EP3849498A1

EP3849498A1 - Multi-layered cleansing composition

Info

Publication number: EP3849498A1
Application number: EP18773877.8A
Authority: EP
Inventors: Hiroko Tsuda; Chihiro Ueyama; Siyarat DILOKPHONGYOTIN; Thanawon CHAISONTIKULWAT
Original assignee: Kao Corp
Current assignee: Kao Corp
Priority date: 2018-09-10
Filing date: 2018-09-10
Publication date: 2021-07-21
Also published as: TW202017557A; JP2022508452A; JP7245912B2; WO2020053945A1; CN112702988A; TWI730390B; CN112702988B

Abstract

A multi-layered cleansing composition capable of removing a stubborn makeup cosmetic such as waterproof mascara, giving a non-oily feeling during wiping and a non-sticky feeling immediately after use. A multi-layered cleansing composition comprising the following compornent (A) to (E): (A) from 0.003 to 0.3 mass% of a polymer comprising a monomer chosen from (a1), (a2) and (a3): (a1) a monomer chosen from acrylic acid and methacrylic acid, (a2) a monomer chosen from alkyl ester acrylate and alkyl ester methacrylate, and (a3) a monomer chosen from polyoxyethylene alkyl ester of acrylic acid and polyoxyethylene alkyl ester of methacrylic acid, (B) from 5 to 40 mass% of an oil agent, (C) from 0.01 to 1.5 mass% of a nonionic surfactant, (D) from 0.005 to 0.9 mass% of one or more chosen from (d1) a water-soluble salt and (d2) an acid and (E) water.

Description

MULTI-LAYERED CLEANSING COMPOSITION

The present invention relates to a multi-layered cleansing composition.

Recently, a skin cleansing sheet where a liquid skin cleaning agent is impregnated in nonwoven and a skin cleansing agent which is to be impregnated in cotton etc. in use have been developed, because they do not require rinsing after use and thus they may remove a makeup cosmetic regardless of place or time. There are two types in the cleansing sheet/composition: one is a surfactant-based type containing a surfactant as a cleansing base, by which a makeup cosmetic is removed with the surfactant after emulsification (see PTL1), and the other is an oil-based type containing an oil agent as a cleansing base, by which a makeup cosmetic is removed by dissolving in oil (see PTL2).

The surfactant-based type contains very little oil, and it provides a fresh feeling during wiping, but it was difficult to remove waterproof mascara containing stubborn components firmly adhering to the skin, such as polymeric silicone and an oily film-former. The oil-based type has excellent cleansability against a makeup cosmetic such as waterproof mascara, but it may give an oily feeling during wiping and there remains stickiness on the skin immediately after use (wiping).

Recently, among the oil-based type, a skin cleaning agent for wiping with a reduced oily feeling during wiping has been proposed. For example, a bi-layered composition consisting of an aqueous layer and an oil layer, which is shaken upon use and impregnated in a pad for wiping (see PTL3) and an emulsified skin cleansing composition which a low-viscosity oil agent is dispersed by emulsification have been proposed (see PTL4).

(PTL1) Japanese Laid-open Patent Publication No. 2011-37782
(PTL2) Japanese Laid-open Patent Publication No. 1995-223922
(PTL3) Japanese Laid-open Patent Publication No. 2004-285047
(PTL4) Japanese Laid-open Patent Publication No. 2014-218437

The present invention relates to the following [1] and [2].
[1] A multi-layered cleansing composition comprising the following component (A) to (E).(A) from 0.003 to 0.3 mass% of a polymer comprising a monomer chosen from (a1), (a2) and (a3):
(a1) a monomer chosen from acrylic acid and methacrylic acid,
(a2) a monomer chosen from alkyl ester acrylate and alkyl ester methacrylate, and
(a3) a monomer chosen from polyoxyethylene alkyl ester of acrylic acid and polyoxyethylene alkyl ester of methacrylic acid,
(B) from 5 to 40 mass% of an oil agent,
(C) from 0.01 to 1.5 mass% of a nonionic surfactant,
(D) from 0.005 to 0.9 mass% of one or more chosen from (d1) a water-soluble salt and (d2) an acid, and
(E) water.

[2] A method for manufacturing a multi-layered cleansing composition according to [1], comprising the following steps 1 to 3:
(step 1) mixing component (A), component (B) and component (E) to give a mixture 1,
(step 2) adding component (C) to the mixture 1 to give a mixture 2, and
(step 3) adding component (D) to the mixture 2.

Detailed Description of Invention

Even if the bi-layered composition described in PTL3 is brought to a uniform emulsion by shaking, it may be substantially separated out to an aqueous layer and an oil layer when impregnated in cotton, a large amount of oil agent directly contacts the skin, by which a user may feel oily during wiping. Regardless of mixing by shaking, the composition is quickly brought back to a bi-layered state, when left to stand for a short while. It forces a user to shake the composition frequently, which is quite bothersome.

Regarding the skin cleansing composition described in PTL4, though it is a cleansing composition which imparts a fresh feeling during use and exerts high cleansability against stubborn makeup cosmetic such as waterproof mascara, it has relatively high viscosity (1,000 mPa・s or more at 30℃) because it is a polymer-based emulsion. Therefore, it requires a whole day or a certain physical force for the composition to be impregnated in cotton, which is unsuitable for wiping.

The present inventors endeavored to develop a cleansing composition which has an optimal physical property for impregnation in cotton, exerts a high cleansability against a makeup cosmetic which may be used without giving an oily feeling during wiping and a sticky feeling immediately after use. As a result, the present inventors have found that a combination of a specific polymer, an oil, a nonionic surfactant, water in a specific ratio, and further a water-soluble salt or an acid, renders a multi-layered cleansing composition which is easy to impregnate in a wiping material such as cotton or nonwoven, does not cause the skin to feel oily during wiping and to feel sticky immediately after use, and may remove a stubborn makeup cosmetic such as waterproof mascara, to complete the present invention.

While the multi-layered cleansing composition of the present invention contains a large amount of an oil agent in a polymer-based emulsion, it may be quickly impregnated in a wiping material such as cotton. Additionally, the multi-layered cleansing composition is uniformly mixed such as by shaking and impregnated in a wiping material for use, then it is possible to remove a stubborn makeup cosmetic such as waterproof mascara. Moreover, the composition does not cause the skin to feel oily during wiping and to feel sticky immediately after use, and the user may realize a skin fresh feeling after use. What is more, once the composition is uniformly mixed, the composition may retain a uniform emulsion while the user is using the multi-layered cleansing composition of the present invention and saves the user re-shaking during changing wiping materials.

In the multi-layered cleansing composition of the present invention, the oil agent goes up to the upper layer with retaining the emulsion state (an emulsion layer such as O/W) and the aqueous phase goes down to the lower layer (aqueous layer). It is what is called creaming, in which the composition is separated out to at least two layers of an emulsion layer and an aqueous layer. However, when the composition is mixed, the oil droplet (emulsified particle) may be easily redispersed uniformly. While the user is using the multi-layered cleansing composition of the present invention, it may be a uniform emulsion state having low viscosity.

In a conventional multi-layered cleansing composition which is separated out to an oil layer and an aqueous layer in a stationary state, when mixed, the oil phase and the aqueous phase are dispersed to form an emulsion. However, intensity of surface film of the oil droplets is weak because the composition needs to cause a phase separation, and the emulsion state easily collapses to separate out to an oil layer and an aqueous layer. Therefore, when the composition is impregnated in cotton, the composition is almost separated out to an oil layer and an aqueous layer immediately, where large amount of oil agent may contact the skin and the user may feel a strong oily feeling during wiping.

In contrast, in the present invention, when mixed, an oil droplet which was previously present in the emulsion layer may be dispersed uniformly in the whole composition. The intensity of surface film of the oil droplet is strong enough not to be broken in the stage of impregnation in cotton, but the oil droplet is broken by a physical force caused by wiping and a moderate amount of the oil agent is released to exert high cleansability. Therefore, when cotton impregnated with the composition is contacted with the skin, the oil agent is not released out of the oil droplet to the skin and the user feels a fresh sensation, and during wiping, an excess oil agent is not released out of the oil droplet, and suppresses an oily feeling and the user may realize a skin fresh feeling after use.

The polymer of component (A) used in the present invention contains one or more of monomer chosen from the following (a1), (a2) and (a3):
(a1) a monomer chosen from acrylic acid and methacrylic acid,
(a2) a monomer chosen from alkyl ester acrylate and alkyl ester methacrylate, and
(a3) a monomer chosen from polyoxyethylene alkyl ester of acrylic acid and polyoxyethylene alkyl ester of methacrylic acid.

The polymer of component (A) used in the present invention is adsorbed on the oil/water interface and forms an adsorption layer which prevents integration of the oil droplet. Then the oil droplet is stabilized and the oil agent is dispersed in the aqueous layer. Unlike micro O/W emulsification using a low-molecular surfactant such as polyoxyethylene hydrogenated castor oil as the main emulsifying agent, the polymer of component (A) coarsely (non-uniformly) emulsifies an oil agent. Then the oil agent may be easily released out of the oil droplet by a physical force during wiping. The released oil agent dissolves a makeup cosmetic, and the composition of the present invention may exert high cleansability.

In addition, it is assumed that component (A) contributes to suppressing an oily feeling during wiping because suppressed distribution in the composition without greatly impairing the stabilizing effect of oil droplet due to the interaction with component (C) (nonionic surfactant) and component (D) (water-soluble salt or acid).

The polymer of component (A) is not particularly limited as long as the polymer contains a monomer chosen from (a1), (a2) and (a3) as the constitutional unit, and there is no limitation in the content ratio and bonding mode such as block bonding or random bonding. The polymer of component (A) may contain a monomer other than the monomer chosen from (a1), (a2) and (a3). The polymer of component (A) may be crosslinked. In terms of improving impregnation in a wiping material and improving skin fresh feeling after use, it is preferable to contain the polymer including (a1) as the constitutional unit, and it is more preferable to contain a copolymer containing (a1) and (a2) as the constitutional unit.

In the polymer of component (A), when it contains a monomer other than the monomer chosen from (a1), (a2) and (a3), the content is preferably less than 10 mol%, more preferably 5 mol% or less, and further preferably 1 mol% or less, in the total monomer.

In the monomer (a2) (alkyl ester acrylate and alkyl ester methacrylate), the alkyl of the alkyl ester may preferably be from C1 to C50, more preferably of from C1 to C40, and further preferably of from C1 to C30.

In the monomer (a3) (polyoxyethylene alkyl ester of acrylic acid and polyoxyethylene alkyl ester of methacrylic acid), the addition mol number of the polyoxyethylene is preferably from 10 to 30, and more preferably from 12 to 25. The alkyl group of the alkyl ester is preferably from C12 to C22, more preferably C18 to C22. The monomer (a3) preferably includes, for example, one or more chosen from an ester of acrylic acid and polyoxyethylene(20)stearyl ether, an ester of methacrylic acid and polyoxyethylene(20)stearyl ether, an ester of acrylic acid and polyoxyethylene(25)behenyl ether, and an ester of methacrylic acid and polyoxyethylene(25)behenyl ether.

Examples of the polymer of component (A) include the following.
Examples of the polymer containing the monomer (a1) as the constitution unit and not containing the monomers (a2) and (a3) include, polyacrylic acid, polymethacrylic acid, carboxyvinyl polymer (crosslinked polyacrylic acid; Carbopol 980, Carbopol 981, Carbopol ETD 2050 polymer, Carbopol Ultrez 10 polymer (Lubrizol Advanced Materials), acrylic acid-methacrylic acid copolymer, and the like.

Examples of the copolymer containing the monomers (a1) and (a2) and not containing the monomer (a3) as the constitutional unit include, acrylic acid-alkyl (meth)acrylate copolymer (acrylates/C10-30 alkyl acrylate crosspolymer; PEMULEN TR-1, PEMULEN TR-2, Carbopol ETD 2020 (Lubrizol Advanced Materials)), acrylates copolymer (a copolymer consisting of more than one of (C1-4) alkyl acrylate, (C1-4) alkyl methacrylate, acrylic acid and methacrylic acid); Aculyn 33 (Roam and Haas)), (acrylates/vinyl neodecanate crosspolymer)copolymer ((meth)acrylates/alkyl (meth)acrylate/vinyl neodecanoate crosspolymer; Aculyn 38 (Roam and Haas), (acrylic acid / stearyl acrylate) copolymer (described in JP 2007-238549), (acrylates/steareth-20 itaconate) copolymer (STRUCTURE 2001, STRUCTURE 3001 (Akzo Nobel N.V.)) and the like.

Examples of the copolymer containing the monomers (a1), (a2) and (a3) as the constitutional unit include, acrylates/steareth-20 methacrylate copolymer (Aculyn 22 (Roam and Haas)), acrylates/beheneth-25 methacrylate copolymer (Aculyn 28 (Roam and Haas)), acrylates/steareth-20 methacrylate crosspolymer (Aculyn 88 (Roam and Haas)), and the like.

In terms of improving cleansing speed and cleansability, suppressing oily feeling during wiping and suppressing sticky feeling immediately after use, providing skin fresh feeling after use and retaining the emulsion state even at a high-temperature storage, component (A) may include one or more chosen from carboxyvinyl polymer, acrylic acid-methacrylic acid alkyl crosspolymer, acrylates copolymer, (acrylic acid/stearyl acrylate) copolymer, (acrylates/steareth-20 methacrylate) copolymer, (acrylates/beheneth-25 methacrylate) and (acrylates/steareth-20 methacrylate) crosspolymer, more preferably one or more chosen from acrylic acid-methacrylic acid alkyl crosspolymer, (acrylates/steareth-20 methacrylate) copolymer, (acrylates/beheneth-25 methacrylate) and (acrylates/steareth-20 methacrylate) crosspolymer, further preferably one or more chosen from acrylic acid-methacrylic acid alkyl crosspolymer and (acrylates/steareth-20 methacrylate) crosspolymer.

Component (A) may be chosen from one or more of monomers (a1), (a2) and (a3) singly or in combination. In terms of improving cleansing speed, impregnation in cotton and cleansability, suppressing oily feeling during wiping, and retaining in-use emulsion state, the content of component (A) is 0.003 mass% or more, preferably 0.005 mass% or more, more preferably 0.008 mass% or more, further preferably 0.01 mass% or more, further preferably 0.03 mass% or more, 0.30 mass% or less, preferably 0.25 mass% or less, more preferably 0.18 mass% or less, further preferably 0.12 mass% or less, further preferably 0.08 mass% or less in the total composition. The content of component (A) is from 0.003 to 0.3 mass%, preferably from 0.005 to 0.25 mass%, more preferably from 0.008 to 0.18 mass%, further preferably from 0.01 to 0.12 mass%, and further preferably from 0.03 to 0.08 mass%.

Component (B) used in the present invention is an oil agent. Component (B) is not particularly limited, but in terms of providing penetration to a makeup cosmetic in or covered on skin fine structures (e.g., wrinkles, pores, rough textures), improving cleansing speed and cleansability when used for cleansing a makeup cosmetic, it is preferable to contain an oil agent having viscosity of 18 mPa・s or less at 30℃. Here, viscosity may be measured by BM-type viscometer (Tokyo Keiki Inc., TVB-10 type viscometer, measurement condition: Rotor No. 1, 60 rpm, 1 minute). Especially, when the composition of the present invention is used for cleansing a stubborn makeup cosmetic such as waterproof mascara, in terms of dissolving a makeup cosmetic, and improving cleansing speed and cleansability, the viscosity of component (B) is preferably 15 mPa・s or less, more preferably 10 mPa・s or less. In terms of suppressing dripping during use, the viscosity of component (B) is preferably 1 mPa・s or more.

In terms of maintaining excellent cleansability, suppressing an oily feeling during wiping, suppressing a sticky feeling immediately after use and improving a skin fresh feeling after use, the oil agent having viscosity of 18 mPa・s or less at 30℃ preferably contains one or more chosen from (b1) hydrocarbon oil, (b2) ether oil and (b3) silicone oil, more preferably one or more chosen from component (b1) and component (b2), and further preferably at least component (b1).

Examples of component (b1) (hydrocarbon oil having viscosity of 18 mPa・s or less at 30℃) include isoparaffin such as light isoparaffin, light liquid isoparaffin, liquid isoparaffin; isododecane, isohexadecane. Among them, in terms of improving cleansing speed and cleansability and providing a skin fresh feeling to the skin after use, those having viscosity of 10 mPa・s or less at 30℃ are preferable, it is more preferable to contain one or more chosen from liquid isoparaffin, isododecane and isohexadecane, and it is further preferable to contain one or more chosen from isododecane and isohexadecane.

The content of component (b1) is preferably 1 mass% or more, more preferably 3 mass% or more, further preferably 5 mass% or more, further preferably 10 mass% or more, further preferably 12 mass% or more, and preferably 35 mass% or less, more 30 mass% or less, further preferably 25 mass% or less, and further preferably 20 mass% or less in the total composition. The content of component (b1) is preferably from 1 to 35 mass%, more preferably from 3 to 35 mass%, more preferably from 5 to 35 mass%, further preferably from 10 to 30 mass%, further preferably from 12 to 25 mass%, and further preferably from 12 to 20 mass% in the total composition.

Examples of component (b2) (ether oil having viscosity of 18 mPa・s or less at 30℃), preferably include dialkyl ether, in terms of providing the skin with a non-oily feeling during wiping and suppressing a sticky feeling immediately after use. The dialkyl ether preferably consists of C2-18 alkyl, and more preferably consists of C6-16 alkyl. Specifically, dilauryl ether, dicapylyl ether, and cetyl-1,3-dimethylbutyl ether are preferable. In terms of improving cleansing speed and cleansability, dicaprylyl ether is more preferable.

The content of component (b2) is preferably 0.5 mass% or more, more preferably 1 mass% or more, and further preferably 2 mass% or more, and preferably 20 mass% or less, more preferably 15 mass% or less, and further preferably 10 mass% or less in the total composition. The content of component (b2) is preferably from 0.5 to 20 mass%, more preferably from 1 to 15 mass%, and further preferably from 2 to 10 mass% in the total composition.

Examples of component (b3) (silicone oil having viscosity 18 mPa・s or less at 30℃) include dimethylpolysiloxane (PDMS) having viscosity of 1.5 mm²/s, 2 mm²/s, 5 mm²/s, 10 mm²/s and the like; dimethylcyclopolysiloxane such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane; branched siloxane such as tris(trimethylsilyl)methylsilane, tetrakis(trimethylsilyl)silane, and the like; methylphenylpolysiloxane, and the like. Among them, in terms of providing a sensation of quick drying after cleansing and providing a skin fresh feeling after use, component (b3) is preferably one or more of dimethylpolysiloxane having viscosity of 1.5 mm²/s or 2 mm²/s, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and tris(trimethylsilyl)methylsilane, and more preferably dimethylpolysiloxane having viscosity of 2 mm²/s.

The content of component (b3) is preferably 0.5 mass%, more preferably 1 mass% or more, further preferably 2 mass% or more, and preferably 30 mass% or less, more preferably 25 mass% or less, and further preferably 20 mass% or less in the total composition. The content of component (b3) is preferably from 0.5 to 30 mass%, more preferably from 1 to 25 mass%, and further preferably from 2 to 20 mass% in the total composition.

In terms of suppressing an oily feeling during wiping and a sticky feeling immediately after use and improving a skin fresh feeling after use, all or part of components (b1), (b2) and (b3) are preferably a volatile oil which hardly remains on the skin. In the present invention, the volatile oil indicates an oil agent which evaporates in the atmosphere and has a boiling point of 300℃ or less.

Volatile oil is not particularly limited as long as it may be used in conventional cosmetics, for example, linear dimethylpolysiloxane such as dimethylpolysiloxane (1.5 mm²/s) (boiling point: 190℃), dimethylpolysiloxane (2 mm²/s) (boiling point: 230℃); branched siloxane such as tris(trimethylsilyl)methylsilane (boiling point: 191℃), tetrakis(trimethylsilyl)silane (boiling point: 267℃); volatile silicone oil such as cyclic dimethylsiloxane such as octamethylcyclotetrasiloxane (boiling point: 176℃), decamethylcyclopentasiloxane (boiling point: 210℃), dodecamethylcyclohexasiloxane (boiling point: 245℃); volatile hydrocarbon oil such as isododecane (boiling point: 177℃), isohexadecane (boiling point: 210-250℃), light isoparaffin, light liquid isoparaffin, liquid isoparaffin; dicaprylyl ether (boiling point: 291℃), dilauryl ether (boiling point 190-195℃). Especially, in terms of improving a skin fresh feeling after use and excellent cleansability, it is preferable to contain one or more chosen from hydrocarbon oil, ether oil and silicone oil having a boiling point of 150℃ or more, more preferable to contain one or more chosen from hydrocarbon oil, ether oil and silicone oil having a boiling point of 170℃ or more, and further preferably one or more chosen from dimethylpolysiloxane (2 mm²/s), isododecane, isohexadecane, tris(trimethylsilyl)methylsilane and dicaprylyl ether.

In terms of suppressing an oily feeling during wiping, suppressing a sticky feeling immediately after use and improving a skin fresh feeling after use, the content of the volatile oil in components (b1), (b2) and (b3) are preferably 30 mass% or more, more preferably 60 mass% or more, and further preferably 90 mass% or more, and preferably 100 mass% or less in the total content of component (B).

In the present invention, in terms of improving a skin moist feeling after use, the composition of the present invention may contain an oil agent other than components (b1), (b2) and (b3). Examples of the oil agent other than components (b1), (b2) and (b3) include ester oil, fatty acid, higher alcohol (C8 or higher), fluorine oil, and hydrocarbon oil, ether oil, silicone oil each having viscosity of 18 mPa・s or more at 30℃, and the like .

Examples of the ester oil, the fatty acid, the higher alcohol (C8 or higher), fluorine oil, and hydrocarbon oil, ether oil and silicone oil each having viscosity of 18 mPa・s or more at 30℃ include, isopropyl myristate (6.6 mPa・s), isopropyl palmitate (10 mPa・s), isononyl isononate (9 mPa・s), neopentyl glycol dicaprate (19 mPa・s), tri (caprylic/capric)diglyceryl (26 mPa・s), jojoba oil (46 mPa・s), olive oil (90 mPa・s), liquid paraffin (22.5 mPa・s). The numerals in the parenthesis indicate viscosity at 30℃.

In terms of retaining in-use emulsion state, improving cleansing speed, cleansability, non-oily feeling during wipe, non-sticky feeling immediately after use and providing excellent impregnation in a wiping material such as cotton, the content of component (B) (oil agent) is 5 mass% or more, preferably 8 mass% or more, more preferably 10 mass% or more and further preferably 12 mass% or more, and 40 mass% or less, preferably 35 mass% or less, more preferably 30 mass% or less and further preferably 25 mass% or less in the total composition. The content of component (B) isfrom 5 to 40 mass%, preferably from 8 to 35 mass%, more preferably from 10 to 30 mass%, further preferably from 12 to 30 mass% and further preferably from 12 to 25 mass% in the total composition.

Further, in terms of improving cleansing speed and cleansability and suppressing an oily feeling during wiping and suppressing a sticky feeling immediately after use, the total content of components (b1), (b2) and (b3) in component (B) is preferably 70 mass% or more, more preferably 80 mass% or more, further preferably 90 mass% or more, further preferably 95 mass% or more, and further preferably 99 mass% or more. It is even more preferable that component (B) consists of components (b1), (b2) and (b3).

Component (C) used in the present invention is a nonionic surfactant. The multi-layered cleansing composition of the present invention tends to impair emulsion stability because co-presence of component (A) and component (D) reduces the polymer dissociation degree in water and then lowers the thickening effect of component (A). It follows that an oil agent may be separated out from the emulsion layer being the upper layer. However, component (C), nonionic surfactant, if used, may suppress the separation of the oil agent from the emulsion layer and may keep the composition in a stabilized state. It is believed that the nonionic surfactant of component (C) contributes to quick cleansing because it maintains the oil droplet stable at a low amount while retaining low viscosity by the interaction with the polymer of component (A) and component (D), and that component (C) improves impregnation in a wiping material and the composition penetrates to a makeup cosmetic in or covered on skin fine structures.

In terms of retaining the emulsion state at high-temperature storage, maintaining the skin fresh feeling till after use, and improving cleansing speed and cleansability, component (C) (nonionic surfactant) may preferably have HLB of 2 or more, more preferably 8 or more, further preferably 10 or more, further preferably 11 or more, further preferably 12 or more and preferably 20 or less, more preferably 18 or less, further preferably 16 or less, further preferably 14 or less, and further preferably 13.8 or less. Component (C) may preferably have HLB of from 2 to 20, more preferably from 8 to 18, further preferably from 10 to 16, further preferably from 11 to 14, further preferably from 12 to 13.8.

Here, the HLB (hydrophilic-lipophilic balance) represents the molecular weight of hydrophilic moiety in the total molecular weight of the surfactant. For nonionic surfactant, the HLB value at 25℃ as defined by GRIFFIN is employed. The HLB value by GRIFFIN is defined in J. Soc. Cosm. Chem., 1954, 5: 249-256. When multiple nonionic surfactants are used, HLB is that of a surfactant mixture consisting of multiple nonionic surfactants. The HLB of surfactant mixture may be given by arithmetic means according to the following equation on the basis of the content ratio of each nonionic surfactant.

in which HLBx represents an HLB of a nonionic surfactant X and Wx represents a mass weight (g) of the nonionic surfactant X having the HLBx value.

Examples of component (C) (nonionic surfactant) may include, for example, polyglycerin fatty acid ester, polyethyleneglycol fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene polyoxypropyleneglycol, polyoxyethylene sorbitan fatty acid ester,
polyoxyethylene sorbitol fatty acid ester, polyoxyethylene castor oil,
polyoxyethylene hydrogenated castor oil, polyoxyethylene hydrogenated castor oil fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkyl ether fatty acid ester, sucrose fatty acid ester,
sorbitan fatty acid ester, alkyl polyglycoside, (poly)alkyl glyceryl ether, and the like.

Among them, in terms of low stimulus against skin or mucosa, improving emulsion retention and providing an excellent freshness during wiping, it is preferable to contain one or more nonionic surfactant chosen from polyglycerin fatty acid ester, polyethyleneglycol fatty acid ester, polyoxyethylene glycerol fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene hydrogenated castor oil, sucrose fatty acid ester and sorbitan fatty acid ester; more preferable to contain one or more nonionic surfactant chosen from polyglycerin fatty acid ester, polyethyleneglycol fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and polyoxyethylene hydrogenated castor oil; further preferable to contain one or more nonionic surfactant chosen from polyglycerin fatty acid ester and polyoxyethylene hydrogenated castor oil.

Component (C) may be used singly or in combination of two or more. In terms of suppressing an oily feeling during wiping, retaining in-use emulsion stability, and providing an excellent cleansing speed, the content of component (C) is 0.01 mass% or more, preferably 0.05 mass% or more, and further preferably 0.1 mass% or more in the total composition. In terms of not interfering with oil releasability and maintaining cleansability, the content of component (C) is 1.5 mass% or less, preferably 1.0 mass% or less, more preferably 0.8 mass% or less, and further preferably 0.45 mass% or less in the total composition. The content of component (C) is from 0.01 to 1.5 mass%, preferably from 0.05 to 1.0 mass%, more preferably from 0.05 to 0.8 mass%, and further preferably from 0.1 to 0.45 mass% in the total composition.

Component (D) used in the present invention may include one or more component chosen from component (d1) a water-soluble salt and component (d2) an acid. Component (D) may reduce viscosity of the emulsion containing components (A), (B) and (C), thus achieving high impregnation in a wiping material such as cotton. Among them, it is preferable to employ component (d2) which may reduce viscosity of the emulsion to avoid an oily feeling, with less amount than component (d1).

Among component (D), component (d1) (water-soluble salt) is a salt which is soluble in water, and is preferably a salt which becomes acidic or neutral in 1 mass% of aqueous solution at 25℃. For example, sodium chloride, potassium chloride, calcium chloride, magnesium chloride, sodium sulfate, potassium sulfate, magnesium sulfate, calcium sulfate, disodium EDTA, sodium hydrogen sulfate, potassium hydrogen sulfate, sodium dihydrogen phosphate, and potassium dihydrogen phosphate may be preferably used.

Among component (D), component (d2) (acid) includes an organic acid or an inorganic acid. Both the organic acid and the inorganic acid may be used, and an organic acid is preferable in terms of imparting an antiseptic effect to the emulsion. One or more of organic acid chosen from hydroxycarboxylic acid and dicarboxylic acid is more preferable, and one or more organic acid chosen from dicarboxylic acid is further preferable. Examples of the hydroxycarboxylic acid include glycolic acid, lactic acid, glyceric acid, gluconic acid, pantothenic acid, and citric acid. Examples of the dicarboxylic acid include malic acid, oxalic acid, malonic acid, maleic acid, succinic acid, gluraric acid, and adipic acid.

In term of improving cleansing speed, cleansability, suppressing oily feeling during wipe, retaining in-use emulsion state and providing excellent impregnation of the composition in wiping material, the content of component (D) (total content of component (d1) and component (d2)) is preferably 0.005 mass% or more, more preferably 0.010 mass% or more, and further preferably 0.012 mass% or more, and further preferably 0.018 mass% or more, and preferably 0.9 mass% or less, more preferably 0.8 mass% or less, and further preferably 0.7 mass% or less, and further preferably 0.6 mass% or less in the total composition. The content of component (D) is preferably from 0.005 to 0.9 mass%, more preferably from 0.010 to 0.8 mass%, further preferably from 0.012 to 0.7 mass% and further preferably from 0.018 to 0.6 mass% in the total composition.

When component (D) consists component (d1) (water-soluble salt), in terms of suppressing gelification of the emulsion, retaining in-use emulsion state and suppressing an oily feeling, the content of component (d1) is preferably 0.03 mass% or more, more preferably 0.05 mass% or more, further preferably 0.08 mass% or more, and preferably 0.9 mass% or less, more preferably 0.8 mass% or less, and further preferably 0.6 mass% or less in the total composition. The content of component (d1) is preferably from 0.03 to 0.9 mass%, and further preferably from 0.08 to 0.6 mass% in the total composition.

When component (D) consists component (d2) (acid), in terms of suppressing gelification of the emulsion, retaining in-use emulsion state and suppressing an oily feeling, the content of component (d2) is preferably 0.012 mass% or more, more preferably 0.013 mass% or more, further preferably 0.018 mass% or more, and preferably 0.5 mass% or less, more preferably 0.3 mass% or less, and further preferably 0.12 mass% or less in the total composition. The content of component (d2) is preferably from 0.012 to 0.5 mass%, more preferably from 0.013 to 0.3 mass%, and further preferably from 0.018 to 0.12 mass% in the total composition.

When the composition of the invention contains component (d2) acid as component (D), in terms of reducing viscosity of emulsion upon being mixed, providing excellent impregnation of the composition in a wiping material such as cotton, improving cleansing speed, cleansability and reducing stimulus against the skin, the pH of the composition of the present invention is preferably 3.0 or more, more preferably 4.0 or more, and preferably 6.0 or less, and more preferably 5.5 or less. When the composition of the invention does not contain component (d2) acid as component (D), from the same viewpoint as above, the pH of the composition of the present invention is preferably 4.0 or more, more preferably 5.0 or more, and preferably 7.0 or less, and more preferably 6.5 or less. Note that pH measurement may be conducted with a pH meter (Horiba, Ltd., model number: F-22), using a composition which was stored in a vertical position on its bottom in an isothermal bath at 30℃ for 2 hours or more, subsequently shaken up and down 15 times (shaking stroke length: 15 cm; shaking speed of 5 reciprocal motions per 3 seconds), and immediately afterwards (measurement started 10 seconds after the shaking was stopped).

Component (E) used in the present invention is water. Component (E) may include tap water, purified water (including filtered water through ion-exchange resin), spa water, distilled water (including plant-derived distilled water such as rose water and lavender water), mineral water, one or more of which may be used appropriately. In terms of maintaining excellent cleansability and improving a skin fresh feeling after use, the content of component (E) is preferably 25 mass% or more, more preferably 30 mass% or more, 35 mass% or more, and preferably 95 mass% or less, 90 mass% or less, and 85 mass% or less in the total composition. The content of component (E), water, is preferably from 25 to 95 mass%, more preferably from 30 to 90 mass%, and further preferably from 35 to 85 mass% in the total composition.

The multi-layered cleansing composition of the present invention may optionally comprise a component (F) (powder). Component (F) remains on the skin after the composition is wiped off and it may impart a long-lasting skin smooth feeling after use. It may even impart aesthetic appearance and/or UV protective effect. Component (F) is preferably not soluble in any of component (E) (water), component (B) (oil agent), component (G) (ethanol), or component (H) (polyol).

Component (F) (powder) is not particularly limited as long as it may be normally used in cosmetics. As inorganic powders, examples thereof include titanium oxide, zinc oxide, magnesium oxide, zirconium oxide, calcium carbonate, magnesium carbonate, magnesium silicate, barium sulfate, silica (anhydrous silicic acid), mica, talc, kaolin, sericite, rouge, yellow iron oxide, black iron oxide, carbon black, manganese violet, glass beads, zeolite, pearl pigment (rouge-coated mica, titanium oxide-coated mica, and the like), and a complex inorganic powder thereof. As organic powders, example thereof include acryl resin, styrene resin, polyolefin, silicone resin, fluoride resin, polyester resin, polyamide resin, epoxy resin, phenol resin, urethane resin; fiber powder such as silk powder, hemp fiber powder, a powder consisting of cellulose or its derivative; a sugar powder such as starch or its derivative. These may be used singly or in combination or two or more.

Specifically, talc such as SA-talc SW special (Miyoshi Kasei Inc.), talc JA-46R (Asada Milling Co., Ltd.); silica such as silica microbead P-4000, silica microbead P-1505, silica microbead P-1500, HCS 160M5, Satinier M5 (JGC Catalysts and Chemicals Ltd.), Sunsphere H-52, Sunsphere H-121, Sunsphere NP-30, Sunsphere NP-100, Sunsphere NP-200 (AGC Sitech), mica such as A-11, A21-S, AB-25S (Yamaguchi Mica Co., Ltd.); silicone resin powder such as KMP-599, KSP-100, KSP-105, KSP-300, X-52-1621 (Shin-Etsu Chemical Co., Ltd.), Tospearl 120A, Tospearl 145A (Momentive Performance Materials Japan), Torayfill E506S, Torayfill E508, BY29-129 (Toray Dow Corning), Ganz-paru AI-045C, Ganz-paru SIG-070； acryl resin powder such as Sofcare ST ((lauryl methacrylate/sodium methacrylate) crosspolymer, Kao Corporation）, Ganz-paru GMP-0800 , Ganz-paru GMP-0820 (Aica Kogyo Co., Ltd.), Matsumoto Microsphere M-201, Matsumoto Microsphere M-305, Matsumoto Microsphere M-312 (Matsumoto Yushi Seiyaku Co., Ltd.).

Among them, in terms of improving skin slipperiness and imparting an excellent skin smooth feeling after use, it is preferable to contain one or more chosen from talc, silica, mica, silicone resin powder and acryl resin powder, more preferable to contain one or more chosen from silica, silicone resin powder and acryl resin powder, and further preferable to contain one or more chosen from (lauryl methacrylate/sodium methacrylate) crosspolymer and silica.

The shape of the powder is not particularly limited, and any of spherical, rod-shaped, fusiform, needle-shaped, and amorphous form may be used. In terms of improving skin slipperiness and providing a skin smooth feeling after use at a low amount, a spherical powder is preferable. In the present invention, 'spherical' represents that, an image of a single powder projected by a smayning electron microscope is an exact circle or that the projected image has such a shape that a circumcircle of the projected image is drawn and the contour of the projected image is all included in between the concentric circle having 90% radius of the circumradius and the circumcircle.

Component (F) (powder) may have its surface hydrophilically or hydrophobically treated. Examples of the hydrophilic treatment may include silica treatment, alumina treatment, silica-alumina treatment, amino acid treatment, and polyacrylic acid treatment. Examples of the hydrophobic treatment may include an oil adsorption method subjecting the powder surface to adsorption with fat and oil; lipophilic treatment on the powder by esterification or etherification of a functional group such as a hydroxy group, metal soap treatment using a zinc salt, a magnesium salt or an aluminum salt of fatty acid; silicone treatment using a silicone compound such as dimethylsiloxane or methyl hydrogen siloxane; fluorine treatment such as treatment with a fluorine compound having a perfluoroalkyl group. A combination of a hydrophilically treated powder and a hydrophobically treated powder may be formulated in the multi-layered cleansing composition of the present invention.

The multi-layered cleansing composition of the present invention becomes an O/W emulsion upon being mixed, and it is preferable to use a hydrophilic powder which is easily dispersible in water in terms of improving the dispersibility of the powder in the composition. Hydrophilicity may be determined by the following evaluation method.

(Hydrophilicity evaluation)
In a 50 mL volume glass bottle, water (10 g), hexane (10 g) and powder (1 g) are added, and the contents are mixed with the lid closed by shaking lightly. Then the glass bottle is subjected to ultrasonic processing (38 kHz) for 2 minutes and stored in a vertical position on its bottom for 5 minutes, during which the appearance is observed. The powder is determined to be hydrophilic when the powder is present in the lower phase (water phase), and hydrophobic when the powder is present in the upper phase (hexane phase), on the basis of the water/hexane interface.

When component (F) (powder) has a specific gravity higher than 1, such as an inorganic powder containing a metal ion, it is deposited and accumulates at the bottom as time elapses. When such a heavy powder is used in the composition, it is preferable that component (F) be in a combination of different particle sizes in terms of improving redispersion of the powder which is deposited at the bottom, and in terms of providing an excellent skin smooth feeling after use. It is preferable that component (F) (powder) contain both a powder having a particle size of from 0.2 to 10 μm and a powder having a particle size of more than 10 μm and 50 μm or less, and more preferable to contain both a powder having a particle size of from 2 to 7 μm and a powder having a particle size of from 15 to 30 μm. In the present invention, particle size indicates a mode diameter, which is a most frequent value in the volume-based particle size distribution. When the volume-based particle size distribution shows multiple peaks, each mode diameter may be derived from each mode of the peaks.

From the above viewpoint, the volume ratio of the powder having a particle size of from 0.2 to 10 μm to the powder having a particle size of more than 10 μm and 50 μm or less is, preferably 0.2 or more, more preferably 1.0 or more and further preferably 1.5 or more, and preferably 20 or less, more preferable 15 or less, and further preferably 10 or less.

The median diameter of the volume-based particle size of component (F) (powder) is preferably 0.2 μm or more, more preferably 1 μm or more, and further preferably 2 μm or more, and 50 μm or less, more preferably 40 μm or less, and further preferably 30 μm or less.

In the present invention, the distribution of the volume-based particle size may be measured by the following method.
(Measurement of volume-based particle size)
A water dispersion containing a powder at 10 mass% in ion-exchanged water is subjected to measurement with a condition of (refraction index: 1.45, circulation speed (scale: 5), stirring speed (scale: 5)) by Laser Scattering Particle Distribution Analyzer (Partrica LA-920, Horiba, Ltd.). Ion exchanged water is used as a solvent.

In terms of imparting a skin smooth feeling after use and aesthetic appearance of the composition and retaining the emulsion state, the content of component (F) (powder) is 0.1 mass% or more, preferably 1 mass% or more, and more preferably 3 mass% or more, and 20 mass% or less, preferably 15 mass% or less, and further preferably 12.5 mass% or less in the total composition. The content of component (F) (powder) is preferably from 0.1 to 20 mass%, more preferably from 1 to 15 mass%, and further preferably from 3 to 12.5 mass% in the total composition.

When the specific gravity of component (F) is 1 or more, in terms of providing excellent redispersibility of the powder after its sedimentation and improving a skin smooth feeling after use, the mass ratio of component (F) to component (A), [(F)/(A)] is preferably 1 or more, more preferably 10 or more, and further preferably 50 or more, and preferably 1,000 or less, more preferably 700 or less, and further preferably 500 or less. [(F)/(A)] is preferably from 1 to 1,000, more preferably from 10 to 700, and further preferably from 50 to 500.

In terms of providing a skin fresh feeling after use, the multi-layered cleansing composition of the present invention may optionally contain component (G) (ethanol).

When the multi-layered cleansing composition of the present invention contains component (G) (ethanol), in terms of suppressing an oily feeling during wiping, suppressing a sticky feeling immediately after use and providing a skin cool feeling after use, the content of component (G) is preferably 0.1 mass% or more, more preferably 1 mass% or more, and further preferably 3 mass% or more; in terms of retaining the emulsion state, the content of component (G) ethanol is preferably 20 mass% or less, more preferably 15 mass% or less, and further preferably 10 mass% or less. The content of component (G) is from 0.1 to 20 mass%, more preferably from 1 to 15 mass% and further preferably from 2 to 10 mass% in the composition.

In terms of improving a skin moist feeling after use, the multi-layered cleansing composition of the present invention may further contain component (H) (polyol). The polyol includes a polyvalent alcohol, examples of which include divalent alcohols such as ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, isoprene glycol, propanediol, 1,3-butylene glycol, hexylene glycol; trivalent or more of alcohols such as trimethylolpropane, glycerin, diglycerin, triglycerin, tetraglycerin, hexaglycerine, decaglycerin, polyglycerin (sugars and sugar alcohols are excluded); sugars or sugar alcohols such as erhthritol, pentaerhthritol, dipentaerhthritol, glucose, mannose, galactose, sucrose, fructose, maltose, maltitol, xylitol, inositol, sorbitan, sorbitol, polyoxyethylene methyl glycoside, and the like. Among them, in terms of suppressing a sticky feeling immediately after use and improving a skin moist feeling after use, component (H) is preferably one or more selected from the group consisting of ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol, polypropyleneglycol, propanediol, glycerin 1,3-butyleneglycol, sorbitol, polyoxyethylenemethyglycoside, and maltitol, more preferably one or more selected from the group consisting of ethyleneglycol, diethyleneglycol, propyleneglycol, dipropyleneglycol, polyethyleneglycol, polypropyleneglycol, propanediol, polyoxyethylenemethyglycoside, and 1,3-butyleneglycol, further preferably one or more selected from the group consisting of propyleneglycol, dipropyleneglycol, 1,3-butyleneglycol, propanediol, and polyoxyethylene methyl glycoside.

Component (H) (polyol) may be used singly or in combination of two or more. In terms of suppressing an oily feeling during wiping, suppressing a sticky feeling immediately after use and improving a skin moist feeling after use, the content of component (H) polyol is 0.1 mass% or more, preferably 0.5 mass% or more, more preferably 1 mass% or more, and 20 mass% or less, preferably 15 mass% or less, and more preferably 10 mass% or less in the total composition. The content of component (H) is preferably from 0.1 to 20 mass%, more preferably from 0.5 to 15 mass%, and further preferably from 1 to 10 mass%.

In terms of improving cleansing speed, clensability, impregnation in cotton, suppressing an oily feeling during wiping, a sticky feeling after use, providing an excellent fresh feeling after use and retaining in-use emulsion state, the mass ratio of component (A) to component (B), [(A)/(B)] is preferably 0.0001 or more, more preferably 0.0005 or more, and further preferably 0.001 or more, and preferably 0.01 or less, more preferably 0.008 or less and further preferably 0.007 or less. [(A)/ (B)] is preferably from 0.0001 to 0.1, more preferably from 0.0005 to 0.008 and further preferably from 0.001 to 0.007.

In terms of improving cleansing speed, cleansability, suppressing an oily feeling during wiping, a sticky feeling after use, providing an excellent skin fresh feeling after use and retaining in-use emulsion state, the mass ratio of component (A) to component (C), [(A)/(C)] is preferably 0.001 or more, more preferably 0.005 or more, further preferably 0.01 or more, further preferably 0.03 or more, further preferably 0.08 or more, and further preferably 0.15 or more, and preferably 2.0 or less, more preferably 1.5 or less, further preferably 1.0 or less and further preferably 0.7 or less. [(A)/(C)] is preferably from 0.001 to 2.0, more preferably from 0.005 to 2.0, further preferable from 0.01 to 1.5, further preferable from 0.03 to 1.5, further preferable from 0.08 to 1.0, and further preferably from 0.15 to 0.7.

In terms of suppressing aggregation of component (A), improving impregnation of the composition to cotton, cleansing speed, cleansability, suppressing an oily feeling during wiping, a sticky feeling after use, providing an excellent skin fresh feeling after use and retaining in-use emulsion state, the mass ratio of component (A) to component (D), [(A)/(D)] is preferably 0.05 or more, more preferably 0.1 or more, and further preferably 0.2 or more, and preferably 20 or less, more preferably 10 or less, and further preferably 5 or less. [(A)/(D)] is preferably from 0.05 to 20, more preferably from 0.1 to 10, and further preferably from 0.2 to 5.

In terms of improving cleansing speed, cleansability, impregnation of the composition to cotton, suppressing an oily feeling during wiping, a sticky feeling after use, providing an excellent skin fresh feeling after use, retaining in-use emulsion state and improving a stability of emulsion at high , the mass ratio of component (C) to component (D), [(C)/ (D)] is preferably 0.2 or more, more preferably 0.3 or more, and further preferably 0.4 or more, and preferably 30 or less, more preferably 20 or less, further preferably 15 or less and further preferably 7 or less. [(C)/(D)] is preferably from 0.2 to 30, more preferably from 0.3 to 20, further preferably from 0.4 to 15, and further preferably from 0.4 to 7.

The multi-layered cleansing composition of the present invention may, in addition to the above components, further contain optional components which may be normally formulated in cleansing compositions, as long as they do not interfere with the technical effect of the present invention. For example, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a disinfecting agent, an anti-inflammatory agent, an antiperspirant, a preserving agent, a chelating agent, a salt, a pearling agent, a perfume, a cooling agent, a pigment, an ultraviolet absorbing agent, an antioxidant, a plant extract, and the like may be used. These optional components may be used for not only the intended purpose but also for other purposes (for example, an antiperspirant may be used as a perfume) or in combination with multiple purposes (for example, an agent may function as both an antiperspirant and a perfume).

In terms of providing a skin fresh feeling after use, the multi-layered cleansing composition of the present invention may contain an anionic surfactant. In terms of maintaining excellent cleansability and suppressing stimulus on the skin, the content of the anionic surfactant is preferably 1 mass% or less, more preferably 0.5 mass% or less, further preferably 0.1 mass% or less, and further preferably 0 mass% in the total composition.

In terms of improving a skin moist feeling after use, the multi-layered cleansing composition of the present invention may contain a cationic surfactant and/or amphoteric surfactant. In terms of maintaining excellent cleansability, suppressing an oily feeling during wiping and suppressing a sticky feeling immediately after use, the total content of the cationic surfactant and amphoteric surfactant is preferably 1 mass% or less, more preferably 0.5 mass% or less, further preferably 0.1 mass% or less, and further preferably 0 mass% in the total composition.

In terms of improving light resistance, the multi-layered cleansing composition of the present invention may further contain an ultraviolet absorbing agent. In terms of maintaining excellent cleansability and improving a skin fresh feeling after use, the content of the ultraviolet absorbing agent is preferably 1 mass% or less, more preferably 0.5 mass% or less, further preferably 0.1 mass% or less, and further preferably 0.05 mass% or less in the total composition.

In the manufacture of the multi-layered cleansing composition of the present invention, if component (A) exerts thickening effect by neutralization, then, it is preferable to add component (K) (alkaline neutralizing agent) after component (A) is dispersed in component (E) (water). In the present invention, the term alkaline neutralizing agent represents a substance which is capable of receiving proton from another substance (i.e., proton receptor). Adding component (K) after component (A) is dispersed in component (E) thickens hydrogel by component (A). In the course of thickening, component (B) (oil agent) is taken in by a hydrogel, causing the oil agent to be emulsified coarsely.

Among the polymer of component (A), examples of polymers providing a thickening effect by neutralization include a polymer containing the monomer (a1) as the constitution unit. Examples of polymers containing the monomer (a1) as the constitution unit are as described hereinbefore.

Examples of component (K) (alkaline neutralizing agent) may include an inorganic alkali compound, an organic amine compound, and a basic amino acid. Specifically, an inorganic alkali compound such as sodium hydroxide, potassium hydroxide; an organic amine compound such as (mono, di, tri)ethanolamine, (mono, di, tri)isopropanolamine, 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-hydroxymethyl-1,3-propanediol; a basic amino acid such as arginine, lysine, histidine may be used. Among them, it is preferable to employ one or more chosen from sodium hydroxide, potassium hydroxide, triethanolamine, 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1,3-propanediol, 2-amio-2-methyl-1,3-propanediol and arginine. The content of component (K) may be an amount sufficient for component (A) to exert its performance, preferably an amount to correspond to neutralization ratio of component (A) of from 0.3 to 1.2 and more preferably an amount to correspond to the neutralization ratio of from 0.4 to 1.1.

(Manufacturing Method)
The multi-layered cleansing composition of the present invention may be manufactured by mixing each component in a routine method. When the composition contains a solid material at a normal temperature, the solid material may be preheated to melt or dissolved in another component, and subsequently all the components may be uniformly mixed to manufacture.

When component (A) (polymer), component (B) (oil agent), and component (E) (water) are mixed, component (A) is adsorbed on the oil-water interface and an adsorption layer is formed, which prevents integration of the oil droplets. Then the oil droplets are stabilized. However, the emulsified composition with component (A) relatively tends to increase viscosity, and the composition is often hard to be impregnated in a wiping material such as cotton. However, adding component (D) ((d1) water-soluble salt or (d2) acid) may interfere with hydrated gel formation and then reduce viscosity, but it may cause polymer aggregation and oil agent may be eluted out of the oil droplets. To address this, in the present invention, component (C) (nonionic surfactant) is added to an emulsion having been pre-emulsified with component (A) prior to adding component (D). Owing to this, the polymer may retain emulsion state and suppress polymer aggregation after component (D) is added. The composition may release oil agent during wiping and may exert high cleansability of a makeup cosmetic.

For polymer of component (A) which exerts a thickening effect by neutralization, component (A) contains at least a carboxylic acid such as acrylic acid or methacrylic acid. These polymers are neutralized with component (K) (alkaline neutralizing agent) in a mixture with component (E) (water) to form a hydrogenated gel, to exert a thickening effect. In the course of thickening, when component (B) (oil agent) is present, the oil agent is captured in the hydrogenated gel, leading to coarsely emulsifying the oil agent. However, thus emulsified state caused by component (A) may increase the viscosity of the composition, which may impair impregnation in a wiping material such as cotton. Therefore, as described in the above manufacturing method, by adding component (C) (nonionic surfactant) to the emulsion pre-emulsified with component (A) prior to adding component (D), the state where polymer coarsely emulsify the oil agent may be retained and aggregation of the polymer may be suppressed after component (D) is added. During wiping, the composition releases an oil agent to exert high cleansability of a makeup cosmetic.

Regarding a specific method for manufacturing, component (A) (polymer), component (B) (oil agent), component (E) (water) and optional component (K) (alkaline neutralizing agent) and further optionally other optional components are mixed (and neutralized) to give a mixture 1. Next, to the mixture 1, component (C) (nonionic surfactant) and optionally a surfactant other than component (C) are added to give a mixture 2. Mixing the mixture 2 and component (C) may suppress aggregation of oil droplets. Subsequently, to the mixture 2, component (D) (component (d1) (water-soluble salt) or component (d2) (acid)) is added to give the composition of the present invention. The obtained composition may achieve low viscosity while maintaining oil droplets, and therefore it provides excellent impregnation in a wiping material such as cotton and even achieves an excellent cleansing effect and usability.

The manufacturing method of the multi-layered cleansing composition more specifically includes
(step 1) mixing component (A), component (B) and component (E), and optionally component (K) alkaline neutralizing agent, and further optionally the other optional components, to give a mixture 1,
(step 2) adding component (C) to the mixture 1, optionally a surfactant other than component (C), to give a mixture 2, and
(step 3) adding component (D) to the mixture 2.

(Viscosity)
The viscosity of the multi-layered cleansing composition of the present invention is 100 mPa・s or less at 30℃ immediately after shaking 15 times (stroke length: 15 cm, at a speed of 5 reciprocal motions per 3 seconds) where measurement is started 10 seconds after the shaking is suspended. The condition for the measurement of viscosity is as follows. In terms of suppressing dripping of the composition during use out of the hand and providing excellent permeability in cotton, the viscosity at 30℃ immediately after stirring is preferably 50 mPa・s or less, more preferably 30 mPa・s or less, and further preferably 25 mPa・s, and preferably 1 mPa・s or more, more preferably 3 mPa・s or more, and further preferably 5 mPa・s or more. The viscosity at 30℃ immediately after stirring is preferably from 1 to 50 mPa・s, more preferably from 3 to 30 mPa・s, and further preferably from 5 to 25 mPa・s.

(Layers)
In a stationary state, the multi-layered cleansing composition is separated in at least two layers including an emulsion layer and an aqueous layer. The multi-layered cleansing composition may have more than two layers. For example, the composition may contain component (F) (powder) to be a tri-layered composition consisting of an emulsion layer, an aqueous layer and a powder layer. The composition may further contain an oil which is non-miscible with the emulsion layer (such as a fluorine-based oil agent such as perfluoropolymethylisopropyl), which is different from component (B), to form a tri-layered composition consisting of an emulsion layer, an aqueous layer and an oil layer. A pigment and/or a dye may be added to each of the layers to beautify the appearance, by which a user may enjoy the color change in the course of mixing. In terms of aesthetics, it is preferable that the appearance evaluation of the composition of the present invention be unchanged for 24 hours in a stationary state.

(Method for Use)
A user may use the multi-layered cleansing composition of the present invention after converting to a uniform emulsion by mixing. Means for mixing include shaking for several times. Specifically, a user may grasp a container containing the multi-layered cleansing composition and shake the container up and down by hand with 15 cm of stroke length from 1 to 15 times, preferably 1 to 10 times, more preferably 1 to 5 times, to emulsify the cleansing composition uniformly which was separated in a stationary state. In the present invention, the obtained emulsion may become an O/W emulsion. It is preferable to make a headspace of from 3% to 10% in relation to the total container volume such that the contents may be efficiently mixed. Especially, among component (F), a powder having a specific gravity higher than 1 is contained (e.g., silica, zinc oxide, titanium oxide), the composition may be sometimes difficult to redisperse uniformly even though it is shaken, which may prevent from providing a skin smooth feeling after use. Therefore, it is preferable to equip a stirring member such that the content may be physically mixed. Examples of the stirring member include a metal ball (e.g., stainless ball), a stirring bar and a stirring blade. Among them, a metal ball is preferably used in terms of easy manufacture.

When a user uses the multi-layered cleansing composition of the present invention, the user conducts the shaking operation as described above. Then while the user uses the multi-layered composition of the present invention (e.g., 1 minute or more, preferably 5 minutes or more, further preferably 10 minutes or more), an emulsion state (i.e., uniform state) is retained. Further after a certain period of time passes (for example, within 3 days, preferably within 2 days, and further preferably within 1 day), the composition reverts to the initial multi-layer state in which an aqueous layer is separated from the emulsion layer to a creaming state.

The multi-layered cleansing composition of the present invention may be applied to skin, preferably skin other than scalp, more preferably any one of face, body, limbs, further preferably face. The multi-layered cleansing composition of the present invention may be suitably used as a face wash, a cleansing agent, or the like, and preferably as a cleansing agent. In particular, it is preferable to use it as a makeup remover for cleaning a makeup cosmetic applied to face (e.g., foundation, mascara, eye shadow, lipstick). Preferably, the multi-layered cleansing composition of the present invention is a makeup remover to be wiped off.

Regarding the using method of the multi-layered cleansing composition of the present invention, for example, the user may, at the outset, mix it uniformly. Then, in a first embodiment, the user may wipe with a wiping material (e.g., cotton, gauze, woven, nonwoven, puff, tissue paper) impregnated with the composition an intended site (e.g., a skin with makeup) on which a makeup cosmetic has been applied, to remove the makeup cosmetic from the skin. In a second embodiment, the user may apply the composition by hand to the intended site to remove a makeup cosmetic by wiping the skin with a wiping material. In a third embodiment, the user may apply the composition to a skin by hand and rinse off the skin. In a fourth embodiment, the user may apply the composition impregnated in a wiping material to a skin and rinse off the skin. In a fifth embodiment, the user may wipe a skin in as described in the first or second embodiment and rinse off the skin. In a sixth embodiment, the user may wipe a skin with a sheet impregnated with the composition. Alternatively, the user may leave a wiping material impregnated with the composition at the intended site and rinse off the skin to remove a makeup cosmetic off.

Regarding the above embodiment, the present invention further discloses the following <1> to <53>.

<1> A multi-layered cleansing composition comprising the following (A) to (E).
(A) from 0.003 to 0.3 mass% of a polymer comprising a monomer chosen from (a1), (a2) and (a3):
(a1) a monomer chosen from acrylic acid and methacrylic acid,
(a2) a monomer chosen from alkyl ester acrylate and alkyl ester methacrylate, and
(a3) a monomer chosen from polyoxyethylene alkyl ester of acrylic acid and polyoxyethylene alkyl ester of methacrylic acid,
(B) from 5 to 40 mass% of an oil agent,
(C) from 0.01 to 1.5 mass% of a nonionic surfactant,
(D) from 0.005 to 0.9 mass% of one or more chosen from (d1) a water-soluble salt and (d2) an acid, and
(E) water.

<2> The multi-layered cleansing composition according to <1>, wherein the viscosity of the composition at 30℃ immediately after shaking is 100 mPa・s or less, preferably 50 mPa・s or less, more preferably 30 mPa・s or less, and further preferably 25 mPa・s, and preferably 1 mPa・s or more, more preferably 3 mPa・s or more, and further preferably 5 mPa・s or more, and preferably from 1 to 50 mPa・s, more preferably from 3 to 30 mPa・s, and further preferably from 5 to 25 mPa・s.

<3> The multi-layered cleansing composition according to <1> or <2>, wherein component (A) contains one or more chosen from carboxyvinyl polymer, acrylic acid-methacrylic acid alkyl crosspolymer, acrylates copolymer, (acrylic acid/stearyl acrylate) copolymer, (acrylates/steareth-20 methacrylate) copolymer, (acrylates/beheneth-25 methacrylate) and (acrylates/steareth-20 methacrylate) crosspolymer

<4> The multi-layered cleansing composition according to any one of <1> to <3>, wherein component (A) contains one or more chosen from acrylic acid-methacrylic acid alkyl crosspolymer, acrylates/steareth-20 methacrylate copolymer, acrylates/beheneth-25 methacrylate copolymer, and acrylates/steareth-20 methacrylate crosspolymer.

<5> The multi-layered cleansing composition according to any one of <1> to <4>, wherein the content of component (A) is preferably 0.003 mass% or more, more preferably 0.005 mass% or more, further preferably 0.008 mass% or more, further preferably 0.01 mass% or more, further preferably 0.03 mass% or more, preferably 0.3 mass% or less, more preferably 0.25 mass% or less, further preferably 0.18 mass% or less, further preferably 0.12 mass% or less, further preferably 0.08 mass% or less in the total composition, and the content of component (A) is preferably from 0.003 to 0.3 mass%, more preferably from 0.005 to 0.25 mass%, further preferably from 0.008 to 0.18 mass%, further preferably from 0.01 to 0.12 mass%, and further preferably from 0.03 to 0.08 mass%.

<6> The multi-layered cleansing composition according to any one of <1> to <5>, wherein the content of component (B) is preferably 5 mass% or more, more preferably 8 mass% or more, and further preferably 12 mass% or more, and preferably 40 mass% or less, more preferably 35 mass% or less, and further preferably 30 mass% or less in the total composition, and the content of component (B) is preferably from 5 to 40 mass%, more preferably from 8 to 35 mass%, and from 12 to 30 mass% in the total composition.

<7> The multi-layered cleansing composition according to any one of <1> to <6>, wherein component (B) contains (b1) hydrocarbon oil, preferably the (b1) hydrocarbon oil has viscosity of 10 mPa・s or less at 30℃, more preferably the (b1) hydrocarbon oil contains one or more chosen from liquid isoparaffin, isododecane and isohexadecane, and further preferably the (b1) hydrocarbon oil contains one or more chosen from isododecane and isohexadecane.

<8> The multi-layered cleansing composition according to <7>, wherein the content of component (b1) is preferably 1 mass% or more, more preferably 3 mass% or more, further preferably 5 mass% or more, and preferably 30 mass% or less, more preferably 25 mass% or less, and further preferably 20 mass% or less in the total composition, and the content of component (b1) is preferably from 1 to 30 mass%, more preferably from 3 to 25 mass%, and further preferably from 5 to 20 mass% in the total composition.

<9> The multi-layered cleansing composition according to any one of <1> to <8>, wherein component (B) contains (b2) ether oil, preferably the (b2) ether oil is dialkyl ether, more preferably the dialkyl ether consists of C2-18 alkyl, and further preferably the dialkyl ether consists of C6-16 alkyl.

<10> The multi-layered cleansing composition according to <9>, wherein the (b2) ether oil is preferably dilauryl ether, dicaprylyl ether or cetyl-1,3-dimethylbutyl ether, more preferably dicaprylyl ether.

<11> The multi-layered cleansing composition according to <9> or <10>, wherein the content of component (b2) (ether oil) is preferably 0.5 mass% or more, more preferably 1 mass% or more, and further preferably 2 mass% or more, and preferably 20 mass% or less, more preferably 15 mass% or less, and further preferably 10 mass% or less in the total composition, and the content of component (b2) is preferably from 0.5 to 20 mass%, more preferably from 1 to 15 mass%, and further preferably from 2 to 10 mass% in the total composition.

<12> The multi-layered cleansing composition according to any one of <1> to <11>, wherein component (B) contains component (b3) silicone oil, and component (b3) (silicone oil) preferably one or more of dimethylpolysiloxane having viscosity of 1.5 mm²/s or 2 mm²/s, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and tris(trimethylsilyl)methylsilane, and more preferably dimethylpolysiloxane having viscosity of 2 mm²/s.

<13> The multi-layered cleansing composition according to <12>, wherein the content of component (b3) (silicone oil) is preferably 0.5 mass%, more preferably 1 mass% or more, further preferably 2 mass% or more, and preferably 30 mass% or less, more preferably 25 mass% or less, and further preferably 20 mass% or less in the total composition. The content of component (b3) is preferably from 0.5 to 30 mass%, more preferably from 1 to 25 mass%, and further preferably from 2 to 20 mass% in the total composition.

<14> The multi-layered cleansing composition according to any one of <1> to <13>, wherein the content of the volatile oil in components (b1), (b2) and (b3) are preferably 30 mass% or more, more preferably 60 mass% or more, and further preferably 90 mass% or more, and preferably 100 mass% or less.

<15> The multi-layered cleansing composition according to any one of <1> to <14>, wherein component (C) (nonionic surfactant) may preferably have HLB of 2 or more, more preferably 8 or more, further preferably 10 or more, further preferably 11 or more, further preferably 12 or more and preferably 20 or less, more preferably 18 or less, further preferably 16 or less, further preferably 14 or less, and further preferably 13.8 or less, and preferably have HLB of from 2 to 20, more preferably from 8 to 18, further preferably from 10 to 16, further preferably from 11 to 14, further preferably from 12 to 13.8.

<16> The multi-layered cleansing composition according to any one of <1> to <15>, wherein the content of component (C) (nonionic surfactant) is preferably 0.01 mass% or more, more preferably 0.05 mass% or more, and further preferably 0.1 mass% or more and preferably 1.5 mass% or less, more preferably 1.0 mass% or less, further preferably 0.8 mass% or less, and further preferably 0.4 mass% or less in the total composition, and the content of component (C) is preferably from 0.01 to 1.5 mass%, more preferably from 0.05 to 1.0 mass%, further preferably from 0.05 to 0.8 mass%, and further preferably from 0.1 to 0.4 mass% in the total composition.

<17> The multi-layered cleansing composition according to any one of <1> to <16>, wherein component (D) is a component (d1) (water-soluble salt) selected from the group consisting of sodium chloride, potassium chloride, calcium chloride, magnesium chloride, sodium sulfate, potassium sulfate, magnesium sulfate, calcium sulfate, disodium EDTA, sodium hydrogen sulfate, potassium hydrogen sulfate, sodium dihydrogen phosphate, and potassium dihydrogen phosphate.

<18> The multi-layered cleansing composition according to any one of <1> to <16>, wherein component (D) is selected from the group consisting of hydroxycarboxylic acid and dicarboxylic acid.

<19> The multi-layered cleansing composition according to any one of <1> to <16>, wherein component (D) is selected from the group consisting of glycolic acid, lactic acid, glyceric acid, gluconic acid, pantothenic acid, citric acid, malic acid, oxalic acid, malonic acid, maleic acid, succinic acid, glutaric acid, and adipic acid.

<20> The multi-layered cleansing composition according to any one of <1> to <19>, wherein the content of component (D) (total content of component (d1) and component (d2)) is preferably 0.005 mass% or more, more preferably 0.010 mass% or more, and further preferably 0.012 mass% or more, and further preferably 0.018 mass% or more, and preferably 0.9 mass% or less, more preferably 0.8 mass% or less, and further preferably 0.7 mass% or less , and further preferably 0.6 mass% or less in the total composition, and the content of component (D) is preferably from 0.005 to 0.9 mass%, more preferably from 0.010 to 0.8 mass%, further preferably from 0.012 to 0.7 mass% and further preferably from 0.018 to 0.6 mass% in the total composition.

<21> The multi-layered cleansing composition according to any one of <1> to <20>, wherein the content of component (E) (water) is preferably 25 mass% or more, more preferably 30 mass% or more, 35 mass% or more, and preferably 95 mass% or less, 90 mass% or less, and 85 mass% or less in the total composition, and the content of component (E), water, is preferably from 25 to 95 mass%, more preferably from 30 to 90 mass%, and further preferably from 35 to 85 mass% in the total composition.

<22> The multi-layered cleansing composition according to any one of <1> to <21>, further comprising component (F) (powder), preferably the content of component (F) being 0.1 mass% or more, preferably 1 mass% or more, and more preferably 3 mass% or more, and 20 mass% or less, preferably 15 mass% or less, and further preferably 12.5 mass% or less in the total composition, and the content of component (F) being preferably from 0.1 to 20 mass%, more preferably from 1 to 15 mass%, and further preferably from 3 to 12.5 mass% in the total composition.

<23> The multi-layered cleansing composition according to any one of <1> to <22>, further comprising component (G) (ethanol), the content of component (G) being preferably 0.1 mass% or more, more preferably 1 mass% or more, and further preferably 3 mass% or more and preferably 20 mass% or less, more preferably 15 mass% or less, and further preferably 10 mass% or less, and the content of component (G) being from 0.1 to 20 mass%, more preferably from 1 to 15 mass% and further preferably from 2 to 10 mass% in the composition.

<24> The multi-layered cleansing composition according to any one of <1> to <23>, further comprising component (H) (polyol).

<25> The multi-layered cleansing composition according to <24>, wherein component (H) is selected from the group consisting of one or more chosen from ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol, polypropyleneglycol, propanediol, glycerin 1,3-butyleneglycol, sorbitol, polyoxyethylenemethyglycoside, and maltitol, more preferably ethyleneglycol, diethyleneglycol, propyleneglycol, dipropyleneglycol, polyethyleneglycol, polypropyleneglycol, propanediol, polyoxyethylenemethyglycoside, and 1,3-butyleneglycol, further preferably propyleneglycol, dipropyleneglycol, 1,3-butyleneglycol, propanediol, and polyoxyethylenemethyglycoside, and further preferably one or more selected from the group consisting of 1,3-butylene glycol and glycerin.

<26> The multi-layered cleansing composition according to <24> or <25>, wherein the content of component (H) polyol is 0.1 mass% or more, preferably 0.5 mass% or more, more preferably 1 mass% or more, and 20 mass% or less, preferably 15 mass% or less, and more preferably 10 mass% or less in the total composition. The content of component (H) is preferably from 0.1 to 20 mass%, more preferably from 0.5 to 15 mass%, and further preferably from 1 to 10 mass%.

<27> The multi-layered cleansing composition according to any one of <1> to <26>, wherein the mass ratio of component (A) to component (B), [(A)/(B)] is preferably 0.0001 or more, more preferably 0.0005 or more, and further preferably 0.001 or more, and preferably 0.01 or less, more preferably 0.008 or less and further preferably 0.0075 or less, and [(A)/(B)] is preferably from 0.0001 to 0.1, more preferably from 0.0005 to 0.008 and further preferably from 0.001 to 0.0075.

<28> The multi-layered cleansing composition according to any one of <1> to <27>, wherein the mass ratio of component (A) to component (C), [(A)/(C)] is preferably 0.001 or more, more preferably 0.005 or more, and further preferably 0.01 or more, and preferably 2.0 or less, more preferably 1.5 or less and further preferably 1.0 or less, and [(A)/(C)] is preferably from 0.001 to 2.0, more preferably from 0.005 to 1.5 and further preferably from 0.01 to 1.0.

<29> The multi-layered cleansing composition according to any one of <1> to <28>, wherein the mass ratio of component (A) to component (D), [(A)/(D)] is preferably 0.05 or more, more preferably 0.1 or more, and further preferably 0.2 or more, and preferably 20 or less, more preferably 10 or less, and further preferably 5 or less, and [(A)/(D)] is preferably from 0.05 to 20, more preferably from 0.1 to 10, and further preferably from 0.2 to 5.

<30> The multi-layered cleansing composition according to any one of <1> to <29>, wherein the mass ratio of component (C) to component (D), [(C)/(D)] is preferably 0.2 or more, more preferably 0.3 or more, and further preferably 0.4 or more, and preferably 30 or less, more preferably 20 or less, further preferably 15 or less and further preferably 7 or less, and [(C)/(D)] is preferably from 0.2 to 30, more preferably from 0.3 to 20, further preferably from 0.4 to 15, and further preferably from 0.4 to 7.

<31> The multi-layered cleansing composition according to any one of <1> to <30>, wherein the mass ratio of component (F) to component (A), [(F)/(A)] is preferably 1 or more, more preferably 10 or more, and further preferably 50 or more, and preferably 1,000 or less, more preferably 700 or less, and further preferably 500 or less, and [(F)/(A)] is preferably from 1 to 1,000, more preferably from 10 to 700, and further preferably from 50 to 500.

<32> The multi-layered cleansing composition according to any one of <1> to <31>, further comprising component (K) (alkaline neutralizing agent), preferably at an amount to correspond to neutralization ratio of component (A) (polymer) of from 0.3 to 1.2 and more preferably an amount to correspond to the neutralization ratio of from 0.4 to 1.1.

<33> A method for using the cleansing composition according to any one of <1> to <32>, comprising a first step of mixing the composition uniformly, and a second step selected from the group consisting of
(1) wiping a skin with a wiping material impregnated with the composition,
(2) wiping a skin with a wiping material after applying the composition to the skin by hand,
(3) rinsing off a skin after applying the composition to the skin by hand,
(4) rinsing off a skin after applying the composition impregnated in a wiping material to the skin,
(5) rinsing off a skin after wiping the skin according to any one of the above method and
(6) wiping a skin with a sheet impregnated with the composition.

<34> A method for manufacturing a multi-layered cleansing composition according to <1>, comprising the following steps 1 to 3:
(step 1) mixing component (A), component (B) and component (E) to give a mixture 1,
(step 2) adding component (C) to the mixture 1 to give a mixture 2, and
(step 3) adding component (D) to the mixture 2.

<35> A multi-layered cleansing composition comprising the following component (A) to (E):
(A) from 0.008 to 0.18 mass% of a polymer comprising a monomer chosen from (a1), (a2) and (a3), wherein the polymer comprising at least (a1) as the constitutional unit.
(a1) a monomer chosen from acrylic acid and methacrylic acid,
(a2) a monomer chosen from alkyl ester acrylate and alkyl ester methacrylate, and
(a3) a monomer chosen from polyoxyethylene alkyl ester of acrylic acid and polyoxyethylene alkyl ester of methacrylic acid,
(B) from 12 to 30 mass% of an oil agent having viscosity of 1 mPa・s or more and 18 mPa・s or less at 30℃,
(C) from 0.01 to 1.5 mass% of a nonionic surfactant having HLB of from 8 to 18,
(D) from 0.005 to 0.9 mass% of one or more chosen from (d1) a water-soluble salt and (d2) an acid, and
(E) water.

<36> A multi-layered cleansing composition comprising the following component (A) to (E):
(A) from 0.008 to 0.18 mass% of a polymer comprising a monomer chosen from (a1), (a2) and (a3), wherein the polymer comprising at least (a1) as the constitutional unit.
(a1) a monomer chosen from acrylic acid and methacrylic acid,
(a2) a monomer chosen from alkyl ester acrylate and alkyl ester methacrylate, and
(a3) a monomer chosen from polyoxyethylene alkyl ester of acrylic acid and polyoxyethylene alkyl ester of methacrylic acid,
(B) from 12 to 30 mass% of an oil agent having viscosity of 1 mPa・s or more and 18 mPa・s or less at 30℃,
(C) from 0.01 to 1.5 mass% of a nonionic surfactant having HLB of from 8 to 18,
(D) from 0.08 to 0.6 mass% of (d1) a water-soluble salt, and
(E) water.

<37> A multi-layered cleansing composition comprising the following component (A) to (E):
(A) from 0.008 to 0.18 mass% of a polymer comprising a monomer chosen from (a1), (a2) and (a3), wherein the polymer comprising at least (a1) as the constitutional unit.
(a1) a monomer chosen from acrylic acid and methacrylic acid,
(a2) a monomer chosen from alkyl ester acrylate and alkyl ester methacrylate, and
(a3) a monomer chosen from polyoxyethylene alkyl ester of acrylic acid and polyoxyethylene alkyl ester of methacrylic acid,
(B) from 12 to 30 mass% of an oil agent having viscosity of 1 mPa・s or more and 18 mPa・s or less at 30℃,
(C) from 0.01 to 1.5 mass% of a nonionic surfactant having HLB of from 8 to 18,
(D) from 0.013 to 0.3 mass% of (d2) an acid, and
(E) water.

<38> A multi-layered cleansing composition comprising the following component (A) to (E):
(A) from 0.008 to 0.18 mass% of a polymer comprising a monomer chosen from (a1), (a2) and (a3), wherein the polymer comprising at least (a1) as the constitutional unit.
(a1) a monomer chosen from acrylic acid and methacrylic acid,
(a2) a monomer chosen from alkyl ester acrylate and alkyl ester methacrylate, and
(a3) a monomer chosen from polyoxyethylene alkyl ester of acrylic acid and polyoxyethylene alkyl ester of methacrylic acid,
(B) from 12 to 30 mass% of an oil agent having viscosity of 1 mPa・s or more and 18 mPa・s or less at 30℃,
(C) from 0.01 to 1.5 mass% of a nonionic surfactant having HLB of from 8 to 18,
(D) from 0.005 to 0.9 mass% of one or more chosen from (d1) a water-soluble salt and (d2) an acid,
(E) water, and
(F) from 1 to 15 mass% of a powder.

<39> A multi-layered cleansing composition comprising the following component (A) to (E):
(A) from 0.008 to 0.18 mass% of a polymer comprising a monomer chosen from (a1), (a2) and (a3), wherein the polymer comprising at least (a1) as the constitutional unit.
(a1) a monomer chosen from acrylic acid and methacrylic acid,
(a2) a monomer chosen from alkyl ester acrylate and alkyl ester methacrylate, and
(a3) a monomer chosen from polyoxyethylene alkyl ester of acrylic acid and polyoxyethylene alkyl ester of methacrylic acid,
(B) from 12 to 30 mass% of an oil agent having viscosity of 1 mPa・s or more and 18 mPa・s or less at 30℃,
(C) from 0.01 to 1.5 mass% of a nonionic surfactant having HLB of from 8 to 18,
(D) from 0.08 to 0.6 mass% of (d1) a water-soluble salt,
(E) water, and
(F) from 1 to 15 mass% of a powder.

<40> A multi-layered cleansing composition comprising the following component (A) to (E):
(A) from 0.008 to 0.18 mass% of a polymer comprising a monomer chosen from (a1), (a2) and (a3), wherein the polymer comprising at least (a1) as the constitutional unit.
(a1) a monomer chosen from acrylic acid and methacrylic acid,
(a2) a monomer chosen from alkyl ester acrylate and alkyl ester methacrylate, and
(a3) a monomer chosen from polyoxyethylene alkyl ester of acrylic acid and polyoxyethylene alkyl ester of methacrylic acid,
(B) from 12 to 30 mass% of an oil agent having viscosity of 1 mPa・s or more and 18 mPa・s or less at 30℃,
(C) from 0.01 to 1.5 mass% of a nonionic surfactant having HLB of from 8 to 18,
(D) from 0.013 to 0.3 mass% of (d2) an acid,
(E) water, and
(F) from 1 to 15 mass% of a powder.

<41> The multi-layered cleansing composition according to any one of <35> to <40>, wherein the content of component (A) is one or more chosen from carboxyvinyl polymer, acrylic acid-methacrylic acid alkyl crosspolymer, acrylates copolymer, (acrylic acid/stearyl acrylate) copolymer, (acrylates/steareth-20 methacrylate) copolymer, (acrylates/beheneth-25 methacrylate) and (acrylates/steareth-20 methacrylate) crosspolymer, more preferably one or more chosen from acrylic acid-methacrylic acid alkyl crosspolymer, (acrylates/steareth-20 methacrylate) copolymer, (acrylates/beheneth-25 methacrylate) and (acrylates/steareth-20 methacrylate) crosspolymer.

<42> The multi-layered cleansing composition according to any one of <35> to <40>, wherein the content of component (A) is one or more chosen from acrylic acid-methacrylic acid alkyl crosspolymer and (acrylates/steareth-20 methacrylate) crosspolymer.

<43> The multi-layered cleansing composition according to any one of <35> to <42>, wherein the component (B) comprising one or more chosen from (b1) hydrocarbon oil, (b2) ether oil and (b3) silicone oil, wherein the total content of components (b1), (b2) and (b3) in component (B) is 90 mass% or more and 100 mass% or less.

<44> The multi-layered cleansing composition according to any one of <35> to <42>, wherein the component (B) consists of components (b1) hydrocarbon oil, (b2) ether oil and (b3) silicone oil.

<45> The multi-layered cleansing composition according to any one of <35> to <42>, wherein the component (B) comprising one or more chosen from (b1) hydrocarbon oil, (b2) ether oil and (b3) silicone oil, wherein the total content of components (b1), (b2) and (b3) in component (B) is 90 mass% or more and 100 mass% or less, and the content of the volatile oil in components (b1), (b2) and (b3) is 60 mass% or more and 100 mass% or less.

<46> The multi-layered cleansing composition according to any one of <35> to <42>, wherein the component (B) consists of components (b1) hydrocarbon oil, (b2) ether oil and (b3) silicone oil, and the content of the volatile oil in components (b1), (b2) and (b3) is 60 mass% or more and 100 mass% or less.

<47> The multi-layered cleansing composition according to any one of <35> to <42>, wherein the component (B) comprising one or more chosen from (b1) hydrocarbon oil, (b2) ether oil and (b3) silicone oil, wherein the total content of components (b1), (b2) and (b3) in component (B) is 90 mass% or more and 100 mass% or less, and wherein the content of the volatile oil in components (b1), (b2) and (b3) is 90 mass% or more and 100 mass% or less.

<48> The multi-layered cleansing composition according to any one of <35> to <42>, wherein the component (B) consists of components (b1) hydrocarbon oil, (b2) ether oil and (b3) silicone oil, and wherein the content of the volatile oil in components (b1), (b2) and (b3) is 90 mass% or more and 100 mass% or less.

<49> The multi-layered cleansing composition according to any one of <47> to <48>, wherein the content of the volatile oil is one or more chosen from dimethylpolysiloxane (1.5 mm²/s), dimethylpolysiloxane (2 mm²/s), tris(trimethylsilyl)methylsilane, tetrakis(trimethylsilyl)silane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, isododecane, isohexadecane, light isoparaffin, light liquid isoparaffin, liquid isoparaffin, dicaprylyl ether, and dilauryl ether.

<50> The multi-layered cleansing composition according to any one of <47> to <48>, wherein the content of the volatile oil is one or more chosen from dimethylpolysiloxane (2 mm²/s), isododecane, isohexadecane, tris(trimethylsilyl)methylsilane and dicaprylyl ether.

<51> The multi-layered cleansing composition according to any one of <35> to <51>, wherein the viscosity of the composition at 30℃ immediately after shaking is from 1 to 50 mPa・s.

<52> The multi-layered cleansing composition according to any one of <35> to <51>, wherein the viscosity of the composition at 30℃ immediately after shaking is from 3 to 30 mPa・s.

<53> The multi-layered cleansing composition according to any one of <35> to <51>, wherein the viscosity of the composition at 30℃ immediately after shaking is from 5 to 25 mPa・s.

Examples

The present invention is explained by way of Examples and Comparative Examples, but the present invention is not limited to the Examples.

Examples 1 to 58 and Comparative Examples 1 to 11
Samples shown in Tables 1 to 9 were manufactured. The samples were subjected to evaluation for (1) viscosity, (2) appearance (25℃, stationary state for 24 hours), (3) impregnation in cotton, (4) cleansing speed of waterproof mascara, (5) cleansability against waterproof mascara , (6) (6-1) non-oily feeling during wiping and (6-2) non-sticky feeling immediately after use, (7) skin fresh feeling after use, and (8) emulsion retention during use. The samples shown in Table 4 were further subjected to evaluation for (13) appearance (50℃, stationary state for one month), the samples shown in Table 7 were further subjected to evaluation for (10) redispersibility of deposited powder and (11) skin smooth feeling after use, the samples shown in Table 8 were further subjected to evaluation for (11) skin smooth feeling after use and (12) skin cool feeling after use, and the samples shown in Table 9 were further subjected to evaluation for (9) skin moist feeling after use. The formulations and evaluation results are shown in Tables 1 to 9.

(Manufacturing method)
(1) Components (A), (B) and (E) were mixed at 25 ℃ uniformly to give a preparation A.
(2) To the preparation A, potassium hydroxide (48% aqueous solution) was added to neutrality, and the mixture was mixed uniformly to give a preparation B.
(3) To the preparation B, component (C) was added and the mixture was mixed uniformly to give a preparation C.
(4) To the preparation C, component (D) was added and the mixture was mixed uniformly to give a preparation D.
(5) The preparation D was dispensed (45 mL) to a glass bottle (standard bottle No.5K, Volume 50 mL, body diameter 38 mm, height 68.5 mm, mouth inner diameter: 24.7 mm) to give a sample.

(Evaluation Method)
(1) Viscosity
Each sample was stored in a vertical position on its bottom in a thermostatic chamber of 30℃ for over two hours. The sample was shaken up and down by hand with 15 cm of stroke length 15 times at a speed of 5 reciprocal motions per 3 seconds. Immediately after, the viscosity of each sample was measured.

The viscosity of each sample was measured by B-type viscometer (Viscometer TVB-10M, TOKI SANGYO Co., Ltd.) with rotor No. M1 at 60 rpm for 1 minute, at 30℃. When the viscosity was 100 mPa・s or more, the measurement was resumed at 30 rpm. Note that in case layer separation was caused within 1 minute so that measuring viscosity was not successful, then measurement was not conducted, which is shown by "-".

(2) Appearance after storage for 24 hours at room temperature (25℃) (stationary state)
Each sample was shaken up and down by hand with 15 cm of stroke length 15 times at a speed of 5 reciprocal motions per 3 seconds. Then the sample was stored in a vertical position on its bottom for 24 hours at room temperature (25℃). The appearance was visually observed and evaluation was conducted on the state of layer separation. “Tri-layer” indicates that the composition is separated out to three layers, "Bi-layer" indicates that the composition is separated out to two layers, "mono-layer" indicates a uniform liquid. The word in parentheses indicates detailed state of layer separation; W represents an aqueous layer, O represents an oil layer, P represents a powder sediment layer, and O/W indicates an oil-in-water emulsion layer, the word on the left indicates the state of the upper layer. For example, "O/W+W" indicates that the upper layer is an oil-in-water emulsion layer and the lower layer is an aqueous layer. "O/W+W+P" indicates that the upper layer is an oil-in-water emulsion layer, the middle layer is an aqueous layer, and the lower layer is a powder sediment layer.

(3) Impregnation in cotton
Each sample was stored in a vertical position on its bottom in a thermostatic chamber at 25℃ for over two hours. The sample was shaken up and down by hand with 15 cm of stroke length 15 times at a speed of 5 reciprocal motions per 3 seconds. Each sample (1 mL) was dripped from the height of 1 cm to cotton (LilyBell patting cotton, Suzuran Sanitary Goods Co., Ltd.). The impregnation of each sample in the cotton surface was visually observed and evaluated by the following criteria.
5: Impregnated instantaneously (liquid membrane was not made)
4: A liquid membrane is made instantaneously; impregnated within 1 second after dripping
3: A liquid membrane is made on the surface; impregnated more than 1 second and3 or less seconds after dripping
2: A liquid membrane is made on the surface; impregnated more than 3 seconds and 5 or less seconds after dripping
1: No impregnation was observed even after more than 5 seconds' passage after dripping

(4) Cleansing speed against waterproof mascara
Waterproof mascara (Maybelline Volume Express Magnum Waterproof N Black, Nihon L'Oreal) (abbreviated to WP hereafter) (3 mg) was uniformly applied to a glass plate (Micro Slide Glass, Matsunami Glass Ind. Ltd.) in a circle having a diameter of 1.2 cm and the WP was dried by allowing it to stand for over 12 hours. Each sample was stored in a vertical position on its bottom in a thermostatic chamber at 25℃ for over 2 hours. The sample was shaken up and down by hand with 15 cm of stroke length 15 times at a speed of 5 reciprocal motions per 3 seconds. In cotton (LilyBell patting cotton, Suzuran Sanitary Goods Co., Ltd.) each sample (1 mL) was impregnated. After a stable pressure (7.8 kPa) was applied onto the WP with the cotton for 10 seconds, wiping was performed once. The remaining WP was visually evaluated by the following criteria.
5: WP attaches to the overall cotton densely
4: WP attaches to the overall cotton relatively densely
3: WP attaches to the overall cotton slightly
2: WP attaches to part of cotton
1: No WP attaches to cotton

(5) Cleansability against waterproof mascara
WP (3 mg) was uniformly applied on a glass plate (Micro Slide Glass, Matsunami Glass Ind. Ltd.) in a circle having a diameter of 1.2 cm, and the WP was dried by allowing it to stand for over 12 hours. Each sample was stored in a vertical position on its bottom in a thermostatic chamber at 25℃ for over 2 hours. Each sample was shaken up and down by hand with 15 cm of stroke length 15 times at a speed of 5 reciprocal motions per 3 seconds. In cotton (LilyBell patting cotton, Suzuran Sanitary Goods Co., Ltd.) each sample (1 mL) was impregnated. After a constant pressure (7.8 kPa) was applied onto the WP with the cotton for 10 seconds, wiping was performed for five times. The remaining WP was visually observed on an area basis and the cleansability was evaluated by the following criteria.
5: WP was almost removed (5% or less of WP remains) by wiping 3 times or less.
4: WP was almost removed (5% or less of WP remains) by wiping 4 or 5 times
3: More than 5% and 10% or less of WP remains after wiping 5 times
2: More than 10% and 50% or less of WP remains after wiping 5 times
1: More than 50% of WP remains after wiping 5 times

(6) (6-1)Non-oily feeling during wiping and (6-2) Non-sticky feeling immediately after use
Each sample was shaken up and down by hand with 15 cm of stroke length 15 times at a speed of 5 reciprocal motions per 3 seconds. In cotton (LilyBell patting cotton, Suzuran Sanitary Goods Co., Ltd.) each sample (1 mL) was impregnated. 10 professional panelists in their 20's to 40's who made up on their faces with Liquid foundation (Prima Vista, Makeup Adhesion Realization Liquid Foundation, Ochre No. 5, Kao Corporation) (abbreviated to FD hereafter) conducted removing the makeup cosmetic using the cotton impregnated with sample. On the basis of the number who affirmed a non-oily feeling during wiping and non-sticky feeling immediately after use, judgment was done by the following five grades.

(6-1) Non-oily feeling during wiping
5: 1 panelist or less out of 10 affirmed an oily feeling during wiping
4: 2 or 3 panelists out of 10 affirmed an oily feeling during wiping
3: 4 or 5 panelists out of 10 affirmed an oily feeling during wiping
2: 6 or 7 panelists out of 10 affirmed an oily feeling during wiping
1: 8 panelists or more out of 10 affirmed an oily feeling during wiping

(6-2) Non-sticky feeling immediately after use
5: 1 panelist or less out of 10 affirmed a sticky feeling immediately after use
4: 2 or 3 panelists out of 10 affirmed a sticky feeling immediately after use
3: 4 or 5 panelists out of 10 affirmed a sticky feeling immediately after use
2: 6 or 7 panelists out of 10 affirmed a sticky feeling immediately after use
1: 8 panelists or more out of 10 affirmed a sticky feeling immediately after use

(7) Skin fresh feeling after use
FD (5 mg) was spread to a forearm of professional female panelists in their 20's to 40's in a range of 2 cm x 2 cm uniformly, and it was dried for 30 minutes. Each sample was shaken up and down by hand with 15 cm of stroke length 15 times at a speed of 5 reciprocal motions per 3 seconds. Each sample (1 mL) was impregnated to cotton (LilyBell patting cotton, Suzuran Sanitary Goods Co., Ltd.). FD was removed by wiping with the cotton. On the basis of the number who affirmed a skin fresh feeling without a remaining feeling after use, judgment was done by the following five grades.
5: 9 or 10 panelists out of 10 affirmed a skin fresh feeling without a remaining feeling after use
4: 7 or 8 panelists out of 10 affirmed a skin fresh feeling without a remaining feeling after use
3: 5 or 6 panelists out of 10 affirmed a skin fresh feeling without a remaining feeling after use
2: 3 or 4 panelists out of 10 affirmed a skin fresh feeling without a remaining feeling after use
1: 2 panelists or less out of 10 affirmed a skin fresh feeling without a remaining feeling after use

(8) Emulsion retention during use
Each sample was shaken up and down by hand with 15 cm of stroke length 15 times at a speed of 5 reciprocal motions per 3 seconds. The samples were stored in a vertical position on its bottom in a thermostatic chamber of 25℃. The time from termination of shaking to start of layer separation through visual observation was measured and evaluated by the following criteria.
3: 5 minutes or more
2: 1 minute or more and less than 5 minutes
1: less than 1 minute

(9) Skin moist feeling after use
FD (5 mg) was spread to the forearm of 10 professional panelists (female in their 20's to 40's) and the FD was dried for 30 minutes. Each sample was shaken up and down by hand with 15 cm of stroke length 15 times at a speed of 5 reciprocal motions per 3 seconds. Each sample (1 mL) was impregnated to cotton (LilyBell patting cotton, Suzuran Sanitary Goods Co., Ltd.). FD was removed by wiping with the cotton. On the basis of the number who affirmed a skin moist feeling after use, judgment was done by the following five grades.
5: 9 or 10 panelists out of 10 affirmed a skin moist feeling after use
4: 7 or 8 panelists out of 10 affirmed a skin moist feeling after use
3: 5 or 6 panelists out of 10 affirmed a skin moist feeling after use
2: 3 or 4 panelists out of 10 affirmed a skin moist feeling after use
1: 2 panelists or less out of 10 affirmed a skin moist feeling after use

(10) Redispersibility of powder
Each sample was shaken (stroke length: 15 cm, shaking speed: 5 reciprocal motions per 3 seconds) to completely disperse the powder and the sample was stored in a vertical position on its bottom at room temperature (25℃) for 24 hours to let the powder deposit. The appearance of the sample was visually observed after shaking 5 times, 10 times and 15 times (stroke length: 15 cm, shaking speed: 5 reciprocal motions per 3 seconds) and evaluated by the following criteria.
5: After shaking 5 times, the powder was completely dispersed in the emulsion
4: After shaking 10 times, the powder was completely dispersed in the emulsion
3: After shaking 15 times, the powder was completely dispersed in the emulsion
2: After shaking 15 times, a slight amount of sediment powder was observed at the bottom
1: After shaking 15 times, sediment powder was obviously observed at the bottom
-: Evaluation was not conducted when powder was not contained in the sample or powder was not deposited after 24 hours storage at room temperature (25℃)

(11) Skin smooth feeling after use
FD (5 mg) was spread to the forearm of 10 professional panelists (female in their 20's to 40's) in a range of 2 cm x 2 cm uniformly and the FD was dried for 30 minutes. Each sample was shaken up and down by hand with 15 cm of stroke length 15 times at a speed of 5 reciprocal motions per 3 seconds. Each sample (1 mL) was impregnated in cotton (LilyBell patting cotton, Suzuran Sanitary Goods Co., Ltd.). The forearm was wiped with the impregnated cotton to remove the FD. The evaluation was made on the basis of the number who affirmed skin smooth feeling after use.
5: 9 or 10 panelists out of 10 affirmed a skin smooth feeling after use
4: 7 or 8 panelists out of 10 affirmed a skin smooth feeling after use
3: 5 or 6 panelists out of 10 affirmed a skin smooth feeling after use
2: 3 or 4 panelists out of 10 affirmed a skin smooth feeling after use
1: 2 or less panelists out of 10 affirmed a skin smooth feeling after use

(12) Skin cool feeling after use
FD (5 mg) was spread to the forearm of 10 professional panelists (female in their 20's to 40's) in a range of 2 cm x 2 cm uniformly and the FD was dried for 30 minutes. Each sample was shaken up and down by hand with 15 cm of stroke length 15 times at a speed of 5 reciprocal motions per 3 seconds. Each sample (1 mL) was impregnated in cotton (LilyBell patting cotton, Suzuran Sanitary Goods Co., Ltd.). The forearm was wiped with the impregnated cotton to remove the FD. The evaluation was made on the basis of the number who affirmed skin cool feeling after use by the following criteria.
5: 9 or 10 panelists out of 10 affirmed a skin cool feeling after use
4: 7 or 8 panelists out of 10 affirmed a skin cool feeling after use
3: 5 or 6 panelists out of 10 affirmed a skin cool feeling after use
2: 3 or 4 panelists out of 10 affirmed a skin cool feeling after use
1: 2 or less panelists out of 10 affirmed a skin cool feeling after use

(13) Appearance after storage in a thermostatic chamber of 50℃ for 1 month (stationary state)
Appearance of each sample was visually observed after storage in a thermostatic chamber of 50℃ for 1 month, with respect to layer separation.
Each sample (100 mL) was put into a glass bottle (standard bottle No.10K, Volume 108 mL, body diameter: 48.5 mm, height 87 mm, mouth inner diameter: 31.9 mm). The glass bottle was stored in a vertical position on its bottom in a thermostatic chamber at 50℃ for 1 month. Subsequently, the thickness of oil layer which exuded from the emulsion layer was measured. Evaluation was made on the basis of thickness of the oil layer by the following criteria.
5: not discernible
4: less than 1.5 mm
3: 1.5 mm or more and less than 3.5 mm
2: 3.5 mm or more and less than 5 mm
1: 5 mm or more

In Examples and Comparative Examples, the ingredients affixed with label * are as follows.
*1: PEMULEN TR-2 (Lubrizol Advanced Materials)
*2: MARUKAZOL R (Maruzen Petrochemical Co., Ltd., viscosity: 3 mPa・s, boiling point: 177℃)
*3: EMANON1112 (Kao Corporation, (HLB: 13.7))
*4: Asapic (Asahi Kasei Corp.)
*5: Carbopol ETD2020 Polymer (Lubrizol Advanced Materials)
*6: Aculyn 22 (The Dow Chemical Company, active content: 30 mass%)
*7: Carbopol 981 (Lubrizol Advanced Materials)
*8: Sodium chloride (Toagosei Co., Ltd.)
*9: Magnesium sulfate heptahydrate (UMAI CHEMICAL CO., LTD.)
*10: Clewat N (Nagase ChemteX Corporation)
*11: EMANON CH-40 (Kao Corporation, HLB: 12.5)
*12: RHEODOL TW-L120 (Kao Corporation, HLB: 16.7)
*13: PENETOL GE-IS (U) (Kao Corporation, HLB: 2.0)
*14: PARLEAM EX (NOF Corporation, viscosity: 14 mPa・s, nonvolatile oil)
*15: Cetiol OE (BASF SE, viscosity: 3 mPa・s, boiling point: 291℃)
*16: ASE166K (Kao Corporation, viscosity: 5mPa・s, nonvolatile oil）
*17: Silicone KF96 2 cs (Shin-Etsu Chemical Co., Ltd., viscosity: 2 mPa・s, boiling point: 230℃)
*18: Silicone KF96 5 cs (Shin-Etsu Chemical Co., Ltd., viscosity: 5 mPa・s, nonvolatile oil)
*19: TMF-1.5 (Shin-Etsu Chemical Co., Ltd.)
*20: CROPURE OL (Croda Japan KK, viscosity : 90 mPa・s, nonvolatile oil)
*21: Sofcare ST (Kao Corporation, particle size: 3 μm)
*22: Sunsphere NP-30 (AGC Sitech, particle size: 4 μm)
*23: HCS 160M5 (JGC Catalysts and Chemicals Ltd., particle size: 5 μm)
*24: Sunsphere NP-200 (AGC Sitech, particle size: 20 μm）
*25: MACBIOBRIDE MG-20E (MS) (NOF Corporation）

Claims

A multi-layered cleansing composition comprising the following component (A) to (E):
(A) from 0.003 to 0.3 mass% of a polymer comprising a monomer chosen from (a1), (a2) and (a3):
(a1) a monomer chosen from acrylic acid and methacrylic acid,
(a2) a monomer chosen from alkyl ester acrylate and alkyl ester methacrylate, and
(a3) a monomer chosen from polyoxyethylene alkyl ester of acrylic acid and polyoxyethylene alkyl ester of methacrylic acid,
(B) from 5 to 40 mass% of an oil agent,
(C) from 0.01 to 1.5 mass% of a nonionic surfactant,
(D) from 0.005 to 0.9 mass% of one or more chosen from (d1) a water-soluble salt and (d2) an acid, and
(E) water.
The multi-layered cleansing composition according to claim 1, wherein the mass ratio of component (A) to component (D), [(A)/(D)] is from 0.05 to 20.
The multi-layered cleansing composition according to claim 1 or 2, further comprising (F) a powder.
The multi-layered cleansing composition according to claim 3, wherein the mass ratio of component (F) to component (A), [(F)/(A)] is from 1 to 1000.
The multi-layered cleansing composition according to any one of claims 1 to 4, further comprising (G) ethanol.
The multi-layered cleansing composition according to any one of claims 1 to 5, which has viscosity at 30℃ after stirring of 100 mPa・s or less.
The multi-layered cleansing composition according to any one of claims 1 to 6, which is a wipe-off type makeup remover.
A method for manufacturing a multi-layered cleansing composition according to claim 1, comprising
(step 1) mixing component (A), component (B) and component (E) to give a mixture 1,
(step 2) adding component (C) to the mixture 1 to give a mixture 2, and
(step 3) adding component (D) to the mixture 2.