阅读说明：本技术 多层清洁组合物 (Multi-layer cleaning composition ) 是由 津田博子 上山千纮 S·迪洛彭由廷 T·猜颂提夸特 于 2018-09-10 设计创作，主要内容包括：本发明提供一种多层清洁组合物,其能够除去顽固化妆用化妆品比如防水睫毛膏,提供擦拭过程中的不油腻感和使用后即刻不发粘感。本发明的多层清洁组合物,其包含以下成分(A)～(E)：(A)0.003-0.3质量％的包含选自(a1)、(a2)和(a3)的单体的聚合物：(a1)选自丙烯酸和甲基丙烯酸的单体,(a2)选自丙烯酸烷基酯和甲基丙烯酸烷基酯的单体,和(a3)选自丙烯酸的聚氧乙烯烷基酯和甲基丙烯酸的聚氧乙烯烷基酯的单体；(B)5-40质量％的油剂；(C)0.01-1.5质量％的非离子表面活性剂；(D)0.005-0.9质量％的选自(d1)水溶性盐和(d2)酸的一种或多种；和(E)水。(The present invention provides a multi-layer cleansing composition that is capable of removing stubborn make-up cosmetics such as waterproof mascara, providing a non-greasy feel during wiping and a non-sticky feel immediately after use. The multi-layer cleaning composition of the present invention comprises the following components (a) to (E): (A)0.003 to 0.3 mass% of a polymer comprising a monomer selected from the group consisting of (a1), (a2) and (a 3): (a1) monomers selected from acrylic acid and methacrylic acid, (a2) monomers selected from alkyl acrylates and alkyl methacrylates, and (a3) monomers selected from polyoxyethylene alkyl acrylates and polyoxyethylene alkyl methacrylates; (B)5-40 mass% of an oil agent; (C)0.01 to 1.5 mass% of a nonionic surfactant; (D)0.005-0.9 mass% of one or more selected from (d1) water-soluble salts and (d2) acids; and (E) water.)

1. A multi-layer cleaning composition, wherein,

comprises the following components (A) to (E):

(A)0.003 to 0.3 mass% of a polymer comprising a monomer selected from the group consisting of (a1), (a2) and (a 3):

(a1) a monomer selected from the group consisting of acrylic acid and methacrylic acid,

(a2) a monomer selected from the group consisting of alkyl acrylates and alkyl methacrylates, and

(a3) a monomer selected from the group consisting of polyoxyethylene alkyl esters of acrylic acid and polyoxyethylene alkyl esters of methacrylic acid;

(B)5-40 mass% of an oil agent;

(C)0.01 to 1.5 mass% of a nonionic surfactant;

(D)0.005-0.9 mass% of one or more selected from (d1) water-soluble salts and (d2) acids; and

(E) and (3) water.

2. A multi-layer cleaning composition according to claim 1,

the mass ratio (A)/(D) of the component (A) to the component (D) is 0.05 to 20.

3. A multi-layer cleaning composition according to claim 1 or 2,

also comprises (F) powder.

4. A multi-layer cleaning composition according to claim 3,

the mass ratio of the component (F) to the component (A), (F)/(A), is 1 to 1000.

5. A multi-layer cleaning composition according to any one of claims 1 to 4,

further comprises (G) ethanol.

6. A multi-layer cleaning composition according to any one of claims 1 to 5,

the viscosity at 30 ℃ after stirring is 100 mPas or less.

7. A multi-layer cleaning composition according to any one of claims 1 to 6,

is a wiping type makeup remover.

8. A method for making the multi-layer cleaning composition of claim 1, wherein,

the method comprises the following steps:

(step 1) mixing component (a), component (B) and component (E) to obtain a mixture 1;

(step 2) adding component (C) to the mixture 1 to obtain a mixture 2; and

(step 3) adding component (D) to the mixture 2.

Technical Field

The present invention relates to a multi-layer cleaning composition.

Background

Recently, skin cleansing sheets in which a liquid skin cleanser is impregnated in a non-woven fabric and skin cleansers to be impregnated in a cotton fabric or the like at the time of use have been developed, and since they do not require rinsing after use, they can remove makeup cosmetics regardless of place or time. There are two types of cleaning sheets/compositions: one is a surfactant-based type containing a surfactant as a cleansing base, by which makeup cosmetics are removed with a surfactant after emulsification (see PTL1), and the other is an oil-based type containing an oil agent as a cleansing base, by which makeup cosmetics are removed by dissolution in oil (see PTL 2).

Surfactant-based types contain little oil and provide a light feel during wiping, but it is difficult to remove water-resistant mascaras that contain tough ingredients (e.g., polymeric silicones and oily film formers) that adhere strongly to skin. The oil-based type has excellent cleansing properties for makeup cosmetics such as waterproof mascara, but may give a greasy feeling during wiping, leaving stickiness on the skin immediately after use (wiping).

Recently, among oil-based types, a skin cleanser for wiping, which has reduced greasy feeling during wiping, has been proposed. For example, there have been proposed a two-layer composition consisting of an aqueous layer and an oil layer, which is shaken and impregnated in a pad for wiping at the time of use (see PTL3), and an emulsified skin cleansing composition in which a low-viscosity oil agent is dispersed by emulsification (see PTL 4).

(PTL1) Japanese patent laid-open publication No. 2011-37782

(PTL2) Japanese patent laid-open No. 1995-223922

(PTL3) Japanese patent laid-open No. 2004-285047

(PTL4) Japanese patent laid-open No. 2014-218437

Disclosure of Invention

The present invention relates to the following [1] and [2 ].

[1] A multi-layer cleaning composition comprising the following ingredients (a) to (E):

(A)0.003 to 0.3 mass% of a polymer comprising a monomer selected from the group consisting of (a1), (a2) and (a 3):

(a1) a monomer selected from the group consisting of acrylic acid and methacrylic acid,

(a2) a monomer selected from the group consisting of alkyl acrylates and alkyl methacrylates, and

(a3) a monomer selected from the group consisting of polyoxyethylene alkyl esters of acrylic acid and polyoxyethylene alkyl esters of methacrylic acid;

(B)5-40 mass% of an oil agent;

(C)0.01 to 1.5 mass% of a nonionic surfactant;

(D)0.005-0.9 mass% of one or more selected from (d1) water-soluble salts and (d2) acids; and

(E) and (3) water.

[2] A method for producing a multi-layer cleaning composition according to [1], comprising the following steps 1 to 3:

(step 1) mixing component (a), component (B) and component (E) to obtain a mixture 1;

(step 2) adding the component (C) to the mixture 1 to obtain a mixture 2; and

(step 3) component (D) was added to mixture 2.

Detailed Description

Even if the two-layer composition described in PTL3 forms a uniform emulsion by shaking, it may substantially separate into an aqueous layer and an oily layer when immersed in a cotton fabric, a large amount of oil agent is in direct contact with the skin, and the user may feel greasy during wiping. Regardless of the shaking mixing, the composition quickly returned to a bilayer state when left to stand for a while. This forces the user to shake the composition frequently, which is cumbersome.

As for the skin cleansing composition described in PTL4, although it is a cleansing composition that imparts a refreshing feeling upon use and has high cleansing properties to a tough makeup cosmetic such as a waterproof mascara, since it is a polymer-based emulsion, it has a relatively high viscosity (1,000 mPa · s or more at 30 ℃). Therefore, the impregnation of the composition in cotton fabric requires physical force for a whole day or a certain amount, which is not suitable for wiping.

The present inventors have made an effort to develop a cleaning composition having optimum physical properties for impregnation in cotton fabric, exerting high cleaning performance for a makeup cosmetic that can be used, without giving a greasy feeling during wiping and being sticky immediately after use. As a result, the present inventors have found that a combination of a specific polymer, oil, nonionic surfactant, water in a specific ratio and further a water-soluble salt or acid provides a multi-layer cleansing composition which is easily impregnated in a wiping material such as a cotton fabric or a nonwoven fabric, does not make the skin feel greasy during wiping, and does not feel sticky immediately after use, and can remove a tough make-up cosmetic such as a water-resistant mascara, thereby completing the present invention.

Although the multi-layer cleaning composition of the present invention contains a large amount of oil in the polymer-based emulsion, it can be rapidly impregnated in a wiping material such as cotton fabric. In addition, multiple layers of the cleaning composition are uniformly mixed and impregnated in a wipe material for use, for example, by shaking, and then stubborn make-up cosmetics such as water-resistant mascara can be removed. Further, the composition does not make the skin feel greasy during wiping and does not feel sticky immediately after use, and the user can achieve a refreshing feeling of the skin after use. Moreover, once the composition is uniformly mixed, the composition can maintain a uniform emulsion when the user uses the multi-layer cleaning composition of the present invention, and save the user from re-shaking during wipe material changes.

In the multi-layer cleaning composition of the present invention, the oil agent rises to the upper layer (emulsion layer, such as O/W) while maintaining the emulsion state, and the aqueous phase falls to the lower layer (aqueous layer). This is so-called creaming (generating) in which the composition is separated into at least two layers of an emulsion layer and an aqueous layer. However, when the composition is mixed, oil droplets (emulsified particles) may be easily and uniformly redispersed. When a user uses the multi-layered cleaning composition of the present invention, it may be in a uniform emulsion state having a low viscosity.

In a conventional multi-layer cleansing composition that separates into an oil layer and an aqueous layer in a static state, when mixed, the oil phase and the aqueous phase disperse to form an emulsion. However, since the composition needs to cause phase separation, the surface film of oil droplets is weak in strength, and the emulsion state is easily disintegrated to separate an oil layer and a water layer. Therefore, when the composition is impregnated in a cotton fabric, the composition almost immediately separates into an oil layer and a water layer, wherein a large amount of oil agent may contact the skin, and the user may feel a strong greasy feeling during wiping.

In contrast, in the present invention, when mixed, the oil droplets previously present in the emulsion layer may be uniformly dispersed throughout the composition. The surface film of the oil droplets is strong enough not to break at the stage of impregnation of the cotton fabric, but the oil droplets break due to physical force generated by wiping and an appropriate amount of oil is released to exert high cleanability. Therefore, when the cotton fabric impregnated with the composition is in contact with the skin, the oil is not released from the oil droplets onto the skin and the user feels a fresh feeling, and during wiping, an excessive amount of the oil is not released from the oil droplets, the greasy feeling is suppressed, and the user can achieve skin refreshment after use.

The polymer of component (a) used in the present invention contains one or more monomers selected from the following (a1), (a2) and (a 3):

(a1) monomers of acrylic acid and methacrylic acid, and,

(a2) monomers of alkyl acrylates and alkyl methacrylates, and

(a3) polyoxyethylene alkyl acrylate and polyoxyethylene alkyl methacrylate.

The polymer of component (a) used in the present invention adsorbs at the oil/water interface and forms an absorption layer that prevents oil droplet integration. Then the oil droplets were stabilized and the oil solution was dispersed in the aqueous layer. Unlike micro O/W emulsification using a low-molecular surfactant such as polyoxyethylene hydrogenated castor oil as a main emulsifier, the polymer of the component (a) emulsifies the oil agent roughly (unevenly). Then, the oil agent is easily released by physical force during wiping. The released oil dissolves the makeup cosmetic, and the composition of the present invention can exert high cleansing properties.

Further, it is assumed that the component (a) contributes to suppression of greasy feeling during wiping because the distribution of the composition is suppressed without greatly impairing the stabilizing effect of the oil droplets due to the interaction with the component (C) (nonionic surfactant) and the component (D) (water-soluble salt or acid).

The polymer of the component (a) is not particularly limited as long as the polymer contains a monomer selected from (a1), (a2) and (a3) as a constituent unit, and there is no limitation on the content ratio and the bonding manner such as block bonding or random bonding. The polymer of ingredient (a) may comprise a monomer other than the monomer selected from (a1), (a2), and (a 3). The polymer of component (a) may be crosslinked. From the viewpoint of improving the impregnation property in the wipe material and improving the skin-refreshing feeling after use, it is preferable to contain a polymer containing (a1) as a constituent unit, and more preferable to contain a copolymer containing (a1) and (a2) as constituent units.

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

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

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

Examples of the polymer of the component (a) include the following.

Examples of the polymer containing the monomer (a1) as a constituent unit but 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 a constituent unit include acrylic acid- (meth) acrylic acid alkyl ester copolymer (acrylic acid ester/C10-30 alkyl ester crosslinked polymer; PEMULEN TR-1, PEMULEN TR-2, Carbopol ETD 2020(Lubrizol Advanced Materials)), acrylic acid ester copolymer (copolymer composed of one or more of (C1-4) acrylic acid alkyl ester, (C1-4) methacrylic acid alkyl ester, acrylic acid and methacrylic acid); aculyn 33(Roam and Haas)), (acrylate/vinyl neodecanoate crosspolymer) copolymer ((meth) acrylate/alkyl (meth) acrylate/vinyl neodecanoate crosspolymer; aculyn 38(Roam and Haas), (acrylic acid/stearyl acrylate) copolymer (described in JP 2007-238549), (acrylate/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 constituent units include acrylate/steareth-20 methacrylate copolymer (Aculyn 22(Roam and Haas)), acrylate/beheneth-25 methacrylate copolymer (Aculyn 28(Roam and Haas)), acrylate/steareth-20 methacrylate crosspolymer (Aculyn 88(Roam and Haas)), and the like.

From the viewpoints of improving the cleaning speed and the cleansing property, suppressing the greasy feeling during wiping, suppressing the sticky feeling immediately after use, providing the skin-refreshing feeling after use, and maintaining the emulsion state even when stored at high temperature, the component (a) may include one or more selected from the group consisting of a carboxyvinyl polymer, an acrylic acid-alkyl methacrylate crosspolymer, an acrylate copolymer, an acrylic acid/stearyl acrylate copolymer, an acrylic acid/steareth-20 methacrylate copolymer, an acrylic acid/beheneth-25 methacrylate, and an (acrylic acid/steareth-20 methacrylate) crosspolymer, more preferably from the group consisting of an acrylic acid-alkyl methacrylate crosspolymer, an acrylic acid/steareth-20 methacrylate copolymer, a water-soluble acrylic acid, a water, One or more of (acrylate/beheneth-25 methacrylate) and (acrylate/steareth-20 methacrylate) cross-linked polymers, further preferably one or more selected from the group consisting of alkyl acrylate-methacrylate cross-linked polymers and (acrylate/steareth-20 methacrylate) cross-linked polymers.

Ingredient (a) may be selected from one or more of monomers (a1), (a2), and (a3), alone or in combination. The content of the component (a) in the total composition 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, and is 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, from the viewpoints of improving the cleaning speed, impregnation into a cotton fabric and cleaning property, suppressing greasy feeling during wiping, and maintaining the state of an emulsion in use. The content of the component (A) is 0.003 to 0.3% by mass, preferably 0.005 to 0.25% by mass, more preferably 0.008 to 0.18% by mass, further preferably 0.01 to 0.12% by mass, and further preferably 0.03 to 0.08% by mass.

The component (B) used in the present invention is an oil agent. The component (B) is not particularly limited, but when used in a cleansing cosmetic, it is preferable to contain an oil agent having a viscosity of 18mPa · s or less at 30 ℃ from the viewpoint of providing permeability to a cosmetic in or coated on a fine structure of skin (for example, wrinkles, pores, rough texture), improving cleansing speed and cleansing property. Here, the viscosity can be measured by a BM-type viscometer (Tokyo Keiki Inc., model TVB-10 viscometer, measurement conditions: spindle No. 1, 60rpm, 1 minute). In particular, when the composition of the present invention is used for cleaning a tough makeup cosmetic such as a water-repellent mascara, the viscosity of the component (B) is preferably 15mPa · s or less, more preferably 10mPa · s or less, from the viewpoint of dissolving the makeup cosmetic, improving the cleaning speed and the cleaning property. The viscosity of the component (B) is preferably 1mPa · s or more from the viewpoint of suppressing dripping during use.

From the viewpoint of maintaining excellent cleansing properties, suppressing greasy feeling during wiping, suppressing sticky feeling immediately after use, and improving skin-refreshing feeling after use, the oil agent having a viscosity of 18mPa · s or less at 30 ℃ preferably contains one or more selected from (b1) hydrocarbon oils, (b2) ether oils, and (b3) silicone oils, more preferably one or more selected from component (b1) and component (b2), and further preferably at least component (b 1).

Examples of the component (b1) (hydrocarbon oil having a viscosity of 18mPa · s or less at 30 ℃) include isoparaffins such as light isoparaffins, light liquid isoparaffins, liquid isoparaffins; isododecane, isohexadecane. Among them, from the viewpoint of improving the cleaning speed and the cleaning property and providing the skin with a refreshing feeling after use, those having a viscosity of 10mPa · s or less at 30 ℃ are preferable, one or more selected from liquid isoparaffin, isododecane and isohexadecane are more preferable, and one or more selected from isododecane and isohexadecane is further preferable.

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

Examples of the component (b2) (ether oil having a viscosity of 18mPa · s or less at 30 ℃) preferably include dialkyl ethers from the viewpoint of providing a non-greasy feeling to the skin during wiping and suppressing a sticky feeling immediately after use. The dialkyl ether preferably consists of a C2-18 alkyl group, and more preferably consists of a C6-16 alkyl group. Specifically, dilauryl ether, dioctanoyl ether and hexadecyl-1, 3-dimethylbutyl ether are preferred. From the viewpoint of improving the cleaning speed and the cleaning property, dioctanoyl ether is more preferable.

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

Examples of the component (b3) (silicone oil having a viscosity of 18 mPas or less at 30 ℃) include those having a viscosity of 1.5mm²/s、2mm²/s、5mm²/s、10mm²Dimethylpolysiloxane (PDMS) in terms of/s, etc.; dimethylcyclopolysiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane; branched chain silicaAlkanes such as tris (trimethylsilyl) methylsilane, tetrakis (trimethylsilyl) silane, and the like; methylphenylpolysiloxane, and the like. Among them, component (b3) is preferably one having a viscosity of 1.5mm from the viewpoint of providing a quick-drying feeling after cleansing and a refreshing feeling of the skin after use²S or 2mm²One or more of dimethylpolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and tris (trimethylsilyl) methylsilane in a ratio of/s, and more preferably a viscosity of 2mm²Dimethyl polysiloxane per second.

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

From the viewpoint of suppressing greasy feeling during wiping and sticky feeling immediately after use and improving skin-refreshing feeling after use, all or a part of the components (b1), (b2), and (b3) is preferably volatile oil which hardly remains on the skin. In the present invention, the volatile oil is an oil agent which evaporates in the atmosphere and has a boiling point of 300 ℃ or lower.

The volatile oil is not particularly limited as long as it can be used in conventional cosmetics, for example, straight chain dimethylpolysiloxane such as dimethylpolysiloxane (1.5 mm)²S) (boiling point: 190 ℃ C.), dimethylpolysiloxane (2 mm)²S) (boiling point: 230 ℃); branched siloxanes such as tris (trimethylsilyl) methylsilane (boiling point: 191 ℃ C.), tetrakis (trimethylsilyl) silane (boiling point: 267 ℃ C.); volatile silicone oils such as cyclomethicones, e.g., octamethylcyclotetrasiloxane (boiling point: 176 ℃ C.), decamethylcyclopentasiloxane (boiling point: 210 ℃ C.), dodecamethylcyclohexasiloxane (boiling point: 245 ℃ C.); volatile hydrocarbon oils such as isododecane (boiling point: 177 ℃), isohexadecane (boiling point: 210 ℃) 250 ℃, light isoparaffins, light liquid isoparaffins, liquid isoparaffins; dioctanoyl ether (boiling point: 291 ℃ C.), dilauryl ether (boiling point: 190 ℃ C.). In particularFrom the viewpoint of improving the skin-refreshing feeling after use and excellent cleansing properties, it is preferable to contain one or more selected from hydrocarbon oils, ether oils and silicone oils having a boiling point of 150 ℃ or higher, more preferably one or more selected from hydrocarbon oils, ether oils and silicone oils having a boiling point of 170 ℃ or higher, and still more preferably dimethyl polysiloxane (2 mm. degree. C.)²One or more of isododecane, isohexadecane, tris (trimethylsilyl) methylsilane, and dioctanoyl ether.

The content of the volatile oil in the components (B1), (B2), and (B3) is preferably 30% by mass or more, more preferably 60% by mass or more, further preferably 90% by mass or more, and preferably 100% by mass or less of the total content of the component (B), from the viewpoints of suppressing greasy feeling during wiping, suppressing sticky feeling immediately after use, and improving skin-refreshing feeling after use.

In the present invention, the composition of the present invention may contain an oil agent other than the components (b1), (b2) and (b3) from the viewpoint of improving the feeling of skin moisturization after use. Examples of the oil agent other than the components (b1), (b2), and (b3) include ester oils, fatty acids, higher alcohols (C8 or more), fluorine oils, and hydrocarbon oils, ether oils, silicone oils, and the like, each having a viscosity of 18mPa · s or more at 30 ℃.

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

From the viewpoint of maintaining the state of an emulsion in use, improving the cleaning speed, the cleaning property, the non-greasy feeling during wiping, the non-sticky feeling immediately after use, and providing an excellent degree of impregnation into a wiping material (such as a cotton fabric), the content of the component (B) (oil agent) in the total composition is 5 mass% or more, preferably 8 mass% or more, more preferably 10 mass% or more, further preferably 12 mass% or more, and 40 mass% or less, preferably 35 mass% or less, more preferably 30 mass% or less, further preferably 25 mass% or less. The content of the component (B) in the total composition is 5 to 40% by mass, preferably 8 to 35% by mass, more preferably 10 to 30% by mass, still more preferably 12 to 30% by mass, and yet more preferably 12 to 25% by mass.

Further, the total content of the components (B1), (B2) and (B3) in the component (B) is preferably 70% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, further preferably 95% by mass or more, further preferably 99% by mass or more, from the viewpoints of improving the cleansing speed and cleansing properties, suppressing greasy feeling during wiping, and suppressing sticky feeling immediately after use. Even more preferably, component (B) consists of components (B1), (B2) and (B3).

Component (C) used in the present invention is a nonionic surfactant. The multi-layer cleaning composition of the present invention tends to impair emulsion stability because the coexistence of the component (a) and the component (D) reduces the degree of dissociation of the polymer in water, and then reduces the thickening effect of the component (a). Therefore, the oil agent can be separated from the emulsion layer as an upper layer. However, if the component (C) nonionic surfactant is used, separation of the oil agent from the emulsion layer can be suppressed, and the composition can be maintained in a stable state. It is believed that the nonionic surfactant of ingredient (C) contributes to quick cleansing because it keeps oil droplets stable in a small amount while maintaining low viscosity by interaction with the polymers of ingredient (a) and ingredient (D), and ingredient (C) improves impregnation in the wipe material, and the composition penetrates into the fine structure of the skin or the makeup cosmetic covering thereon.

From the viewpoint of maintaining the emulsion state during storage at high temperature, maintaining the skin refreshing feeling until after use, and improving the cleaning speed and the cleaning property, the HLB of the component (C) (nonionic surfactant) may be preferably 2 or more, more preferably 8 or more, more preferably 10 or more, further preferably 11 or more, further preferably 12 or more, preferably 20 or less, more preferably 18 or less, further preferably 16 or less, further preferably 14 or less, further preferably 13.8 or less. The HLB of the component (C) may preferably be 2 to 20, more preferably 8 to 18, still more preferably 10 to 16, still more preferably 11 to 14, and still more preferably 12 to 13.8.

Herein, HLB (hydrophilic-lipophilic balance) represents the molecular weight of a hydrophilic portion in the total molecular weight of the surfactant. For the nonionic surfactant, HLB value at 25 ℃ as defined by GRIFIN was used. The HLB value of GRIFIN is defined in J.Soc.cosm.chem.,1954,5: 249-256. When a plurality of nonionic surfactants are used, the HLB is the HLB of the surfactant mixture consisting of the plurality of nonionic surfactants. The HLB of the surfactant mixture may be mathematically given according to the following equation based on the content ratio of each nonionic surfactant.

HLB ═ Sigma (HLBx. times.Wx)/. Sigma Wx for surfactant mixtures

Wherein HLBx represents the HLB of the nonionic surfactant X, and Wx represents the mass weight (g) of the nonionic surfactant X having an HLBx value.

Examples of the component (C) (nonionic surfactant) may include, for example, polyglycerin fatty acid esters, polyethylene glycol fatty acid esters, polyoxyethylene glycerin fatty acid esters, polyoxyethylene polyoxypropylene glycol, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene alkyl ether fatty acid esters, sucrose fatty acid esters, sorbitan fatty acid esters, alkyl polyglycosides, (poly) alkyl glyceryl ethers and the like.

Among them, from the viewpoint of low irritation to the skin or mucous membrane, improvement in lotion retentivity, and provision of excellent refreshing degree during wiping, it is preferable to contain one or more nonionic surfactants selected from the group consisting of polyglycerin fatty acid esters, polyethyleneglycol fatty acid esters, polyoxyethylene glycerin fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene hydrogenated castor oil, sucrose fatty acid esters, and sorbitan fatty acid esters; more preferably one or more nonionic surfactants selected from the group consisting of polyglycerin fatty acid esters, polyethylene glycol fatty acid esters, polyoxyethylene sorbitan fatty acid esters and polyoxyethylene hydrogenated castor oil; it is further preferred to contain one or more nonionic surfactants selected from the group consisting of polyglycerin fatty acid esters and polyoxyethylene hydrogenated castor oil.

The component (C) may be used alone or in combination of two or more. The content of the component (C) in the total composition is 0.01% by mass or more, preferably 0.05% by mass or more, and more preferably 0.1% by mass or more, from the viewpoint of suppressing greasy feeling during wiping, maintaining emulsion stability in use, and providing excellent cleaning speed. The content of the component (C) in the total composition is 1.5% by mass or less, preferably 1.0% by mass or less, more preferably 0.8% by mass or less, and further preferably 0.45% by mass or less, from the viewpoint of not affecting the oil releasability and maintaining the cleanness. The content of the component (C) in the total composition is 0.01 to 1.5% by mass, preferably 0.05 to 1.0% by mass, more preferably 0.05 to 0.8% by mass, and still more preferably 0.1 to 0.45% by mass.

Ingredient (D) used in the present invention may include one or more ingredients selected from the group consisting of water-soluble salts of ingredient (D1) and acids of ingredient (D2). Ingredient (D) can reduce the viscosity of the emulsion containing ingredients (a), (B) and (C) to achieve high impregnation in wiping materials such as cotton fabrics. Among them, the component (d2) is preferably used in an amount smaller than that of the component (d1) in order to lower the viscosity of the emulsion to avoid greasy feeling.

In the component (D), the component (D1) (water-soluble salt) is a water-soluble salt, and is preferably a salt that becomes acidic or neutral in a1 mass% 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 can be preferably used.

In the component (D), the component (D2) (acid) includes an organic acid or an inorganic acid. Both organic acids and inorganic acids can be used, and organic acids are preferable from the viewpoint of imparting a preservative effect to the emulsion. More preferably one or more organic acids selected from hydroxycarboxylic acids and dicarboxylic acids, and further preferably one or more organic acids selected from dicarboxylic acids. Examples of hydroxycarboxylic acids include glycolic acid, lactic acid, glyceric acid, gluconic acid, pantothenic acid and citric acid. Examples of dicarboxylic acids include malic acid, oxalic acid, malonic acid, maleic acid, succinic acid, glutaric acid, and adipic acid.

From the viewpoint of improving the cleaning speed and the cleaning property, suppressing the greasy feeling during wiping, maintaining the state of an emulsion in use, and imparting excellent impregnation property to the composition in the wiping material, the content of the component (D) (the total content of the component (D1) and the component (D2)) in the total composition is preferably 0.005% by mass or more, more preferably 0.010% by mass or more, further preferably 0.012% by mass or more, further preferably 0.018% by mass or more, preferably 0.9% by mass or less, further preferably 0.8% by mass or less, further preferably 0.7% by mass or less, further preferably 0.6% by mass or less. The content of the component (D) in the total composition is preferably 0.005 to 0.9% by mass, more preferably 0.010 to 0.8% by mass, still more preferably 0.012 to 0.7% by mass, and still more preferably 0.018 to 0.6% by mass.

When the component (D) is composed of the component (D1) (water-soluble salt), the content of the component (D1) in the total composition is preferably 0.03 mass% or more, more preferably 0.05 mass% or more, further preferably 0.08 mass% or more, preferably 0.9 mass% or less, more preferably 0.8 mass% or less, further preferably 0.6 mass% or less, from the viewpoints of suppressing gelation of an emulsion, maintaining an emulsion state in use, and suppressing a greasy feeling. The content of the component (d1) in the total composition is preferably 0.03 to 0.9% by mass, more preferably 0.08 to 0.6% by mass.

When the component (D) is composed of the component (D2) (acid), the content of the component (D2) in the total composition is preferably 0.012% by mass or more, more preferably 0.013% by mass or more, further preferably 0.018% by mass or more, preferably 0.5% by mass or less, further preferably 0.3% by mass or less, further preferably 0.12% by mass or less, from the viewpoints of suppressing gelation of an emulsion, maintaining the state of an emulsion in use, and suppressing greasy feeling. The content of the component (d2) in the total composition is preferably 0.012 to 0.5 mass%, more preferably 0.013 to 0.3 mass%, and further preferably 0.018 to 0.12 mass%.

When the composition of the present invention contains the component (D2) acid as the component (D), 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, more preferably 5.5 or less, from the viewpoints of reducing the viscosity of the emulsion upon mixing, providing excellent impregnation in a wiping material such as cotton fabric, improving the cleaning speed, the cleaning property, and reducing the irritation to the skin. When the composition of the present invention does not contain component (D2) as component (D), 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, more preferably 6.5 or less, from the same viewpoint as above. Note that pH measurement can be performed using the composition using a pH meter (Horiba, Ltd., model: F-22) in which the composition is stored vertically upward for 2 hours or more in an isothermal bath at 30 ℃ and then shaken up and down 15 times (shaking stroke length: 15 cm; shaking speed is 5 reciprocations per 3 seconds), and then immediately (measurement is started after shaking is stopped for 10 seconds).

Component (E) used in the present invention is water. Ingredient (E) may include tap water, purified water (including water filtered by ion exchange resin), smoothing toner, distilled water (including distilled water of plant origin, such as rose water and lavender water), mineral water, and one or more may be suitably used. The content of the component (E) in the total composition is preferably 25% by mass or more, more preferably 30% by mass or more, 35% by mass or more, and preferably 95% by mass or less, 90% by mass or less, 85% by mass or less, from the viewpoint of maintaining excellent cleansing properties and improving the skin-refreshing feeling after use. The content of water of the component (E) in the total composition is preferably 25 to 95% by mass, more preferably 30 to 90% by mass, and further preferably 35 to 85% by mass.

The multi-layer cleaning composition of the present invention may optionally comprise ingredient (F) (powder). After the composition is wiped off, the ingredient (F) remains on the skin, which can impart a long-lasting smooth feeling to the skin after use. It may even impart an aesthetic appearance and/or uv protection. The component (F) is preferably insoluble in any of the component (E) (water), the component (B) (oil agent), the component (G) (ethanol), or the component (H) (polyol).

There is no particular limitation on the component (F) (powder) as long as it can be generally used in cosmetics. Examples of the inorganic powder include titanium oxide, zinc oxide, magnesium oxide, zirconium oxide, calcium carbonate, magnesium silicate, barium sulfate, silica (anhydrous silicic acid), mica, talc, kaolin, sericite, annatto, yellow iron oxide, black iron oxide, carbon black, manganese violet, glass beads, zeolite, pearl pigment (annatto-coated mica, titanium oxide-coated mica, etc.), and composite inorganic powders thereof. As the organic powder, examples thereof include acrylic resins, styrene resins, polyolefins, silicone resins, fluoride resins, polyester resins, polyamide resins, epoxy resins, phenol resins, polyurethane resins; fiber powder such as silk powder, hemp powder, and powder composed of cellulose or its derivatives; powdered sugar such as starch or derivatives thereof. These may be used alone or in combination of 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 microbeads P-4000, silica microbeads P-1505, silica microbeads 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), micas such as A-11, A21-S, AB-25S (Yamaguchi Mica Co., Ltd.); silicone resin powders 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), Torayfil E506S, Torayfil E508, BY29-129(Toray Corning), Ganz-paru AI-045C, Ganz-paru SIG-070; acrylic resin powders 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, from the viewpoint of improving the smoothness of the skin and imparting excellent smooth feeling to the skin after use, one or more selected from talc, silica, mica, silicone resin powder and acrylic resin powder is preferably contained, more preferably one or more selected from silica, silicone resin powder and acrylic resin powder is contained, and further preferably one or more selected from (lauryl methacrylate/sodium methacrylate) crosspolymer and silica is contained.

The shape of the powder is not particularly limited, and any of a spherical shape, a rod shape, a shuttle shape, a needle shape, and an amorphous shape may be used. From the viewpoint of improving the skin smoothness and providing a smooth skin feel after a small amount of use, spherical powders are preferable. In the present invention, "spherical" means that an image of a single powder projected with an electron scanning microscope is an exact circle, or the projected image has a shape in which a circumscribed circle of the projected image is drawn and the outline of the projected image is entirely contained between a concentric circle having a radius of 90% of the circumscribed circle and the circumscribed circle.

Ingredient (F) (powder) may have its surface subjected to a hydrophilic or hydrophobic treatment. 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 of subjecting the powder surface to oil adsorption; and lipophilic treatment of the powder by esterification or etherification of functional groups such as hydroxyl groups, metal soap treatment using zinc, magnesium or aluminum salts of fatty acids; silicone treatment using a silicone compound such as dimethylsiloxane or methylhydrogensiloxane; fluorine treatment, such as treatment with a fluorine compound having a perfluoroalkyl group. A combination of hydrophilically treated and hydrophobically treated powders may be formulated in the multi-layer cleaning compositions of the present invention.

The multi-layer cleaning composition of the present invention is an O/W emulsion when mixed, and a hydrophilic powder which is easily dispersible in water is preferably used from the viewpoint of improving the dispersibility of the powder in the composition. Hydrophilicity can be determined by the following evaluation method.

(evaluation of hydrophilicity)

In a glass bottle of 50mL volume, water (10g), hexane (10g) and powder (1g) were added, and the lid was closed and the contents were mixed by gentle shaking. The vials were then sonicated (38kHz) for 2 minutes and stored vertically up for 5 minutes during which time the appearance was observed. A powder is determined to be hydrophilic when present in the lower phase (aqueous phase) based on the water/hexane interface; when the powder was present in the upper phase (hexane phase), the powder was determined to be hydrophobic.

When the specific gravity of the component (F) (powder) is higher than 1, for example, an inorganic powder containing metal ions, it is deposited and accumulated on the bottom as time passes. When such a heavy powder is used in the composition, the component (F) is preferably used in combination of different particle diameters from the viewpoint of improving the redispersibility of the powder deposited on the bottom and from the viewpoint of providing excellent skin smoothness feeling after use. The component (F) (powder) preferably contains both a powder having a particle size of 0.2 to 10 μm and a powder having a particle size of more than 10 μm and not more than 50 μm, and more preferably contains both a powder having a particle size of 2 to 7 μm and a powder having a particle size of 15 to 30 μm. In the present invention, the particle diameter means a mode diameter, which is the most frequent value in the volume-based particle size distribution. When the volume-based particle size distribution displays multiple peaks, each mode diameter can be derived from each mode of the peak.

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

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

In the present invention, the volume-based particle size distribution can be measured by the following method.

(measurement of particle size on a volume basis)

An aqueous dispersion containing 10 mass% of the powder in ion-exchanged water was measured by a laser scattering particle distribution analyzer (Partrica LA-920, Horiba, Ltd.) under conditions (refractive index: 1.45, circulation speed (grade: 5), stirring speed (grade: 5)). Ion-exchanged water is used as the solvent.

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

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

The multi-layer cleansing composition of the present invention may optionally contain ingredient (G) (ethanol) from the viewpoint of providing a skin refreshing feeling after use.

When the multi-layer cleansing composition of the present invention contains the component (G) (ethanol), the content of the component (G) is preferably 0.1% by mass or more, more preferably 1% by mass or more, and further preferably 3% by mass or more, from the viewpoint of suppressing greasy feeling during wiping, suppressing sticky feeling immediately after use, and providing skin cool feeling after use. The content of ethanol as the component (G) is preferably 20% by mass or less, more preferably 15% by mass or less, and still more preferably 10% by mass or less, from the viewpoint of maintaining the emulsion state. The content of the component (G) in the composition is 0.1 to 20% by mass, more preferably 1 to 15% by mass, and still more preferably 2 to 10% by mass.

The multi-layer cleansing composition of the present invention may further comprise ingredient (H) (polyol) from the viewpoint of improving the feeling of skin moisturization after use. The polyhydric alcohol includes polyvalent alcohols, and examples thereof include divalent alcohols such as ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol (propylene glycol), dipropylene glycol, polypropylene glycol, isoprene glycol, propylene glycol (propanediol), 1, 3-butanediol, hexylene glycol; trivalent or more alcohols such as trimethylolpropane, glycerol, diglycerol, triglycerol, tetraglycerol, hexaglycerol, decaglycerol, polyglycerol (excluding sugars and sugar alcohols); sugars or sugar alcohols such as erythritol, pentaerythritol, dipentaerythritol, glucose, mannose, galactose, sucrose, fructose, maltose, maltitol, xylitol, cellosolve, sorbitan, sorbitol, polyoxyethylene methyl glycoside, and the like. Among them, from the viewpoint of suppressing the sticky feeling immediately after use and improving the skin moist feeling after use, the component (H) is preferably one or more selected from the group consisting of ethylene glycol, diethylene glycol, propylene glycol (propylene glycol), dipropylene glycol, polyethylene glycol, polypropylene glycol, propylene glycol (propanediol), glycerin, 1, 3-butanediol, sorbitol, polyoxyethylene methyl glycoside and maltitol, more preferably one or more selected from the group consisting of ethylene glycol, diethylene glycol, propylene glycol (propylene glycol), dipropylene glycol, polyethylene glycol, polypropylene glycol, propylene glycol (propanediol), polyoxyethylene methyl glycoside and 1, 3-butanediol, and further preferably one or more selected from the group consisting of propylene glycol (propylene glycol), dipropylene glycol, 1, 3-butanediol, propylene glycol (propanediol) and polyoxyethylene methyl glycoside.

The component (H) (polyhydric alcohol) may be used alone or in combination of two or more. The content of the component (H) polyol in the total composition is 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1% by mass or more, and 20% by mass or less, preferably 15% by mass or less, more preferably 10% by mass or less, from the viewpoint of suppressing greasy feeling during wiping, suppressing sticky feeling immediately after use, and improving skin moist feeling after use. The content of the component (H) is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass, and still more preferably 1 to 10% by mass.

From the viewpoint of improving the cleaning speed, the cleaning property, the immersion in cotton fabric, suppressing greasy feeling during wiping, and sticky feeling after use, providing excellent refreshing feeling after use, and maintaining the state of an emulsion in use, the mass ratio [ (a)/(B) ] of the component (a) to the component (B) is preferably 0.0001 or more, more preferably 0.0005 or more, further preferably 0.001 or more, and preferably 0.01 or less, further 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, still more preferably from 0.001 to 0.007.

From the viewpoint of improving the cleansing speed and cleansing properties, suppressing greasy feeling during wiping and sticky feeling after use, providing excellent skin-refreshing feeling after use, and maintaining the state of an emulsion during use, the mass ratio [ (a)/(C) ] of the component (a) to the component (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, further preferably 0.15 or more, and preferably 2.0 or less, more preferably 1.5 or less, further preferably 1.0 or less, 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 preferably from 0.01 to 1.5, further preferably from 0.03 to 1.5, further preferably from 0.08 to 1.0, further preferably from 0.15 to 0.7.

From the viewpoint of suppressing aggregation of the component (a), improving the impregnation, cleaning speed, and cleaning properties of the composition into cotton fabric, suppressing greasy feeling during wiping, suppressing sticky feeling after use, providing excellent skin-refreshing feeling after use, and maintaining the state of an emulsion in use, the mass ratio [ (a)/(D) ] of the component (a) to the component (D) is preferably 0.05 or more, more preferably 0.1 or more, further preferably 0.2 or more, and preferably 20 or less, more preferably 10 or less, 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.

The mass ratio [ (C)/(D) ] of the component (C) to the component (D) is preferably 0.2 or more, more preferably 0.3 or more, 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, from the viewpoints of improving the cleaning speed, the cleaning property, the immersion of the composition into cotton fabric, suppressing greasy feeling during wiping, and sticky feeling after use, providing excellent skin-refreshing feeling after use, maintaining the state of the emulsion during use, and improving the stability of the emulsion. [ (C)/(D) ] is preferably 0.2 to 30, more preferably 0.3 to 20, further preferably 0.4 to 15, and further preferably 0.4 to 7.

The multi-layered cleaning composition of the present invention may further comprise optional ingredients that can be generally formulated into cleaning compositions, in addition to the above-mentioned ingredients, as long as they do not interfere with the technical effects of the present invention. For example, anionic surfactants, cationic surfactants, amphoteric surfactants, disinfectants, anti-inflammatory agents, antiperspirants, preservatives, chelating agents, salts, pearlizing agents, fragrances, cooling agents, pigments, ultraviolet light absorbers, antioxidants, plant extracts, and the like can be used. These optional ingredients may serve not only the intended purpose, but also other purposes (e.g., the antiperspirant may serve as a fragrance), or may be combined with multiple purposes (e.g., an agent may serve both as an antiperspirant and as a fragrance).

The multi-layer cleansing composition of the present invention may comprise an anionic surfactant from the viewpoint of providing a skin refreshing feeling after use. From the viewpoint of maintaining excellent cleansing properties and suppressing irritation to the skin, the content of the anionic surfactant in the total composition is preferably 1% by mass or less, more preferably 0.5% by mass or less, further preferably 0.1% by mass or less, and further preferably 0% by mass.

The multi-layer cleansing composition of the present invention may comprise a cationic surfactant and/or an amphoteric surfactant from the viewpoint of improving the feeling of skin moisturization after use. The total content of the cationic surfactant and the amphoteric surfactant in the total composition is preferably 1% by mass or less, more preferably 0.5% by mass or less, further preferably 0.1% by mass or less, and further preferably 0% by mass, from the viewpoint of maintaining excellent cleansing properties, suppressing greasy feeling during wiping, and suppressing sticky feeling immediately after use.

The multi-layer cleaning composition of the present invention may further comprise an ultraviolet absorber from the viewpoint of improving light resistance. The content of the ultraviolet absorber in the total composition is preferably 1% by mass or less, more preferably 0.5% by mass or less, further preferably 0.1% by mass or less, and further preferably 0.05% by mass or less, from the viewpoint of maintaining excellent cleansing properties and improving the skin-refreshing feeling after use.

In the production of the multi-layer cleaning composition of the present invention, if the component (a) exerts a thickening effect by neutralization, it is preferable to add the component (K) (alkaline neutralizing agent) after dispersing the component (a) in the component (E) (water). In the present invention, the term basic neutralizing agent means a substance capable of accepting a proton from another substance (i.e., proton acceptor). After dispersing the component (a) in the component (E), the component (K) is added to thicken the hydrogel with the component (a). During the thickening process, the component (B) (oil agent) is absorbed by the hydrogel, resulting in rough emulsification of the oil agent.

Among the polymers of the component (a), examples of the polymer which provides thickening by neutralization include polymers containing the monomer (a1) as a constituent unit. Examples of the polymer containing the monomer (a1) as a constituent unit are described above.

Examples of ingredient (K) (basic neutralizing agent) may include inorganic basic compounds, organic amine compounds and basic amino acids. Specifically, inorganic alkali compounds such as sodium hydroxide, potassium hydroxide; organic amine compounds 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; basic amino acids such as arginine, lysine, histidine. Among them, one or more selected from the group consisting of sodium hydroxide, potassium hydroxide, triethanolamine, 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1, 3-propanediol and arginine are preferably used. The content of the component (K) may be an amount sufficient for the component (A) to exert its property, preferably an amount corresponding to a neutralization ratio of the component (A) of 0.3 to 1.2, more preferably an amount corresponding to a neutralization ratio of 0.4 to 1.1.

(production method)

The multi-layer cleaning composition of the present invention can be manufactured by mixing each ingredient in a conventional method. When the composition contains a solid material at normal temperature, the solid material may be preheated to be melted or dissolved in another ingredient, and then all the ingredients may be uniformly mixed to manufacture.

When the component (a) (polymer), the component (B) (oil agent), and the component (E) (water) are mixed, the component (a) is adsorbed on the oil-water interface, forming an adsorption layer, preventing the integration of oil droplets. The oil droplets then stabilized. However, emulsified compositions with ingredient (a) have a relative tendency to increase viscosity and the compositions are often difficult to impregnate in wiping materials such as cotton fabrics. However, addition of ingredient (D) ((D1) water-soluble salt or (D2) acid) may interfere with formation of hydrated gel, then reduce viscosity, but may cause aggregation of polymer, and the oil agent may elute from the oil droplets. To solve this problem, in the present invention, before adding component (D), component (C) (nonionic surfactant) is added to the emulsion that has been pre-emulsified with component (a). Therefore, after the addition of the component (D), the polymer can maintain an emulsion state and inhibit the aggregation of the polymer. The composition can release oil agent during wiping, and can exert high cleaning property for cosmetic.

For the polymer of the component (a) which exerts a thickening effect by neutralization, the component (a) contains at least a carboxylic acid such as acrylic acid or methacrylic acid. These polymers are mixed with component (E) (water) to neutralize component (K) (alkaline neutralizing agent) to form a hydrogenated gel, thereby exerting a thickening effect. In the thickening process, when the component (B) (oil agent) is present, the oil agent is trapped in the hydrogenated gel, resulting in coarse emulsification of the oil agent. However, the emulsified state caused by ingredient (a) may increase the viscosity of the composition, which may impair impregnation in wiping materials such as cotton fabrics. Therefore, as described in the above production method, by adding component (C) (nonionic surfactant) to the emulsion pre-emulsified with component (a) before adding component (D), the state of the polymer crude emulsified oil agent can be maintained and aggregation of the polymer can be suppressed after adding component (D). During wiping, the composition releases an oil agent to exert high cleanness for makeup cosmetics.

In a specific production method, component (a) (polymer), component (B) (oil agent), component (E) (water), and optionally component (K) (alkali neutralizing agent), and further optionally other optional components are mixed (and neutralized) to obtain mixture 1. Next, component (C) (nonionic surfactant) and optionally a surfactant other than component (C) are added to mixture 1 to obtain mixture 2. Mixing mixture 2 with component (C) can suppress aggregation of oil droplets. Subsequently, component (D) (component (D1) (water-soluble salt) or component (D2) (acid)) was added to mixture 2 to obtain the composition of the present invention. The obtained composition can achieve low viscosity while maintaining oil droplets, and thus it provides excellent impregnation in wiping materials such as cotton fabrics, and even excellent cleaning effect and usability.

The method of making the multi-layer cleaning composition more specifically comprises:

(step 1) mixing component (a), component (B) and component (E), and optionally component (K) an alkaline neutralizing agent and further optionally other optional components to obtain a mixture 1;

(step 2) adding the component (C) to the mixture 1, optionally adding a surfactant other than the component (C), to obtain a mixture 2; and

(step 3) component (D) was added to mixture 2.

(viscosity)

The viscosity of the multi-layer cleaning composition of the present invention immediately after shaking 15 times (stroke length: 15cm, 5 reciprocations per 3 seconds) was 100 mPas or less at 30 ℃, wherein the measurement was started after pausing the shaking for 10 seconds. The measurement conditions of the viscosity are as follows. The viscosity at 30 ℃ immediately after stirring is preferably 50mPa · s or less, more preferably 30mPa · s or less, further preferably 25mPa · s, and is preferably 1mPa · s or more, more preferably 3mPa · s or more, further preferably 5mPa · s or more, from the viewpoint of suppressing dripping of the composition from the hand at the time of use and providing excellent permeability in a cotton fabric. The viscosity at 30 ℃ immediately after the stirring is preferably 1 to 50 mPas, more preferably 3 to 30 mPas, and still more preferably 5 to 25 mPas.

(layer)

In the quiescent state, the multi-layer cleaning composition separates into at least two layers, including an emulsion layer and an aqueous layer. The multi-layer cleaning composition may have more than two layers. For example, the composition may contain ingredient (F) (powder) to be a three-layer composition consisting of an emulsion layer, a water layer and a powder layer. The composition may further comprise an oil immiscible with the emulsion layer (such as a fluorine-based oil agent, such as perfluoropolymethylisopropyl group) different from the component (B) to form a three-layer composition consisting of an emulsion layer, an aqueous layer and an oil layer. Pigments and/or dyes may be added to each layer to enhance the appearance, whereby the user may enjoy color change during mixing. From the viewpoint of aesthetics, it is preferred that the composition of the present invention has an appearance evaluation which is not changed for 24 hours in a static state.

(method of use)

The user can use the multi-layer cleansing composition of the present invention after conversion to a homogeneous emulsion by mixing. The method of mixing involves shaking several times. Specifically, the user may grasp a container containing multiple layers of the cleaning composition and shake the container up and down by hand 1 to 15 times, preferably 1 to 10 times, more preferably 1 to 5 times, with a stroke length of 15cm to emulsify the cleaning composition separated in a static state uniformly. In the present invention, the obtained emulsion may become an O/W emulsion. The headspace is preferably made 3% to 10% relative to the total container volume so that the contents can be mixed efficiently. In particular, in the component (F), a powder having a specific gravity higher than 1 (e.g., silica, zinc oxide, titanium oxide) is contained, and the composition may sometimes be difficult to redisperse uniformly even if shaken, which may prevent providing a smooth feeling to the skin after use. Therefore, it is preferable to provide a stirring means so that the contents can be physically mixed. Examples of the stirring member include a metal ball (e.g., a stainless steel ball), a stirring rod, and a stirring blade. Among them, metal balls are preferably used from the viewpoint of easy production.

When the user uses the multi-layer cleaning composition of the present invention, the user performs the shaking operation as described above. Then, when the user uses the multi-layer composition of the present invention (for example, 1 minute or more, preferably 5 minutes or more, and further preferably 10 minutes or more), the emulsion state (i.e., homogeneous state) is maintained. After a certain period of time (for example, within 3 days, preferably within 2 days, and more preferably within 1 day), the composition returns to an original multi-layer state in which the water layer is separated from the emulsion layer, and a cream state is achieved.

The multi-layer cleansing composition of the present invention may be applied to the skin, preferably the skin other than the scalp, more preferably to any one of the face, body, limbs, and further preferably to the face. The multi-layer cleansing composition of the present invention can be suitably used as a cleansing cream, a cleanser, etc., and is preferably used as a cleanser. In particular, it is preferably used as a makeup remover for cleansing makeup cosmetics (e.g., foundation, mascara, eye shadow, lipstick) applied to the face. Preferably, the multi-layer cleansing composition of the present invention is a makeup remover to be wiped off.

With respect to the method of use of the multi-layer cleaning composition of the present invention, for example, the user may initially mix it uniformly. Then, in the first embodiment, the user may wipe a desired portion (e.g., the made-up skin) having the makeup cosmetics applied thereto with a wiping material (e.g., cotton fabric, gauze, woven fabric, nonwoven fabric, puff, tissue) impregnated with the composition to remove the makeup cosmetics from the skin. In a second embodiment, the user may apply the composition to the intended site by hand to remove the make-up makeup by wiping the skin with a wipe material. In a third embodiment, the user may apply the composition to the skin by hand and rinse it from the skin. In a fourth embodiment, the user may apply the composition impregnated in the wipe material to the skin and rinse it from the skin. In a fifth embodiment, the user may wipe and rinse from the skin as described in the first or second embodiments. In a sixth embodiment, the user can wipe the skin with the sheet impregnated with the composition. Alternatively, the user may leave the wipe impregnated with the composition in the desired location and then rinse off the skin to remove the make-up makeup.

The present invention further discloses the following <1> to <53> in relation to the above embodiment.

<1> a multi-layer cleaning composition comprising the following (a) to (E):

(A)0.003 to 0.3 mass% of a polymer comprising a monomer selected from the group consisting of (a1), (a2) and (a 3):

(a1) a monomer selected from the group consisting of acrylic acid and methacrylic acid,

(a2) a monomer selected from the group consisting of alkyl acrylates and alkyl methacrylates, and

(a3) a monomer selected from the group consisting of polyoxyethylene alkyl esters of acrylic acid and polyoxyethylene alkyl esters of methacrylic acid;

(B)5-40 mass% of an oil agent;

(C)0.01 to 1.5 mass% of a nonionic surfactant;

(D)0.005-0.9 mass% of one or more selected from (d1) water-soluble salts and (d2) acids; and

(E) and (3) water.

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

<3> the multi-layered cleaning composition according to <1> or <2>, wherein the ingredient (a) comprises one or more selected from the group consisting of carboxyvinyl polymer, acrylic acid-alkyl methacrylate crosspolymer, acrylate copolymer, (acrylic acid/stearyl acrylate) copolymer, (acrylate/steareth-20 methacrylate) copolymer, (acrylate/beheneth-25 methacrylate) and (acrylate/steareth-20 methacrylate) crosspolymer.

<4> the multi-layered cleaning composition according to any one of <1> to <3>, wherein the ingredient (a) comprises one or more selected from the group consisting of acrylic acid-alkyl methacrylate crosspolymer, (acrylate/steareth-20 methacrylate) copolymer, (acrylate/beheneth-25 methacrylate) and (acrylate/steareth-20 methacrylate) crosspolymer.

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

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

<7> the multi-layered cleaning composition according to any one of <1> to <6>, wherein ingredient (B) comprises (B1) a hydrocarbon oil, preferably (B1) a hydrocarbon oil having a viscosity of 10 mPa-s or less at 30 ℃, (B1) a hydrocarbon oil comprising one or more selected from liquid isoparaffins, isododecane, and isohexadecane, and further preferably (B1) a hydrocarbon oil comprising one or more selected from isododecane and isohexadecane.

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

<9> the multi-layered cleaning composition according to any one of <1> to <8>, wherein the ingredient (B) comprises (B2) an ether oil, preferably (B2) the ether oil is a dialkyl ether, more preferably the dialkyl ether consists of a C2-18 alkyl group, and further preferably the dialkyl ether consists of a C6-16 alkyl group.

<10> the multi-layered cleaning composition according to <9>, wherein the (b2) ether oil is preferably dilauryl ether, dioctanoyl ether and hexadecyl-1, 3-dimethylbutyl ether, more preferably dioctanoyl ether.

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

<12>According to<1>To<11>The multi-layered cleaning composition of any one of, wherein the component (B) comprises a component (B3) silicone oil, and the component (B3) (silicone oil) is preferably a silicone oil having a viscosity of 1.5mm²S or 2mm²One or more of dimethylpolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and tris (trimethylsilyl) methylsilane in a ratio of/s, and more preferably a viscosity of 2mm²Dimethyl polysiloxane per second.

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

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

<15> the multi-layered cleaning composition according to any one of <1> to <14>, wherein the HLB of the component (C) (nonionic surfactant) may be preferably 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, further preferably 13.8 or less. And the HLB is preferably 2 to 20, more preferably 8 to 18, further preferably 10 to 16, further preferably 11 to 14, further preferably 12 to 13.8.

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

<17> the multi-layered cleaning composition according to any one of <1> to <16>, wherein the ingredient (D) is an ingredient (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 cleaning composition according to any one of <1> to <16>, wherein the ingredient (D) is selected from hydroxycarboxylic acids and dicarboxylic acids.

<19> the multi-layered cleaning composition according to any one of <1> to <16>, wherein the ingredient (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 cleaning composition according to any one of <1> to <19>, wherein the content of the ingredient (D) (the total content of the ingredient (D1) and the ingredient (D2)) in the total composition is preferably 0.005% by mass or more, more preferably 0.010% by mass or more, further preferably 0.012% by mass or more, further preferably 0.018% by mass or more, and preferably 0.9% by mass or less, further preferably 0.8% by mass or less, further preferably 0.7% by mass or less, further preferably 0.6% by mass or less, and the content of the ingredient (D) in the total composition is preferably 0.005 to 0.9% by mass, more preferably 0.010 to 0.8% by mass, further preferably 0.012 to 0.7% by mass, further preferably 0.018 to 0.6% by mass.

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

<22> the multi-layered cleaning composition according to any one of <1> to <21>, wherein component (F) (powder) is further contained, preferably the content of component (F) in the total composition is 0.1% by mass or more, preferably 1% by mass or more, preferably 3% by mass or more, and 20% by mass or less, preferably 15% by mass or less, further preferably 12.5% by mass or less, and the content of component (F) in the total composition is preferably 0.1 to 20% by mass, more preferably 1 to 15% by mass, further preferably 3 to 12.5% by mass.

<23> the multi-layered cleaning composition according to any one of <1> to <22>, further comprising an ingredient (G) (ethanol), the content of the ingredient (G) in the composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, further preferably 3% by mass or more, and preferably 20% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass or less, and the content of the ingredient (G) is 0.1 to 20% by mass, more preferably 1 to 15% by mass, further preferably 2 to 10% by mass.

<24> the multi-layered cleaning composition according to any one of <1> to <23>, wherein the composition further comprises ingredient (H) (polyol).

<25> the multi-layered cleaning composition according to <24>, wherein the ingredient (H) is selected from the group consisting of ethylene glycol, diethylene glycol, propylene glycol (propylene glycol), dipropylene glycol, polyethylene glycol, polypropylene glycol, propylene glycol (propanediol), glycerin, 1, 3-butanediol, sorbitol, polyoxyethylene methyl glycoside and maltitol, more preferably one or more of ethylene glycol, diethylene glycol, propylene glycol (propylene glycol), dipropylene glycol, polyethylene glycol, polypropylene glycol, propylene glycol (propanediol), polyoxyethylene methyl glycoside and 1, 3-butanediol, further preferably one or more of propylene glycol (propanediol), dipropylene glycol, 1, 3-butanediol, propylene glycol (propanediol) and polyoxyethylene methyl glycoside, and further preferably one or more selected from the group consisting of 1, 3-butanediol and glycerin.

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

<27> the multilayer cleaning composition according to any one of <1> to <26>, wherein the mass ratio [ (a)/(B) ] of the component (a) to the component (B) is preferably 0.0001 or more, more preferably 0.0005 or more, further preferably 0.001 or more, and preferably 0.01 or less, more preferably 0.008 or less, further preferably 0.0075 or less, and [ (a)/(B) ] is preferably 0.0001 to 0.1, more preferably 0.0005 to 0.008, further preferably 0.001 to 0.0075.

<28> the multilayer cleaning composition according to any one of <1> to <27>, wherein the mass ratio [ (a)/(C) ] of the component (a) to the component (C) is preferably 0.001 or more, more preferably 0.005 or more, further preferably 0.01 or more, and preferably 2.0 or less, more preferably 1.5 or less, further preferably 1.0 or less, and [ (a)/(C) ] is preferably 0.001 to 2.0, more preferably 0.005 to 1.5, further preferably 0.01 to 1.0.

<29> the multilayer cleaning composition according to any one of <1> to <28>, wherein the mass ratio of the component (a) to the component (D) [ (a)/(D) ] is preferably 0.05 or more, more preferably 0.1 or more, further preferably 0.2 or more, and preferably 20 or less, more preferably 10 or less, further preferably 5 or less, and [ (a)/(D) ] is preferably 0.05 to 20, more preferably 0.1 to 10, and further preferably 0.2 to 5.

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

<31> the multi-layered cleaning composition according to any one of <1> to <30>, wherein the mass ratio of the ingredient (F) to the ingredient (a) [ (F)/(a) ] is preferably 1 or more, more preferably 10 or more, further preferably 50 or more, and preferably 1000 or less, more preferably 700 or less, further preferably 500 or less, and [ (F)/(a) ] is preferably 1 to 1000, more preferably 10 to 700, and further preferably 50 to 500.

<32> the multi-layered cleaning composition according to any one of <1> to <31>, wherein component (K) (alkaline neutralizing agent) is further contained, preferably in an amount corresponding to a neutralization ratio of component (a) of 0.3 to 1.2, more preferably in an amount corresponding to a neutralization ratio of 0.4 to 1.1.

<33> the use method of the cleaning composition according to any one of <1> to <32>, wherein a first step of uniformly mixing the composition and a second step selected from the group consisting of:

(1) wiping the skin with a wiping material impregnated with the composition,

(2) after applying the composition to the skin by hand, the skin is wiped with a wipe material,

(3) after the composition is applied to the skin by hand, it is rinsed from the skin,

(4) after the composition impregnated in the wiping material is applied to the skin, it is rinsed from the skin,

(5) after being wiped off the skin according to any of the above-mentioned methods, the skin is rinsed off the skin,

(6) the skin was wiped with a sheet impregnated with the composition.

<34> the method for producing a multi-layer cleaning composition according to <1>, comprising the steps of 1 to 3:

(step 1) mixing component (a), component (B) and component (E) to obtain a mixture 1;

(step 2) adding the component (C) to the mixture 1 to obtain a mixture 2; and

(step 3) component (D) was added to mixture 2.

<35> a multi-layer cleaning composition comprising the following components (A) to (E):

(A)0.008 to 0.18 mass% of a polymer containing a monomer selected from the group consisting of (a1), (a2) and (a3), wherein the polymer contains at least (a1) as a constituent unit.

(a1) A monomer selected from the group consisting of acrylic acid and methacrylic acid,

(a2) a monomer selected from the group consisting of alkyl acrylates and alkyl methacrylates, and

(a3) a monomer selected from the group consisting of polyoxyethylene alkyl esters of acrylic acid and polyoxyethylene alkyl esters of methacrylic acid;

(B)12 to 30 mass% of an oil agent having a viscosity of 1 to 18 mPas at 30 ℃;

(C)0.01-1.5 mass% of a nonionic surfactant having an HLB of 8-18;

(D)0.005-0.9 mass% of one or more selected from (d1) water-soluble salts and (d2) acids; and

(E) and (3) water.

<36> a multi-layer cleaning composition comprising the following components (a) to (E):

(A)0.008 to 0.18 mass% of a polymer containing a monomer selected from the group consisting of (a1), (a2) and (a3), wherein the polymer contains at least (a1) as a constituent unit.

(a1) A monomer selected from the group consisting of acrylic acid and methacrylic acid,

(a2) a monomer selected from the group consisting of alkyl acrylates and alkyl methacrylates, and

(a3) a monomer selected from the group consisting of polyoxyethylene alkyl esters of acrylic acid and polyoxyethylene alkyl esters of methacrylic acid;

(B)12 to 30 mass% of an oil agent having a viscosity of 1 to 18 mPas at 30 ℃;

(C)0.01-1.5 mass% of a nonionic surfactant having an HLB of 8-18;

(D)0.08 to 0.6 mass% of a water-soluble salt (d 1); and

(E) and (3) water.

<37> a multi-layer cleaning composition comprising the following components (a) to (E):

(A)0.008 to 0.18 mass% of a polymer containing a monomer selected from the group consisting of (a1), (a2) and (a3), wherein the polymer contains at least (a1) as a constituent unit.

(a1) A monomer selected from the group consisting of acrylic acid and methacrylic acid,

(a2) a monomer selected from the group consisting of alkyl acrylates and alkyl methacrylates, and

(a3) a monomer selected from the group consisting of polyoxyethylene alkyl esters of acrylic acid and polyoxyethylene alkyl esters of methacrylic acid;

(B)12 to 30 mass% of an oil agent having a viscosity of 1 to 18 mPas at 30 ℃;

(C)0.01-1.5 mass% of a nonionic surfactant having an HLB of 8-18;

(D)0.013-0.3 mass% of (d2) acid; and

(E) and (3) water.

<38> a multi-layer cleaning composition comprising the following components (a) to (E):

(A)0.008 to 0.18 mass% of a polymer containing a monomer selected from the group consisting of (a1), (a2) and (a3), wherein the polymer contains at least (a1) as a constituent unit.

(a1) A monomer selected from the group consisting of acrylic acid and methacrylic acid,

(a2) a monomer selected from the group consisting of alkyl acrylates and alkyl methacrylates, and

(a3) a monomer selected from the group consisting of polyoxyethylene alkyl esters of acrylic acid and polyoxyethylene alkyl esters of methacrylic acid;

(B)12 to 30 mass% of an oil agent having a viscosity of 1 to 18 mPas at 30 ℃;

(C)0.01-1.5 mass% of a nonionic surfactant having an HLB of 8-18;

(D)0.005-0.9 mass% of one or more selected from (d1) water-soluble salts and (d2) acids;

(E) water; and

(F)1-15 mass% of powder.

<39> a multi-layer cleaning composition comprising the following components (A) to (E):

(A)0.008 to 0.18 mass% of a polymer containing a monomer selected from the group consisting of (a1), (a2) and (a3), wherein the polymer contains at least (a1) as a constituent unit,

(a1) a monomer selected from the group consisting of acrylic acid and methacrylic acid,

(a2) a monomer selected from the group consisting of alkyl acrylates and alkyl methacrylates, and

(a3) a monomer selected from the group consisting of polyoxyethylene alkyl esters of acrylic acid and polyoxyethylene alkyl esters of methacrylic acid;

(B)12 to 30 mass% of an oil agent having a viscosity of 1 to 18 mPas at 30 ℃;

(C)0.01-1.5 mass% of a nonionic surfactant having an HLB of 8-18;

(D)0.08-0.6 mass% of (d1) a water-soluble salt;

(E) water; and

(F)1-15 mass% of powder.

<40> a multi-layer cleaning composition comprising the following components (A) to (E):

(A)0.008 to 0.18 mass% of a polymer containing a monomer selected from the group consisting of (a1), (a2) and (a3), wherein the polymer contains at least (a1) as a constituent unit,

(a1) a monomer selected from the group consisting of acrylic acid and methacrylic acid,

(a2) a monomer selected from the group consisting of alkyl acrylates and alkyl methacrylates, and

(a3) a monomer selected from the group consisting of polyoxyethylene alkyl esters of acrylic acid and polyoxyethylene alkyl esters of methacrylic acid;

(B)12 to 30 mass% of an oil agent having a viscosity of 1 to 18 mPas at 30 ℃;

(C)0.01-1.5 mass% of a nonionic surfactant having an HLB of 8-18;

(D)0.013-0.3 mass% of (d2) acid;

(E) water; and

(F)1-15 mass% of powder.

<41> the multi-layered cleaning composition according to any one of <35> to <40>, wherein the content of the ingredient (a) is one or more selected from the group consisting of carboxyvinyl polymer, acrylic acid-alkyl methacrylate crosspolymer, acrylic ester copolymer, (acrylic acid/stearyl acrylate) copolymer, (acrylic ester/steareth-20 methacrylate) copolymer, (acrylic ester/beheneth-25 methacrylate) and (acrylic ester/steareth-20 methacrylate) crosspolymer, more preferably selected from the group consisting of acrylic acid-alkyl methacrylate crosspolymer, (acrylic ester/steareth-20 methacrylate) copolymer, (acrylic ester/beheneth-25 methacrylate) and (acrylic ester/steareth-20 methacrylate) crosspolymer One or more of the compounds.

<42> the multi-layered cleaning composition according to any one of <35> to <40>, wherein the content of the component (a) is one or more selected from the group consisting of acrylic acid-methacrylic acid alkyl ester cross-linked polymer and (acrylate/steareth-20 methacrylate) cross-linked polymer.

<43> the multi-layered cleaning composition according to any one of <35> to <42>, wherein the component (B) comprises one or more selected from (B1) hydrocarbon oil, (B2) ether oil and (B3) silicone oil, wherein the total content of the components (B1), (B2) and (B3) in the component (B) is 90 mass% or more and 100 mass% or less.

<44> the multi-layered cleaning composition according to any one of <35> to <42>, wherein the component (B) is composed of the components (B1) hydrocarbon oil, (B2) ether oil and (B3) silicone oil.

<45> the multilayer cleaning composition according to any one of <35> to <42>, wherein the component (B) contains one or more selected from (B1) hydrocarbon oil, (B2) ether oil, and (B3) silicone oil, wherein the total content of the components (B1), (B2), and (B3) in the component (B) is 90 mass% or more and 100 mass% or less, and the content of volatile oil in the components (B1), (B2), and (B3) is 60 mass% or more and 100 mass% or less.

<46> the multi-layered cleaning composition according to any one of <35> to <42>, wherein the component (B) is composed of the components (B1) hydrocarbon oil, (B2) ether oil and (B3) silicone oil, and the content of volatile oil in the components (B1), (B2) and (B3) is 60 mass% or more and 100 mass% or less.

<47> the multi-layered cleaning composition according to any one of <35> to <42>, wherein the component (B) contains one or more selected from (B1) hydrocarbon oil, (B2) ether oil and (B3) silicone oil, wherein the total content of the components (B1), (B2) and (B3) in the component (B) is 90 mass% or more and 100 mass% or less, and wherein the content of volatile oil in the components (B1), (B2) and (B3) is 90 mass% or more and 100 mass% or less.

<48> the multi-layered cleaning composition according to any one of <35> to <42>, wherein the component (B) is composed of the components (B1) hydrocarbon oil, (B2) ether oil, and (B3) silicone oil, and wherein the content of volatile oil in the components (B1), (B2), and (B3) is 90 mass% or more and 100 mass% or less.

<49>According to<47>To<48>A multi-layer cleaning composition according to any one of the preceding claims wherein the volatile oil is present in an amount selected from the group consisting of dimethyl polysiloxane (1.5 mm)²S), dimethylpolysiloxane (2 mm)²S), tris (trimethylsilyl) methylsilane, tetrakis (trimethylsilyl) silane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxaneOne or more of an alkylene oxide, dodecamethylcyclohexasiloxane, isododecane, isohexadecane, light isoparaffin, light liquid isoparaffin, dioctanoyl ether, and dilauryl ether.

<50>According to<47>To<48>A multi-layer cleaning composition according to any one of the preceding claims wherein the volatile oil is present in an amount selected from the group consisting of dimethyl polysiloxane (2 mm)²One or more of isododecane, isohexadecane, tris (trimethylsilyl) methylsilane, and dioctanoyl ether.

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

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

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

Examples

The present invention is illustrated by examples and comparative examples, but the present invention is not limited to these examples.

Examples 1 to 58 and comparative examples 1 to 11

Samples shown in tables 1 to 9 were produced. The samples were evaluated in the following ways: (1) viscosity, (2) appearance (25 ℃, 24 hours at rest), (3) immersion in cotton fabric, (4) cleaning speed of waterproof mascara, (5) cleaning of waterproof mascara, (6) non-greasy feeling during wiping and (6-2) non-sticky feeling immediately after use, (7) skin-refreshing feeling after use and (8) emulsion retention during use. The samples shown in Table 4 were further subjected to (13) evaluation of appearance (at 50 ℃ C., held at rest for 1 month), the samples shown in Table 7 were further evaluated for (10) redispersibility of the deposited powder and (11) smooth feeling of the skin after use, the samples shown in Table 8 were further evaluated for (11) smooth feeling of the skin after use and (12) cool feeling of the skin after use, and the samples shown in Table 9 were further evaluated for (9) moist feeling of the skin after use. The formulations and evaluation results are shown in tables 1 to 9.

(production method)

(1) The components (A), (B) and (E) were mixed uniformly at 25 ℃ to obtain preparation A.

(2) Potassium hydroxide (48% aqueous solution) was added to the preparation a to be neutral, and the mixture was uniformly mixed to obtain a preparation B.

(3) Adding the component (C) to the preparation B, and uniformly mixing the mixture to obtain a preparation C.

(4) Adding the component (D) to the preparation C, and uniformly mixing the mixture to obtain a preparation D.

(5) The preparation D was dispensed (45mL) into a glass bottle (5K standard bottle, capacity 50mL, body diameter: 38mm, height: 68.5mm, oral diameter: 24.7mm) to obtain a sample.

(evaluation method)

(1) Viscosity of the oil

Each sample was placed vertically up in a 30 ℃ incubator for two hours or more. The sample was shaken up and down by hand 15 times with a stroke length of 15cm at a speed of 5 reciprocations per 3 seconds. Immediately thereafter, the viscosity of each sample was measured.

The measurement was carried out with a type B viscometer (viscometer TVB-10M, TOKI SANGYO Co., Ltd.) at 30 ℃ with a spindle M1 at 60rpm for 1 minute. When the viscosity was 100 mPas or more, the measurement was recovered at 30 rpm. Note that if layer separation is caused within 1 minute, resulting in unsuccessful viscosity measurement, no measurement is performed, indicated by "-".

(2) Appearance after 24 hours storage at room temperature (25 ℃ C.) (static state)

Each sample was shaken up and down by hand 15 times with a stroke length of 15cm at a speed of 5 reciprocations per 3 seconds. The sample was then placed vertically upwards at room temperature (25 ℃) for 24 hours. The appearance was visually observed, and the state of layer separation was evaluated. "three layers" means the composition separates into three layers, "two layers" means the composition separates into two layers, "single layer" means a homogeneous liquid. The words in parentheses represent detailed states of layer separation; w represents a water layer, O represents an oil layer, P represents a powder sediment layer, and O/W represents an oil-in-water emulsion layer, the left word representing 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 a water layer, and the lower layer is a powder sediment layer.

(3) Impregnation of cotton fabrics

Each sample was stored in an incubator at 25 ℃ for 2 hours or more with each sample facing vertically upward. The sample was shaken up and down by hand 15 times with a stroke length of 15cm at a speed of 5 reciprocations per 3 seconds. Each sample (1mL) was dropped from a height of 1cm onto cotton fabric (LilyBell patted cotton fabric, Suzuran Sanitary Goods co., Ltd.). The impregnation of each sample in the surface of the cotton fabric was visually observed and evaluated by the following criteria.

5: instantaneous impregnation (not forming a liquid film)

4: immediately forming a liquid film; dipping within 1 second after dropping

3: forming a liquid film on the surface; dipping for more than 1 second and 3 seconds or less after dropping

2: forming a liquid film on the surface; dipping for more than 3 seconds and 5 seconds or less after dripping

1: no dipping was observed even after more than 5 seconds after dripping

(4) Cleaning speed of waterproof mascara

Waterproof mascara (hereinafter abbreviated as WP) (3mg) was uniformly applied to a Glass plate (Micro Slide Glass, Matsunami Glass ind. ltd.) in a circle having a diameter of 1.2cm in a round shape, and WP was left to stand for 12 hours or more to be dried. Each sample was stored in an incubator at 25 ℃ for 2 hours or more with each sample facing vertically upward. The sample was shaken up and down by hand 15 times with a stroke length of 15cm at a speed of 5 reciprocations per 3 seconds. Each sample (1mL) was impregnated in cotton fabric (LilyBell patted cotton fabric, Suzuran beauty Goods co., Ltd.). After applying a steady pressure (7.8kPa) on the WP for 10 seconds with cotton fabric, it was wiped once. The remaining WP was visually evaluated by the following criteria.

5: WP is tightly attached to the integral cotton fabric

4: WP is relatively densely attached to the overall cotton fabric

3: slight adhesion of WP to the Whole Cotton Fabric

2: WP attachment to partial Cotton Fabric

1: without WP attachment to the cotton fabric

(5) Cleaning of water-resistant mascara

WP (3mg) was uniformly coated on a Glass plate (Micro Slide Glass, Matsunami Glass ind. ltd.) in a circle having a diameter of 1.2cm, and was left to stand for 12 hours or more to be dried. Each sample was stored in an incubator at 25 ℃ for 2 hours or more with each sample facing vertically upward. Each sample was shaken up and down by hand 15 times with a stroke length of 15cm at a speed of 5 reciprocations per 3 seconds. Each sample (1mL) was impregnated in cotton fabric (LilyBell patted cotton fabric, Suzuran beauty Goods co., Ltd.). After applying a steady pressure (7.8kPa) on the WP with cotton fabric for 10 seconds, 5 wipes were performed. The remaining WP was visually observed on an area basis, and the cleanability was evaluated by the following criteria.

5: by wiping 3 times or less, WP was almost removed (remaining 5% or less of WP).

4: by wiping 4 or 5 times, WP was almost removed (5% or less of WP remained)

3: after 5 times of wiping, more than 5% and 10% or less of WP remains

2: after 5 times of wiping, more than 10% and 50% or less of WP remains

1: after 5 wipes, more than 50% WP remains

(6) (6-1) non-greasy feeling during wiping, (6-2) non-tacky feeling immediately after use

Each sample was shaken up and down by hand 15 times with a stroke length of 15cm at a speed of 5 reciprocations per 3 seconds. Each sample (1mL) was impregnated in cotton fabric (LilyBell patted cotton fabric, Suzuran beauty Goods co., Ltd.). 10 professional panelists who applied Makeup to the face using a Liquid Foundation (Prima Vista, Makeup addition reaction Liquid Foundation, Ochre No.5, Kao Corporation) (hereinafter referred to as FD) between 20 and 40 years old, used cotton fabric impregnated with the sample to remove Makeup cosmetics. The number of people who confirmed no greasy feeling during wiping and no sticky feeling immediately after use was judged by the following five grades.

(6-1) non-greasy feeling during wiping

5: less than 1 out of 10 panelists confirmed greasy feeling during wiping

4: of 10 persons, 2 or 3 panelists confirmed a greasy feel during wiping

3: of 10, 4 or 5 panelists confirmed a greasy feel during rubbing

2: of 10, 6 or 7 panelists confirmed a greasy feel during the wiping period

1: more than 8 out of 10 panelists confirmed greasy feeling during wiping

(6-2) non-tacky feeling immediately after use

5: among 10 persons, 1 or less panelists confirmed that they had sticky feeling immediately after use

4: 2 or 3 of 10 panelists confirmed that they had a sticky feeling immediately after use

3: of 10, 4 or 5 panelists confirmed that they had a sticky feeling immediately after use

2: 6 or 7 of 10 panelists confirmed that they had a sticky feeling immediately after use

1: more than 8 of 10 panelists confirmed that they had a sticky feeling immediately after use

(7) The skin feel of the product after application is clear

FD (5mg) was spread evenly in a range of 2 cm. times.2 cm onto the forearms of professional female panelists aged 20 to 40 years and dried for 30 minutes. Each sample was shaken up and down by hand 15 times with a stroke length of 15cm at a speed of 5 reciprocations per 3 seconds. Each sample (1mL) was impregnated in cotton fabric (LilyBell patted cotton fabric, Suzuran beauty Goods co., Ltd.). The FD was wiped off with cotton fabric. The number of people who confirmed a refreshing feeling of the skin after use without any feeling of residue was judged by the following five grades.

5: of 10 persons, 9 or 10 panelists confirmed the skin refreshing feeling after use without feeling of residue

4: of 10 persons, 7 or 8 panelists confirmed the skin refreshing feeling after use without residual feeling

3: of 10 persons, 5 or 6 panelists confirmed the skin refreshing feeling after use without residual feeling

2: of 10 persons, 3 or 4 panelists confirmed the skin refreshing feeling after use without feeling of residue

1: among 10 persons, 2 or less panelists confirmed that the skin was refreshing after use without feeling of residue

(8) Emulsion retention during use

Each sample was shaken up and down by hand 15 times with a stroke length of 15cm at a speed of 5 reciprocations per 3 seconds. The sample was placed vertically up in a 25 ℃ incubator. The time from the termination of shaking to the onset of layer separation was measured by visual observation and evaluated by the following criteria.

3: over 5 minutes

2: 1 minute or more and less than 5 minutes

1: less than 1 minute

(9) Feeling of skin moisturization after use

FD (5mg) was scattered on the forearms of 10 professional panelists (women aged 20 to 40 years), and FD was allowed to dry for 30 minutes. Each sample was shaken up and down by hand 15 times with a stroke length of 15cm at a speed of 5 reciprocations per 3 seconds. Each sample (1mL) was impregnated in cotton fabric (LilyBell patted cotton fabric, Suzuran beauty Goods co., Ltd.). The FD was wiped off with cotton fabric. The number of people who confirmed the sense of skin moisturization after use was determined by the following five scales.

5: of 10 persons, 9 or 10 panelists confirmed the feeling of skin moisturization after use

4: among 10 persons, 7 or 8 panelists confirmed the feeling of skin moisturization after use

3: among 10 persons, 5 or 6 panelists confirmed the feeling of skin moisturization after use

2: among 10 persons, 3 or 4 panelists confirmed the feeling of skin moisturization after use

1: among 10 persons, less than 2 panelists confirmed the feeling of skin moisturization after use

(10) Redispersibility of powders

Each sample was shaken (stroke length: 15cm, shaking speed: 5 reciprocations per 3 seconds) to completely disperse the powder, and the sample was kept vertically upward at room temperature (25 ℃) for 24 hours to deposit the powder. After shaking 5 times, 10 times and 15 times (stroke length: 15cm, shaking speed: 5 reciprocations per 3 seconds), the appearance of the sample was visually observed and evaluated according to the following criteria.

5: after shaking 5 times, the powder was completely dispersed in the emulsion

4: after 10 shaking the powder was completely dispersed in the emulsion

3: after shaking 15 times, the powder was completely dispersed in the emulsion

2: after 15 shaking times, a small amount of sediment powder was observed at the bottom

1: after 15 shaking times, a powder of sediment was clearly observed at the bottom

-: when no powder was contained in the sample or no powder was precipitated after storing at room temperature (25 ℃ C.) for 24 hours, evaluation was not performed

(11) Smooth feeling of skin after use

FD (5mg) was spread evenly in a range of 2 cm. times.2 cm on the forearms of 10 professional panelists (women aged 20 to 40 years), and the FD was allowed to dry for 30 minutes. Each sample was shaken up and down by hand 15 times with a stroke length of 15cm at a speed of 5 reciprocations per 3 seconds. Each sample (1mL) was impregnated in cotton fabric (LilyBell patted cotton fabric, Suzuran beauty Goods co., Ltd.). The forearm was wiped with impregnated cotton fabric to remove FD. Evaluation was made based on the number of people who confirmed smooth feeling of skin after use.

5: of 10, 9 or 10 panelists confirmed the smooth feeling of skin after use

4: of 10, 7 or 8 panelists confirmed the smooth feeling of skin after use

3: of 10, 5 or 6 panelists confirmed the smooth feeling of skin after use

2: of 10, 3 or 4 panelists confirmed the smooth feeling of skin after use

1: among 10 persons, less than 2 panelists confirmed smooth feeling of skin after use

(12) The skin has good cooling effect

FD (5mg) was spread evenly in a range of 2 cm. times.2 cm on the forearms of 10 professional panelists (women aged 20 to 40 years), and the FD was allowed to dry for 30 minutes. Each sample was shaken up and down by hand 15 times with a stroke length of 15cm at a speed of 5 reciprocations per 3 seconds. Each sample (1mL) was impregnated in cotton fabric (LilyBell patted cotton fabric, Suzuran beauty Goods co., Ltd.). The forearm was wiped with impregnated cotton fabric to remove FD. The number of people who confirmed a cool feeling of the skin after use was evaluated by the following criteria.

5: of 10 persons, 9 or 10 panelists confirmed the skin cooling after use

4: of 10 persons, 7 or 8 panelists confirmed the skin cooling after use

3: of 10 persons, 5 or 6 panelists confirmed the skin cooling after use

2: of 10 persons, 3 or 4 panelists confirmed the skin cooling after use

1: among 10 persons, less than 2 panelists confirmed the skin cooling after use

(13) Appearance after 1 month storage in a 50 ℃ incubator (static state)

In terms of layer separation, the appearance of each sample was visually observed after being stored in an incubator at 50 ℃ for 1 month.

Each sample (100mL) was placed in a glass vial (10K standard vial, volume 108mL, body diameter: 48.5mm, height: 87mm, intraoral diameter: 31.9 mm). The glass bottles were stored vertically upwards in a thermostat at 50 ℃ for 1 month. Subsequently, the thickness of the oil layer exuded from the emulsion layer was measured. Based on the thickness of the oil layer, evaluation was performed by the following criteria.

5: is not obvious

4: less than 1.5mm

3: 1.5mm or more and less than 3.5mm

2: 3.5mm or more and less than 5mm

1: 5mm or more

In the examples and comparative examples, the components with labels are as follows.

*1:PEMULEN TR-2(Lubrizol Advanced Materials)

2 Maruzakol R (Maruzen Petrochemical Co., Ltd., viscosity: 3 mPa. multidot.s, boiling point: 177 ℃ C.)

*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 ingredient content: 30% by 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. multidot.s, fixed oil)

15 Cetiol OE (BASF SE, viscosity: 3 mPa. multidot.s, boiling point: 291 ℃ C.)

16: ASE166K (Kao Corporation, viscosity: 5 mPa. multidot.s, fixed oil)

17 silicon KF 962 cs (Shin-Etsu Chemical Co., Ltd., viscosity: 2 mPas, boiling point: 230 ℃ C.)

18 silicon KF 965 cs (Shin-Etsu Chemical Co., Ltd., viscosity: 5 mPa. multidot.s, fixed oil)

*19:TMF-1.5(Shin-Etsu Chemical Co.,Ltd.)

20 CROPURE OL (Croda Japan KK, viscosity: 90 mPa. multidot.s, fixed 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 μ M)

24 Sunsphere NP-200(AGC Sitech, particle size: 20 μm)

*25:MACBIOBRIDE MG-20E(MS)(NOF Corporation)