WO2012039350A1 - Skin cleanser composition - Google Patents

Skin cleanser composition Download PDF

Info

Publication number
WO2012039350A1
WO2012039350A1 PCT/JP2011/071189 JP2011071189W WO2012039350A1 WO 2012039350 A1 WO2012039350 A1 WO 2012039350A1 JP 2011071189 W JP2011071189 W JP 2011071189W WO 2012039350 A1 WO2012039350 A1 WO 2012039350A1
Authority
WO
WIPO (PCT)
Prior art keywords
mass
polyoxyethylene
liquid crystal
acid
skin cleanser
Prior art date
Application number
PCT/JP2011/071189
Other languages
French (fr)
Japanese (ja)
Inventor
恭史 柿澤
光俊 森部
幸治 二宮
Original Assignee
ライオン株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by ライオン株式会社 filed Critical ライオン株式会社
Priority to KR1020137006662A priority Critical patent/KR101790822B1/en
Priority to JP2012535019A priority patent/JP5861639B2/en
Publication of WO2012039350A1 publication Critical patent/WO2012039350A1/en

Links

Classifications

    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/36Carboxylic acids; Salts or anhydrides thereof
    • A61K8/361Carboxylic acids having more than seven carbon atoms in an unbroken chain; Salts or anhydrides thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/36Carboxylic acids; Salts or anhydrides thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0295Liquid crystals
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/34Alcohols
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/41Amines
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/86Polyethers
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • A61Q19/10Washing or bathing preparations

Definitions

  • the semi-solid detergent composition can keep particles such as scrubs dispersed in the preparation, and can improve the appearance and feel.
  • a gel-like cleaning agent having a transparent to translucent appearance can provide consumers with a high quality feeling.
  • Patent Document 2 JP-A-2007-511168. Publication). This is not a thickening due to the polymer compound but gelation by the liquid crystal phase of the surfactant, so stringing during use is difficult to occur, but it is difficult to remove from the container due to its high viscosity, and water was added. In some cases, the preparation is difficult to extend and falls from the hand.
  • a skin cleanser composition containing the following components (A), (B), (C) and (D) and in a liquid crystal state at 25 ° C. (A) 15 to 45% by mass of higher fatty acid salt having 8 to 26 carbon atoms (B) Betaine amphoteric surfactant 7 to 25% by mass (C) 1 to 5% by mass of the following nonionic surfactant Three hydroxyl groups of polyoxyethylene (average added mole number of ethylene oxide 10 to 80) glyceryl, glycerin, or polyoxyethylene (average added mole number of ethylene oxide 10 to 80) trimethylolpropane are esterified or etherified.
  • liquid-form skin cleanser composition that has excellent stability during storage at high and low temperatures and has good usability even when the hand is wet.
  • the skin cleanser composition of the present invention is a skin cleanser composition containing the following components (A), (B), (C) and (D) and being in a liquid crystal state at 25 ° C. .
  • (C) 1 to 5% by mass of the following nonionic surfactant Three hydroxyl groups of polyoxyethylene (average added mole number of ethylene oxide 10 to 80) glyceryl, glycerin, or polyoxyethylene (average added mole number of ethylene oxide 10 to 80) trimethylolpropane are esterified or etherified.
  • the esterified or etherified moiety is a saturated or unsaturated, linear or branched monovalent hydrocarbon group having 7 to 25 carbon atoms, and part of the hydrogen atoms are substituted with hydroxyl groups.
  • the polyoxyethylene having an average addition mole number of 10 to 80 may be added to this hydroxyl group, provided that the total number of polyoxyethylene added to the nonionic surfactant is the average addition mole number. 10 to 80. (D) 15 to 35% by mass of polyhydric alcohol
  • 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 moiety is either linear or branched, saturated or unsaturated. It may be used alone or in combination of two or more. Among these, higher fatty acid salts represented by the following general formula (1) are preferable.
  • R 1 COOM (1) (In the formula, R 1 represents a linear or branched, saturated or unsaturated monovalent hydrocarbon group having 7 to 25 carbon atoms, and part or all of the hydrogen atoms of the monovalent hydrocarbon group are hydroxyl groups. (M may be potassium, sodium, monoethanolamine, diethanolamine, triethanolamine, 2-amino-2-methyl-1-propanol or diisopropanolamine.)
  • Component (A) includes caproic acid, heptanoic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, caproleic acid, undecylenic acid, lauroleic acid, 2-ethylbutanoic acid, isopentanoic acid, 2-ethylpentanoic acid 2-ethylhexanoic acid, isononanoic acid, 3,5,5-trimethylhexanoic acid, tridecanoic acid, tetramethylnonanoic acid, myristic acid, pentadecanoic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cellotine Acid, myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, gondoic acid, erucic acid, cerakoleic acid, linoleic acid, linoelai
  • component (A) is 15 to 45% by mass in the skin cleanser 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, 17 to 40% by mass, particularly 20 to 35% by mass, and particularly 25 to 35% by mass are preferable.
  • Betaine-type amphoteric surfactant examples include imidazoline type (amidoamine type), carbobetaine type, sulfobetaine type, and phosphobetaine type. These can be used individually by 1 type or in combination of 2 or more types. Among these, the carbobetaine type is preferable in that it easily forms liquid crystals.
  • the amphoteric surfactant may contain sodium chloride in the production process, and is desalted from the viewpoint of improving low-temperature stability, so that sodium chloride is reduced to 1% by mass or less in the amphoteric surfactant aqueous solution. Is more preferable.
  • component (B) is 7 to 25% by mass, preferably 9 to 15% by mass, in the skin cleanser composition. If it is less than 7% by mass, no liquid crystal is formed, and if it exceeds 25% by mass, precipitation tends to occur at a low temperature.
  • the component (C) of the present invention contains polyoxyethylene (average added mole number of ethylene oxide 10 to 80) glyceryl, glycerin, or polyoxyethylene (average added mole number of ethylene oxide) 10 to 80) A compound in which three hydroxyl groups of trimethylolpropane are esterified or etherified, and the esterified or etherified moiety is a saturated or unsaturated, linear or branched chain having 7 to 25 carbon atoms.
  • the solubility of the preparation in water decreases.
  • the total number of polyoxyethylenes added to the nonionic surfactant is more preferably 15 to 40 mol. If the amount is less than 10 moles, the solubility of the preparation in water and the low-temperature stability may decrease, and the cloudiness may result in loss of transparency. If the amount exceeds 80 moles, the high-temperature stability is deteriorated.
  • nonionic surfactants (i) to (iii) having the following structures are excellent in stability during storage at high temperatures and low temperatures, and have good usability even when the hands are wet. It is preferable because a cleaning composition can be obtained.
  • nonionic surfactant examples include PEG-20 glyceryl triisostearate, PEG-20 glyceryl tristearate, PEG-20 glyceryl trioleate, and the like.
  • (Ii) A compound in which three hydroxyl groups of glycerin are esterified or etherified, and the esterified or etherified moiety is a saturated or unsaturated, linear or branched monovalent carbonization having 7 to 25 carbon atoms.
  • Nonionic surfactant in which a part of hydrogen atom is substituted with a hydroxyl group, and polyoxyethylene having an average addition mole number of 10 to 80 is added to this hydroxyl group (however, nonionic surfactant The total number of polyoxyethylenes added to is an average addition mole number of 10 to 80).
  • Nonionic surfactant to which oxyethylene may be added (however, the total number of polyoxyethylene added to the nonionic surfactant is 10 to 80 in terms of the average number of moles added)
  • nonionic surfactant examples include PEG-20 trimethylolpropane triisostearate.
  • the esterified or etherified moiety is a monovalent hydrocarbon group having 7 to 25 carbon atoms, preferably 16 to 20 carbon atoms, and the monovalent hydrocarbon group may be saturated or unsaturated, linear or branched, A part of hydrogen atoms may be substituted with a hydroxyl group.
  • a branched hydrocarbon chain or a hydrocarbon chain having a hydroxyl group at a portion other than the terminal of the hydrocarbon chain is more preferable.
  • the nonionic surfactant corresponding to said (ii) is more preferable at the point of the solubility of a formulation to water, and polyoxyethylene hydrogenated castor oil and polyoxyethylene castor oil are more preferable.
  • the esterified fatty acid residue portion of polyoxyethylene castor oil (the portion combining the hydrocarbon chain and the ester group) is an unsaturated fatty acid (87% by mass of ricinoleic acid, 7% by mass of oleic acid, and linoleic acid 3 mass%) and a small amount of saturated fatty acid (palmitic acid, stearic acid 3 mass%).
  • the fatty acid is hydrogenated.
  • the fatty acid distribution of the fatty acid residue contains 80% by mass or more of ricinoleic acid having a hydroxyl group at position 12 or a hydrogenated product thereof.
  • polyoxyethylene hydrogenated castor oil (EO.20) [POE (20) hydrogenated castor oil], polyoxyethylene hydrogenated castor oil (E.O.40) [POE (40) hydrogenated castor oil], polyoxy Ethylene castor oil (E.O.20) [POE (20) castor oil], POE (40) castor oil [POE (40) castor oil] have excellent stability during high-temperature and low-temperature storage and wet hands It is most preferable from the viewpoint that a liquid skin cleansing composition having good usability even in a state can be obtained.
  • the mechanism is unknown, but POE hydrogenated castor oil and POE castor oil are considered to have loosened the liquid crystal structure because of the structure in which the polyoxyethylene chain is branched from the hydroxyl group present in the hydrocarbon group.
  • component (C) is 1 to 5% by mass, particularly 2 to 4% by mass, and particularly preferably 2 to 3% by mass in the skin cleanser composition. If it is less than 1% by mass, the preparation is not sufficiently soluble in water, and if it exceeds 5% by mass, the high-temperature stability is deteriorated.
  • the polyhydric alcohol is preferably a dihydric to hexahydric one, such as ethylene glycol, diethylene glycol, polyethylene glycol 200 (a quasi-drug raw material standard 2006 equivalent), polyethylene glycol 300 (a quasi-drug raw material).
  • polyethylene glycol 400 (quasi-drug raw material standard 2006 equivalent), polyethylene glycol 600 (quasi-drug raw material standard 2006 equivalent), propylene glycol, dipropylene glycol, 1,3-butylene glycol, Isopentyldiol, pentylene glycol, 1,2-hexanediol, hexylene glycol, glycerin, diglycerin, sorbit, xylitol, mannitol and the like are preferable, and these are used alone or in appropriate combination of two or more. Can be used.
  • polyethylene glycol corresponds to those defined in Cosmetic Material Standard 2nd Edition Comment, Quasi-drug Raw Material Standard 2006, Japanese Pharmacopoeia Pharmaceutical Standard 2002, 15th revised Japanese Pharmacopoeia.
  • propylene glycol, polyethylene glycol 200, polyethylene glycol 300, polyethylene glycol 400, polyethylene glycol 600, propylene glycol, glycerin, and sorbit are preferable from the viewpoint of easy formation of liquid crystals.
  • a mixture of divalent and trivalent polyhydric alcohols is more preferable, a combination of propylene glycol and glycerin is more preferable, and the mass (%) of propylene glycol / glycerin The mass (%) is particularly preferably 20/80 to 50/50.
  • the ratio of propylene glycol exceeds 50/50, the liquid crystal formability may be lowered and high-temperature stability may be lowered, and when it is less than 20/80, the viscosity may be too high.
  • the mass ratio of (A) higher fatty acid salt and (B) betaine-type amphoteric surfactant is preferably 85/15 to 60/40.
  • the ratio of the component (A) exceeds 85/15, the stability at low temperatures may be deteriorated, and when it is less than 60/40, it may cause luster during rinsing.
  • the mass ratio of (A) higher fatty acid salt and (D) polyhydric alcohol is preferably 70/30 to 40/60.
  • the ratio of the component (A) exceeds 70/30, the low temperature stability may be deteriorated, and when it is less than 40/60, the high temperature stability and transparency may be deteriorated.
  • the skin cleanser composition of the present invention is in a liquid crystal state at 25 ° C.
  • the liquid crystal refers to hexagonal liquid crystal, lamellar liquid crystal, and cubic liquid crystal.
  • hexagonal liquid crystals are preferable in terms of usability and a transparent appearance.
  • a lamellar liquid crystal has a low viscosity and hangs down from the hand during use or thickens with added water, which may deteriorate the usability.
  • liquid crystal is a molecular assembly of surfactants, and a liquid crystal state in which a cylindrical surfactant becomes a rod-like molecule due to the presence of an ionic polymer compound having a high concentration or an opposite charge.
  • anisotropy based on this orientation order exhibited by the liquid crystal is “spontaneous” derived from the shape of the molecule and intermolecular force, and is not induced by any external force.
  • a flow is applied to a concentrated solution of a polymer compound, molecular orientation occurs and optical anisotropy is observed. However, when the flow stops, such orientation is not spontaneous.
  • Liquid crystals are extremely peculiar in that they have both liquid properties of fluidity and liquid crystal properties of optical anisotropy, and cannot be classified as solid or liquid. It is considered to be the “fourth state” of the substance.
  • Component (B) is lauryldimethylaminoacetic acid betaine, and its content is 7 to 15% by mass in the skin cleanser composition.
  • Component (C) consists of PEG-20 glyceryl triisostearate, PEG-20 glyceryl trioleate, PEG-20 trimethylolpropane triisostearate, POE (20-80) hydrogenated castor oil and POE (20-80) castor oil The content thereof is 2 to 5% by mass in the skin cleanser composition.
  • Component (D) is a combination of propylene glycol and glycerin, propylene glycol or polyethylene glycol 400, and its content is 25 to 35% by mass in the skin cleanser composition. When propylene glycol and glycerin are used in combination Has a propylene glycol ratio of 20/80 or more.
  • other appropriately selected components can be blended within a range that does not interfere with the object of the present invention.
  • Other components can be appropriately selected from those commonly used in skin cleanser compositions, such as oils, silicones, alcohols such as lower or higher alcohols, lanolin derivatives, protein derivatives, acrylic resins.
  • Dispersions, drugs such as vitamins, bactericides, antiseptics, pH adjusters such as potassium hydroxide and citric acid, antioxidants, sequestering agents, UV absorbers, animal and plant extracts or their derivatives, dyes, fragrances, pigments And water-insoluble polymer powder such as inorganic powder, clay mineral, nylon and polyethylene.
  • the pH of the skin cleansing composition of the present invention is preferably 9.0 to 11.0 from the viewpoint of low temperature stability and liquid crystal formation, and more preferably 9.4 to 10.6 from the viewpoint of low temperature stability. .
  • the pH is less than 9.0, the low-temperature stability may deteriorate, and when it exceeds 11.0, it may be difficult to form a liquid crystal.
  • a skin cleanser composition was prepared as follows. Components (A), (C), (D) and purified water were weighed into a vessel of a vacuum emulsification kettle. Under reduced pressure, it was heated to 80 ° C. to dissolve. After dissolution, the component (B) was added and dissolved while stirring the paddle, cooled to 35 ° C. at 1 ° C./min in a reduced pressure state, and sufficiently depressurized and stirred for deaeration. After deaeration, cooling was performed to 25 ° C. at 1 ° C./min.
  • the pH was measured using a pH meter HM-30R (manufactured by Toa DKK Co., Ltd.), and the target pH was set using potassium hydroxide or citric acid.
  • the pH was measured after the electrode was immersed in a sample at 25 ° C. for 2 minutes. The following evaluation was performed about the obtained skin cleaning composition. The results are also shown in the table.
  • the confirmation of the liquid crystal state was carried out using a polarizing microscope AX70 (Olympus Corporation) with the skin cleansing composition at 25 ° C.
  • the interference pattern was observed as a scaly mosaic texture, it was a hexagonal liquid crystal, when a cross-shaped cross Nicol was observed, it was a lamellar liquid crystal, and when no interference pattern was observed, it was a micelle phase.
  • the liquid crystal of the present invention refers to hexagonal liquid crystal, lamellar liquid crystal, and cubic liquid crystal.
  • a hard transparent glass bottle (capacity 55 mL) with a height of 8 cm and a diameter of 3 cm is filled with 50 mL of the skin cleansing composition, stored in each environment at 50 ° C. and 0 ° C., observed for appearance at each storage temperature, and judged as follows: Based on the criteria, the stability of the skin cleanser composition was evaluated.
  • a to B After storage for 4 weeks, there is no phase separation or precipitate, but a part of the appearance looks slightly cloudy.
  • After storage for 4 weeks, there is no phase separation or precipitates, but the appearance appears to be uniformly and slightly turbid.
  • No phase separation or precipitates after storage for 2 weeks, but phase separation or precipitates after storage for 4 weeks.
  • X After storage for 2 weeks, there is phase separation or precipitate.
  • 3 points The sample melts and foams 4 to 7 times after rubbing the palm.
  • Standard of average score ⁇ : 4.5 to 5 points ⁇ to ⁇ : 4.0 points to less than 4.5 points ⁇ : 3.0 points to less than 4.0 points ⁇ : 2.0 points to less than 3.0 points ⁇ : 2 Less than 0 points
  • bactericidal power tests were conducted on Examples 1 and 36.
  • ⁇ Bactericidal power> (1) Preparation of Bacterial Solution A bacterial solution was prepared so that the initial number of the following bacteria was 10 8 / mL. Staphylococcus aureus: Staphylococcus aureus ATCC 6538 (2) Test solution The skin cleanser composition obtained in Examples 1 and 36 was diluted 5-fold with tap water to prepare a test solution.
  • ⁇ Sterilizing power test method> At 25 ° C., 1 mL of the bacterial solution was added to 9 mL of the test solution and stirred sufficiently.
  • SCDLP medium Soybean-Casein Broth with Lectin & Polysorbate 80: manufactured by Wako Pure Chemical Industries, Ltd.
  • a 10-fold diluted solution was obtained.
  • the same method was repeated to obtain each diluted solution. Collect 1.0 mL from each diluted solution in a petri dish, add 15 mL of SCDLP agar medium (Soybean-Casein Digest Age with Lectin & Polysorbate 80: manufactured by Wako Pure Chemical Industries, Ltd.), homogenize, and culture for 2 days (agar plate dilution) Method), colonies were counted and the number of viable bacteria was measured.
  • Example 1 The bactericidal power of Example 1 is “ ⁇ 1.1”, the bactericidal power of Example 36 is “ ⁇ 3.2”, and the bactericidal power is improved by using a monoethanolamine salt as the component (A). Was confirmed. Further, Example 36 was “ ⁇ ” even at low temperature stability ( ⁇ 5 ° C., 1 month), and was excellent in low temperature stability.
  • a skin cleanser composition was prepared as follows. Common components other than lauryldimethylaminoacetic acid betaine and flavor were weighed in a vessel of a vacuum emulsification kettle. Under reduced pressure, it was heated to 80 ° C. to dissolve. After dissolution, while stirring the paddle, lauryldimethylaminoacetic acid betaine was added and dissolved, and the mixture was cooled to 35 ° C. at 1 ° C./min under reduced pressure. At this time, degassing was performed by sufficiently reducing pressure and stirring. After deaeration, a fragrance was added and cooled to 25 ° C. at 1 ° C./min.

Landscapes

  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Public Health (AREA)
  • Animal Behavior & Ethology (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Emergency Medicine (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Dermatology (AREA)
  • Cosmetics (AREA)
  • Detergent Compositions (AREA)

Abstract

Provided is a skin cleanser composition in a liquid crystal state which has high stability in hot and cold storage and shows good usability even handled with wet hands, namely, a skin cleanser composition characterized by containing components (A), (B), (C) and (D) and being in a liquid crystal state at 25°C. (A) 15-45 mass% of a higher fatty acid salt having 8 to 26 carbons. (B) 7-25 mass% of a betaine type amphoteric surfactant. (C) 1-5 mass% of a nonionic surfactant as specified below: a compound wherein 3 hydroxyl groups of polyoxyethylene glyceryl, glycerol or polyoxyethylene trimethylolpropane are esterified or etherified and the esterified or etherified moiety is a monovalent hydrocarbon group having 7-25 carbons. (D) 15-35 mass% of a polyhydric alcohol.

Description

皮膚洗浄剤組成物Skin cleanser composition
 本発明は、高温・低温保存時の安定性に優れ、手が濡れた状態でも良好な使用性を有する、液晶状態の皮膚洗浄剤組成物に関するものである。 The present invention relates to a skin cleansing composition in a liquid crystal state, which is excellent in stability during storage at high temperatures and low temperatures and has good usability even when the hand is wet.
 半固形状の洗浄剤組成物は、スクラブ等の粒子をその製剤の中に分散したまま保持することができ、見た目の美しさや、使用感を向上させることができる。なかでも、透明から半透明の外観を有するジェル状の洗浄剤は、消費者に高品質感の提供が可能である。 The semi-solid detergent composition can keep particles such as scrubs dispersed in the preparation, and can improve the appearance and feel. Among these, a gel-like cleaning agent having a transparent to translucent appearance can provide consumers with a high quality feeling.
 高級脂肪酸塩を含む洗浄剤組成物は、泡性能、すすぎ性能が優れているが、半固形状とした場合に性能、安定性が不良になるという課題があった。例えば、高級脂肪酸塩とアクリル酸アルキルコポリマーを用いた透明ゲル状の皮膚洗浄剤が提案されている(特許文献1:特開2007-126396号公報)。しかしながら、外観は透明なゲル状であるが、高分子化合物で増粘してゲル状としているため、泡立ちが遅く、製剤を手に取る際に糸を引くために使用性が不良であった。 The detergent composition containing a higher fatty acid salt is excellent in foam performance and rinsing performance, but has a problem that performance and stability are poor when it is semi-solid. For example, a transparent gel-like skin cleanser using a higher fatty acid salt and an alkyl acrylate copolymer has been proposed (Patent Document 1: JP 2007-126396 A). However, although the appearance is a transparent gel, it is thickened with a polymer compound to form a gel, so that foaming is slow and the usability is poor because a thread is pulled when picking up the preparation.
 また、特定の高級脂肪酸塩、両性界面活性剤、グリセリン及び脂肪酸アルカノールアミド型非イオン性界面活性剤を用いた透明ゲル状の洗浄剤が提案されている(特許文献2:特開2007-51168号公報)。これは、高分子化合物による増粘ではなく、界面活性剤の液晶相によるゲル化であるので、使用時の糸引きは発生し難いが、粘性が高いため容器から出し難く、さらに水を加えた際に製剤が伸ばし難く、手から落ちてしまうという課題があった。 Further, a transparent gel-like cleaning agent using a specific higher fatty acid salt, an amphoteric surfactant, glycerin and a fatty acid alkanolamide type nonionic surfactant has been proposed (Patent Document 2: JP-A-2007-511168). Publication). This is not a thickening due to the polymer compound but gelation by the liquid crystal phase of the surfactant, so stringing during use is difficult to occur, but it is difficult to remove from the container due to its high viscosity, and water was added. In some cases, the preparation is difficult to extend and falls from the hand.
特開2007-126396号公報JP 2007-126396 A 特開2007-51168号公報JP 2007-511168 A
 本発明は上記事情に鑑みなされたもので、高温・低温保存時の安定性に優れ、手が濡れた状態でも良好な使用性を有する、液晶状態の皮膚洗浄剤組成物を提供することを目的とする。 The present invention has been made in view of the above circumstances, and an object thereof is to provide a skin cleansing composition in a liquid crystal state that has excellent stability during storage at high temperatures and low temperatures and has good usability even when the hands are wet. And
 本発明者らは、上記目的を達成するため鋭意検討した結果、(A)高級脂肪酸塩と、(B)ベタイン型両性界面活性剤と、(C)特定の非イオン性界面活性剤と、(D)多価アルコールとを、それぞれ特定量で配合し、25℃において液晶状態で、透明である皮膚洗浄剤組成物とすることで、高温・低温保存時の安定性に優れ、手が濡れた状態でも良好な使用性(溶け易さ、泡立ち)が可能となることを知見し、本発明をなすに至ったものである。 As a result of intensive studies to achieve the above object, the present inventors have found that (A) a higher fatty acid salt, (B) a betaine amphoteric surfactant, (C) a specific nonionic surfactant, D) A specific amount of each of the polyhydric alcohols is blended, and a transparent skin cleanser composition in a liquid crystal state at 25 ° C. is excellent in stability at high and low temperature storage, and the hands are wet. It has been found that good usability (easiness of melting, foaming) is possible even in a state, and the present invention has been made.
 従って、本発明は下記皮膚洗浄剤組成物を提供する。
[1].下記(A)、(B)、(C)及び(D)成分を含有し、25℃において液晶状態であることを特徴とする皮膚洗浄剤組成物。
(A)炭素数8~26の高級脂肪酸塩15~45質量%
(B)ベタイン型両性界面活性剤7~25質量%
(C)下記非イオン性界面活性剤1~5質量%
 ポリオキシエチレン(エチレンオキサイドの平均付加モル数10~80)グリセリル、グリセリン、又はポリオキシエチレン(エチレンオキサイドの平均付加モル数10~80)トリメチロールプロパンの3つの水酸基が、エステル化又はエーテル化された化合物であって、エステル化又はエーテル化部分は、炭素数7~25の飽和又は不飽和、直鎖又は分岐鎖の一価炭化水素基であり、水素原子の一部が水酸基で置換されていてもよく、この水酸基に平均付加モル数が10~80のポリオキシエチレンが付加されていてもよい、ただし、非イオン性界面活性剤に付加されるポリオキシエチレンの総数は、平均付加モル数で10~80である。
(D)多価アルコール15~35質量%
[2].(C)成分が、エステル化又はエーテル化部分の炭素数7~25の一価炭化水素基が、水素原子の一部が水酸基で置換されていることを特徴とする[1]記載の皮膚洗浄剤組成物。
[3].(C)成分が、ポリオキシエチレン硬化ヒマシ油又はポリオキシエチレンヒマシ油である[1]又は[2]記載の皮膚洗浄剤組成物。
[4].液晶が、ヘキサゴナル液晶である[1]、[2]又は[3]記載の皮膚洗浄剤組成物。
Accordingly, the present invention provides the following skin cleanser composition.
[1]. A skin cleanser composition containing the following components (A), (B), (C) and (D) and in a liquid crystal state at 25 ° C.
(A) 15 to 45% by mass of higher fatty acid salt having 8 to 26 carbon atoms
(B) Betaine amphoteric surfactant 7 to 25% by mass
(C) 1 to 5% by mass of the following nonionic surfactant
Three hydroxyl groups of polyoxyethylene (average added mole number of ethylene oxide 10 to 80) glyceryl, glycerin, or polyoxyethylene (average added mole number of ethylene oxide 10 to 80) trimethylolpropane are esterified or etherified. The esterified or etherified moiety is a saturated or unsaturated, linear or branched monovalent hydrocarbon group having 7 to 25 carbon atoms, and part of the hydrogen atoms are substituted with hydroxyl groups. The polyoxyethylene having an average addition mole number of 10 to 80 may be added to this hydroxyl group, provided that the total number of polyoxyethylene added to the nonionic surfactant is the average addition mole number. 10 to 80.
(D) 15 to 35% by mass of polyhydric alcohol
[2]. The skin cleanser according to [1], wherein the component (C) is a monovalent hydrocarbon group having 7 to 25 carbon atoms in the esterified or etherified moiety, wherein a part of the hydrogen atoms is substituted with a hydroxyl group Agent composition.
[3]. (C) The skin cleaning composition according to [1] or [2], wherein the component is polyoxyethylene hydrogenated castor oil or polyoxyethylene castor oil.
[4]. The skin cleanser composition according to [1], [2] or [3], wherein the liquid crystal is hexagonal liquid crystal.
 本発明によれば、高温・低温保存時の安定性に優れ、手が濡れた状態でも良好な使用性を有する、液晶状態の皮膚洗浄剤組成物を提供することができる。 According to the present invention, it is possible to provide a liquid-form skin cleanser composition that has excellent stability during storage at high and low temperatures and has good usability even when the hand is wet.
 以下、本発明について詳細に説明する。
 本発明の皮膚洗浄剤組成物は、下記(A)、(B)、(C)及び(D)成分を含有し、25℃において液晶状態であることを特徴とする皮膚洗浄剤組成物である。
(A)炭素数8~26の高級脂肪酸塩15~45質量%
(B)ベタイン型両性界面活性剤7~25質量%
(C)下記非イオン性界面活性剤1~5質量%
 ポリオキシエチレン(エチレンオキサイドの平均付加モル数10~80)グリセリル、グリセリン、又はポリオキシエチレン(エチレンオキサイドの平均付加モル数10~80)トリメチロールプロパンの3つの水酸基が、エステル化又はエーテル化された化合物であって、エステル化又はエーテル化部分は、炭素数7~25の飽和又は不飽和、直鎖又は分岐鎖の一価炭化水素基であり、水素原子の一部が水酸基で置換されていてもよく、この水酸基に平均付加モル数が10~80のポリオキシエチレンが付加されていてもよい、ただし、非イオン性界面活性剤に付加されるポリオキシエチレンの総数は、平均付加モル数で10~80である。
(D)多価アルコール15~35質量%
Hereinafter, the present invention will be described in detail.
The skin cleanser composition of the present invention is a skin cleanser composition containing the following components (A), (B), (C) and (D) and being in a liquid crystal state at 25 ° C. .
(A) 15 to 45% by mass of higher fatty acid salt having 8 to 26 carbon atoms
(B) Betaine amphoteric surfactant 7 to 25% by mass
(C) 1 to 5% by mass of the following nonionic surfactant
Three hydroxyl groups of polyoxyethylene (average added mole number of ethylene oxide 10 to 80) glyceryl, glycerin, or polyoxyethylene (average added mole number of ethylene oxide 10 to 80) trimethylolpropane are esterified or etherified. The esterified or etherified moiety is a saturated or unsaturated, linear or branched monovalent hydrocarbon group having 7 to 25 carbon atoms, and part of the hydrogen atoms are substituted with hydroxyl groups. The polyoxyethylene having an average addition mole number of 10 to 80 may be added to this hydroxyl group, provided that the total number of polyoxyethylene added to the nonionic surfactant is the average addition mole number. 10 to 80.
(D) 15 to 35% by mass of polyhydric alcohol
(A)高級脂肪酸塩
 本発明の(A)高級脂肪酸塩は炭素数8~26の高級脂肪酸塩であり、一価炭化水素基部分は、直鎖又は分岐鎖、飽和又は不飽和のいずれであってもよく、1種単独で又は2種以上を適宜組み合わせて用いることができる。中でも、下記一般式(1)で表される高級脂肪酸塩が好ましい。
 R1COOM   (1)
(式中、R1は、炭素数7~25の直鎖又は分岐鎖、飽和又は不飽和の一価炭化水素基を示し、この一価炭化水素基の水素原子の一部又は全部が水酸基で置換されていてもよい。Mは、カリウム、ナトリウム、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、2-アミノ-2-メチル-1-プロパノール又はジイソプロパノールアミンを示す。)
(A) Higher fatty acid salt 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 moiety is either linear or branched, saturated or unsaturated. It may be used alone or in combination of two or more. Among these, higher fatty acid salts represented by the following general formula (1) are preferable.
R 1 COOM (1)
(In the formula, R 1 represents a linear or branched, saturated or unsaturated monovalent hydrocarbon group having 7 to 25 carbon atoms, and part or all of the hydrogen atoms of the monovalent hydrocarbon group are hydroxyl groups. (M may be potassium, sodium, monoethanolamine, diethanolamine, triethanolamine, 2-amino-2-methyl-1-propanol or diisopropanolamine.)
 (A)成分としては、カプロン酸、ヘプタン酸、カプリル酸、ペラルゴン酸、カプリン酸、ウンデカン酸、ラウリン酸、カプロレイン酸、ウンデシレン酸、ラウロレイン酸、2-エチルブタン酸、イソペンタン酸、2-エチルペンタン酸、2-エチルヘキサン酸、イソノナン酸、3,5,5-トリメチルヘキサン酸、トリデカン酸、テトラメチルノナン酸、ミリスチン酸、ペンタデカン酸、パルミチン酸、ステアリン酸、アラキン酸、ベヘン酸、リグノセリン酸、セロチン酸、ミリストレイン酸、パルミトレイン酸、オレイン酸、エライジン酸、ゴンドイン酸、エルカ酸、セラコレイン酸、リノール酸、リノエライジン酸、リノレン酸、アラキドン酸、2-ヘキシルデカン酸、イソステアリン酸、12-ヒドロキシステアリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、カプリン酸等の混合物であるヤシ油脂肪酸等の塩が挙げられる。 Component (A) includes caproic acid, heptanoic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, caproleic acid, undecylenic acid, lauroleic acid, 2-ethylbutanoic acid, isopentanoic acid, 2-ethylpentanoic acid 2-ethylhexanoic acid, isononanoic acid, 3,5,5-trimethylhexanoic acid, tridecanoic acid, tetramethylnonanoic acid, myristic acid, pentadecanoic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cellotine Acid, myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, gondoic acid, erucic acid, cerakoleic acid, linoleic acid, linoelaidic acid, linolenic acid, arachidonic acid, 2-hexyldecanoic acid, isostearic acid, 12-hydroxystearic acid Laurin , Myristic acid, palmitic acid, salts of coconut oil fatty acids are mixtures of such capric acid.
 中でも、炭素数が10、12、14、16であるカプリン酸塩、ラウリン酸塩、ミリスチン酸塩、パルミチン酸塩が好ましい。炭素数が10未満だと高温での安定性が悪く、16を超えると低温での安定性が悪い場合がある。炭素数が12以下の高級脂肪酸塩と炭素数が14以上の高級脂肪酸塩の質量比は80/20~40/60が好ましく、75/25~50/50がより好ましく、70/30~60/40がさらに好ましい。炭素数が12以下の高級脂肪酸塩の比が80/20を超えると高温安定性が悪く、40/60未満であると、低温安定性と水への溶解性が悪くなる場合がある。 Of these, caprates, laurates, myristates and palmitates having 10, 12, 14, and 16 carbon atoms are preferred. If the number of carbon atoms is less than 10, the stability at high temperature is poor, and if it exceeds 16, the stability at low temperature may be poor. The mass ratio of the higher fatty acid salt having 12 or less carbon atoms and the higher fatty acid salt having 14 or more carbon atoms is preferably 80/20 to 40/60, more preferably 75/25 to 50/50, and 70/30 to 60 / 40 is more preferable. When the ratio of the higher fatty acid salt having 12 or less carbon atoms exceeds 80/20, the high temperature stability is poor, and when it is less than 40/60, the low temperature stability and the solubility in water may be deteriorated.
 M(対イオン)はCOOM塩を形成する。Mとしては、低温安定性の点から、カリウム、ナトリウム、モノエタノールアミン、ジエタノールアミン、トリエタノールアミンが好ましく、低温安定性の点から、カリウム、モノエタノールアミンがより好ましい。また、殺菌力と低温安定性の点から、高級脂肪酸塩量を100質量%としたとき、モノエタノールアミン塩の割合が1~35質量%とすることが好ましく、3~15質量%がより好ましい。 M (counter ion) forms a COOM salt. As M, potassium, sodium, monoethanolamine, diethanolamine, and triethanolamine are preferable from the viewpoint of low-temperature stability, and potassium and monoethanolamine are more preferable from the viewpoint of low-temperature stability. From the viewpoint of bactericidal activity and low-temperature stability, when the amount of higher fatty acid salt is 100% by mass, the proportion of monoethanolamine salt is preferably 1 to 35% by mass, more preferably 3 to 15% by mass. .
 (A)成分の含有量は、皮膚洗浄剤組成物中15~45質量%である。15質量%未満であると、液晶を形成しない。一方、45質量%を超えると低温で析出物を生ずる。さらに、泡立ちと低温安定性の点から、17~40質量%、特に20~35質量%、とりわけ25~35質量%が好ましい。 The content of component (A) is 15 to 45% by mass in the skin cleanser 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, 17 to 40% by mass, particularly 20 to 35% by mass, and particularly 25 to 35% by mass are preferable.
(B)ベタイン型両性界面活性剤
 ベタイン型両性界面活性剤としては、例えば、イミダゾリン型(アミドアミン型)、カルボベタイン型、スルホベタイン型、ホスホベタイン型等が挙げられる。これらは1種単独で又は2種以上を適宜組み合わせて用いることができる。これらの中でも、液晶を形成しやすい点で、カルボベタイン型が好ましい。
(B) Betaine-type amphoteric surfactant Examples of the betaine-type amphoteric surfactant include imidazoline type (amidoamine type), carbobetaine type, sulfobetaine type, and phosphobetaine type. These can be used individually by 1 type or in combination of 2 or more types. Among these, the carbobetaine type is preferable in that it easily forms liquid crystals.
 カルボベタイン型としては、ラウリルベタイン、ラウリルジメチルアミノ酢酸ベタイン等のアルキルベタイン、ラウリン酸アミドプロピルベタイン、ヤシ油脂肪酸アミドプロピルベタイン等のアルキルアミドベタイン等が挙げられる。この中でも、液晶の形成性の点から、ラウリルジメチルアミノ酢酸ベタイン、ラウリン酸アミドプロピルベタインがより好ましく、特に低温の安定性の点から、ラウリルジメチルアミノ酢酸ベタインが好ましい。上記両性界面活性剤は、製造工程で塩化ナトリウムを含有している場合があり、低温安定性を向上させる観点から脱塩処理し、前記両性界面活性剤水溶液中に塩化ナトリウムを1質量%以下にしたものがより好ましい。 Examples of the carbobetaine type include alkyl betaines such as lauryl betaine and lauryl dimethylaminoacetic acid betaine, alkylamide betaines such as lauric acid amidopropyl betaine and coconut oil fatty acid amidopropyl betaine. Among these, lauryl dimethylaminoacetic acid betaine and lauric acid amidopropyl betaine are more preferable from the viewpoint of liquid crystal formability, and lauryldimethylaminoacetic acid betaine is particularly preferable from the viewpoint of low-temperature stability. The amphoteric surfactant may contain sodium chloride in the production process, and is desalted from the viewpoint of improving low-temperature stability, so that sodium chloride is reduced to 1% by mass or less in the amphoteric surfactant aqueous solution. Is more preferable.
 (B)成分の含有量は、皮膚洗浄剤組成物中7~25質量%であり、9~15質量%が好ましい。7質量%未満では液晶を形成せず、25質量%を超えると低温で析出を生じやすい。 The content of component (B) is 7 to 25% by mass, preferably 9 to 15% by mass, in the skin cleanser composition. If it is less than 7% by mass, no liquid crystal is formed, and if it exceeds 25% by mass, precipitation tends to occur at a low temperature.
(C)下記非イオン性界面活性剤
 本発明の(C)成分は、ポリオキシエチレン(エチレンオキサイドの平均付加モル数10~80)グリセリル、グリセリン、又はポリオキシエチレン(エチレンオキサイドの平均付加モル数10~80)トリメチロールプロパンの3つの水酸基が、エステル化又はエーテル化された化合物であって、エステル化又はエーテル化部分は、炭素数7~25の飽和又は不飽和、直鎖又は分岐鎖の一価炭化水素基であり、水素原子の一部が水酸基で置換されていてもよく、この水酸基に平均付加モル数が10~80のポリオキシエチレンが付加されていてもよい、ただし、非イオン性界面活性剤に付加されるポリオキシエチレンの総数は、平均付加モル数で10~80である。
(C) The following nonionic surfactant The component (C) of the present invention contains polyoxyethylene (average added mole number of ethylene oxide 10 to 80) glyceryl, glycerin, or polyoxyethylene (average added mole number of ethylene oxide) 10 to 80) A compound in which three hydroxyl groups of trimethylolpropane are esterified or etherified, and the esterified or etherified moiety is a saturated or unsaturated, linear or branched chain having 7 to 25 carbon atoms. It is a monovalent hydrocarbon group, a part of hydrogen atoms may be substituted with a hydroxyl group, and polyoxyethylene having an average addition mole number of 10 to 80 may be added to this hydroxyl group, provided that it is nonionic The total number of polyoxyethylenes added to the surfactant is 10-80 in terms of the average number of moles added.
 エステル化又はエーテル化された水酸基が2つ以下の場合、製剤の水への溶解性が低下する。また、非イオン性界面活性剤に付加されるポリオキシエチレンの総数は、15~40モルがより好ましい。10モル未満だと、製剤の水への溶解性や低温安定性が低下するほか、白濁して透明性が失われる場合があり、80モルを超えると高温安定性が悪くなる。 When the number of esterified or etherified hydroxyl groups is 2 or less, the solubility of the preparation in water decreases. The total number of polyoxyethylenes added to the nonionic surfactant is more preferably 15 to 40 mol. If the amount is less than 10 moles, the solubility of the preparation in water and the low-temperature stability may decrease, and the cloudiness may result in loss of transparency. If the amount exceeds 80 moles, the high-temperature stability is deteriorated.
 中でも、以下の構造をもつ非イオン性界面活性剤(i)~(iii)が、高温・低温保存時の安定性に優れ、手が濡れた状態でも良好な使用性を有する、液晶状態の皮膚洗浄剤組成物を得ることができるから好ましい。 Among them, nonionic surfactants (i) to (iii) having the following structures are excellent in stability during storage at high temperatures and low temperatures, and have good usability even when the hands are wet. It is preferable because a cleaning composition can be obtained.
(i)ポリオキシエチレン(エチレンオキサイドの平均付加モル数10~80)グリセリルの3つの水酸基が、エステル化又はエーテル化された化合物であって、エステル化又はエーテル化部分は、炭素数7~25の飽和又は不飽和、直鎖又は分岐鎖の一価炭化水素基であり、水素原子の一部が水酸基で置換されていてもよく、この水酸基に平均付加モル数が10~80のポリオキシエチレンが付加されていてもよい非イオン性界面活性剤(ただし、非イオン性界面活性剤に付加されるポリオキシエチレンの総数は、平均付加モル数で10~80である。)。 (I) Polyoxyethylene (average addition mole number of ethylene oxide: 10 to 80) A compound in which three hydroxyl groups of glyceryl are esterified or etherified, wherein the esterified or etherified moiety has 7 to 25 carbon atoms. A saturated or unsaturated, linear or branched monovalent hydrocarbon group, in which part of the hydrogen atoms may be substituted with a hydroxyl group, and the polyoxyethylene having an average addition mole number of 10 to 80 May be added to the nonionic surfactant (however, the total number of polyoxyethylene added to the nonionic surfactant is from 10 to 80 in terms of the average number of moles added).
 上記(i)に該当する非イオン性界面活性剤としては、トリイソステアリン酸PEG-20グリセリル、トリステアリン酸PEG-20グリセリル、トリオレイン酸PEG-20グリセリル等が挙げられる。 Examples of the nonionic surfactant corresponding to the above (i) include PEG-20 glyceryl triisostearate, PEG-20 glyceryl tristearate, PEG-20 glyceryl trioleate, and the like.
(ii)グリセリンの3つの水酸基が、エステル化又はエーテル化された化合物であって、エステル化又はエーテル化部分は、炭素数7~25の飽和又は不飽和、直鎖又は分岐鎖の一価炭化水素基であり、水素原子の一部が水酸基で置換され、この水酸基に平均付加モル数が10~80のポリオキシエチレンが付加された非イオン性界面活性剤(ただし、非イオン性界面活性剤に付加されるポリオキシエチレンの総数は、平均付加モル数で10~80である。)。 (Ii) A compound in which three hydroxyl groups of glycerin are esterified or etherified, and the esterified or etherified moiety is a saturated or unsaturated, linear or branched monovalent carbonization having 7 to 25 carbon atoms. Nonionic surfactant in which a part of hydrogen atom is substituted with a hydroxyl group, and polyoxyethylene having an average addition mole number of 10 to 80 is added to this hydroxyl group (however, nonionic surfactant The total number of polyoxyethylenes added to is an average addition mole number of 10 to 80).
 上記(ii)に該当する非イオン性界面活性剤としては、ポリオキシエチレン硬化ヒマシ油(E.O.10)、ポリオキシエチレンヒマシ油(E.O.20)、ポリオキシエチレン硬化ヒマシ油(E.O.20)、ポリオキシエチレン硬化ヒマシ油(E.O.40)、ポリオキシエチレンヒマシ油(E.O.40)、ポリオキシエチレン硬化ヒマシ油(E.O.80)等が挙げられる。 Nonionic surfactants corresponding to the above (ii) include polyoxyethylene hydrogenated castor oil (EO.10), polyoxyethylene castor oil (EO.20), polyoxyethylene hydrogenated castor oil ( EO20), polyoxyethylene hydrogenated castor oil (EO40), polyoxyethylene castor oil (EO40), polyoxyethylene hydrogenated castor oil (EO80), and the like. It is done.
(iii)ポリオキシエチレン(エチレンオキサイドの平均付加モル数10~80)トリメチロールプロパンの3つの水酸基が、エステル化又はエーテル化された化合物であって、エステル化又はエーテル化部分は、炭素数7~25の飽和又は不飽和、直鎖又は分岐鎖の一価炭化水素基であり、水素原子の一部が水酸基で置換されていてもよく、この水酸基に平均付加モル数が10~80のポリオキシエチレンが付加されていてもよい非イオン性界面活性剤(ただし、非イオン性界面活性剤に付加されるポリオキシエチレンの総数は、平均付加モル数で10~80である。) (Iii) Polyoxyethylene (average addition mole number of ethylene oxide 10 to 80) A compound in which three hydroxyl groups of trimethylolpropane are esterified or etherified, wherein the esterified or etherified moiety has a carbon number of 7 A saturated or unsaturated, linear or branched monovalent hydrocarbon group having from 25 to 25, a part of the hydrogen atoms may be substituted with a hydroxyl group, and an average added mole number of 10 to 80 is added to the hydroxyl group. Nonionic surfactant to which oxyethylene may be added (however, the total number of polyoxyethylene added to the nonionic surfactant is 10 to 80 in terms of the average number of moles added)
 上記(iii)に該当する非イオン性界面活性剤としては、トリイソステアリン酸PEG-20トリメチロールプロパン等が挙げられる。 Examples of the nonionic surfactant corresponding to the above (iii) include PEG-20 trimethylolpropane triisostearate.
 具体的には、下記のものが挙げられる。以下、PEGはポリエチレングリコール、POEはポリオキシエチレンを示す。例えば、POE(20)は、ポリオキシエチレンの平均付加モル数が20を示す。
トリイソステアリン酸PEG-20グリセリル(日本エマルジョン、GWIS-320)HLB=8
トリステアリン酸PEG-20グリセリル(日本エマルジョン、GWS-320、HLB=8)
トリオレイン酸PEG-20グリセリル(日本エマルジョン、GWO-320、HLB=8)
トリイソステアリン酸PEG-20トリメチロールプロパン(日本エマルジョン、TPIS-320、HLB=8)
POE(20)ヒマシ油(日本エマルジョン、C-20、HLB=9)
POE(10)硬化ヒマシ油(日本エマルジョン、HC-10、HLB=7)
POE(10)硬化ヒマシ油(日光ケミカルズ、HCO-10、HLB=6.5)
POE(20)硬化ヒマシ油(日本エマルジョン、HC-20、HLB=9)
POE(20)硬化ヒマシ油(日光ケミカルズ、HCO-20、HLB=10.5)
POE(40)硬化ヒマシ油(日本エマルジョン、HC-40、HLB=12)
POE(40)硬化ヒマシ油(日光ケミカルズ、HCO-40、HLB=12.5)
POE(80)硬化ヒマシ油(日本エマルジョン、HC-80、HLB=15)
POE(80)硬化ヒマシ油(日光ケミカルズ、HCO-80、HLB=15.0)
Specific examples include the following. Hereinafter, PEG represents polyethylene glycol, and POE represents polyoxyethylene. For example, POE (20) shows an average addition mole number of polyoxyethylene of 20.
PEG-20 glyceryl triisostearate (Japan emulsion, GWIS-320) HLB = 8
PEG-20 glyceryl tristearate (Japan Emulsion, GWS-320, HLB = 8)
PEG-20 glyceryl trioleate (Japan Emulsion, GWO-320, HLB = 8)
PEG-20 trimethylolpropane triisostearate (Japan emulsion, TPIS-320, HLB = 8)
POE (20) castor oil (Japanese emulsion, C-20, HLB = 9)
POE (10) hydrogenated castor oil (Japan emulsion, HC-10, HLB = 7)
POE (10) hydrogenated castor oil (Nikko Chemicals, HCO-10, HLB = 6.5)
POE (20) hydrogenated castor oil (Japan emulsion, HC-20, HLB = 9)
POE (20) hydrogenated castor oil (Nikko Chemicals, HCO-20, HLB = 10.5)
POE (40) hydrogenated castor oil (Japan emulsion, HC-40, HLB = 12)
POE (40) hydrogenated castor oil (Nikko Chemicals, HCO-40, HLB = 12.5)
POE (80) hydrogenated castor oil (Japan emulsion, HC-80, HLB = 15)
POE (80) hydrogenated castor oil (Nikko Chemicals, HCO-80, HLB = 15.0)
 エステル化又はエーテル化した部分は、炭素数7~25、好ましくは16~20の一価炭化水素基であり、一価炭化水素基は飽和又は不飽和、直鎖又は分岐鎖のいずれでもよく、水素原子の一部が水酸基で置換されていてもよい。製剤の水への溶けやすさの点で、分岐炭化水素鎖、又は炭化水素鎖の末端でない部分に水酸基をもつ炭化水素鎖がより好ましい。中でも、製剤の水への溶けやすさの点で、上記(ii)に該当する非イオン性界面活性剤がさらに好ましく、ポリオキシエチレン硬化ヒマシ油、ポリオキシエチレンヒマシ油がより好ましい。ポリオキシエチレンヒマシ油のエステル化された脂肪酸残基の部分(炭化水素鎖とエステル基を合わせた部分)は、不飽和脂肪酸(リシノール酸が87質量%、オレイン酸が7質量%、リノール酸が3質量%)と少量の飽和脂肪酸(パルミチン酸、ステアリン酸等が3質量%)であり、硬化ヒマシ油の場合は、上記脂肪酸を水素添加したものである。特に、製剤の水への溶けやすさの点から、上記脂肪酸残基の脂肪酸分布において、12位に水酸基を持つリシノール酸、又はその水素添加したものを80質量%以上含むものが好ましい。 The esterified or etherified moiety is a monovalent hydrocarbon group having 7 to 25 carbon atoms, preferably 16 to 20 carbon atoms, and the monovalent hydrocarbon group may be saturated or unsaturated, linear or branched, A part of hydrogen atoms may be substituted with a hydroxyl group. From the viewpoint of solubility of the preparation in water, a branched hydrocarbon chain or a hydrocarbon chain having a hydroxyl group at a portion other than the terminal of the hydrocarbon chain is more preferable. Especially, the nonionic surfactant corresponding to said (ii) is more preferable at the point of the solubility of a formulation to water, and polyoxyethylene hydrogenated castor oil and polyoxyethylene castor oil are more preferable. The esterified fatty acid residue portion of polyoxyethylene castor oil (the portion combining the hydrocarbon chain and the ester group) is an unsaturated fatty acid (87% by mass of ricinoleic acid, 7% by mass of oleic acid, and linoleic acid 3 mass%) and a small amount of saturated fatty acid (palmitic acid, stearic acid 3 mass%). In the case of hydrogenated castor oil, the fatty acid is hydrogenated. In particular, from the viewpoint of the solubility of the preparation in water, it is preferable that the fatty acid distribution of the fatty acid residue contains 80% by mass or more of ricinoleic acid having a hydroxyl group at position 12 or a hydrogenated product thereof.
 中でも、ポリオキシエチレン硬化ヒマシ油(E.O.20)[POE(20)硬化ヒマシ油]、ポリオキシエチレン硬化ヒマシ油(E.O.40)[POE(40)硬化ヒマシ油]、ポリオキシエチレンヒマシ油(E.O.20)[POE(20)ヒマシ油]、POE(40)ヒマシ油[POE(40)ヒマシ油]が、高温・低温保存時の安定性に優れ、手が濡れた状態でも良好な使用性を有する、液晶状態の皮膚洗浄剤組成物を得ることができる点から最も好ましい。その機構は不明であるが、POE硬化ヒマシ油やPOEヒマシ油は炭化水素基に存在する水酸基にポリオキシエチレン鎖が分岐して存在する構造のため、液晶構造を緩めているものと考えられる。 Among them, polyoxyethylene hydrogenated castor oil (EO.20) [POE (20) hydrogenated castor oil], polyoxyethylene hydrogenated castor oil (E.O.40) [POE (40) hydrogenated castor oil], polyoxy Ethylene castor oil (E.O.20) [POE (20) castor oil], POE (40) castor oil [POE (40) castor oil] have excellent stability during high-temperature and low-temperature storage and wet hands It is most preferable from the viewpoint that a liquid skin cleansing composition having good usability even in a state can be obtained. The mechanism is unknown, but POE hydrogenated castor oil and POE castor oil are considered to have loosened the liquid crystal structure because of the structure in which the polyoxyethylene chain is branched from the hydroxyl group present in the hydrocarbon group.
 (C)成分の含有量は、皮膚洗浄剤組成物中1~5質量%であり、特に2~4質量%、とりわけ2~3質量%が好ましい。1質量%未満では、製剤の水への溶けやすさが充分ではなく、5質量%を超えると高温安定性が悪くなる。 The content of component (C) is 1 to 5% by mass, particularly 2 to 4% by mass, and particularly preferably 2 to 3% by mass in the skin cleanser composition. If it is less than 1% by mass, the preparation is not sufficiently soluble in water, and if it exceeds 5% by mass, the high-temperature stability is deteriorated.
(D)多価アルコール
 多価アルコールとしては、2~6価のものが好ましく、エチレングリコール、ジエチレングリコール、ポリエチレングリコール200(医薬部外品原料規格2006相当品)、ポリエチレングリコール300(医薬部外品原料規格2006相当品)、ポリエチレングリコール400(医薬部外品原料規格2006相当品)、ポリエチレングリコール600(医薬部外品原料規格2006相当品)、プロピレングリコール、ジプロピレングリコール、1,3-ブチレングリコール、イソペンチルジオール、ペンチレングリコール、1,2-ヘキサンジオール、ヘキシレングリコール、グリセリン、ジグリセリン、ソルビット、キシリトール、マンニトール等が好ましく、これらは1種単独で又は2種以上を適宜組み合わせて用いることができる。なお、ここでポリエチレグリコールとは、化粧品原料基準第二版注解、医薬部外品原料規格2006、日本薬局方医薬品規格2002、第15改定日本薬局方に定められたものに相当する。中でも、液晶の形成しやすさの点から、プロピレングリコール、ポリエチレングリコール200、ポリエチレングリコール300、ポリエチレングリコール400、ポリエチレングリコール600、プロピレングリコール、グリセリン、ソルビットが好ましい。さらに、低温安定性と液晶を形成しやすい点から、2価と3価の多価アルコールの混合がより好ましく、プロピレングリコールとグリセリンとの組み合わせがさらに好ましく、プロピレングリコールの質量(%)/グリセリンの質量(%)が、20/80~50/50が特に好ましい。プロピレングリコールの比率が、50/50を超えると、液晶形成性が低下し、高温安定性が低下する場合があり、20/80未満であると粘度が高すぎる場合がある。
(D) Polyhydric alcohol The polyhydric alcohol is preferably a dihydric to hexahydric one, such as ethylene glycol, diethylene glycol, polyethylene glycol 200 (a quasi-drug raw material standard 2006 equivalent), polyethylene glycol 300 (a quasi-drug raw material). Standard 2006 equivalent), polyethylene glycol 400 (quasi-drug raw material standard 2006 equivalent), polyethylene glycol 600 (quasi-drug raw material standard 2006 equivalent), propylene glycol, dipropylene glycol, 1,3-butylene glycol, Isopentyldiol, pentylene glycol, 1,2-hexanediol, hexylene glycol, glycerin, diglycerin, sorbit, xylitol, mannitol and the like are preferable, and these are used alone or in appropriate combination of two or more. Can be used. Here, the polyethylene glycol corresponds to those defined in Cosmetic Material Standard 2nd Edition Comment, Quasi-drug Raw Material Standard 2006, Japanese Pharmacopoeia Pharmaceutical Standard 2002, 15th revised Japanese Pharmacopoeia. Among these, propylene glycol, polyethylene glycol 200, polyethylene glycol 300, polyethylene glycol 400, polyethylene glycol 600, propylene glycol, glycerin, and sorbit are preferable from the viewpoint of easy formation of liquid crystals. Furthermore, from the viewpoint of low temperature stability and easy formation of liquid crystals, a mixture of divalent and trivalent polyhydric alcohols is more preferable, a combination of propylene glycol and glycerin is more preferable, and the mass (%) of propylene glycol / glycerin The mass (%) is particularly preferably 20/80 to 50/50. When the ratio of propylene glycol exceeds 50/50, the liquid crystal formability may be lowered and high-temperature stability may be lowered, and when it is less than 20/80, the viscosity may be too high.
 (D)成分の含有量は、皮膚洗浄剤組成物中15~35質量%であり、20~30質量%が好ましい。15質量%未満だと低温安定性が悪く、35質量%を超えると液晶を形成しにくくなる。 The content of component (D) is 15 to 35% by mass, preferably 20 to 30% by mass, in the skin cleanser composition. If it is less than 15% by mass, the low-temperature stability is poor, and if it exceeds 35% by mass, it becomes difficult to form a liquid crystal.
 (A)高級脂肪酸塩と(B)ベタイン型両性界面活性剤との質量比は、85/15~60/40が好ましい。(A)成分の比が85/15を超えると低温での安定性が悪くなるおそれがあり、60/40未満だと、すすぎ時にぬるつきを生じることがある。 The mass ratio of (A) higher fatty acid salt and (B) betaine-type amphoteric surfactant is preferably 85/15 to 60/40. When the ratio of the component (A) exceeds 85/15, the stability at low temperatures may be deteriorated, and when it is less than 60/40, it may cause luster during rinsing.
 (A)高級脂肪酸塩と(D)多価アルコールとの質量比は、70/30~40/60が好ましい。(A)成分の比が70/30を超えると低温安定性が悪くなる場合があり、40/60未満では高温安定性と透明度が低下するおそれがある。 The mass ratio of (A) higher fatty acid salt and (D) polyhydric alcohol is preferably 70/30 to 40/60. When the ratio of the component (A) exceeds 70/30, the low temperature stability may be deteriorated, and when it is less than 40/60, the high temperature stability and transparency may be deteriorated.
 本発明の皮膚洗浄剤組成物は、25℃において液晶状態である。本発明でいうところの液晶は、ヘキサゴナル液晶、ラメラ液晶、キュービック液晶をいう。中でも、ヘキサゴナル液晶が、使用性、透明な外観を有する点で好ましい。ラメラ液晶だと粘度が低く、使用時に手から垂れ落ちたり、添加する水により増粘したりするので、使用性が悪くなるおそれがある。 The skin cleanser composition of the present invention is in a liquid crystal state at 25 ° C. In the present invention, the liquid crystal refers to hexagonal liquid crystal, lamellar liquid crystal, and cubic liquid crystal. Among these, hexagonal liquid crystals are preferable in terms of usability and a transparent appearance. A lamellar liquid crystal has a low viscosity and hangs down from the hand during use or thickens with added water, which may deteriorate the usability.
 なお、本発明において「液晶」とは、界面活性剤の分子集合体であり、高濃度や反対電荷を持つイオン性高分子化合物の存在により、シリンダー型の界面活性剤が棒状分子になる液晶状態をいう。このような、液晶の示すこの配向秩序に基づく異方性は、分子の形や分子間力に由来する「自発的」なものであって、何かの外力によって誘起されるものではない。高分子化合物の濃厚溶液には、流れを与えてやると分子の配向が起こり、光学的異方性が見られるが、流れが止まればこのような配向は自発的ではないのである。流動性という液体の特性と光学的異方性という液晶の特性とを兼ね備えているという点で、液晶は極めて特異な状態であり、固体にも液体にも分類することができず、このために物質の「第4の状態」であると考えられる。 In the present invention, “liquid crystal” is a molecular assembly of surfactants, and a liquid crystal state in which a cylindrical surfactant becomes a rod-like molecule due to the presence of an ionic polymer compound having a high concentration or an opposite charge. Say. Such anisotropy based on this orientation order exhibited by the liquid crystal is “spontaneous” derived from the shape of the molecule and intermolecular force, and is not induced by any external force. When a flow is applied to a concentrated solution of a polymer compound, molecular orientation occurs and optical anisotropy is observed. However, when the flow stops, such orientation is not spontaneous. Liquid crystals are extremely peculiar in that they have both liquid properties of fluidity and liquid crystal properties of optical anisotropy, and cannot be classified as solid or liquid. It is considered to be the “fourth state” of the substance.
 「液晶状態」の確認は、偏光顕微鏡による干渉紋の観察から判断できる。干渉紋がうろこ状のモザイクテクスチャーとして観察された場合はヘキサゴナル液晶、十字模様のクロスニコルが観察された場合はラメラ液晶、干渉紋が見られない場合はミセル相、又はキュービック相である。これらの典型的な干渉紋様はR.B.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)に例示されている。なお、25℃で固形物が見られる場合には、これらの干渉紋が見られても、液晶相とは判断しない。一方、非常に粘性が高く干渉紋が見られないキュービック層の判定や、偏光顕微鏡で判断しにくい場合は、小角X線散乱の干渉パターンから判断できる。(100),(110)、(200)面に対応して、1:√3:2:・・・の面間距離比に対応する散乱角にピークが現れるものがヘキサゴナル液晶相、(100)、(200)、(300)面に対応して1:2:3:・・・の面間隔比に対応する散乱角にピークが現れるものがラメラ液晶、(100)、(111)、(200)面の面間隔に対応した1:√3/2:√2:・・・・や、(211)、(220)、(321)、(400)面に対応した1:√4/3:√7/3:√8/3:・・・にピークが現れるものがキュービック液晶である。また、小角部分のX線散乱に明確なピークが見られず、散乱ベクトルq=0.1~0.5nm-1付近にブロードなピークが見られる場合には、ミセル相である。 Confirmation of the “liquid crystal state” can be judged from observation of interference patterns with a polarizing microscope. When the interference pattern is observed as a scaly mosaic texture, it is a hexagonal liquid crystal, when a cross-shaped cross Nicol is observed, it is a lamellar liquid crystal, and when no interference pattern is observed, it is a micellar phase or a cubic phase. These typical interference patterns are illustrated in RBO 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). In addition, when a solid substance is seen at 25 degreeC, even if these interference patterns are seen, it is not judged as a liquid crystal phase. On the other hand, when it is difficult to determine a cubic layer with very high viscosity and no interference pattern, or when it is difficult to determine with a polarizing microscope, it can be determined from the interference pattern of small-angle X-ray scattering. Corresponding to the (100), (110), (200) planes, a hexagonal liquid crystal phase has a peak at a scattering angle corresponding to a distance ratio of 1: √3: 2:. , (200), (300) corresponding to the plane spacing ratio of 1: 2: 3:... Is a lamellar liquid crystal, (100), (111), (200 ) 1: √3 / 2 corresponding to the surface spacing of the surfaces: √2:..., And 1: √4 / 3 corresponding to the (211), (220), (321), (400) surfaces: A liquid crystal having a peak at √7 / 3: √8 / 3:... Is cubic liquid crystal. In addition, when no clear peak is observed in the X-ray scattering in the small-angle portion and a broad peak is observed in the vicinity of the scattering vector q = 0.1 to 0.5 nm −1 , it is a micellar phase.
 なお、皮膚洗浄剤組成物は、見た目の美しさ等から、透明であることが好ましい。なお、「透明」とは、後述する実施例の〈透明度〉の測定において、評価基準で「◎」、「○」をいう。後述する実施例の〈透明度〉の測定において、透明度が◎の「透明」な組成物を得るためには、(A)~(D)成分は、以下の条件を満たすことが好ましい。
(A)成分の含有量は、皮膚洗浄剤組成物中20~35質量%であり、炭素数が12以下の高級脂肪酸塩と炭素数が14以上の高級脂肪酸塩の質量比は80/20~50/50である。
(B)成分はラウリルジメチルアミノ酢酸ベタインであり、その含有量は、皮膚洗浄剤組成物中7~15質量%である。
(C)成分は、トリイソステアリン酸PEG-20グリセリル、トリオレイン酸PEG-20グリセリル、トリイソステアリン酸PEG-20トリメチロールプロパン、POE(20~80)硬化ヒマシ油及びPOE(20~80)ヒマシ油から選ばれ、その含有量は、皮膚洗浄剤組成物中2~5質量%である。
(D)成分は、プロピレングリコールとグリセリンとの併用、プロピレングリコール又はポリエチレングリコール400であり、その含有量は、皮膚洗浄剤組成物中25~35質量%であり、プロピレングリコールとグリセリンを併用する場合は、プロピレングリコールの比率が20/80以上である。
In addition, it is preferable that a skin cleansing composition is transparent from the beauty of appearance etc. Note that “transparent” means “「 ”and“ ◯ ”in the evaluation criteria in the measurement of <Transparency> in Examples described later. In the measurement of <Transparency> in Examples described later, in order to obtain a “transparent” composition having a transparency of ◎, the components (A) to (D) preferably satisfy the following conditions.
The content of the component (A) is 20 to 35% by mass in the skin cleanser composition, and the mass ratio of the higher fatty acid salt having 12 or less carbon atoms and the higher fatty acid salt having 14 or more carbon atoms is 80/20 to 50/50.
Component (B) is lauryldimethylaminoacetic acid betaine, and its content is 7 to 15% by mass in the skin cleanser composition.
Component (C) consists of PEG-20 glyceryl triisostearate, PEG-20 glyceryl trioleate, PEG-20 trimethylolpropane triisostearate, POE (20-80) hydrogenated castor oil and POE (20-80) castor oil The content thereof is 2 to 5% by mass in the skin cleanser composition.
Component (D) is a combination of propylene glycol and glycerin, propylene glycol or polyethylene glycol 400, and its content is 25 to 35% by mass in the skin cleanser composition. When propylene glycol and glycerin are used in combination Has a propylene glycol ratio of 20/80 or more.
 本発明の皮膚洗浄剤組成物には、適宜選択したその他成分を本発明の目的を妨げない範囲で配合することができる。その他成分としては、皮膚洗浄剤組成物に通常用いられているものの中から適宜選択することができ、例えば、油分、シリコーン類、低級又は高級アルコール等のアルコール類、ラノリン誘導体、蛋白誘導体、アクリル樹脂分散液、ビタミン等の薬剤、殺菌剤、防腐剤、水酸化カリウム、クエン酸等のpH調整剤、酸化防止剤、金属封鎖剤、紫外線吸収剤、動植物抽出物又はその誘導体、色素、香料、顔料、無機粉体、粘土鉱物、ナイロン、ポリエチレン等の水不溶性ポリマー粉体等が挙げられる。 In the skin cleansing composition of the present invention, other appropriately selected components can be blended within a range that does not interfere with the object of the present invention. Other components can be appropriately selected from those commonly used in skin cleanser compositions, such as oils, silicones, alcohols such as lower or higher alcohols, lanolin derivatives, protein derivatives, acrylic resins. Dispersions, drugs such as vitamins, bactericides, antiseptics, pH adjusters such as potassium hydroxide and citric acid, antioxidants, sequestering agents, UV absorbers, animal and plant extracts or their derivatives, dyes, fragrances, pigments And water-insoluble polymer powder such as inorganic powder, clay mineral, nylon and polyethylene.
 本発明の皮膚洗浄剤組成物のpHは、低温安定性や、液晶形成性の面から、9.0~11.0が好ましく、低温安定性の点から9.4~10.6がより好ましい。pHが9.0未満であると、低温安定性が悪くなる場合があり、11.0を超えると、液晶を形成しにくくなる場合がある。 The pH of the skin cleansing composition of the present invention is preferably 9.0 to 11.0 from the viewpoint of low temperature stability and liquid crystal formation, and more 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 deteriorate, and when it exceeds 11.0, it may be difficult to form a liquid crystal.
 本発明の皮膚洗浄剤組成物の粘度は、25℃で20~500Pa・sが好ましく、130~350Pa・sがより好ましい。20Pa・s未満では、高温安定性が悪くなるおそれがあり、500Pa・sを超えると、製剤の水への溶解性が悪くなる場合がある。なお、粘度は、BH型粘度計(株式会社東京計器製)を用いて、試料温度25℃にて、ローターNo.7、回転数4rpm、1分間後の粘度を測定する。 The viscosity of the skin cleanser composition of the present invention is preferably 20 to 500 Pa · s at 25 ° C., more preferably 130 to 350 Pa · s. If it is less than 20 Pa · s, the high-temperature stability may be deteriorated, and if it exceeds 500 Pa · s, the solubility of the preparation in water may be deteriorated. The viscosity was measured using a BH type viscometer (manufactured by Tokyo Keiki Co., Ltd.) at a sample temperature of 25 ° C. 7. Measure the viscosity after 1 minute at 4 rpm.
 本発明の皮膚洗浄剤組成物は、顔用、身体用いずれでもよく、皮膚であれば、その対象は特に限定されない。 The skin cleansing composition of the present invention may be used for both face and body, and the target is not particularly limited as long as it is skin.
 以下、実施例及び比較例を示し、本発明を具体的に説明するが、本発明は下記の実施例に制限されるものではない。なお、下記の例において特に明記のない場合は、組成の「%」は質量%、比率は質量比を示し、表中の各成分の量は純分換算した量である。 Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In the following examples, unless otherwise specified, “%” in the composition indicates mass%, the ratio indicates the mass ratio, and the amount of each component in the table is an amount converted into a pure component.
  [実施例1~38、比較例1~12]
 皮膚洗浄剤組成物を以下のように調製した。(A)、(C)、(D)成分及び精製水を真空乳化釜のベッセルに秤取した。減圧状態で、80℃に加温して溶解した。溶解後、パドルを攪拌しながら、(B)成分を加え溶解し、減圧状態で1℃/分で35℃まで冷却し、充分に減圧・攪拌を行い脱気した。脱気後、25℃まで1℃/分で冷却を行った。続いてpHメーターHM-30R(東亜ディーケーケー株式会社製)を用いてpHを測定し、水酸化カリウム又はクエン酸を用いて、目標のpHとした。なお、pHは、25℃にしたサンプルに、電極を2分間浸した後の値を測定した。得られた皮膚洗浄剤組成物について、下記評価を行った。結果を表中に併記する。
[Examples 1 to 38, Comparative Examples 1 to 12]
A skin cleanser composition was prepared as follows. Components (A), (C), (D) and purified water were weighed into a vessel of a vacuum emulsification kettle. Under reduced pressure, it was heated to 80 ° C. to dissolve. After dissolution, the component (B) was added and dissolved while stirring the paddle, cooled to 35 ° C. at 1 ° C./min in a reduced pressure state, and sufficiently depressurized and stirred for deaeration. After deaeration, cooling was performed to 25 ° C. at 1 ° C./min. Subsequently, the pH was measured using a pH meter HM-30R (manufactured by Toa DKK Co., Ltd.), and the target pH was set using potassium hydroxide or citric acid. The pH was measured after the electrode was immersed in a sample at 25 ° C. for 2 minutes. The following evaluation was performed about the obtained skin cleaning composition. The results are also shown in the table.
〈粘度〉
 BH型粘度計(株式会社東京計器製)を用いて、試料温度25℃にて、ローターNo.7、回転数4rpm、1分間後の粘度を測定した。
<viscosity>
Using a BH type viscometer (manufactured by Tokyo Keiki Co., Ltd.), the sample temperature was 25 ° C. and the rotor No. 7. Viscosity after 1 minute at 4 rpm was measured.
〈液晶状態の確認〉
 液晶状態の確認は、皮膚洗浄剤組成物を25℃にし、偏光顕微鏡AX70(オリンパス(株))を用いて観察した。干渉紋がうろこ状のモザイクテクスチャーとして観察された場合をヘキサゴナル液晶、十字模様のクロスニコルが観察された場合はラメラ液晶、干渉紋が見られない場合はミセル相とした。本発明の液晶は、ヘキサゴナル液晶、ラメラ液晶、キュービック液晶をいう。これらの典型的な干渉紋様はR.B.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)等に例示されている。なお、25℃で固形物の分散が見られる場合には、これらの干渉紋が見られても、液晶相とは判断しなかった。
 一方、非常に粘性が高く干渉紋が見られないキュービック液晶層の判定や、偏光顕微鏡で判断しにくい場合は、小角用受光ユニットとX線集光ミラーを取り付けたX線回折装置X’ Pert Pro(PANalitical社)を用いて、小角部分のX線散乱の干渉パターンから判断した。(100),(110)、(200)面に対応して、1:√3:2:・・・の面間距離比に対応する散乱角にピークが現れるものをヘキサゴナル液晶相、(100)、(200)、(300)面に対応して1:2:3:・・・の面間隔比に対応する散乱角にピークが現れるものをラメラ液晶、(100)、(111)、(200)面の面間隔に対応した1:√3/2:√2:・・・・や、(211)、(220)、(321)、(400)面に対応した1:√4/3:√7/3:√8/3:・・・にピークが現れるものをキュービック液晶とした。また、小角部分のx線散乱に明確なピークが見られず、散乱ベクトルq=0.1~0.5nm-1付近にブロードなピークが見られる場合には、ミセル相とした。表中に下記記号で示した。
 ラメラ液晶:L
 キュービック層:C
 ヘキサゴナル液晶:H
 ミセル:M
 固体分散:S
<Checking the LCD status>
The confirmation of the liquid crystal state was carried out using a polarizing microscope AX70 (Olympus Corporation) with the skin cleansing composition at 25 ° C. When the interference pattern was observed as a scaly mosaic texture, it was a hexagonal liquid crystal, when a cross-shaped cross Nicol was observed, it was a lamellar liquid crystal, and when no interference pattern was observed, it was a micelle phase. The liquid crystal of the present invention refers to hexagonal liquid crystal, lamellar liquid crystal, and cubic liquid crystal. These typical interference patterns are exemplified in RBRosevere, “The microscopy of the Liquid Crystalline Neat and Middle Phase of soaps and synthetic detergents” J. Am. Oil Chemist's Soc., 628, 31 (1954). In addition, when dispersion | distribution of the solid substance was seen at 25 degreeC, even if these interference patterns were seen, it was not judged as a liquid crystal phase.
On the other hand, if it is difficult to determine a cubic liquid crystal layer that is very viscous and has no interference pattern, or if it is difficult to determine with a polarizing microscope, an X-ray diffractometer X 'Pert Pro with a small-angle light receiving unit and an X-ray condenser mirror (PANalitical) was used to determine from the X-ray scattering interference pattern in the small-angle part. Corresponding to the (100), (110), (200) planes, a hexagonal liquid crystal phase having a peak at a scattering angle corresponding to the inter-plane distance ratio of 1: √3: 2:... (100) , (200), (300) corresponding to the plane spacing ratio of 1: 2: 3:..., Lamellar liquid crystal, (100), (111), (200 ) 1: √3 / 2 corresponding to the surface spacing of the surfaces: √2:..., And 1: √4 / 3 corresponding to the (211), (220), (321), (400) surfaces: A liquid crystal having a peak at √7 / 3: √8 / 3:. In addition, when no clear peak was observed in the x-ray scattering in the small-angle portion and a broad peak was observed in the vicinity of the scattering vector q = 0.1 to 0.5 nm −1 , the micelle phase was set. The following symbols are used in the table.
Lamella liquid crystal: L
Cubic layer: C
Hexagonal liquid crystal: H
Micelle: M
Solid dispersion: S
〈高温・低温安定性〉
 高さ8cm、口径3cmの硬質透明ガラス瓶(容量55mL)に、皮膚洗浄剤組成物を50mL充填し、50℃・0℃の各環境下において保存し、各保存温度における外観を観察し、下記判断基準に基づき、皮膚洗浄剤組成物の安定性を評価した。
[判断基準]
◎:4週間保存後、相分離や析出物がなく、透明で、均一な状態。
◎~○:4週間保存後、相分離や析出物がないが、外観の一部がわずかに濁ってみえる。
○:4週間保存後、相分離や析出物がないが、外観が均一にわずかに濁ってみえる。
△:2週間保存後は相分離や析出物がないが、4週間保存後、相分離又は析出物がある。
×:2週間保存後、相分離又は析出物がある。
<High temperature / low temperature stability>
A hard transparent glass bottle (capacity 55 mL) with a height of 8 cm and a diameter of 3 cm is filled with 50 mL of the skin cleansing composition, stored in each environment at 50 ° C. and 0 ° C., observed for appearance at each storage temperature, and judged as follows: Based on the criteria, the stability of the skin cleanser composition was evaluated.
[Judgment criteria]
A: After storage for 4 weeks, it is transparent and uniform with no phase separation or precipitates.
A to B: After storage for 4 weeks, there is no phase separation or precipitate, but a part of the appearance looks slightly cloudy.
○: After storage for 4 weeks, there is no phase separation or precipitates, but the appearance appears to be uniformly and slightly turbid.
Δ: No phase separation or precipitates after storage for 2 weeks, but phase separation or precipitates after storage for 4 weeks.
X: After storage for 2 weeks, there is phase separation or precipitate.
〈透明度〉
 高さ8cm、口径3cmの硬質透明ガラス瓶(容量55mL)に、皮膚洗浄剤組成物を50mL(高さ6cm)充填し、25℃の環境下に1日保存した。MSゴシック体で「あ」と印刷した紙の上に、各試料を充填した上記ガラス瓶を置き、ガラス瓶の上から紙に印刷された文字の判別性を下記判断基準に基づき、皮膚洗浄剤組成物の透明度を評価した。
[判断基準]
◎:MSゴシック体20ポントで印刷した「あ」が、明確に判別できる。
○:MSゴシック体20ポントで印刷した「あ」が、ぼやけてみえるが、判別できる。
△:MSゴシック体20ポントで印刷した「あ」は判別できないが、24ポントで印刷した「あ」は、判別できる。
×:MSゴシック体24ポントで印刷した「あ」が判別できない。
<Transparency>
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 (6 cm in height) of the skin cleansing composition and stored in an environment at 25 ° C. for one day. The above glass bottle filled with each sample is placed on a paper printed with MS Gothic "A", and the skin cleansing composition is based on the following criteria for the discrimination of characters printed on the paper from the top of the glass bottle The transparency of was evaluated.
[Judgment criteria]
A: “A” printed with 20 points of MS Gothic body can be clearly identified.
○: “A” printed with 20 points of MS Gothic font appears blurry but can be distinguished.
Δ: “A” printed with 20 points of MS Gothic cannot be discriminated, but “A” printed with 24 points can be discriminated.
X: “A” printed with 24 points of MS Gothic cannot be identified.
〈使用時の溶け易さ〉
 使用時の皮膚洗浄剤組成物の溶け易さは、専門評価パネル10名が、皮膚洗浄剤組成物を使用して評価した。チューブ容器(直径3cm、高さ8cm、口径5mm)に皮膚洗浄剤組成物を充填し、水で濡らした手のひらに各試料1gをとり、両手で延ばして泡立てて、溶け易さを評価した。評価は、下記に示す判断基準に基づき5段階の評点を付け、各試料の評点の平均値をとり、平均値から下記基準に基づいて行った。
[判断基準]
5点:手のひらをこすりはじめと同時に試料が溶けて、泡立つ。
4点:手のひらをこすりはじめて2~3回で試料が溶けて、泡立つ。
3点:手のひらをこすりはじめて4~7回で試料が溶けて、泡立つ。
2点:手のひらをこすりはじめて、8~12回で試料が溶けて、泡立つ。
1点:手から試料剤が滑り落ちるか、手のひらや指に試料が付着して、13回以上手のひらをこすっても泡立たせることができない。
[評点平均値の基準]
◎  :4.5点~5点
◎~〇:4.0点~4.5点未満
○  :3.0点~4.0点未満
△  :2.0点~3.0点未満
×  :2.0点未満
<Ease of melting during use>
The ease of dissolution of the skin cleanser composition during use was evaluated by 10 professional evaluation panels using the skin cleanser composition. A tube container (3 cm in diameter, 8 cm in height, 5 mm in diameter) was filled with the skin cleanser composition, 1 g of each sample was taken into the palm wetted with water, and foamed by extending with both hands, and the ease of melting was evaluated. Evaluation was made based on the following criteria based on the following criteria based on the five-point score based on the following criteria.
[Judgment criteria]
5 points: At the same time as rubbing the palm, the sample melts and foams.
4 points: The sample melts and foams 2 to 3 times after rubbing the palm.
3 points: The sample melts and foams 4 to 7 times after rubbing the palm.
2 points: Starting to rub the palm, the sample melts and bubbles in 8-12 times.
1 point: The sample agent slides down from the hand, or the sample adheres to the palm or finger, and even if the palm is rubbed 13 times or more, foaming cannot be made.
[Standard of average score]
◎: 4.5 to 5 points ◎ to ○: 4.0 points to less than 4.5 points ○: 3.0 points to less than 4.0 points Δ: 2.0 points to less than 3.0 points ×: 2 Less than 0 points
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
 なお、本発明の皮膚洗浄剤組成物の殺菌力を確認するため、実施例1,36について、下記殺菌力試験を行った。
〈殺菌力〉
(1)菌液の調製
 下記菌を初発菌数が10の8乗個/mLとなるように菌液を調製した。
黄色ブドウ球菌:スタフィロコッカス アウレウス(Staphylococcus aureus)ATCC6538
(2)試験液
 実施例1,36で得られた皮膚洗浄剤組成物を水道水で5倍に希釈し、試験液を調製した。
〈殺菌力試験法〉
 25℃にて、試験液9mLに菌液1mLを添加して充分撹拌し、添加1分後に4.5mLのSCDLP培地(Soybean-Casein Digest Broth with Lectin&Polysorbate 80:和光純薬工業(株)製)に加え、10倍希釈液とした。同様の方法を繰り返して各希釈液を得た。各希釈液から1.0mLをシャーレに採取し、SCDLP寒天培地(Soybean-Casein Digest Ager with Lectin&Polysorbate 80:和光純薬工業(株)製)15mLを加えて均一化し、2日間培養し(寒天平板希釈法)、コロニーをカウントして生存菌数を測定した。初発菌数と生存菌数から、下記式に基づいて殺菌力を算出し、下記評価基準で殺菌効果を評価した。
 殺菌力=log(生存菌数/初発菌数)
なお、殺菌力は数値が小さいほど効果が高い。
In addition, in order to confirm the bactericidal power of the skin cleansing composition of the present invention, the following bactericidal power tests were conducted on Examples 1 and 36.
<Bactericidal power>
(1) Preparation of Bacterial Solution A bacterial solution was prepared so that the initial number of the following bacteria was 10 8 / mL.
Staphylococcus aureus: Staphylococcus aureus ATCC 6538
(2) Test solution The skin cleanser composition obtained in Examples 1 and 36 was diluted 5-fold with tap water to prepare a test solution.
<Sterilizing power test method>
At 25 ° C., 1 mL of the bacterial solution was added to 9 mL of the test solution and stirred sufficiently. One minute after the addition, 4.5 mL of SCDLP medium (Soybean-Casein Broth with Lectin & Polysorbate 80: manufactured by Wako Pure Chemical Industries, Ltd.) In addition, a 10-fold diluted solution was obtained. The same method was repeated to obtain each diluted solution. Collect 1.0 mL from each diluted solution in a petri dish, add 15 mL of SCDLP agar medium (Soybean-Casein Digest Age with Lectin & Polysorbate 80: manufactured by Wako Pure Chemical Industries, Ltd.), homogenize, and culture for 2 days (agar plate dilution) Method), colonies were counted and the number of viable bacteria was measured. Based on the following formula, bactericidal power was calculated from the initial bacterial count and viable bacterial count, and the bactericidal effect was evaluated according to the following evaluation criteria.
Bactericidal power = log (number of viable bacteria / number of initial bacteria)
In addition, the effect is so high that a sterilization power is small.
 実施例1の殺菌力は「-1.1」、実施例36の殺菌力は「-3.2」であり、(A)成分としてモノエタノールアミン塩を用いることで、殺菌力が向上することが確認された。また、実施例36は低温安定性(-5℃・1ヶ月)でも「◎」であり、低温安定性に優れるものであった。 The bactericidal power of Example 1 is “−1.1”, the bactericidal power of Example 36 is “−3.2”, and the bactericidal power is improved by using a monoethanolamine salt as the component (A). Was confirmed. Further, Example 36 was “低温” even at low temperature stability (−5 ° C., 1 month), and was excellent in low temperature stability.
  [実施例39]
 皮膚洗浄剤組成物を以下のように調製した。ラウリルジメチルアミノ酢酸ベタイン及び香料以外の共通成分を真空乳化釜のベッセルに秤取した。減圧状態で、80℃に加温して溶解した。溶解後、パドルを攪拌しながら、ラウリルジメチルアミノ酢酸ベタインを加え溶解し、減圧状態で1℃/分で35℃まで冷却した。この時点で、充分に減圧・攪拌を行い脱気した。脱気後、香料を添加し、25℃まで1℃/分で冷却を行った。続いてpHメーターHM-30R(東亜ディーケーケー株式会社製)を用いてpHを測定し、水酸化カリウム又はクエン酸を用いて、目標のpHとした。
組成                            %
ラウリン酸カリウム                    21
ミリスチン酸カリウム                    9
ラウリルジメチルアミノ酢酸ベタイン*1           9
ポリオキシエチレン硬化ヒマシ油(E.O.20)*10    3
プロピレングリコール                    9
グリセリン                        21
イソプロピルメチルフェノール*19             0.1
モノエタノールアミン                    0.5
エデト酸                          0.1
ビタミンE*20                      0.1
ポリエチレン末*21                    0.3
香料                            0.4
精製水                           残部
 合計                         100.0
水酸化カリウム(48%)又はクエン酸で、pHを10.2に調整した。
〈評価結果〉
粘度:118Pa・s
透明度:◎
結晶相:H
安定性(50℃):◎
安定性(0℃):◎
安定性(-5℃):◎
[Example 39]
A skin cleanser composition was prepared as follows. Common components other than lauryldimethylaminoacetic acid betaine and flavor were weighed in a vessel of a vacuum emulsification kettle. Under reduced pressure, it was heated to 80 ° C. to dissolve. After dissolution, while stirring the paddle, lauryldimethylaminoacetic acid betaine was added and dissolved, and the mixture was cooled to 35 ° C. at 1 ° C./min under reduced pressure. At this time, degassing was performed by sufficiently reducing pressure and stirring. After deaeration, a fragrance was added and cooled to 25 ° C. at 1 ° C./min. Subsequently, the pH was measured using a pH meter HM-30R (manufactured by Toa DKK Co., Ltd.), and the target pH was set using potassium hydroxide or citric acid.
Composition%
Potassium laurate 21
Potassium myristate 9
Lauryldimethylaminoacetic acid betaine * 1 9
Polyoxyethylene hydrogenated castor oil (E.O.20) * 10 3
Propylene glycol 9
Glycerin 21
Isopropyl methylphenol * 19 0.1
Monoethanolamine 0.5
Edetic acid 0.1
Vitamin E * 20 0.1
Polyethylene powder * 21 0.3
Fragrance 0.4
Purified water balance 100.0
The pH was adjusted to 10.2 with potassium hydroxide (48%) or citric acid.
<Evaluation results>
Viscosity: 118 Pa · s
Transparency: ◎
Crystal phase: H
Stability (50 ° C): ◎
Stability (0 ° C): ◎
Stability (-5 ° C): ◎
 実施例及び比較例を調製する際に用いた原料を以下に示す。
*1:アモーゲンSH(第一工業製薬)
*2:アモーゲンSHをステンレスバットに取り、真空乾燥機(40℃)にて乾燥し、純分量を80%に濃縮したもの。
*3:LPB-R(一方社油脂工業)
*4:エマレックスGWIS-320(日本エマルジョン、HLB=8)
*5:GWS-320(日本エマルジョン、HLB=8)
*6:GWO-320(日本エマルジョン、HLB=8)
*7:TPIS-320(日本エマルジョン、HLB=8)
*8:C-20(日本エマルジョン、HLB=9)
*9:HC-10(日本エマルジョン、HLB=7)
*10:HC-20(日本エマルジョン、HLB=9)
*11:HC-40(日本エマルジョン、HLB=12)
*12:HC-80(日本エマルジョン、HLB=15)
*13:PEG#400K(ライオン)
*14:NEOSORB70/02SB(ロケットジャパン)
*15:HC-5(日本エマルジョン、HLB=5)
*16:HC-100(日本エマルジョン、HLB=15)
*17:GWIS-220EX(日本エマルジョン、HLB=10)
*18:GWIS-120(日本エマルジョン、HLB=13)
*19:IPMP(大阪化成)
*20:dl-αトコフェロール(DSMニュートリションジャパン)
*21:フロービーズCL-8007(住友精化)
*22:化粧品用濃グリセリン
The raw materials used in preparing the examples and comparative examples are shown below.
* 1: Amorgen SH (Daiichi Kogyo Seiyaku)
* 2: Ammogen SH is taken in a stainless steel vat, dried with a vacuum dryer (40 ° C), and the pure content is concentrated to 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 Kasei)
* 20: dl-α Tocopherol (DSM Nutrition Japan)
* 21: Flow beads CL-8007 (Sumitomo Seika)
* 22: Concentrated glycerin for cosmetics

Claims (4)

  1.  下記(A)、(B)、(C)及び(D)成分を含有し、25℃において液晶状態であることを特徴とする皮膚洗浄剤組成物。
    (A)炭素数8~26の高級脂肪酸塩15~45質量%
    (B)ベタイン型両性界面活性剤7~25質量%
    (C)下記非イオン性界面活性剤1~5質量%
     ポリオキシエチレン(エチレンオキサイドの平均付加モル数10~80)グリセリル、グリセリン、又はポリオキシエチレン(エチレンオキサイドの平均付加モル数10~80)トリメチロールプロパンの3つの水酸基が、エステル化又はエーテル化された化合物であって、エステル化又はエーテル化部分は、炭素数7~25の飽和又は不飽和、直鎖又は分岐鎖の一価炭化水素基であり、水素原子の一部が水酸基で置換されていてもよく、この水酸基に平均付加モル数が10~80のポリオキシエチレンが付加されていてもよい、ただし、非イオン性界面活性剤に付加されるポリオキシエチレンの総数は、平均付加モル数で10~80である。
    (D)多価アルコール15~35質量%
    A skin cleanser composition containing the following components (A), (B), (C) and (D) and in a liquid crystal state at 25 ° C.
    (A) 15 to 45% by mass of higher fatty acid salt having 8 to 26 carbon atoms
    (B) Betaine amphoteric surfactant 7 to 25% by mass
    (C) 1 to 5% by mass of the following nonionic surfactant
    Three hydroxyl groups of polyoxyethylene (average added mole number of ethylene oxide 10 to 80) glyceryl, glycerin, or polyoxyethylene (average added mole number of ethylene oxide 10 to 80) trimethylolpropane are esterified or etherified. The esterified or etherified moiety is a saturated or unsaturated, linear or branched monovalent hydrocarbon group having 7 to 25 carbon atoms, and part of the hydrogen atoms are substituted with hydroxyl groups. The polyoxyethylene having an average addition mole number of 10 to 80 may be added to this hydroxyl group, provided that the total number of polyoxyethylene added to the nonionic surfactant is the average addition mole number. 10 to 80.
    (D) 15 to 35% by mass of polyhydric alcohol
  2.  (C)成分が、エステル化又はエーテル化部分の炭素数7~25の一価炭化水素基が、水素原子の一部が水酸基で置換されていることを特徴とする請求項1記載の皮膚洗浄剤組成物。 The skin cleanser according to claim 1, wherein the component (C) is a monovalent hydrocarbon group having 7 to 25 carbon atoms in the esterified or etherified moiety, wherein a part of the hydrogen atoms is substituted with a hydroxyl group. Agent composition.
  3.  (C)成分が、ポリオキシエチレン硬化ヒマシ油又はポリオキシエチレンヒマシ油である請求項1又は2記載の皮膚洗浄剤組成物。 The skin cleansing composition according to claim 1 or 2, wherein the component (C) is polyoxyethylene hydrogenated castor oil or polyoxyethylene castor oil.
  4.  液晶が、ヘキサゴナル液晶である請求項1、2又は3記載の皮膚洗浄剤組成物。 4. The skin cleanser composition according to claim 1, 2 or 3, wherein the liquid crystal is hexagonal liquid crystal.
PCT/JP2011/071189 2010-09-21 2011-09-16 Skin cleanser composition WO2012039350A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
KR1020137006662A KR101790822B1 (en) 2010-09-21 2011-09-16 Skin cleanser composition
JP2012535019A JP5861639B2 (en) 2010-09-21 2011-09-16 Skin cleanser composition

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2010-210990 2010-09-21
JP2010210990 2010-09-21

Publications (1)

Publication Number Publication Date
WO2012039350A1 true WO2012039350A1 (en) 2012-03-29

Family

ID=45873837

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2011/071189 WO2012039350A1 (en) 2010-09-21 2011-09-16 Skin cleanser composition

Country Status (4)

Country Link
JP (1) JP5861639B2 (en)
KR (1) KR101790822B1 (en)
TW (1) TWI515013B (en)
WO (1) WO2012039350A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021078412A1 (en) * 2019-10-21 2021-04-29 Jallal Messadek Fractal formulations

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102099325B1 (en) * 2014-11-24 2020-04-09 주식회사 엘지생활건강 Skin cleansing composition

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01151510A (en) * 1987-12-09 1989-06-14 Lion Corp Detergent composition
JPH0762389A (en) * 1993-06-18 1995-03-07 Shiseido Co Ltd Detergent composition
JPH09279192A (en) * 1996-04-09 1997-10-28 Nof Corp Transparent gel-like cleansing agent composition
JP2005008682A (en) * 2003-06-17 2005-01-13 Pola Chem Ind Inc Cream-like detergent
JP2007169248A (en) * 2005-12-26 2007-07-05 Lion Corp Liquid skin cleanser composition
JP2007211232A (en) * 2005-10-31 2007-08-23 Kao Corp Thickening/foam boosting agent

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6357699A (en) * 1986-08-28 1988-03-12 株式会社資生堂 Transparent gel like composition
JPH07215841A (en) * 1994-01-31 1995-08-15 Shiseido Co Ltd Skin-cleansing agent
JP4667164B2 (en) * 2005-08-12 2011-04-06 花王株式会社 Transparent gel detergent composition
JP4692358B2 (en) 2006-03-31 2011-06-01 日油株式会社 Hot cleansing fee
JP4953695B2 (en) * 2006-06-08 2012-06-13 株式会社 資生堂 Transparent liquid cleaning material
JP5153352B2 (en) * 2008-01-18 2013-02-27 小林製薬株式会社 Cleansing cosmetic composition

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01151510A (en) * 1987-12-09 1989-06-14 Lion Corp Detergent composition
JPH0762389A (en) * 1993-06-18 1995-03-07 Shiseido Co Ltd Detergent composition
JPH09279192A (en) * 1996-04-09 1997-10-28 Nof Corp Transparent gel-like cleansing agent composition
JP2005008682A (en) * 2003-06-17 2005-01-13 Pola Chem Ind Inc Cream-like detergent
JP2007211232A (en) * 2005-10-31 2007-08-23 Kao Corp Thickening/foam boosting agent
JP2007169248A (en) * 2005-12-26 2007-07-05 Lion Corp Liquid skin cleanser composition

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021078412A1 (en) * 2019-10-21 2021-04-29 Jallal Messadek Fractal formulations

Also Published As

Publication number Publication date
KR20130110157A (en) 2013-10-08
TW201302226A (en) 2013-01-16
TWI515013B (en) 2016-01-01
KR101790822B1 (en) 2017-11-20
JPWO2012039350A1 (en) 2014-02-03
JP5861639B2 (en) 2016-02-16

Similar Documents

Publication Publication Date Title
EP2644185B1 (en) Thick cleaning composition
JP4976184B2 (en) Liquid detergent composition
JP5591436B2 (en) Low temperature stable cream detergent composition
BR112015013023B1 (en) skin cleansing composition
WO2014171238A1 (en) Cleansing composition for pump foamer
JP5838816B2 (en) Liquid skin cleanser products
JP6240085B2 (en) Cleaning composition
JP5623723B2 (en) Skin cleanser
JP5861639B2 (en) Skin cleanser composition
EP1411892B1 (en) Aqueous narceous concentrate compositions comprising ethoxylated glycerides
JP5125333B2 (en) Gelling agent, gel-like composition and use thereof
CN108348430B (en) Cleaning agent composition for pump bubbler
JP2015172041A (en) detergent composition
JP6555595B2 (en) Method for reducing critical micelle concentration
WO2013141118A1 (en) Liquid detergent composition
JP2016113510A (en) Thixotropy-imparting agent
JP2009057515A (en) Gelling agent, gel-like composition, and its use
JP5691292B2 (en) Skin cleanser composition
JP7039967B2 (en) Acyl amino acid high compound composition
JP2017066048A (en) Creamy detergent compositions and production methods thereof
JP6645817B2 (en) Pearlescent brightener
JP2024037116A (en) Cleansing cosmetic
JP2019001847A (en) Detergent composition
JP2010043231A (en) Gelling agent and gel composition
WO2018101370A1 (en) Acyl amino acid-rich composition

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11826795

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2012535019

Country of ref document: JP

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 20137006662

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11826795

Country of ref document: EP

Kind code of ref document: A1