles, and particularly preferably 0.82 to 0.89 moles. In the manufacturing method of the present invention, relative to 1 mole of (b) alanine, the amount of (c) one or more selected from alkali metal hydroxides and amines is preferably 0.5 to 1.5 moles, more preferably 0.8 to 1.3 moles.

[0035] In the manufacturing method of the present invention, (a) a fatty acid having 8 to 22 carbon atoms, (b) alanine, and (c) one or more selected from alkali metal hydroxides and amines are mixed and reacted at 147°C to 190°C, causing the fatty acid having 8 to 22 carbon atoms and (b) alanine to undergo heating and dehydration condensation. The above-mentioned heating and dehydration condensation reaction is preferably carried out at 160°C to 180°C, more preferably at 160°C to 170°C. Furthermore, the above-mentioned heating and dehydration condensation reaction is preferably carried out at the above temperature for 15 hours to 30 hours, more preferably for 18 hours to 28 hours.

[0036] In the manufacturing method of the present invention, to prevent coloration caused by heating of the reaction mixture, the above-mentioned heating dehydration condensation reaction is preferably carried out under an inert gas atmosphere such as nitrogen or helium. Furthermore, in the manufacturing method of the present invention, it is preferable to carry out the reaction while removing water generated in the above-mentioned reaction, i.e., water generated during neutralization based on an alkaline substance and water generated by the condensation reaction. The removal of water generated in the reaction can be carried out by removing it along with an inert gas stream or by removing it under reduced pressure.

[0037] The reaction mixture obtained by the manufacturing method of the present invention contains: N-acylalanine or a salt thereof having an acyl group of 8 to 22 carbon atoms, which is a product of the above-described heating dehydration condensation reaction; unreacted fatty acid or a salt thereof having an acyl group of 8 to 22 carbon atoms; and unacylated alanine or a salt thereof. In the reaction mixture, the N-acylalanine salt and fatty acid salt are in the form of alkali metal salts or amine salts using the alkaline substance used. By using (a) a fatty acid having an acyl group of 8 to 22 carbon atoms, (b) alanine, and (c) one or more selected from alkali metal hydroxides and amines in the above-described usage ratio, and reacting under the above-described reaction conditions, a reaction mixture can be obtained. This reaction mixture contains N-acylalanine or a salt thereof having an acyl group of 8 to 22 carbon atoms, a fatty acid or a salt thereof having an acyl group of 8 to 22 carbon atoms, and alanine or a salt thereof in the above-described weight ratio of 100:45 to 245:10 to 150. Therefore, the above-described reaction mixture can be used directly as the cleaning agent composition of the present invention.

[0038] It should be noted that by neutralizing the above reaction mixture with inorganic acids such as hydrochloric acid and sulfuric acid, N-acylalanine salt and fatty acid salt can be converted into free N-acylalanine and fatty acid, respectively. Then, by neutralizing with an appropriate base, the desired N-acylalanine salt and fatty acid salt can be obtained.

[0039] Furthermore, in the manufacturing method of the present invention, a reaction mixture containing N-acylalanine or its salt having an acyl group having 8 to 22 carbon atoms can be obtained based on the ratio of (a) a fatty acid having 8 to 22 carbon atoms, (b) alanine, and (c) one or more selected from alkali metal hydroxides and amines, and the reaction conditions.

[0040] In the manufacturing method of the present invention, the environmental impact is minimal, the reaction is carried out under relatively mild conditions, and the resulting reaction mixture can be used directly as a cleaning agent composition.

[0041] Furthermore, the present invention provides a cleaning article. In this specification, "cleaning article" refers to a composition for cleaning skin or hair. The cleaning article of the present invention contains the cleaning agent composition of the present invention described above. In the cleaning article of the present invention, the cleaning agent composition of the present invention may be included as a cleaning agent component or a cleaning aid. In this specification, "cleaning agent component" refers to a component used for the purpose of cleaning skin or hair, and "cleaning aid" refers to a component added for the purpose of enhancing the cleaning power of the cleaning agent component. When the cleaning agent composition of the present invention is included as a cleaning agent component, its content in the cleaning article of the present invention, as the sum of (A) selected from one or more N-acylalanines having an acyl group having 8 to 22 carbon atoms and their salts, (B) selected from one or more fatty acids having 8 to 22 carbon atoms and their salts [(A)+(B)+(C)], is preferably 1% to 50% by weight, more preferably 1% to 30% by weight, and even more preferably 10% to 30% by weight. When the cleaning agent composition of the present invention is included as a cleaning aid, its content in the cleaning article of the present invention is, as the sum of (A) selected from one or more N-acylalanine having an acyl group having 8 to 22 carbon atoms and its salts, (B) selected from one or more fatty acids having 8 to 22 carbon atoms and their salts, and (C) selected from one or more alanine and its salts [(A)+(B)+(C)], preferably 0.5% to 10% by weight, more preferably 1% to 7% by weight.

[0042] When the cleaning agent composition of the present invention contains one or more of (D) selected from N-acylalanylalanine having an acyl group having 8 to 22 carbon atoms and its salts, the content of the cleaning agent composition of the present invention as a cleaning agent component in the cleaning article of the present invention is, as the total amount of (A) selected from one or more of N-acylalanine having an acyl group having 8 to 22 carbon atoms and its salts, (B) selected from one or more of fatty acids having 8 to 22 carbon atoms and their salts, (C) selected from one or more of alanine and its salts, and (D) selected from one or more of N-acylalanylalanine having an acyl group having 8 to 22 carbon atoms and its salts [(A)+(B)+(C)+(D)], preferably 1% to 50% by weight, more preferably 1% to 30% by weight, and even more preferably 10% to 30% by weight. Furthermore, the content of the cleaning agent composition of the present invention, when included as a cleaning aid in the cleaning article of the present invention, is preferably 0.5% to 10% by weight, more preferably 1% to 7% by weight, as the sum of (A) selected from one or more of N-acylalanine and its salts having an acyl group having 8 to 22 carbon atoms, (B) selected from one or more of fatty acids and their salts having 8 to 22 carbon atoms, (C) selected from one or more of alanine and its salts, and (D) selected from one or more of N-acylalanylalanine and its salts having an acyl group having 8 to 22 carbon atoms [(A) + (B) + (C) + (D)].

[0043] Without prejudice to the features of the present invention, the cleaning products of the present invention may, as needed, contain solvents (water, ethanol, etc.), various surfactants (anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants other than components (A), (B), and (D) above), oils, emollients, humectants, thickeners, hair conditioning agents, anti-inflammatory agents, ultraviolet absorbers, preservatives, antioxidants, chelating agents, pH adjusters, pigments, fragrances, and other general additives.

[0044] The cleaning products of the present invention can be provided in liquid, emulsion, gel, paste, cream, powder, and solid forms, and can be used as facial cleansing products such as facial foam, cleansing powder, makeup remover, and makeup remover cream; body cleansing products such as hand soap, shower gel, and bath soap; and hair cleansing products such as shampoo and rinse-in-shampoo. The cleaning products of the present invention can be manufactured according to conventional formulation methods, depending on their form. For example, if it is a liquid cleaning product, the cleaning agent composition of the present invention and general additives as needed can be added to a solvent such as water and mixed to make it uniform; if it is an emulsion or cream cleaning product, the cleaning agent composition of the present invention and hydrophilic additives as needed can be added to a solvent such as water and dissolved, and a substance containing lipophilic additives such as oils as needed can be added, mixed, and dissolved, and then emulsified.

[0045] It should be noted that, from the viewpoint of usability and operability, the cleaning article of the present invention preferably has moderate viscosity. For example, the viscosity measured using a type B viscometer at 25°C is preferably 500 mPa·s to 60000 mPa·s, more preferably 1000 mPa·s to 60000 mPa·s, and even more preferably 2000 mPa·s to 60000 mPa·s. In the cleaning article of the present invention, the above-mentioned viscosity can be imparted by containing the cleaning agent composition of the present invention as a cleaning agent component or cleaning aid, or by further containing a thickener.

[0046] Furthermore, from the viewpoint of low skin irritation, the cleaning product of the present invention is preferably weakly acidic to weakly alkaline, and the pH at 25°C is preferably 5 to 8.5, more preferably 5 to 7.5. Regarding the pH of the cleaning product of the present invention, for liquid cleaning products, it can be directly measured; for solid cleaning products, it can be dissolved or suspended in water and measured using a glass electrode method. In the cleaning product of the present invention, by containing the cleaning agent composition of the present invention as a cleaning agent component or cleaning aid, or by further containing a pH adjuster, the pH of the cleaning product can be kept within the above-mentioned range.

[0047] As one embodiment of the present invention, a cleaning product comprising the cleaning agent composition of the present invention and further thickened by a thickener can be provided. As a thickener, hydroxypropyl starch phosphate as processed starch, fatty acid alkanolamides as nonionic surfactants, glycine-type, glycine-betaine-type, sulfobetaine-type, and amide amine oxide-type amphoteric surfactants are preferred. Hydroxypropyl starch phosphate is a hydroxypropyl ether of a diester of phosphoric acid and starch. Fatty acid alkanolamides are obtained by condensing an alkanolamine with a fatty acid having about 8 to 22 carbon atoms, preferably 8 to 18 carbon atoms; examples include: lauric acid monoethanolamide, lauric acid diethanolamide, myristic acid monoethanolamide, myristic acid diethanolamide, palmitic acid monoethanolamide, palmitic acid diethanolamide, stearic acid monoethanolamide, stearic acid diethanolamide, coconut oil fatty acid monoethanolamide, and coconut oil fatty acid diethanolamide. From the perspective of thickening effect on cleaning products, lauric acid diethanolamide, coconut oil fatty acid monoethanolamide, and coconut oil fatty acid diethanolamide are preferred. Examples of glycine-type amphoteric surfactants include: 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazoline betaine, N-cocoyl-N-carboxymethoxyethyl-N-carboxymethyl ethylenediamine disodium, and N-lauroyl-N'-carboxymethyl-N'-hydroxyethyl ethylenediamine sodium. Examples of aminoacetic acid betaine-type amphoteric surfactants include: lauramidopropyl betaine, myristamidopropyl betaine, cocamidopropyl betaine, palm kernel oleamidopropyl betaine, and other fatty acid amamidopropyl betaines; lauryl dimethylaminoacetic acid betaine, coconut oil alkyl dimethylaminoacetic acid betaine, and other alkyl dimethylaminoacetic acid betaines. Examples of sulfobetaine-type amphoteric surfactants include lauryl hydroxysulfobetaine, lauramidopropyl hydroxysulfobetaine, and fatty acid amidopropyl hydroxysulfobetaine. Examples of amide amine oxide-type amphoteric surfactants include lauramidopropyl dimethylamine oxide.

[0048] In the cleaning product of the present invention, as a thickener, one of the above-mentioned hydroxypropyl starch phosphate, fatty acid alkanolamide, glycine-type amphoteric surfactant, glycine betaine-type amphoteric surfactant, sulfobetaine-type amphoteric surfactant, and amide amine oxide-type amphoteric surfactant may be used alone, or two or more may be used in combination. It should be noted that, from the viewpoint of thickening effect in the cleaning product of the present invention, hydroxypropyl starch phosphate, fatty acid alkanolamide, and fatty acid amamidopropyl betaine are preferred, and hydroxypropyl starch phosphate, coconut oil fatty acid monoethanolamide, and cocamidopropyl betaine are more preferred.

[0049] Furthermore, in a certain embodiment of the present invention, a cleaning article containing the cleaning agent composition of the present invention as a cleaning agent component, and further containing a thickener, can be prepared. The content of the cleaning agent composition of the present invention in the cleaning article of this embodiment, as the total amount of components (A), (B), and (C) or the total amount of components (A), (B), (C), and (D), is preferably 1% to 50% by weight, more preferably 1% to 30% by weight, and even more preferably 10% to 30% by weight. In the cleaning article of this embodiment, as a thickener, it is preferable to use one or more selected from the following: hydroxypropyl starch phosphate, fatty acid alkanolamide, glycine-type amphoteric surfactant, glycine betaine-type amphoteric surfactant, sulfobetaine-type amphoteric surfactant, and amide amine oxide-type amphoteric surfactant. The content of the thickener in the cleaning article of this embodiment is preferably 1% to 5% by weight, more preferably 2% to 5% by weight.

[0050] Furthermore, in other embodiments of the present invention, a cleaning article containing the cleaning agent composition of the present invention as a cleaning aid, and further containing a thickener, can be prepared. The content of the cleaning agent composition of the present invention in the cleaning article of this embodiment, as the total amount of components (A), (B), and (C) or the total amount of components (A), (B), (C), and (D), is preferably 0.5% to 10% by weight, more preferably 1% to 7% by weight. In the cleaning article of this embodiment, as a thickener, it is preferable to use one or more selected from the following: hydroxypropyl starch phosphate, fatty acid alkanolamide, glycine-type amphoteric surfactant, glycine betaine-type amphoteric surfactant, sulfobetaine-type amphoteric surfactant, and amide amine oxide-type amphoteric surfactant. The content of the thickener is also the same as in the cleaning article of the above embodiments.

[0051] The cleaning products described above, namely those containing the cleaning agent composition of the present invention as a cleaning agent component or cleaning aid, and further containing a thickener, can have their viscosity adjusted to an appropriate range according to their form by appropriately setting the content of the cleaning agent composition of the present invention, the type and content of the thickener, or by further combining them with other cleaning agent components, cleaning aids, or general additives. In the cleaning products of the present invention described above, the viscosity measured at 25°C using a type B viscometer can preferably be adjusted within the range of 500 mPa·s to 400000 mPa·s, and can be formed into liquid, paste, or cream forms. In the cleaning article of the present invention described above, the viscosity measured using a type B viscometer at 25°C is preferably 500 mPa·s or more, 1000 mPa·s or more, 2000 mPa·s or more, 10000 mPa·s or more, 30000 mPa·s or more, or 100000 mPa·s or more, and can be 1000 mPa·s to 60000 mPa·s, 2000 mPa·s to 60000 mPa·s, 10000 mPa·s to 60000 mPa·s, 30000 mPa·s to 400000 mPa·s, or 100000 mPa·s to 300000 mPa·s. For example, in a cleaning product containing the cleaning agent composition of the present invention as a cleaning agent component or cleaning aid, and further containing fatty acid alkanolamide and fatty acid amamidopropyl betaine as thickeners, the viscosity measured using a type B viscometer at 25°C can be thickened to 500 mPa·s or more. In the cleaning product, the viscosity measured using a type B viscometer at 25°C is preferably 1000 mPa·s to 60000 mPa·s, more preferably 2000 mPa·s to 60000 mPa·s, and even more preferably 10000 mPa·s to 60000 mPa·s. The cleaning product of the manner described in the present invention, exhibiting a viscous liquid to cream-like consistency, can be suitably provided as a shampoo, shower gel, etc. Furthermore, in cleaning products containing the cleaning agent composition of the present invention as a cleaning agent component or cleaning aid, and further containing hydroxypropyl starch phosphate as a thickener, the viscosity measured using a type B viscometer at 25°C is preferably 30,000 mPa·s to 400,000 mPa·s, more preferably 100,000 mPa·s to 300,000 mPa·s. The cleaning products of the manner described in the present invention are in the form of a paste or cream, and can be suitably provided as facial cleansing foam, facial cleansing cream, makeup remover, etc. Example

[0052] The present invention will now be described in more detail through embodiments.

[0053] [Examples 1-3, Reference Examples 1-3] Preparation of Cleaning Composition 50 g (0.56 mol) of L-alanine, 9 g (0.05 mol) of capric acid, 76 g (0.38 mol) of lauric acid, 15 g (0.07 mol) of myristic acid, and 18 g (0.45 mol) of sodium hydroxide were mixed and reacted under a nitrogen atmosphere at temperatures of 162°C, 170°C, and 147°C for 23 hours while removing the generated water. The reaction mixture was then cooled to obtain the cleaning agent compositions of Examples 1-3. Alternatively, capric acid, lauric acid, and myristic acid were used individually as fatty acids, and the reaction was carried out at 162°C in the same manner as above. The resulting reaction mixture was then cooled to obtain the cleaning agent compositions of Examples 1-3. It should be noted that commercially available products were used as L-alanine, capric acid, lauric acid, myristic acid, and sodium hydroxide. Specifically, L-alanine was supplied by Anhui Huaheng Biotechnology Co., Ltd.; decanoic acid, dodecanoic acid, and tetradecanoic acid were supplied by Fujifilm and Kojun Pharmaceutical Co., Ltd.; and sodium hydroxide was supplied by Showa Denko Co., Ltd.

[0054] The appearance of the cleaning agent compositions prepared in Examples 1-3 and Reference Examples 1-3, respectively, when added to water and diluted with a solid content of 30% by weight, was observed. Next, for the cleaning agent compositions prepared in Examples 1-3 and Reference Example 1, which exhibited a liquid appearance, the components contained in the compositions were analyzed by high-speed liquid chromatography (HPLC) (HPLC: "Chromaster", Hitachi High Technology Co., Ltd., column: reversed-phase column (C18 column) "Inertsil ODS-3, particle size = 5μm, 4.6mm × 250mm", GL Sciences Co., Ltd.). Furthermore, shampoos containing the cleaning agent compositions prepared in Examples 1-3 and Reference Example 1, according to the compositions in Table 5 described below, were prepared, and their foaming properties and foam quality (fineness of foam) were evaluated as follows. However, the content of each component in the cleaning agent compositions prepared in Examples 1-3 and Reference Example 1 was 30% by weight, based on the solid content. (1) Foaming properties Shampoos containing the above-prepared cleaning agent compositions were diluted with water at a concentration of 1.5% by weight of the cleaning agent components (based on solid content). The shampoos were then stirred for 20 seconds at 25°C using a dynamic foam analyzer (“DFA100”, KRUESS). The foam volume was measured after 60 seconds, and the results were evaluated according to the following criteria: <Evaluation Criteria> A: 55mL or more B: 40 mL or more but less than 55 mL C: Less than 40mL (2) Fineness of the foam Similar to the foaming performance evaluation described above, shampoos containing each detergent composition were diluted with water at a concentration of 1.5% by weight of the detergent components (based on solid content). The shampoos were then stirred using a dynamic foam analyzer. The particle size of the foam after 10 seconds was calculated using two-dimensional image analysis, and the evaluation was performed according to the following criteria: <Evaluation Criteria> A: 2250μm 2 the following B: Exceeding 2250μm 2 And it is 3500μm 2 the following C: Exceeding 3500μm 2 Table 1 shows the above-mentioned observations of the appearance of the cleaning agent compositions manufactured in Examples 1-3 and Reference Examples 1-3, the above-mentioned analytical results of the cleaning agent compositions manufactured in Examples 1-3 and Reference Example 1, and the evaluation results of foaming properties and foam quality.

[0055] [Table 1] *: In the table, "-" indicates that the analysis or evaluation was not performed; **: In the table, the content of each component is expressed as the weight ratio when the content of N-acyl-DL-alanine and its sodium salt is set to 100.

[0056] As shown in Table 1, when a mixture of decanoic acid, dodecanoic acid, and tetradecanoic acid with different carbon chain lengths was used as the fatty acid reacting with L-alanine (Examples 1-3), the resulting cleaning agent composition exhibited good solubility in water, and the shampoo containing the obtained cleaning agent composition showed good foaming properties and good foam quality, confirming the formation of fine foam. On the other hand, when dodecanoic acid or tetradecanoic acid was used alone as the fatty acid reacting with L-alanine (Refer to Examples 2 and 3), the resulting cleaning agent composition had poor solubility in water. When decanoic acid was used (Refer to Example 1), the resulting cleaning agent composition showed good solubility in water, but the shampoo containing the above-mentioned cleaning agent composition had poor foaming properties and foam quality. Therefore, based on the above evaluation results, the cleaning agent composition of the present invention preferably contains a reaction mixture obtained by reacting a mixture of two or more fatty acids with different carbon chain lengths with L-alanine in the presence of an alkaline substance. In addition, a composition containing N-acyl-DL-alanine and its salt, N-acyl-DL-alanylalanine and its salt, fatty acids and their salts, and unacylated DL-alanine and its salts obtained by reacting the above-mentioned fatty acid mixture with L-alanine at 147°C to 170°C in the presence of an alkaline substance is preferred from the viewpoint of foaming properties and foam quality.

[0057] Next, the low-temperature stability of the cleaning agent compositions prepared in Examples 1-3 was evaluated. The cleaning agent compositions of Examples 1-3 were added to water and diluted to a solid content of 30% by weight. 5g of each diluted solution was dispensed into 10mL glass vials, placed in a constant temperature incubator at 0°C, and after 24 hours, their appearance was observed and evaluated according to the following evaluation criteria: <Evaluation Criteria> A: It has a transparent, liquid appearance, and no change in appearance was observed compared to before storage at 0℃. B: After storage at 0℃, changes in appearance such as turbidity and precipitation of solids were observed. The evaluation results of the low-temperature stability of the cleaning agent compositions manufactured in Examples 1-3 are shown in Table 2.

[0058] [Table 2] *: In the table, the content of each component is expressed as the weight ratio when the content of N-acyl-DL-alanine and its sodium salt is set to 100.

[0059] As shown in Table 2, when L-alanine, fatty acids, and sodium hydroxide were reacted at 162°C and 170°C, respectively, no change in appearance was observed after storing the resulting cleaning agent compositions (Examples 1 and 2) at 0°C for 24 hours. On the other hand, when L-alanine, fatty acids, and sodium hydroxide were reacted at 147°C, turbidity caused by fatty acid precipitation was observed after storing the resulting cleaning agent composition (Example 3) at 0°C for 24 hours.

[0060] [Examples 4-8, Comparative Examples 1-4] Cleaning Compositions L-alanine and cocoyl chloride were reacted using a conventional method (Schotten-Baumann process) to prepare the cleaning agent composition of Comparative Example 1. Furthermore, L-alanine (Junshi Chemical Co., Ltd.) and coconut oil fatty acid (Nippon Yu Co., Ltd.) were added to the cleaning agent composition of Comparative Example 1, as shown in Table 3, to prepare the cleaning agent compositions of Comparative Examples 2-4. Additionally, the cleaning agent composition prepared in Example 1 above was mixed with the cleaning agent composition of Comparative Example 1, and coconut oil fatty acid (Nippon Yu Co., Ltd.) and L-alanine (Junshi Chemical Co., Ltd.) were further added, as shown in Table 3, to prepare the cleaning agent compositions of Examples 4 and 7. Coconut oil fatty acid (Nippon Yu Co., Ltd.) or L-alanine (Junshi Chemical Co., Ltd.) were added to the cleaning agent composition prepared in Example 1 above, as shown in Table 3, to prepare the cleaning agent compositions of Examples 5 or 6. Furthermore, coconut oil fatty acids (Nippon Oil Co., Ltd.) and L-alanine (Junjin Chemical Co., Ltd.) were added to the cleaning agent composition of Comparative Example 1, as shown in Table 3, to prepare the cleaning agent composition of Example 8. The cleaning agent compositions prepared in Examples 1-3, as well as the cleaning agent compositions of Examples 4-8 and Comparative Examples 1-4, were dissolved in water to obtain an aqueous solution with a solid content of 20% by weight. This aqueous solution was further diluted with water to make the solid content 1.5% by weight. (1) Foaming properties The diluted aqueous solutions of the above-prepared cleaning agent compositions were stirred for 20 seconds at 25°C using a dynamic foam analyzer ("DFA100", KRUESS). The foam content was measured after 30 seconds, and the results were evaluated according to the following criteria: <Evaluation Criteria> AA: 50mL or more A: 40 mL or more but less than 50 mL B: 35 mL or more but less than 40 mL C: Less than 35mL (2) Fineness of the foam The diluted aqueous solutions of the above-prepared cleaning agent compositions were stirred for 20 seconds at 25°C using a dynamic foam analyzer. The particle size of the foam after 30 seconds was calculated by image analysis of two-dimensional images, and the results were evaluated according to the following evaluation criteria: <Evaluation Criteria> AA: 5500μm 2 the following A: Exceeding 5500μm 2 And it is 6500μm 2 the following B: Exceeding 6500μm 2 And it is 7000μm 2 the following C: Exceeding 7000μm 2 The evaluation results of foaming properties and foam fineness are shown in Table 3.

[0061] [Table 3] *: In the table, the content of each component is expressed as the weight ratio when the content of N-acyl-DL-alanine and its sodium salt is set to 100.

[0062] As shown in Table 3, in the aqueous solutions of the cleaning agent compositions prepared in Examples 1-3 and the diluted solutions of the aqueous solutions of the cleaning agent compositions of Examples 4-8, both foaming properties and foam fineness were rated as "A" or higher. On the other hand, in the diluted solutions of the aqueous solutions of the cleaning agent composition of Comparative Example 1, which does not contain unacylated L-alanine, DL-alanine and their sodium salts, and whose fatty acid and sodium salt content is less than 45 parts by weight relative to 100 parts by weight of N-acyl-DL-alanine and its sodium salt, and the cleaning agent composition of Comparative Example 2, whose fatty acid and sodium salt content is less than 45 parts by weight relative to 100 parts by weight of N-acyl-DL-alanine and its sodium salt, both foaming properties and foam quality (foam fineness) were rated as "C". Furthermore, in the diluted aqueous solutions of the cleaning agent compositions of Comparative Examples 3 and 4, where the content of fatty acids and their sodium salts was less than 45 parts by weight relative to 100 parts by weight of N-acyl-DL-alanine and its sodium salt, and the content of unacylated L-alanine, DL-alanine and their sodium salts was much more than 150 parts by weight relative to 100 parts by weight of N-acyl-DL-alanine and its sodium salt, the foam quality (fineness of foam) of the former was rated as "B", and the foaming property of the latter was rated as "B".

[0063] Next, the user experience of the cleaning agent compositions manufactured in Example 1, Examples 4, 6, and 8 was evaluated. At this time, the cleaning agent compositions of Comparative Example 5, prepared by adding coconut oil fatty acids (Nippon Yu Co., Ltd.) to the cleaning agent composition of Comparative Example 1 as shown in Table 4, and Comparative Example 6, prepared by adding coconut oil fatty acids (Nippon Yu Co., Ltd.) and L-alanine (Junshikatsu Co., Ltd.) to the cleaning agent composition of Comparative Example 1 as shown in Table 4, were also evaluated. For the evaluation of user experience, aqueous solutions obtained by dissolving each cleaning agent composition in water at a solid content of 20% by weight were used to wash the skin and hair of five researchers. The foaming ability, foam density, moisturizing sensation after washing, smoothness when applied to the skin, and combability when applied to the hair were evaluated according to the following criteria. For each evaluation item, the average score of the five researchers was calculated, and the results determined according to the following criteria are shown in Table 4. <Evaluation Criteria> Excellent: 5 stars Good: 4 points Average: 3 points Slightly worse: 2 points Difference: 1 point <Judgment Criteria> AA: 3.5 points or above A: 3 points or higher but less than 3.5 points B: 2 points or more but less than 3 points C: Less than 2 points.

[0064] [Table 4] *: In the table, the content of each component is expressed as the weight ratio when the content of N-acyl-DL-alanine and its sodium salt is set to 100.

[0065] As shown in Table 4, the cleaning agent compositions prepared in Example 1 and the cleaning agent compositions of Examples 4, 6 and 8 were rated as “AA” or “A” in all items of foaming properties, foam density, moisturizing feeling after washing, smoothness when applied to the skin, and combability when applied to the hair when used in aqueous solutions of each cleaning agent composition. On the other hand, for the cleaning agent compositions of Comparative Examples 5 and 6, which do not contain un-N-acylated L-alanine, DL-alanine and their sodium salts, or whose content is less than 10 parts by weight relative to 100 parts by weight of N-acyl-DL-alanine and its sodium salt, and whose content of fatty acids and their sodium salts is much greater than 245 parts by weight relative to 100 parts by weight of N-acyl-DL-alanine and its sodium salt, the foaming performance when using any of the aqueous solutions was rated as "C". Except for the foam density when using the aqueous solution of the cleaning agent composition of Comparative Example 5 and the moisturizing feeling after washing when using the cleaning agent composition of Comparative Example 6, which were rated as "A", the user experience when using the aqueous solution of each cleaning agent composition was rated as "B".

[0066] Based on the above evaluation results regarding the foaming properties, foam quality, and user experience of the cleaning agent compositions prepared in Examples 1-3, Examples 4-8, and Comparative Examples 1-6, the cleaning agent compositions of the present invention containing components (A) to (D) exhibit excellent foaming properties and foam quality, and also provide an excellent user experience when used for cleaning skin or hair. Furthermore, it is shown that good foaming properties and foam quality can be obtained when the content of components (B) and (C) in the cleaning agent composition is 45 to 245 parts by weight and 10 to 150 parts by weight, respectively, relative to 100 parts by weight of component (A).

[0067] [Example 9, Comparative Examples 7-12] Shampoo The ingredients shown in Table 5 were added sequentially to water, mixed and dissolved evenly to prepare shampoos of Examples 9 and Comparative Examples 7-12. For the shampoos of Examples 9 and Comparative Examples 7-12, the pH value at 25°C was measured using the glass electrode method. The foam quality (fineness of the foam), the coefficient of friction in the washed hair strands, and the feel of the washed hair strands were evaluated as described below. The measurement and evaluation results are shown in Table 5. (1) Evaluation of foam quality (fineness of foam) For each shampoo of the Examples and Comparative Examples, the detergent components were diluted with hard water (hardness = 300 ppm) at a concentration of 1.5% by weight (based on solid content), and then stirred for 20 seconds at 25°C using a dynamic foam analyzer (“DFA100”, KRUESS). The particle size of the foam after 10 seconds and 180 seconds was calculated by image analysis of two-dimensional images, and the evaluation was carried out according to the following evaluation criteria: <Evaluation criteria for the fineness of foam after 10 seconds> AA: 2500μm 2 the following A: Exceeding 2500μm 2 And it is 4000μm 2 the following B: Exceeding 4000μm 2 And it is 5000μm 2 the following C: Exceeding 5000μm 2 <Evaluation criteria for the fineness of foam after 180 seconds> AA: 7500μm 2 the following A: Exceeding 7500μm 2 And it is 10000μm 2 the following B: Exceeding 10000μm 2 And it is 12500μm 2 the following C: Exceeding 12500μm 2 (2) Determination of the coefficient of friction in the washed hair strands Each shampoo from the examples and comparative examples was diluted 7 times with hard water (hardness = 300 ppm). A hair bundle (10g, 30cm) was immersed in 98g of the diluted solution at 25°C for 5 minutes. Then, the hair bundle was immersed in 800g of hard water (hardness = 300 ppm) for 30 seconds, and this process was repeated twice. The hair bundle was then towel-dried for 10 seconds, and the coefficient of friction of the hair bundle was measured three times using a friction measurement device ("TL201Ts", Trinity Lab Co., Ltd.). The average value of the measured values ​​was calculated, and the hair bundle was evaluated according to the following evaluation criteria: <Evaluation Criteria> AA: Coefficient of friction below 0.225 A: The coefficient of friction is greater than 0.225 but less than 0.25. B; Coefficient of friction exceeding 0.25 but below 0.275 C: Coefficient of friction exceeds 0.275 (3) Evaluation of the feel of the hair strands after washing The shampoos of the examples and comparative examples were diluted 7 times with hard water (hardness = 300 ppm). Hair bundles (10 g, 30 cm) were immersed in 98 g of the diluted solution at 25°C for 5 minutes. Then, the hair bundles were immersed in 800 g of hard water (300 ppm) for 30 seconds, repeated twice, and then dried in a constant temperature room (25°C). The feel of the dried hair bundles was evaluated by one researcher according to the following evaluation criteria: <Evaluation Criteria> Excellent: AA Good: A Normal: B Poor: C.

[0068] [Table 5] *: The values ​​in the columns corresponding to each component in the table indicate the content (by weight %) of that component. Additionally, the contents of the cleaning agent composition and surfactants are expressed as solid content. **: In the table, an empty column corresponding to each component indicates that the component is not present.

[0069] As shown in Table 5, the shampoo of Example 9, which contains the cleaning agent composition manufactured in Example 1 as a cleaning agent ingredient, was evaluated as superior in terms of foam quality and smoothness (indicated by the coefficient of friction after washing the hair) compared to the shampoos of Comparative Examples 7-12, which used the cleaning agent composition of Comparative Example 1 and commercially available anionic surfactants (sodium lauryl polyoxyethylene ether sulfate, sodium α-alkenyl sulfonate, sodium N-cocoyl methyl taurate, sodium cocoyl hydroxyethanesulfonate, and sodium N-lauroyl sarcosinate) as cleaning agent ingredients, and the hair felt good to the touch. The evaluation results above indicate that the cleaning product containing the cleaning agent composition of the present invention as a cleaning agent ingredient has good foam quality, imparts a smooth and pleasant feel to the hair, and improves the dryness after washing.

[0070] [Examples 10-14, Comparative Examples 13-17] Shampoo In the shampoo of Example 9 shown in Table 5, the cleaning agent composition prepared in Example 1 was replaced with the cleaning agent components shown in Table 6 (sodium lauryl polyoxyethylene ether sulfate, sodium N-cocoyl methyl taurate, sodium N-lauroyl sarcosinate, sodium α-alkenyl sulfonate, and alkyl polyglucosides) at 10% by weight of solids, and the cleaning agent composition prepared in Example 1 and the cleaning agent composition of Comparative Example 1 at 5% by weight of solids as cleaning aids, respectively, to prepare shampoos of Examples 10-14 and Comparative Examples 13-17. The viscosity of each shampoo of Examples 10-14 and Comparative Examples 13-17 was measured at 25°C using a Type B viscometer and evaluated according to the following evaluation criteria. The evaluation results are shown in Table 6. <Evaluation Criteria> AA: Viscosity above 10000 mPa·s A: Viscosity above 2000 mPa·s and below 10000 mPa·s B: Viscosity above 1000 mPa·s and below 2000 mPa·s C: Viscosity above 500 mPa·s and below 1000 mPa·s D: Viscosity less than 500 mPa·s.

[0071] [Table 6] .

[0072] As shown in Table 6, in the shampoos of Examples 10-14, which contain sodium lauryl polyoxyethylene ether sulfate, sodium N-cocoyl methyl taurate, sodium N-lauroyl sarcosinate, sodium α-alkenyl sulfonate, and alkyl polyglucosides as cleaning agent components, and the cleaning agent composition manufactured in Example 1 as a cleaning aid, and further contain coconut oil fatty acid monoethanolamide and cocamidopropyl betaine as thickeners, good thickening of 1000 mPa·s or more was observed, resulting in excellent workability as cleaning products. On the other hand, in the shampoos of Comparative Examples 13-17, which contain coconut oil fatty acid monoethanolamide and cocamidopropyl betaine as thickeners but contain the cleaning agent composition of Comparative Example 1 as a cleaning aid, no thickening of 500 mPa·s or more was observed except for the shampoo of Comparative Example 16. In addition, the viscosity of the shampoo of Comparative Example 16 was also less than 1000 mPa·s.

[0073] Next, other embodiments of the cleaning articles of the present invention are shown below. It should be noted that the pH of the cleaning articles in the following embodiments was measured using the glass electrode method according to the 18th edition revised Japanese Pharmacopoeia General Test Method 2.54 pH Measurement Method, etc.

[0074] [Example 15] Shampoo In Table 7, (1) to (8) are added to (10) in sequence and mixed to dissolve evenly. The pH is then adjusted to 6.5 using (9).

[0075] [Table 7] *: In the table, the contents of (1) to (3) are expressed as the contents of solid components.

[0076] [Example 16] Shampoo In Table 8, (1) to (7) are added to (9) in sequence and mixed to dissolve evenly. The pH is then adjusted to 7.0 using (8).

[0077] [Table 8] *: In the table, the contents of (1) to (3) are expressed as the contents of solid components.

[0078] [Example 17] Shampoo In Table 9, (1) to (7) are added to (9) in sequence and mixed to dissolve evenly. The pH is then adjusted to 7.0 using (8).

[0079] [Table 9] *: In the table, the contents of (1)~(3) and (5) are expressed as the contents of solid components.

[0080] [Example 18] Shower Gel In Table 10, (1) to (8) are added to (10) in sequence and mixed to dissolve evenly. The pH is then adjusted to 7.0 using (9).

[0081] [Table 10] *: In the table, the contents of (1) to (3) are expressed as the contents of solid components.

[0082] [Example 19] Cleansing Foam In Table 11, (1) to (7) are added to (9) in sequence and mixed to dissolve evenly. The pH is then adjusted to 6.5 using (8).

[0083] [Table 11] *: In the table, the contents of (1) to (3) are expressed as the contents of solid components.

[0084] [Example 20] Facial Cleansing Foam In Table 12, (1) to (13) are added to 30g of (15) to disperse and heated to 70°C to 80°C to dissolve. In addition, (14) is dissolved in the remaining (15) and added slowly while stirring. After the saponification reaction is completed, the mixture is cooled to room temperature.

[0085] [Table 12] *: In the table, the contents of (1) and (10) are expressed as the contents of solid components.

[0086] [Examples 21-24, Comparative Examples 18, 19] Cleansing Foam In Table 13, (1) and (3) to (5) were added to (10) and heated to 70°C to 80°C to dissolve. (7) was dispersed in (6) which was heated to 80°C, and added to the above solution while stirring. After mixing until homogeneous, (8) was added and cooled to 45°C. (9) was added and mixed to prepare the facial cleansing foams of Examples 21 to 24. In addition, in Table 13, the facial cleansing foams of Comparative Examples 18 and 19 were prepared in the same way except that (2) was used instead of (1).

[0087] For each facial cleansing foam of Examples 21-24 and Comparative Examples 18-19, the viscosity was measured using a Type B viscometer at 25°C, and evaluated according to the following evaluation criteria: <Evaluation Criteria> A: Viscosity above 100,000 mPa·s B: Viscosity above 30,000 mPa·s and below 100,000 mPa·s C: Viscosity less than 30000 mPa·s In addition, the appearance of each facial cleansing foam from Examples 21-24 and Comparative Examples 18-19 was observed at room temperature and evaluated according to the following evaluation criteria: <Evaluation Criteria> A: It has a uniform white paste-like consistency. B: Appears as a uniform white liquid. C: Separation of the visible water layer and oil layer The evaluation results are shown in Table 13.

[0088] [Table 13] *: The values ​​in the columns corresponding to each component in the table indicate the content (by weight %) of that component. Additionally, the contents of the cleaning agent composition, surfactant, and alkyl acrylate copolymer emulsion are expressed as solids content. **: In the table, blank columns corresponding to the cleaning agent composition manufactured in Example 1 and the cleaning agent composition of Comparative Example 1 indicate that the component is not present.

[0089] As shown in Table 13, in the facial cleansing foams of Examples 21-24, which contained the cleaning agent composition manufactured in Example 1 as a cleaning agent component, good thickening was observed by adding hydroxypropyl starch phosphate. In the facial cleansing foams of Examples 23 and 24, where the amount of hydroxypropyl starch phosphate added was 3.0% and 4.0% by weight, respectively, a uniform paste-like facial cleansing foam was obtained. On the other hand, the facial cleansing foams of Comparative Examples 18 and 19 did not contain unacylated L-alanine, DL-alanine, and their sodium salts. In the cleaning agent composition of Comparative Example 1, which contained less than 45 parts by weight of fatty acids and their sodium salts relative to 100 parts by weight of N-acyl-DL-alanine and its sodium salt, no thickening due to the addition of hydroxypropyl starch phosphate was observed, and a uniform paste-like facial cleansing foam was not obtained. The above results indicate that in the cleaning articles of the present invention containing the cleaning agent composition of the present invention as a cleaning agent component, good thickening can be obtained by adding hydroxypropyl starch phosphate.

[0090] Industrial availability As detailed above, according to the present invention, a cleaning agent composition with excellent foaming properties and foam quality, a pleasant user experience, and the ability to provide a moisturizing sensation after washing and drying, thereby improving the dryness after washing, can be provided. The cleaning agent composition of the present invention can be used as a cleaning agent component and cleaning aid in cleaning products for skin and hair. Furthermore, according to the present invention, a method for manufacturing a cleaning agent composition with low environmental impact and capable of conducting the reaction under relatively mild conditions can be provided. According to the manufacturing method of the present invention, the reaction-generated mixture can be used directly as a cleaning agent composition. Furthermore, according to the present invention, a cleaning product containing the above-described cleaning agent composition, exhibiting excellent foaming properties and foam quality, providing a pleasant moisturizing sensation to the skin or hair after washing and drying, improving the dryness after washing, and providing a pleasant user experience, can be provided.

[0091] This application is based on Japanese Patent Application No. 2023-156575, the contents of which are fully contained in this specification.

Claims

1. A cleaning agent composition, wherein, contain: (A) Selected from one or more N-acylalanines having an acyl group having 8 to 22 carbon atoms and their salts. (B) One or more fatty acids and their salts selected from those having 8 to 22 carbon atoms, and (C) Selected from one or more of alanine and its salts. The content ratio of the above components (A), (B) and (C) [(A):(B):(C)] is 100:45~245:10~150 by weight.

2. The cleaning agent composition according to claim 1, wherein, It further contains (D) one or more of N-acylalanylalanine and its salts having an acyl group having 8 to 22 carbon atoms.

3. The cleaning agent composition according to claim 2, wherein, The content ratio of component (A) to component (D) [(A):(D)] is 100:1~10 by weight.

4. The cleaning agent composition according to any one of claims 1 to 3, wherein, (A) is selected from one or more N-acylalanines having an acyl group having 8 to 22 carbon atoms and their salts, and contains two or more N-acylalanines having acyl groups having different numbers of carbon atoms or their salts.

5. The cleaning agent composition according to any one of claims 1 to 3, wherein, (B) is selected from one or more fatty acids having 8 to 22 carbon atoms and their salts, and contains two or more fatty acids or their salts with different numbers of carbon atoms.

6. The cleaning agent composition according to claim 2 or 3, wherein, (D) is selected from one or more N-acylalanylalanines having 8 to 22 carbon atoms and their salts, and contains two or more N-acylalanylalanines having different numbers of carbon atoms or their salts.

7. A method for preparing a cleaning agent composition, the method comprising reacting (a) a fatty acid having 8 to 22 carbon atoms, (b) alanine, and (c) one or more selected from alkali metal hydroxides and amines at 147°C to 190°C.

8. The manufacturing method according to claim 7, wherein, For every 1 mole of (b) alanine, use 0.5 to 1.5 moles of (a) fatty acids with 8 to 22 carbon atoms.

9. The manufacturing method according to claim 7 or 8, wherein, Compared to 1 mole of (b) alanine, use 0.5 to 1.5 moles of (c) one or more selected from alkali metal hydroxides and amines.

10. The manufacturing method according to claim 7 or 8, wherein, (a) Fatty acids with 8 to 22 carbon atoms are mixtures of two or more fatty acids with different numbers of carbon atoms.

11. The manufacturing method according to claim 7 or 8, wherein, (b) Alanine is L-alanine or DL-alanine.

12. The manufacturing method according to claim 7 or 8, wherein, (c) Sodium hydroxide is selected from one or more hydroxides of alkali metals and amines.

13. A cleaning product, wherein, The cleaning agent composition according to any one of claims 1 to 3 is used as a cleaning agent component.

14. The cleaning article according to claim 13, wherein, The viscosity measured at 25°C using a Type B viscometer ranges from 500 mPa·s to 60000 mPa·s.

15. A cleaning product, wherein, The cleaning agent composition containing any one of claims 1 to 3 is used as a cleaning aid.

16. The cleaning article according to claim 15, wherein, The viscosity measured at 25°C using a Type B viscometer ranges from 500 mPa·s to 60000 mPa·s.

17. A cleaning product, wherein, The cleaning agent composition according to any one of claims 1 to 3 is included as a cleaning agent component, and further includes a thickener.

18. The cleaning article according to claim 17, wherein, The thickener is selected from one or more of the following: hydroxypropyl starch phosphate, fatty acid alkanolamide, glycine-type amphoteric surfactant, aminoacetic acid betaine-type amphoteric surfactant, sulfobetaine-type amphoteric surfactant, and amide amine oxide-type amphoteric surfactant.

19. The cleaning article according to claim 17, wherein, The thickener content is 1% to 5% by weight relative to the total amount of the cleaning product.

20. The cleaning article according to claim 17, wherein, The viscosity measured at 25°C using a Type B viscometer ranges from 500 mPa·s to 400,000 mPa·s.

21. A cleaning product, wherein, The cleaning agent composition containing any one of claims 1 to 3 as a cleaning aid, and further containing a thickener.

22. The cleaning article according to claim 21, wherein, The thickener is selected from one or more of the following: hydroxypropyl starch phosphate, fatty acid alkanolamide, glycine-type amphoteric surfactant, aminoacetic acid betaine-type amphoteric surfactant, sulfobetaine-type amphoteric surfactant, and amide amine oxide-type amphoteric surfactant.

23. The cleaning article according to claim 21, wherein, The thickener content is 1% to 5% by weight relative to the total amount of the cleaning product.

24. The cleaning article according to claim 21, wherein, The viscosity measured at 25°C using a Type B viscometer ranges from 500 mPa·s to 400,000 mPa·s.

Images