JP2007230897A - Oily composition for cleansing - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an odorless oily composition for cleansing, sufficiently cleansing the face refreshingly by one-time washing while having sufficient detergency, and hardly causing skin irritation. <P>SOLUTION: The oily composition for the cleansing contains 50-97 wt.% of liquid oil (A) and 3-50 wt.% of an ether-carboxylic acid type surfactant (B) represented by general formula (1): R<SP>1</SP>O-(AO)<SB>k</SB>-R<SP>2</SP>COOM [wherein, R<SP>1</SP>is a 15-24C linear or branched aliphatic hydrocarbon group or an 8-24C alicyclic hydrocarbon group; R<SP>2</SP>is a 1-3C alkylene group; A is a 2-12C alkylene group; k is an average number of moles of (AO) and 1-20; and M is one or more kinds selected from a hydrogen atom or a cation]. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an oily cleansing composition.

  Conventionally, gel-like and cream-like compositions have been often used as cleansing compositions. However, in recent years, oil-based cleansing compositions with more excellent removal ability have rapidly spread due to water-resistant foundations, lipsticks that are difficult to remove, and the trend of eye makeup.

As the surfactant used in the composition for oil-based cleansing, nonionic surfactants having good compatibility with oil and excellent emulsifiability with water have been mainly used as in Patent Documents 1 to 4. These are well-familiar with cosmetics such as foundations and are excellent in the ability to remove makeup, but have the disadvantage that it is difficult to wash off the oil after the makeup is removed. On the other hand, Patent Document 5 proposes an example in which a specific ether carboxylic acid type surfactant is used as a composition capable of removing both makeup and oil in one face wash.
JP 2002-241224 A JP 2005-104982 A JP 2005-187355 A JP 2005-306818 A JP 2005-239616 A

However, the ether carboxylic acid proposed in Patent Document 5 is not odorless and has a slight odor. Therefore, even if a fragrance is blended, a product with the desired fragrance is often not obtained, and a good feel is obtained when washing the face. In addition, there is a problem that the washing is not sufficiently refreshed, and further, there is skin irritation.
An object of the present invention is to provide an oil-based cleansing composition that has sufficient detergency and can be washed cleanly even with a single face wash, is odorless and has little skin irritation. .

  As a result of intensive studies to solve the above problems, the present inventors have found that a composition containing a liquid oil and a specific ether carboxylic acid type surfactant in a specific ratio can solve the above problems, The present invention has been reached.

That is, the present invention relates to 50 to 97% by weight of liquid oil (A) based on the weight of the oil-based cleansing composition and an ether carboxylic acid type surfactant (B) represented by the following general formula (1) (in the following) The composition for oil-based cleansing is characterized by containing 3 to 50% by weight of an ether carboxylic acid type surfactant (B).
_{^{R 1 O- (AO) k -R}} 2 COOM (1)

In general formula (1), R ¹ is a linear or branched aliphatic hydrocarbon group having 15 to 24 carbon atoms or an alicyclic hydrocarbon group having 8 to 24 carbon atoms; R ² is an alkylene group having 1 to 3 carbon atoms. A is an alkylene group having 2 to 12 carbon atoms; k is an average number of moles of (AO) and is 1 to 20; M represents one or more selected from a hydrogen atom and a cation.

  Since the oil-based cleansing composition of the present invention is excellent in detergency and excellent in emulsifiability when an arbitrary amount of water is added, it can be washed cleanly with a single face wash. Further, the ether carboxylic acid used is odorless and has little skin irritation.

  The composition for oil-based cleansing of this invention expresses an effect by containing liquid oil (A) and specific ether carboxylic acid type surfactant (B) in the ratio of a specific range.

The liquid oil (A) used in the present invention is an oil component which is liquid at 25 ° C., and examples thereof include hydrocarbons, higher alcohols, higher fatty acids, synthetic ester oils, silicone oils and vegetable oils. Examples of the hydrocarbon include liquid hydrocarbons that are non-volatile at normal temperature, such as liquid paraffin and squalane.
Examples of the higher alcohol include those having 10 to 24 carbon atoms, such as coconut oil alcohol, cetyl alcohol, isostearyl alcohol, and 2-octyldodecanol.
Examples of the higher fatty acid include those having 10 to 24 carbon atoms, such as coconut oil fatty acid and isostearic acid.
Synthetic ester oils include alkyls of higher fatty acids having 10 to 24 carbon atoms (alkyl groups having 1 to 18 carbon atoms) esters (for example, isopropyl myristate, 2-octyldodecyl myristate, octyl palmitate and 2-ethylhexanoic acid). Cetyl, etc.), alkyl esters of polycarboxylic acids (eg, diisostearyl malate), and carboxylic acid esters of polyhydric alcohols (eg, tri (2-ethylhexanoic acid) glyceryl and dineopentanoic acid tripropylene polyglycol, etc.) Can be mentioned.
Examples of the silicone oil include methylpolysiloxane and methylphenylpolysiloxane.
Examples of vegetable oils include safflower oil, sunflower oil, rosemary oil, jojoba oil, macadamia nut oil, olive oil, camellia oil, and castor oil.
These liquid oils (A) can be used alone or in any combination of two or more.

The ether carboxylic acid type surfactant (B) in the present invention is represented by the general formula (1), and the linear or branched aliphatic hydrocarbon group having 15 to 24 carbon atoms in R ¹ is linear or branched. An alkyl group (pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, docosyl, tetracosyl, 2-hexyldecyl, 2-octyldecyl, 2-hexyldecyl, 2-octyldodecyl, etc.); linear or branched alkenyl group (Pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, oleyl, gadolinyl group, etc.); and linear or branched alkadienyl groups (linoleyl group, etc.).
Examples of the alicyclic hydrocarbon group having 8 to 24 carbon atoms in R ¹ include monocyclic hydrocarbon groups (cycloalkyl groups such as ethylcyclohexyl, propylcyclohexyl, octylcyclohexyl, and nonylcyclohexyl groups) and polycyclic hydrocarbons. Group (such as an adamantyl group).
When R ¹ is an aliphatic hydrocarbon group and has 14 or less carbon atoms, or R ¹ is an alicyclic hydrocarbon group and has 7 or less carbon atoms, the ether carboxylic acid type surfactant has an odor and is odorless. It should not be washed out, and the wash-up is rare and the skin is irritating.
Further, when the carbon number of R ¹ exceeds 24, the cleaning power is inferior.
R ¹ is preferably a branched aliphatic hydrocarbon group having 15 to 24 carbon atoms, particularly a branched fat having 16 to 20 carbon atoms, from the viewpoints of good emulsion stability in water, odor and skin irritation. Group hydrocarbon group.

In general formula (1), R ² represents an alkylene group having 1 to 3 carbon atoms. When R ² exceeds 3 carbon atoms, the washing is not sufficiently refreshed. Specific examples of R ² include a methylene group, an ethylene group, a 1,2-propylene group, and a 1,3-propylene group.

  In the general formula (1), A represents an alkylene group having 2 to 12, preferably 2 to 8, more preferably 2 to 4 and particularly preferably 2 or 3 carbon atoms, and the part of (AO) is the number of carbon atoms. It is formed by the addition of two or more alkylene oxides (b1). Examples of the alkylene oxide (b1) include ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), 1,2- or 2,3-butylene oxide, tetrahydrofuran, and styrene oxide. It is done. Preferred is EO and / or PO. These may be added alone, or may be added in blocks or randomly.

In the ether carboxylic acid type surfactant (B) in the present invention, the part (AO) _k is a polyoxyalkylene chain, and its molecular weight usually has a distribution. Therefore, k in the general formula (1) is an average value of the number of moles of (AO), and is usually 1 to 20, preferably 1 to 12. When k exceeds 20, the compatibility with the liquid oil (A) is poor. Since k is an average value, it is not necessarily an integer.

In general formula (1), M represents one or more selected from a hydrogen atom and a cation. Cations include monovalent and divalent cations.
Monovalent cations include alkali metal cations, ammonium ions, organic amine cations, quaternary ammonium cations, basic amino acid cations, and combinations of two or more thereof.
Examples of the alkali metal constituting the alkali metal cation include sodium, potassium, and lithium.
Examples of the organic amine constituting the organic amine cation include primary, secondary and tertiary aliphatic amines (amines having an alkyl group having 1 to 20 carbon atoms and / or a hydroxyalkyl group having 2 to 4 carbon atoms: for example, diethylamine, Triethylamine, monoethanolamine, and monopropanolamine), alicyclic amines (such as cyclohexylamine and dicyclohexylamine), aromatic amines (such as aniline and toluidine), aromatic heterocyclic amines (such as pyridine and quinoline), heterocyclic amines (such as Morpholine, N-methylmorpholine, piperazine and the like), and C2-C4 hydroxyalkyl substituents (N-hydroxyethylmorpholine and the like) at the N position of these cyclic amines.
The quaternary ammonium constituting the quaternary ammonium cation includes aliphatic and alicyclic quaternary ammonium such as tetra (cyclo) alkylammonium [alkyl group having 1 to 12 carbon atoms (methyl, ethyl, propylbutyl, hexyl, octyl). And / or a dodecyl group) and / or a cycloalkyl group (such as a cyclohexyl group); the four (cyclo) alkyl groups may be the same or different. ] Etc. are mentioned.
Examples of the basic amino acid constituting the basic amino acid cation include lysine and arginine.
The (cyclo) alkyl group represents an alkyl group and / or a cycloalkyl group, and hereinafter the same expression is used.
Examples of the divalent cation include alkaline earth metal cations such as magnesium cation and calcium cation. In the case of the divalent cation, M is, for example, 1/2 Mg or 1/2 Ca.

M can be arbitrarily selected from hydrogen atoms and cations, but is preferably less than 40 mol% of M, more preferably from the viewpoint of obtaining a refreshing feeling of the oil-based cleansing composition. Is less than 20 mol% hydrogen atoms, preferably 60 mol% or more, more preferably 80 mol% or more is a cation.
In the ether carboxylic acid type surfactant (B) in the present invention, the case where M is a hydrogen atom is expressed as an acid type ether carboxylic acid type surfactant, and the case where M is a cation is a salt type ether. It is expressed as a carboxylic acid type surfactant.

  Specific examples of the ether carboxylic acid type surfactant (B) in the present invention include polyoxyethylene (average added mole number of EO = 5) 2-octyldecyl ether sodium acetate, polyoxyethylene (average added mole number of EO). = 5) Potassium 2-hexyldecyl ether acetate, polyoxyethylene (average number of added moles of EO = 5) 2-hexyldecyl ether acetate triethanolamine, and the like.

The ether carboxylic acid type surfactant (B) in the present invention is usually produced mainly through the following steps.
Step (1): Addition of alkylene oxide (b1) having 2 to 12 carbon atoms to alcohol (a1) represented by general formula R ¹ OH [R ¹ is the same as in general formula (1)] A step of obtaining (a2).
Step (2): A step of carboxyalkylating (a2) with a halogenated carboxylic acid alkali metal salt or the like.
Step (3): A step of acidifying the system, washing with water and liquid separation, removing a by-produced alkali metal halide, and purifying to obtain an acid ether carboxylic acid type surfactant.
Step (4): A step of neutralizing with an alkaline substance to obtain an ether carboxylic acid type surfactant containing at least part of a salt type ether carboxylic acid type surfactant.
In addition, when obtaining only an acid type ether carboxylic acid type | mold surfactant, a process (4) is unnecessary.

As reaction conditions for the step (1), a catalyst and a solvent as necessary are charged in (a1), and after nitrogen substitution, (b1) is introduced at 80 to 200 ° C. at −0.8 to 5 MPa, Examples include a method of aging after injecting a predetermined amount of (b1) until the pressure in the reaction system becomes equilibrium at 80 to 200 ° C.
Examples of the catalyst include alkali catalysts (alkali metal and alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, and barium hydroxide. Is potassium hydroxide, cesium hydroxide), Lewis acid catalyst (tin tetrachloride, antimony pentachloride, iron trichloride, boron trifluoride, etc.), perhalogen acid or its salt, sulfuric acid or its salt, phosphoric acid or its salt, And nitric acid or a salt thereof.
The metal for forming the salt is not particularly limited, but is preferably a metal other than an alkali metal, and a divalent or trivalent metal (Mg, Ca, Sr, Ba, Zn, Co, Ni, Cu, Al, more preferably Mg, Zn, Ca, Sr, Ba, Al, and particularly preferably Mg, Zn, Al).
Examples of the halogen of the perhalogen acid (salt) include chlorine, bromine and iodine, with chlorine being preferred. Moreover, when there are a plurality of steps (block addition, etc.) in the addition reaction of alkylene oxide (b1), the catalyst used in the first step and the catalyst used in the subsequent step may be different or the same. Good.
The amount of the catalyst used is preferably 0.001 to 1 part by weight per 100 parts by weight of the finished amount from the viewpoint of reaction rate and economy. More preferably, it is 0.003-0.8 weight part, Most preferably, it is 0.005-0.5 weight part.
In addition, as for the usage amount of the catalyst, the solvent and the catalyst, those described in JP-A No. 2001-011489 or the usage amount can be applied.

The alcohol (a1) used in the step (1) may be a natural alcohol or a synthetic alcohol (Ziegler alcohol, oxo alcohol, secondary alcohol, etc.), and may be a primary alcohol or a secondary alcohol.
Among R ¹ OH, R ¹ is particularly preferably a branched aliphatic hydrocarbon group, and therefore alcohols including branched alcohols, particularly synthetic alcohols, especially oxo alcohols and secondary alcohols are preferred. Commercial products of secondary alcohols such as Dovanol, Diadol (Mitsubishi Chemical Co., Ltd.), Oxocol (Kyowa Yuka Co., Ltd.) and Neodol (Shell Chemical Co., Ltd.) Olefin's and Surfactants Co., Ltd.) and Softanol (made by Nippon Shokubai Co., Ltd.).

  Examples of the alkylene oxide (b1) include the above EO and PO.

Examples of the monohalogenated lower carboxylic acid alkali metal salt in the step (2) of carboxyalkylating include sodium monochloroacetate, potassium monochloroacetate, sodium monobromoacetate and potassium monobromoacetate.
As the reaction conditions, the molar ratio of (a2) to the monohalogenated lower carboxylic acid alkali metal salt is 1.0: 0.95 to 1.0: 1.5, the reaction temperature is usually 30 to 100 ° C., preferably 40 The reaction can be carried out in a nitrogen atmosphere at a temperature of ˜70 ° C. using a volatile solvent such as toluene, if necessary, while gradually adding caustic alkali (sodium hydroxide, potassium hydroxide, etc.).

The acid that can be used in the purification step of step (3) is preferably a mineral acid such as hydrochloric acid and sulfuric acid.
By adding an acid to form an acid ether carboxylic acid, it becomes easy to separate from an aqueous salt solution produced during the reaction. The charging equivalent of acid is preferably 1.0 to 1.5 equivalents of the equivalent of caustic in step (2). In addition, water may be added as appropriate so that it can be easily washed and separated. In addition, when a volatile solvent is used in the step (2), the solvent may be distilled off after the liquid separation in the step (3).

  The alkaline substance that can be used in the step of obtaining an ether carboxylic acid type surfactant containing a salt type ether carboxylic acid type surfactant in at least a part of the step (4) is an alkaline substance that forms the cation M in the general formula (1). Examples of the substance include alkali metal hydroxides, ammonia, organic amines, basic amino acids, and quaternary ammonium hydroxides. The amount of the alkaline substance charged is, as described above, an amount such that 60 mol% or more, more preferably 80 mol% or more of M in the general formula (1) becomes a cation.

  The ether carboxylic acid type surfactant (B) can be used alone or in combination of two or more.

  When the oil-based cleansing composition of the present invention comprises only the liquid oil (A) and the ether carboxylic acid type surfactant (B), it is preferably a transparent and uniform liquid at normal temperature.

  The weight of the liquid oil (A) based on the weight of the oil-based cleansing composition of the present invention is usually 50 to 97% (in the following, unless otherwise specified,% represents% by weight), preferably 60 to 95%, More preferably, it is 75 to 90%. If it is less than 50%, sufficient detergency cannot be obtained, and if it exceeds 97%, it becomes sticky when washed with water and cannot be washed cleanly.

  The weight of the ether carboxylic acid type surfactant (B) based on the weight of the oil-based cleansing composition of the present invention is usually 3 to 50%, preferably 5 to 40%, more preferably 10 to 25%. . If it is less than 3%, it will not be sufficiently refreshed when washed with water, and if it exceeds 50%, sufficient detergency cannot be obtained.

The component for oil-based cleansing of the present invention can be blended with other components (C) used in ordinary cosmetics, pharmaceuticals and the like within a range not impairing the effects of the present invention.
Other components (C) include monohydric alcohols, polyhydric alcohol agents, amphoteric surfactants, cationic surfactants, nonionic surfactants, other {other than (B)} anionic surfactants, gels Examples include agents, medicinal agents, anti-inflammatory agents, bactericides, preservatives, ultraviolet absorbers, antioxidants, dyes, fragrances and water.

  Examples of the monohydric alcohol include ethanol and isopropyl alcohol (preferably a lower alcohol having 1 to 6 carbon atoms).

  Examples of the polyhydric alcohol include glycerin, 1,3-butylene glycol, 1,3-butanediol, and propylene glycol.

  Examples of amphoteric surfactants include amino acid type amphoteric surfactants, betaine type amphoteric surfactants, sulfate ester type amphoteric surfactants, and sulfonate type amphoteric surfactants.

  Examples of the cationic surfactant include a quaternary ammonium salt type and an amine salt type.

  Nonionic surfactants include alkylene oxide addition type nonionic surfactants [higher alcohol (aliphatic alcohol having 8 to 14 carbon atoms), alkylphenol (10 to 24 carbon atoms), higher fatty acid (12 to 24 carbon atoms). Alternatively, higher amines (8-18 carbon atoms) with alkylene oxide added, or hydroxyl ethers alkylated with alkylating agents, polyoxyalkylene glycols with higher fatty acids (12-24 carbon atoms), etc. Or an esterified product obtained by reacting a higher fatty acid (12 to 24 carbon atoms) with a hydroxyl group-containing compound such as a diol or a tri- to octavalent polyhydric alcohol, and a higher fatty acid. (C8-24) Amide added with alkylene oxide, polyvalent alcohol (The above-mentioned ones) alkyl (carbon number 8 to 60) ether added with alkylene oxide, etc.] and polyhydric alcohol (carbon numbers 3 to 20) type nonionic surfactant [polyhydric alcohol fatty acid (carbon Number 8-60) ester, polyhydric alcohol alkyl (carbon number 8-60) ether, fatty acid (carbon number 8-60) alkanolamide, etc.].

  Other anionic surfactants include carboxylic acid (saturated or unsaturated fatty acid having 8 to 22 carbon atoms) salt, sulfate ester salt, higher alkyl ether sulfate ester, sulfated oil, sulfated fatty acid ester, sulfated olefin. , Sulfonate and phosphate ester salts.

  Examples of the other component (C) include anionic surfactants, amphoteric surfactants, cationic surfactants and nonionic surfactants described in US Pat. No. 4,331,447. It is done. Gelling agents, medicinal agents, anti-inflammatory agents, bactericides, antiseptics, UV absorbers, antioxidants, pigments and fragrances are published in 1976 by the Japan Hair Science Association, “Cosmetics Science” by Takeo Tamura. A polymer compound as a gelling agent described in p204 to 211, a disinfectant and preservative described in p185 to 196, an ultraviolet absorber described in p177 to 183, an antioxidant described in p199 to p203, p145 148, coloring agents described in 148, and fragrances described in p150 to 176.

The addition amount of monohydric alcohol, polyhydric alcohol, other anionic surfactant, amphoteric surfactant, cationic surfactant, nonionic surfactant, or water is determined by the composition for oil-based cleansing of the present invention. Preferably, it is 0 to 10%, more preferably 0 to 6%, based on the weight of the total, and the total amount of addition is preferably 0 to 20%.
The amount of each of the gelling agent, medicinal agent, anti-inflammatory agent, bactericidal agent, preservative, ultraviolet absorber, antioxidant, pigment or fragrance is preferably based on the weight of the oily cleansing composition of the present invention. It is 0 to 5%, more preferably 0 to 2%, and the total addition amount of these is preferably 0 to 10%.
Further, based on the weight of the oil-based cleansing composition of the present invention, the total amount of (C) added is preferably 0 to 30%, more preferably 0 to 15%, and particularly preferably 0 to 5%.

  The weight percent of each of (A), (B) and (C) in 100% by weight of the oily cleansing composition when the oily cleansing composition of the present invention contains other component (C) is usually , (A) 50-97%, (B) 3-50% and (C) 0-30, preferably (A) 60-95%, (B) 5-40% and (C) 0 to 15%, more preferably (A) is 75 to 90%, (B) is 10 to 25%, and (C) is 0 to 5%.

  Even if the composition for oil-based cleansing of the present invention contains other component (C), it is preferably a uniform transparent liquid at room temperature.

  The dosage form of the oil-based cleansing composition of the present invention is not particularly limited and can be used as a liquid preparation, a gel preparation, an aerosol preparation, a sheet-impregnated preparation, or the like, but is preferably a liquid preparation.

The following method is mentioned as a manufacturing method in case the composition for oil-based cleansing of this invention is a liquid formulation.
(1) A method in which a liquid oil (A) and an ether carboxylic acid type surfactant (B) are mixed in advance to prepare a uniform transparent liquid, and if necessary, other components (C) are further added and mixed.
(2) A method in which the liquid oil (A) and the ether carboxylic acid type surfactant (B) are not mixed in advance, and other components (C) and other components are mixed without any particular limitation.

In the case of a gel-form preparation, a moisture-retaining component (such as the above-mentioned polyhydric alcohol) and other water-soluble components such as anionic surfactant are added to water, and if necessary a gelling agent is added. It can be obtained by gradually adding a mixture of (A) and (B) heated to ° C. and emulsifying with a homomixer.
In the case of an aerosol formulation, dimethyl ether or the like can be used as a volatile component for aerosolization.
The sheet-impregnated preparation can be obtained by impregnating a sheet such as a non-woven fabric with the above-mentioned liquid preparation at 500% by weight or less based on the weight of the sheet.

The oil-based cleansing composition of the present invention is used as a facial cleanser for removing make-up cosmetics, and its blending composition is, for example, as follows.
Liquid oil (A) ・ Hydrocarbon (liquid paraffin etc.) 40-70%
・ Synthetic ester oil (octyl palmitate, etc.) 10-30%
・ Other oils (silicone oil, vegetable oil, etc.) 0.1-30%
Surfactant-Ether carboxylic acid type surfactant (B) 10-25%
・ Other surfactants 0-5%
Moisturizing ingredients (polyhydric alcohol, etc.) 0-10%
Fragrance 0-2%
Dye 0-2%
Preservative 0-2%
0-2% water

  The oil-based cleansing composition of the present invention is non-sticky, has little skin irritation, and can be easily washed away with water. Therefore, it can be used for massage, shaving, emollient and the like.

<Example>
EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to this. Hereinafter, “part” means “part by weight” and “%” means “% by weight”.

Production Example 1
In a stainless steel autoclave with stirring and temperature control function, 276 parts (1 mol) of “Isofall 18T” (manufactured by Sasol Olefins and Surfactants, Inc .: secondary alcohol having 16 to 20 carbon atoms) and sodium methylate 28 After charging and mixing 8 parts of a% methanol solution, the gas phase in the system was replaced with nitrogen. Then, demethanol was performed under reduced pressure (20 mmHg) at 120 ° C. for 2 hours. Next, 132 parts (3 mol) of EO was introduced at 150 ° C. so that the gauge pressure was 0.1 to 0.3 MPa. The time required for the addition polymerization of EO was 3 hours.
306 parts (0.75 mol) of the product and 140 parts (1.2 mol) of sodium monochloroacetate were charged into a glass reaction vessel equipped with stirring and temperature control, and the pressure was gradually reduced while maintaining the temperature at 50 ° C. To 75 mmHg. Thereafter, 54 parts (1.35 mol) of granular sodium hydroxide was charged over 2 hours while dehydrating under reduced pressure. Further aging was performed for 6 hours. 350 parts of water was added, acidified with 148 parts of 35% hydrochloric acid, stirred for 30 minutes, allowed to stand for 3 hours, and separated to discard the lower solution containing by-product salt. At 60 ° C., 62 parts (0.75 mol) of a 48.5% aqueous sodium hydroxide solution was gradually added to neutralize, and then dehydrated under reduced pressure until the water content reached 0.5%. Ethylene (average added mole number of EO = 3 mole) alkyl (residue of a secondary alcohol having 16 to 20 carbon atoms) sodium acetate (B1) was obtained.

Production Example 2
In the same manner as in Production Example 1, except that the amount of EO charged was 220 parts (5 mol) and that of the EO adduct used for carboxymethylation was 372 parts (0.75 mol), polyoxyethylene ( Average number of moles of EO added = 5 moles) Alkyl (residue of secondary alcohol having 16 to 20 carbon atoms) sodium acetate (B2) was obtained.

Production Example 3
In the same manner as in Production Example 1, except that the amount of EO charged was 352 parts (8 mol) and the amount of EO adduct used for carboxymethylation was 471 parts (0.75 mol), polyoxyethylene ( Average addition mole number of EO = 8 moles) Alkyl (residue of secondary alcohol having 16 to 20 carbon atoms) sodium acetate (B3) was obtained.

Production Example 4
218 parts (1 mol) of “Diadol 45” (Mitsubishi Chemical Corporation: oxoalcohol having 14 and 15 carbon atoms) instead of “Isofall 18T”, and charged amount of EO adduct used for carboxymethylation Polyoxyethylene (average number of moles of EO added = 5 moles) alkyl (residue of oxo alcohol having 14 or 15 carbon atoms) acetic acid except that 329 parts (0.75 mole) was used. Sodium (B4) was obtained.

Comparative product 1
An anionic surfactant “Burelite ECA” [polyoxyethylene tridecyl ether sodium acetate (number of oxyethylene groups = 3.5): manufactured by Sanyo Chemical Industries, Ltd.] was used as Comparative Product 1.

Comparison product 2
Nonionic surfactant “EMALEX 600di-ISEX” [polyoxyethylene diisostearic acid (number of oxyethylene groups = 12): manufactured by Nippon Emulsion Co., Ltd.] was used as Comparative Product 2.

Comparison product 3
Nonionic surfactant “Rhedol 430V” [polyoxyethylene sorbite tetraoleate (number of oxyethylene groups = 30): manufactured by Kao Corporation] was designated as Comparative product 3.

Examples 1-6, Comparative Examples 1-7
(B1) to (B4) obtained in the above production examples and comparative products 1 to 3 are shown in Table 1 or Table 2, and liquid paraffin and octyl palmitate as liquid oil are shown in Table 1 or Table 2. An oil-based cleansing composition was prepared by blending the indicated parts.

  About each oil-based cleansing composition of Examples 1-6 and Comparative Examples 1-7 Appearance at 0 ° C. and 25 ° C., skin irritation, odor, ease of washing off, refreshing feeling after washing, emulsification with water, washing The force was evaluated by the following test method. The results are shown in Tables 1 and 2.

<Appearance evaluation>
Each oil-based cleansing composition was prepared, and the appearance after standing for 24 hours at 0 ° C. and 25 ° C. was observed with the naked eye, and evaluated according to the following criteria.
Evaluation criteria ○: Transparent liquid △; Some turbidity / slight separation tendency ×; Extremely turbid / separation

<Evaluation of skin irritation>
Each oil-based cleansing composition was prepared, and a human patch test (closed, 48 hours, upper arm inner side) by 5 males and 5 females was performed, evaluated according to the following criteria, and represented by the total score.
Evaluation criteria No reaction (erythema); 3 points Very mild erythema; 2 points Clear erythema; 1 point Intense erythema; 0 points

<Evaluation of odor, ease of washing, and freshness after washing>
After 20 foundations applied the foundation to the entire face and dried for about 30 minutes, 3 mL of each cleansing composition was taken in hand and stretched over the entire face using fingers to blend well with the foundation. Rinse with hot water. The odor, ease of washing, and freshness after washing were expressed by the following scoring criteria and evaluated by the average score of 20 people.
Odor scoring standards Odorless; 5 points Almost odorless; 4 points Slightly odorous; 3 points Odors present; 2 points Strong odors; 1 point Easier to wash off, refreshing feeling after washing Very good; 5 points Good; 4 points Normal; 3 points Bad; 2 points Very bad; 1 point

<Evaluation of emulsification with water>
1 g of each oil-based cleansing composition and 19 g of water were placed in a 50 mL screw tube, shaken and mixed for 30 seconds, the appearance after standing for 1 hour was observed with the naked eye, and evaluated according to the following criteria.
Evaluation criteria ○; Uniformly milky white (good emulsification)
Δ: Uniform but lightly cloudy (slightly emulsified)
×: Not uniform, oil droplets are separated (emulsified)

<Evaluation of cleaning power>
Makeup (lip color red, 50 mg / 4 cm ² ) was uniformly applied to the forearm and dried at room temperature for 5 minutes. Then, 1.0 g of each cleansing composition was applied to the entire application part for about 30 seconds using a finger in the same manner as a normal makeup remover, and then rinsed off without rubping with 35 ° C. tap water, and the makeup after drying. The residual rate was determined and the cleaning power was evaluated according to the following criteria. The makeup remaining rate is determined by measuring the color before and after applying the lip color using a spectrophotometer (Spectro Photometer SD5000, manufactured by Nippon Denshoku) and after using the cleansing composition, and obtaining the detergency from formula (3). It was.
Detergency (%) = 100 − [(E ₂ −E ₀ ) / (E ₁ −E ₀ )} × 100
E ₀ ; Color before applying lip color E ₁ ; Color after applying lip color E ₂ ; Color after using cleansing material

  As can be seen from Table 1, excellent evaluation results were obtained in Examples 1 to 7 which are the compositions of the present invention.

  The oil-based cleansing composition of the present invention can be suitably used as a facial cleanser for removing makeup cosmetics such as foundations and lipsticks.

Claims (5)

Based on the weight of the composition for oil-based cleansing, 50 to 97% by weight of the liquid oil (A) and 3 to 50% by weight of the ether carboxylic acid type surfactant (B) represented by the general formula (1) are contained. An oil-based cleansing composition characterized by the above.
_{^{R 1 O- (AO) k -R}} 2 COOM (1)
[Wherein, R ¹ is a linear or branched aliphatic hydrocarbon group having 15 to 24 carbon atoms or an alicyclic hydrocarbon group having 8 to 24 carbon atoms; R ² is an alkylene group having 1 to 3 carbon atoms; A Is an alkylene group having 2 to 12 carbon atoms; k is the average number of moles of (AO) and is 1 to 20; M represents one or more selected from a hydrogen atom and a cation. ] The composition for oil-based cleansing according to claim ^1, wherein R ¹ in the general formula (1) is a branched aliphatic hydrocarbon group having 15 to 24 carbon atoms. In the general formula (1) A is an ethylene group, according to claim 1 or 2 oleaginous cleansing composition according R ² is a methylene group. The composition for oil-based cleansing according to any one of claims 1 to 3, wherein 0.1 to 40 mol% of M in the general formula (1) is a hydrogen atom and 60 to 99.9 mol% is a cation. In addition, monohydric alcohols, polyhydric alcohols, amphoteric surfactants, cationic surfactants, nonionic surfactants, other anionic surfactants, gelling agents, medicinal agents, anti-inflammatory agents, bactericides, antiseptics The composition for oil-based cleansing in any one of Claims 1-4 containing 1 or more types of components chosen from the group which consists of an agent, a ultraviolet absorber, antioxidant, a pigment | dye, a fragrance | flavor, and water.