TWI515013B - Skin detergent composition - Google Patents

Description

Skin detergent composition

The present invention relates to a skin cleansing agent composition which is excellent in stability at high temperature and low temperature storage, and which has a good usability in a liquid state even if the hand is wet.

The semi-solid detergent composition can maintain a state in which particles such as frosting are dispersed in the preparation, and can improve the appearance and the feeling of use. Among them, a gel-like detergent having a transparent and translucent appearance can provide a high quality feeling to the consumer.

The detergent composition containing a higher fatty acid salt is excellent in foaming performance and rinsing performance, but when it is semi-solid, it has a problem of poor performance and stability. For example, a transparent gel-like skin cleansing agent using a higher fatty acid salt and an Alkyl acrylate copolymer is disclosed (Patent Document 1: JP-A-2007-126396). However, although the appearance is a transparent gel, since the polymer compound is viscous and gelatinized, the foaming is slow, and since the yarn is taken by hand when the preparation is taken, the usability is not good.

Further, a transparent colloidal detergent using a specific high-grade fatty acid salt, an amphoteric surfactant, glycerin, and a fatty acid alkanosamine-type nonionic surfactant is disclosed (Patent Document 2: JP-A-2007-51168). Since this is not a viscosity of a polymer compound, but is gelled by a liquid crystal phase of a surfactant, it is less likely to be drawn during use, but it is difficult to remove from the container due to high viscosity, and it is difficult to apply the formulation when further adding water. There is a problem of falling by hand.

Prior technical literature

Patent literature

Patent Document 1: JP-A-2007-126396

Patent Document 2: JP-A-2007-51168

In view of the above, the present invention has an object of providing a skin cleansing agent composition having a good usability in a liquid crystal state even when the hand is wet and is excellent in stability at high temperature and low temperature storage.

In order to achieve the above object, the inventors of the present invention have found that (A) a higher fatty acid salt, (B) a betaine type amphoteric surfactant, (C) a specific nonionic surfactant, and a specific amount are added, respectively. And (D) a polyol which is made into a liquid crystal state at 25 ° C, and a transparent skin detergent composition which has good stability at high temperature and low temperature storage, and has good usability even in a wet state ( It is easy to dissolve and foam, and the present invention has been completed.

Accordingly, the present invention provides the following skin cleanser compositions.

[1] A skin cleansing composition comprising the following components (A), (B), (C) and (D) and having a liquid crystal state at 25 °C.

(A) a higher fatty acid salt having a carbon number of 8 to 26, 15 to 45% by mass,

(B) betaine type amphoteric surfactant, 7 to 25% by mass,

(C) the following nonionic surfactant, 1 to 5% by mass;

It is a polyoxyethylene (average addition molar number of ethylene oxide of 10 to 80) glycerol ester, glycerin, or polyoxyethylene (average addition molar number of ethylene oxide 10 to 80) trimethylolpropane a compound in which three hydroxyl groups are esterified or etherified, and the esterified or etherified portion is a saturated or unsaturated, linear or branched monovalent hydrocarbon group having 7 to 25 carbon atoms, or a part of a hydrogen atom. The hydroxyl group may be substituted, and the hydroxyl group may be added to form a polyoxyethylene having a molar number of 10 to 80. However, the total number of polyoxyethylene added by the nonionic surfactant is an average addition molar number. 10 to 80.

(D) Polyol, 15 to 35 mass%.

[2] (C) A skin detergent composition according to [1], characterized in that the hydrogen atom of the esterified or etherified portion of the component is 7 to 25 and the hydrogen atom of the monovalent hydrocarbon group is a hydroxyl group.

[3] The component (C) is a skin detergent composition according to [1] or [2] of polyoxyethylene hydrogenated castor oil or polyoxyethylene castor oil.

[4] A liquid detergent composition according to [1], [2] or [3] of a liquid crystal hexagonal liquid crystal.

According to the present invention, it is possible to provide a skin detergent composition which is excellent in stability at high temperature and low temperature storage, and which has a good usability liquid state even in a wet state.

The best form for implementing the invention

The following is a detailed description of the invention.

The skin detergent composition of the present invention is a skin detergent composition characterized by containing the following components (A), (B), (C) and (D) and having a liquid crystal state at 25 °C.

(A) a higher fatty acid salt having a carbon number of 8 to 26, 15 to 45% by mass

(B) Betaine type amphoteric surfactant, 7 to 25% by mass

(C) the following nonionic surfactant, 1 to 5% by mass

It is a polyoxyethylene (average addition molar number of ethylene oxide of 10 to 80) glycerol ester, glycerin, or polyoxyethylene (average addition molar number of ethylene oxide 10 to 80) trimethylolpropane a compound in which three hydroxyl groups are esterified or etherified, and the esterified or etherified portion is a saturated or unsaturated, linear or branched monovalent hydrocarbon group having 7 to 25 carbon atoms, or a part of a hydrogen atom. The hydroxyl group may be substituted, and the hydroxyl group may be added to form a polyoxyethylene having a molar number of 10 to 80. However, the total number of polyoxyethylene added by the nonionic surfactant is an average addition molar number. 10 to 80.

(D) Polyol, 15 to 35 mass%

(A) Higher fatty acid salts

The (A) higher fatty acid salt of the present invention is a higher fatty acid salt having 8 to 26 carbon atoms, and the monovalent hydrocarbon group may be linear or branched, and either one of saturated or unsaturated may be used alone or in combination. Two or more types are used. Among them, a higher fatty acid salt represented by the following general formula (1) is preferred.

R ¹ COOM (1)

(wherein R ¹ represents a straight or branched chain of 7 to 25, a saturated or unsaturated monovalent hydrocarbon group, and part or all of the hydrogen atom of the monovalent hydrocarbon group may be substituted with a hydroxyl group. M means potassium, Sodium, monoethanolamine, diethanolamine, triethanolamine, 2-amino-2-methyl-1-propanol or diisopropanolamine.)

The (A) component may, for example, be caproic acid, heptanoic acid, caprylic acid, capric acid, capric acid, undecanoic acid, lauric acid, decenoic acid, undecylenic acid, lauric acid, 2-ethylbutyl Acid, isovaleric acid, 2-ethylpentanoic acid, 2-ethylhexanoic acid, isophthalic acid, 3,5,5-trimethylhexanoic acid, tridecanoic acid, tetramethylnonanoic acid, myristic acid , pentadecanoic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, tetracosanoic acid, hexadecanoic acid, myristoleic acid, palmitoleic acid, oleic acid, oleic acid, Dodecanoic acid, erucic acid, squalic acid, linoleic acid, trans-9, cis-12-octadecadienoic acid, linolenic acid, arachidonic acid, 2-hexyl decanoic acid, isostearyl A mixture of acid, 12-hydroxystearic acid, lauric acid, myristic acid, palmitic acid, citric acid or the like or a salt of coconut oil fatty acid or the like.

Among them, a citrate having a carbon number of 10, 12, 14, or 16 is preferably a laurate, a myristate or a palmitate. When the carbon number is less than 10, the stability at high temperatures is poor, and when it exceeds 16, the stability at low temperatures is poor. The mass ratio of the higher fatty acid salt having a carbon number of 12 or less and the higher fatty acid salt having a carbon number of 14 or more is preferably 80/20 to 40/60, particularly preferably 75/25 to 50/50, and 70/30 to 60/ 40 is better. When the ratio of the higher fatty acid salt having a carbon number of 12 or less exceeds 80/20, the high-temperature stability is poor, and if it is less than 40/60, the low-temperature stability and the solubility in water may be deteriorated.

M (pair of ions) forms a COOM salt. As M, potassium, sodium, monoethanolamine, diethanolamine, and triethanolamine are preferable from the viewpoint of low-temperature stability, and potassium or monoethanolamine is particularly preferable from the viewpoint of low-temperature stability. Further, in view of the sterilizing power and the low-temperature stability, when the amount of the higher fatty acid salt is 100% by mass, the ratio of the monoethanolamine salt is preferably from 1 to 35% by mass, particularly preferably from 3 to 15% by mass.

The component (A) is 15 to 45% by mass in the skin detergent composition. If it is less than 15% by mass, no liquid crystal is formed. On the other hand, when it exceeds 45 mass%, a precipitate is produced at a low temperature. Further, from the viewpoint of foaming and low-temperature stability, it is preferably from 17 to 40% by mass, preferably from 20 to 35% by mass, particularly preferably from 25 to 35% by mass.

(B) Betaine type amphoteric surfactant

Examples of the betaine-type amphoteric surfactant include imidazoline type (amidoamine type), carboxybetaine type, sulfobetaine type, phosphobetaine type, and the like. . These may be used alone or in combination of two or more. From the viewpoint of easily forming a liquid crystal, it is preferred to use a carboxybetaine type in these.

Examples of the carboxybetaine type include alkylbetaine such as lauryl betaine, lauryl dimethylaminoacetate betaine, melamine propyl citrate, coconut fatty acid guanamine propyl betaine, and the like. Alkyl guanamine betaine and the like. Among them, from the viewpoint of liquid crystal formability, it is preferable to use lauryl dimethylaminoacetate acetate betaine or lysine propyl propyl citrate, especially from the viewpoint of low temperature stability, and lysine propyl citrate is preferred. . The amphoteric surfactant may contain sodium chloride in the production step, and desalting treatment is carried out from the viewpoint of improving the low-temperature stability. The aqueous solution of the amphoteric surfactant is preferably 1% by mass or less based on sodium chloride.

The component (B) is 7 to 25% by mass in the skin detergent composition, and preferably 9 to 15% by mass. When it is less than 7% by mass, liquid crystal is not formed, and when it exceeds 25% by mass, precipitation is likely to occur at a low temperature.

(C) The following nonionic surfactants

The component (C) of the present invention is a polyoxyethylene (average addition molar number of ethylene oxide of 10 to 80) glyceride, glycerin, or polyoxyethylene (the average addition molar number of ethylene oxide is 10 to 10) 80) a compound in which three hydroxyl groups of trimethylolpropane are esterified or etherified, and the esterified or etherified portion is a saturated or unsaturated, linear or branched monovalent hydrocarbon group having 7 to 25 carbon atoms. Alternatively, some of the hydrogen atoms may be substituted by a hydroxyl group, and the hydroxyl group may be added to form an average of 10 to 80 moles of polyoxyethylene, but the total amount of polyoxyethylene added by the nonionic surfactant is The average addition mole number is 10 to 80.

When the number of hydroxyl groups which are esterified or etherified is two or less, the solubility in water of the preparation is lowered. Further, the total amount of polyoxyethylene added by the nonionic surfactant is preferably from 15 to 40 moles. When it is less than 10 moles, in addition to the solubility in water of the preparation or the low-temperature stability, it may be cloudy and lose transparency, and if it exceeds 80 moles, the high-temperature stability may be deteriorated.

Among them, the nonionic surfactants (i) to (iii) having the following structure are excellent in stability at high temperature and low temperature storage, and have good usability in liquid crystal state even in a wet state. The skin cleanser composition is suitable.

(i) a compound which is esterified or etherified with three hydroxyl groups of polyoxyethylene (average addition molar number of ethylene oxide of 10 to 80), esterified or etherified, carbon number 7 ～25 of a saturated or unsaturated, linear or branched monovalent hydrocarbon group, or a part of a hydrogen atom may be substituted by a hydroxyl group, or an average addition of a hydroxyl group of 10 to 80 polyoxyethylene. The nonionic surfactant (however, the total amount of polyoxyethylene added by the nonionic surfactant is an average addition molar number of 10 to 80.).

The nonionic surfactant corresponding to the above (i) may, for example, be PEG-20 glyceryl triisostearate, PEG-20 glyceryl tristearate or PEG-20 glycerol trioleate.

(ii) a compound which is esterified or etherified with three hydroxyl groups of glycerol. The esterified or etherified moiety is a saturated or unsaturated, linear or branched monovalent hydrocarbon group having 7 to 25 carbon atoms. Part of the hydrogen atom is replaced by a hydroxyl group, and the hydroxyl group is added to form a polyoxyethylene nonionic surfactant having an average molar number of 10 to 80 (however, the polyoxygen added by the nonionic surfactant) The total number of ethylene added is 10 to 80.

The nonionic surfactant conforming to the above (ii) may, for example, be polyoxyethylene hydrogenated castor oil (EO10), polyoxyethylene castor oil (EO20), polyoxyethylene hydrogenated castor oil (EO20), polyoxygen Ethylene hydrogenated castor oil (EO40), polyoxyethylene castor oil (EO40), polyoxyethylene hydrogenated castor oil (EO80), and the like.

(iii) a compound in which esterified or etherified compound is esterified or etherified with polyoxyethylene (average addition molar number of ethylene oxide of 10 to 80) of three hydroxyl groups of trimethylolpropane. a saturated or unsaturated, linear or branched monovalent hydrocarbon group having 7 to 25 carbon atoms, or a partial hydrogen atom may be substituted by a hydroxyl group, or an average addition molar number of 10 to 80 in the hydroxyl group addition. A nonionic surfactant of polyoxyethylene (however, the total amount of polyoxyethylene added by the nonionic surfactant is an average addition mole number of 10 to 80.)

The nonionic surfactant corresponding to the above (iii) may, for example, be triisostearic acid PEG-20 trimethylolpropane or the like.

Specifically, for example, the following may be mentioned. The following PEG represents polyethylene glycol, and the POE represents polyoxyethylene. For example, POE (20) means that the average addition molar number of polyoxyethylene is 20.

Triisostearic acid PEG-20 glyceride (Japan Emulsion, GWIS-320) HLB=8

Tristearate PEG-20 glyceride (Japan Emulsion, GWS-320, HLB=8)

Triolein PEG-20 glyceride (Japan Emulsion, GWO-320, HLB=8)

Triisostearic acid PEG-20 trimethylolpropane (Japan Emulsion, TPIS-320, HLB=8)

POE (20) castor oil (Japan Emulsion, C-20, HLB=9)

POE (10) hydrogenated castor oil (Japan Emulsion, HC-10, HLB=7)

POE (10) hydrogenated castor oil (Sunlight Chemicals, HCO-10, HLB=6)

POE (20) hydrogenated castor oil (Japan Emulsion, HC-20, HLB=9)

POE (20) hydrogenated castor oil (Sunlight Chemicals, HCO-20, HLB=10.5)

POE (40) hydrogenated castor oil (Japan Emulsion, HC-40, HLB=12)

POE (40) hydrogenated castor oil (Sunlight Chemicals, HCO-40, HLB = 12.5)

POE (80) hydrogenated castor oil (Japan Emulsion, HC-80, HLB=15)

POE (80) hydrogenated castor oil (Sunlight Chemicals, HCO-80, HLB = 15.0)

The esterified or etherified fraction is a carbon number of 7 to 25, preferably 16 to 20, preferably a monovalent hydrocarbon group, and the monovalent hydrocarbon group is saturated or unsaturated, either linear or branched, or partially The hydrogen atom is replaced by a hydroxyl group. From the viewpoint of easy dissolution of the water of the preparation, a hydrocarbon chain having a hydrocarbon branch or a hydrocarbon having a non-terminal portion is particularly preferable. Among them, in view of the fact that the water of the preparation is easily dissolved, the above-mentioned nonionic surfactant conforming to (ii) is particularly preferable, and polyoxyethylene hydrogenated castor oil and polyoxyethylene castor oil are particularly preferable. The esterified fatty acid residue portion (part of the hydrocarbon chain and the ester group) of the polyoxyethylene castor oil is an unsaturated fatty acid (87% by mass of ricinoleic acid, 7% by mass of oleic acid, and 3% by mass) The linoleic acid) and a small amount of a saturated fatty acid (3 mass% of palmitic acid, stearic acid, etc.), and hydrogenated castor oil are those which hydrogenate the said fatty acid. In particular, in view of the fact that the water of the preparation is easily dissolved, it is preferred that the fatty acid distribution of the fatty acid residue is 80% by mass or more of the ricinic acid having a hydroxyl group at 12 positions or a hydrogenated product thereof.

It is excellent in stability at high temperature and low temperature storage, and it has a good usability liquid crystal state of the skin detergent composition even in the case where the hand is wet, and the polyoxyethylene hydrogenated castor oil (EO20) is obtained. [POE (20) hydrogenated castor oil], polyoxyethylene hydrogenated castor oil (EO40) [POE (40) hydrogenated castor oil], polyoxyethylene hydrogenated castor oil (EO20) [POE (20) castor oil], POE (40) Castor oil [POE (40) hydrogenated castor oil] is best. This mechanism is not known, but it is considered that POE hydrogenated castor oil or POE castor oil is present on the hydroxyl group of the hydrocarbon group, and the polyoxyethylene chain is branched to form a structure to relax the liquid crystal structure.

The component (C) is preferably 1 to 5% by mass, particularly 2 to 4% by mass, particularly preferably 2 to 3% by mass, based on the skin detergent composition. When the amount is less than 1% by mass, the ease of dissolution of water in the preparation is insufficient, and when it exceeds 5% by mass, the stability at high temperature is deteriorated.

(D) polyol

It is suitable for the polyol to be 2 to 6 yuan, and ethylene glycol, diethylene glycol, polyethylene glycol 200 (the equivalent of the pharmaceutical raw materials specifications 2006), polyethylene glycol 300 (medical department external supplies) Raw material specifications 2006 equivalent), polyethylene glycol 400 (medical department raw materials specifications 2006 equivalent), polyethylene glycol 600 (medical department raw materials specifications 2006 equivalent), propylene glycol, dipropylene glycol, 1,3- Butylene glycol, isoamyl glycol, pentanediol, 1,2-hexanediol, hexanediol, glycerin, diglycerin, sorbitol, xylitol, mannitol, etc. are suitable. One type or two or more types may be used in combination as appropriate. In addition, the polyethylene glycol system is equivalent to the second edition of the cosmetic raw material reference, the pharmaceutical raw material raw material specification 2006, the Japanese Pharmacy Pharmaceutical Standard 2002, and the 15th revised Japanese Pharmacopoeia. Among them, propylene glycol, polyethylene glycol 200, polyethylene glycol 300, polyethylene glycol 400, polyethylene glycol 600, propylene glycol, glycerin, and sorbitol are preferred from the viewpoint of easiness of liquid crystal formation. Further, from the viewpoints of low-temperature stability and easy formation of liquid crystal, it is preferred to mix a divalent or trivalent polyol, preferably a combination of propylene glycol and glycerin, and the mass (%) of propylene glycol/mass (%) of glycerol is 20/80~50/50 is especially good. When the ratio of propylene glycol exceeds 50/50, the liquid crystal formability may be lowered, and the high temperature stability may be lowered. If it is less than 20/80, the viscosity may be too high.

The component (D) is 15 to 35 mass% in the skin detergent composition, and preferably 20 to 30 mass%. When it is less than 15% by mass, the low-temperature stability is poor, and when it exceeds 35% by mass, it becomes difficult to form a liquid crystal.

The mass ratio of (A) the higher fatty acid salt to the (B) betaine type amphoteric surfactant is preferably from 85/15 to 60/40. (A) If the composition ratio exceeds 85/15, the stability of low temperature deteriorates. If it is less than 60/40, a sticky feeling will occur when washing.

The mass ratio of (A) the higher fatty acid salt to the (D) polyol is preferably from 70/30 to 40/60. (A) When the composition ratio exceeds 70/30, the stability of low temperature may be deteriorated. If it is less than 40/60, the stability of high temperature and the decrease in transparency may occur.

The skin cleansing composition of the present invention is in a liquid crystal state at 25 °C. The liquid crystal in the present invention means a hexagonal liquid crystal, a lamellar liquid crystal, or a cubic liquid crystal. In terms of usability and a transparent appearance, hexagonal liquid crystals are preferred. Since the lamellar liquid crystal has a low viscosity, it is dripped by hand or thickened by the added water during use, so that the usability is deteriorated.

Further, the term "liquid crystal" as used in the present invention means a molecular polymer of a surfactant, and a cylindrical surfactant becomes a liquid crystal of a rod-shaped molecule by the presence of a high concentration or an ionic polymer compound having a different charge. status. Such anisotropy based on liquid crystals indicates that the orientation of the orientation is derived from the "spontaneity" of molecular shape or intermolecular forces, and is not caused by any external force. In the thick solution of the polymer compound, if the molecular orientation occurs when flowing, optical anisotropy can be seen, but if the flow is stopped, such orientation is not spontaneous. From the viewpoint of the liquid property of the so-called fluidity and the liquid crystal characteristics of the optical anisotropy, the liquid crystal system is extremely specific and cannot be classified into a solid or a foreign body. Therefore, the "fourth state" of the substance is considered.

It is confirmed that the "liquid crystal state" can be judged by observing interference fringes by a polarizing microscope. Hexagonal liquid crystal was observed when the interference fringe was a fish scale-like mosaic texture, and lamellar liquid crystal was observed when a cross-type cross-crossing was observed. When no interference fringes were observed, it was a micro-micelle type (micelle). Phase), or cubic liquid crystal phase. Such typical interference fringes are exemplified in RB Rosevere, "The microscopy of the Liquid Crystalline Neat and Middle Phase of soaps and synthetic detergents" J. Am. Oil Chemist's Soc., 628, 31 (1954). Further, when a solid matter was observed at 25 ° C, even if such interference fringes were observed, it was not possible to judge the liquid crystal phase. On the other hand, the viscosity is very high, and when no cubic layer of interference fringes is judged or it is difficult to determine by a polarizing microscope, it can be judged by the interference mode of small angle X-ray scattering. Corresponding to (100), (110), (200) faces, corresponding to 1:3:2:‧‧‧ The interplanar spacing ratio is the hexagonal liquid crystal phase, which corresponds to (100), (200) ), (300) plane, corresponding to the 1:2:3: ‧ ‧ the plane spacing ratio of the scattering angle appears as a layered liquid crystal phase, corresponding to the (100), (111), (200) surface crystal Face spacing 1: √3/2: √2: ‧‧‧, or corresponding to (211), (220), (321), (400) face 1: √ 4/3: √ 7/3: √ 8 /3:‧‧‧ The peak appears as a cubic liquid crystal phase. In addition, there is no clear peak in the X-ray scattering of the small-angle portion, and the scattering vector q is near 0.1 to 0.5 nm ^-1 , and when there is a broad peak, it is a micro-micelle type.

Further, in terms of aesthetic appearance and the like, the skin detergent composition is preferably transparent. In addition, "transparency" means that the evaluation criteria are "◎" and "○" in the <transparency> measurement of the embodiment described later. In the "transparency" measurement of the examples described later, in order to obtain a "transparent" composition of transparency ◎, the components (A) to (D) are preferably satisfying the following conditions.

(A) The content of the component is 20 to 35 mass% in the skin detergent composition, and the mass ratio of the higher fatty acid salt having a carbon number of 12 or less and the higher fatty acid salt having a carbon number of 14 or more is 80/20 to 50/50.

The component (B) is lauryl dimethylaminoacetate betaine, and the content thereof is 7 to 15% by mass in the skin detergent composition.

The component (C) is selected from the group consisting of PEG-20 glyceryl triisostearate, PEG-20 glycerol trioleate, PEG-20 trimethylolpropane triisostearate, and POE (20-80) hydrogenated castor oil. And POE (20-80) castor oil, the content of which is 2 to 5% by mass in the skin detergent composition.

(D) The component is a combination of propylene glycol, glycerin, propylene glycol or polyethylene glycol 400 in an amount of 25 to 35% by mass in the skin detergent composition, and when propylene glycol and glycerin are used, the ratio of propylene glycol is 20/80 or more.

The skin cleansing composition of the present invention may be incorporated into other ingredients which are suitably selected, without departing from the scope of the present invention. As the other ingredients, it can be appropriately selected from the usual use of the skin detergent composition, for example, an oil such as an oil, a polyoxyalkylene, a lower or higher alcohol, an aqueous lanolin derivative, a protein derivative, or an acrylic resin dispersion. Liquid, vitamins, etc., bactericides, preservatives, pH adjusters such as potassium hydroxide and citric acid, antioxidants, metal blocking agents, ultraviolet absorbers, animal and plant extracts or derivatives thereof, pigments, perfumes, pigments, Water-insoluble polymer powders such as inorganic powders, clay minerals, nylons, and polyethylenes.

The pH of the skin detergent composition of the present invention is preferably 9.0 to 11.0 on the low-temperature stability or liquid crystal-forming surface, and particularly preferably 9.4 to 10.6 from the viewpoint of low-temperature stability. When the pH is less than 9.0, the low-temperature stability may be deteriorated, and if it exceeds 11.0, it may become difficult to form a liquid crystal.

The viscosity of the skin detergent composition of the present invention is preferably from 20 to 500 Pa s at 25 ° C, particularly preferably from 130 to 350 Pa ‧ s. When the temperature is less than 20 Pa ‧ , the stability of the high temperature is deteriorated. If it exceeds 500 Pa ‧ , the solubility in the water of the preparation may be deteriorated. In addition, the viscosity was measured using a BH-type viscometer (manufactured by Tokyo Keiki Co., Ltd.), and the sample temperature was 25 ° C, the number of revolutions No. 7, the number of rotations of 4 rpm, and the viscosity after one minute.

The skin detergent composition of the present invention can also be used for the face or the body, and the object is not particularly limited as long as it is skin.

Example

Hereinafter, the present invention will be specifically described by way of examples and comparative examples, but the present invention is not limited to the following examples. In the following examples, unless otherwise specified, the "%" of the composition is % by mass, and the ratio is the mass ratio, and the amount of each component in the table is the amount converted by the pure amount.

[Examples 1 to 38, Comparative Examples 1 to 12]

The skin cleanser composition was prepared as follows. Weigh (A), (C), (D) components and purified water in a container of a vacuum emulsification kettle. In a reduced pressure state, it was dissolved at 80 ° C by heating. After the dissolution, the component (B) was dissolved in a paddle stirring, and the mixture was cooled to 35 ° C at a reduced pressure of 1 ° C / min, and the mixture was thoroughly depressurized, stirred, and then degassed. After degassing, it was cooled to 25 ° C at 1 ° C / min. Next, the pH was measured using a pH meter HM-30R (manufactured by Toa DKK Co., Ltd.), and adjusted to a target pH using potassium hydroxide or citric acid. The pH was measured after the sample was immersed in the sample at 25 ° C for 2 minutes. The obtained skin detergent composition was evaluated as follows. The results are recorded in the table.

<viscosity>

The viscosity of the sample was measured at 25 ° C, the rotor No. 7, the number of rotations of 4 rpm, and the viscosity after 1 minute using a BH type viscometer (Tokyo Keiki Co., Ltd.).

<Confirm LCD status>

The liquid crystal state was confirmed to be 25 ° C in the skin detergent composition, and observed using a polarizing microscope AX70 (Olympus). It was observed that the interference fringe was a hexagonal liquid crystal when it was a fish scale-like mosaic structure, and it was a lamellar liquid crystal when a cross nicol of a cross pattern was observed, and a micro-micelle type (micelle phase) when no interference fringe was observed. The liquid crystal of the present invention means a hexagonal liquid crystal, a layered liquid crystal, or a cubic liquid crystal. Such typical interference fringes are exemplified in RB Rosevere, "The microscopy of the Liquid Crystalline Neat and Middle Phase of soaps and synthetic detergents" J. Am. Oil Chemist's Soc., 628, 31 (1954) and the like. Further, when the solid matter dispersion was observed at 25 ° C, even if such interference fringes were observed, the liquid crystal phase could not be judged.

On the other hand, when the viscosity is very high, and the cubic liquid crystal layer having interference fringes is not judged or difficult to be judged by a polarizing microscope, the X-ray diffraction device X' Pert Pro (PANalitical) for mounting the small-angle light receiving group and the X-ray condenser is used. (Social), judged by the interference mode of small-angle X-ray scattering. Corresponding to (100), (110), (200) faces, corresponding to 1:3:2:‧‧‧ The interplanar spacing ratio is the hexagonal liquid crystal phase, which corresponds to (100), (200) ), (300) plane, corresponding to the 1:2:3: ‧ ‧ the plane spacing ratio of the scattering angle appears as a layered liquid crystal phase, corresponding to the (100), (111), (200) surface crystal Face spacing 1: √3/2: √2: ‧‧‧, or corresponding to (211), (220), (321), (400) face 1: √ 4/3: √ 7/3: √ 8 /3:‧‧‧ The peak appears as a cubic liquid crystal phase. In addition, there is no clear peak in the X-ray scattering of the small-angle portion, and the scattering vector q is near 0.1 to 0.5 nm ^-1 , and when there is a broad peak, it is a micro-micelle type. The table is indicated by the following symbols.

Layered liquid crystal: L

Cubic LCD: C

Hexagonal liquid crystal: H

Micro-micule type: M

Solid dispersion: S

<High temperature, low temperature stability>

A hard transparent glass bottle (capacity: 55 ml) having a height of 8 cm and a diameter of 3 cm was filled with 50 ml of a skin detergent composition, and stored at 50 ° C and 0 ° C in each environment to observe the appearance at each storage temperature. The stability of the skin detergent composition was evaluated based on the following criteria.

[Judgement benchmark]

◎: After 4 weeks of storage, there was no phase separation or precipitate, and it was in a transparent and uniform state.

◎~○: After 4 weeks of storage, although there was no phase separation or precipitate, some of the appearance was slightly turbid.

○: After 4 weeks of storage, although there was no phase separation or precipitate, the appearance was observed to be slightly turbid.

△: After 2 weeks of storage, there was no phase separation or precipitate, but after 4 weeks of storage, the phases were separated or precipitated.

×: After 2 weeks of storage, the phases were separated or precipitated.

<transparency>

A hard transparent glass bottle (capacity: 55 ml) having a height of 8 cm and a diameter of 3 cm was filled with a 50 ml (height 6 cm) skin detergent composition and stored at 25 ° C for 1 day. For printing MS corners (Gothic) On the paper, the glass bottle filled with each sample was placed, and the transparency of the skin detergent composition was evaluated based on the discriminability of the printed characters on the top of the glass bottle based on the following criteria.

[Judgement benchmark]

◎: It is possible to clearly discriminate the print with the MS angle round body 20pt" "."

○: Printed in MS angle round body 20pt" Although it is a bit fuzzy, it can still be judged.

△: Although it is impossible to discriminate the print with the MS angle round body 20pt" "But it can be judged to be printed at 24pt" "."

×: It is impossible to discriminate "200pt printed with MS angle round body" "."

<Ease of dissolution at the time of use>

The ease of dissolution of the skin cleanser composition at the time of use was evaluated by 10 professional assessors using a skin cleanser composition. The skin detergent composition was filled in a tubular container (diameter: 3 cm, height: 8 cm, caliber: 5 mm), and the palm of the hand was wet with water, and 1 g of each sample was taken, and both hands were foamed to evaluate ease of dissolution. The evaluation was based on the criteria shown below, and a 5-stage score was given, and the average value of the scores of each sample was taken, and the average value was based on the following criteria.

[Judgement benchmark]

5 points: At the same time as the palm of the hand began, the sample dissolved and foamed.

4 points: Start the palm of your hand 2 to 3 times, the sample dissolves and foams.

3 points: Start the palm of your hand 4 to 7 times, the sample dissolves and foams.

2 points: Start the palm of your hand 8 to 12 times, the sample dissolves and foams.

1 point: The sample agent slips from the hand, or the sample adheres to the palm or the finger. Even if the palm is more than 13 times, it cannot be foamed.

[Base of rating average]

◎: 4.5 minutes to 5 minutes

◎~○: 4.0 points to less than 4.5 points

○: 3.0 minutes to less than 4.0 minutes

△: 2.0 minutes - less than 3.0 minutes

×: less than 2 points

Further, in order to confirm the sterilizing power of the skin detergent composition of the present invention, the following bactericidal power tests were carried out for Examples 1 and 36.

<bactericidal power>

(1) Modulation of bacterial liquid

The following bacterial solution was prepared so that the number of starting bacteria was 10 ⁸ /ml.

Staphylococcus aureus: Staphylococcus aureus ATCC6538

(2) Test solution

The skin detergent compositions obtained in Examples 1 and 36 were diluted 5 times with tap water to prepare a test solution.

<Bactericidal test method>

1 ml of the bacterial solution was added to 9 ml of the test solution at 25 ° C, and the mixture was stirred for 1 minute, and then added to 4.5 ml of SCDLP medium (Soybean-Casein Digest Broth with Lectin & Polysorbate 80: manufactured by Wako Pure Chemical Industries, Ltd.). , as a 10-fold dilution. The same procedure was repeated to obtain each dilution. 1.0 ml of each dilution was taken in a Petri dish, and 15 ml of SCDLP agar medium (Soybean-Casein Digest Ager with Lectin & Polysorbate 80: manufactured by Wako Pure Chemical Industries, Ltd.) was added to homogenize and culture for 2 days (agar plate dilution method). Count colonies and determine the number of viable cells. The bactericidal power was calculated from the number of starting bacteria and the number of viable cells based on the following formula, and the bactericidal effect was evaluated by the following evaluation criteria.

Bactericidal power = log (number of viable cells / number of starting bacteria)

In addition, the smaller the bactericidal force coefficient value, the higher the effect.

The sterilizing power of Example 1 was "-1, 1", and the sterilizing power of Example 36 was "-3, 2". It was confirmed that the monoethanolamine salt was used as the component (A), and the sterilizing power was improved. Further, in Example 36, the low-temperature stability (-5 ° C, one month) was "◎", and the low-temperature stability was good.

[Example 39]

The skin cleanser composition was prepared as follows. The common ingredients other than lauryl dimethylaminoacetate acetate and betaine were weighed into a container of a vacuum emulsification kettle. In a reduced pressure state, it was dissolved at 80 ° C by heating. After dissolving, the mixture was dissolved in lauryl dimethylaminoacetic acid betaine by stirring under a paddle, and cooled to 35 ° C at a reduced pressure of 1 ° C / min. At this moment, the pressure was reduced, stirred, and degassed. After degassing, the perfume was added and cooled to 25 ° C at 1 ° C / min. Next, the pH was measured using a pH meter HM-30R (manufactured by Toa DKK Co., Ltd.), and adjusted to a target pH using potassium hydroxide or citric acid.

It was adjusted to pH 10.2 with potassium hydroxide (48%) or citric acid.

<evaluation result>

Viscosity: 118Pa‧s

Transparency: ◎

Crystalline phase: H

Stability (50 ° C): ◎

Stability (0 ° C): ◎

Stability (-5 ° C): ◎

The materials used in the preparation of the examples and comparative examples are as follows.

*1: AMOGEN SH (First Industrial Pharmaceuticals)

*2: AMOGEN SH was taken in a stainless steel pan, dried in a vacuum dryer (40 ° C), and concentrated to a pure fraction of 80%.

* 3: LPB-R (one company oil industry)

* 4: EMALEX GWIS-320 (Japan Emulsion, HLB=8)

* 5: GWS-320 (Japan Emulsion, HLB=8)

* 6: GWO-320 (Japan Emulsion, HLB=8)

* 7: TPIS-320 (Japan Emulsion, HLB=8)

* 8: C-20 (Japan Emulsion, HLB=9)

* 9: HC-10 (Japan Emulsion, HLB=7)

* 10: HC-20 (Japan Emulsion, HLB=9)

* 11: HC-40 (Japan Emulsion, HLB=12)

* 12: HC-80 (Japan Emulsion, HLB=15)

* 13: PEG # 400K (Lion)

* 14: NEOSORB70/02SB (Rocket Japan)

* 15: HC-5 (Japan Emulsion, HLB=5)

* 16:HC-100 (Japan Emulsion, HLB=15)

* 17: GWIS-220EX (Japan Emulsion, HLB=10)

* 18: GWIS-120 (Japan Emulsion, HLB=13)

* 19: IPMP (Osaka Chemical)

* 20: dl-alpha tocopherol (DSM Nutrition Japan)

* 21: FLO-BEADS CL-8007 (Sumitomo Refined)

* 22: Concentrated glycerin for cosmetics

Claims (10)

A skin detergent composition characterized by containing the following components (A), (B), (C) and (D) and having a liquid crystal state at 25 ° C, (A) the following general formula (1) The higher fatty acid salt shown, 15 to 45 mass%: R ¹ COOM (1) (wherein R ¹ represents a straight or branched chain of 7 to 25, a saturated or unsaturated monovalent hydrocarbon group, and the monovalent hydrocarbon group Part or all of the hydrogen atom may be substituted by a hydroxyl group, M means potassium, sodium, monoethanolamine, diethanolamine, triethanolamine), (B) carboxybetaine type amphoteric surfactant, 7 to 25% by mass, ( C) a nonionic surfactant selected from the following components (i) to (iii), 1 to 5% by mass: (i) polyoxyethylene (average addition molar number of ethylene oxide 20) glyceryl ether Triisostearate, polyoxyethylene (average addition mole number of ethylene oxide 20) glyceryl ether tristearate, polyoxyethylene (average addition mole number of ethylene oxide 20) glycerin Ether trioleate, (ii) polyoxyethylene hydrogenated castor oil (average addition mole number of ethylene oxide 10~80), polyoxyethylene castor oil (average addition mole number of ethylene oxide 20 ~40), and (iii) polyoxyethylene (average addition molar number of ethylene oxide 20) three Methylpropane triisostearic acid, (D) a polyhydric alcohol selected from the group consisting of polyethylene glycol 200, polyethylene glycol 300, polyethylene glycol 400, polyethylene glycol 600, propylene glycol, glycerin and sorbitol, 15 ~35 mass%. The skin detergent composition of claim 1, wherein the component (C) is selected from the group consisting of polyoxyethylene hydrogenated castor oil (average addition molar number of ethylene oxide of 10 to 80) and polyoxyethylene oxime Sesame oil (the average addition of ethylene oxide is 20-40). The skin detergent composition of claim 2, wherein the component (C) is polyoxyethylene hydrogenated castor oil (the average addition molar number of ethylene oxide is 20 to 40). The skin detergent composition according to any one of claims 1 to 3, wherein the component (A) is a combination of a higher fatty acid salt having a carbon number of 12 or less and a higher fatty acid salt having a carbon number of 14 or more. The content ratio is 80/20~40/60. The skin detergent composition according to any one of claims 1 to 3, wherein the component (D) is a combination of propylene glycol and glycerin, and the ratio of the blending ratio is 20/80 to 50/50 by mass. The skin detergent composition according to any one of claims 1 to 3, wherein the ratio of the component (A) to the component (B) is 85/15 to 60/40 by mass. The skin detergent composition according to any one of claims 1 to 3, wherein the ratio of the components (A) to (D) is 70/30 to 40/60 by mass. The skin detergent composition according to any one of claims 1 to 3, wherein the liquid crystal is a hexagonal liquid crystal. The skin detergent composition according to any one of claims 1 to 3, wherein the viscosity at 25 ° C is 20 to 500 Pa. s. The skin detergent composition according to any one of claims 1 to 3, which is transparent in appearance.