WO2006051746A1

WO2006051746A1 - Microgel swellable in organic solvents and process for production thereof

Info

Publication number: WO2006051746A1
Application number: PCT/JP2005/020341
Authority: WO
Inventors: Yoshiko Hiwatari; Yuki Suzuki; Isamu Kaneda; Yumi Ueda; Yuko Nakanishi; Nobuyoshi Koga
Original assignee: Shiseido Company, Ltd.
Priority date: 2004-11-09
Filing date: 2005-11-07
Publication date: 2006-05-18
Also published as: TW200631969A

Abstract

A microgel swellable in organic solvents, which consists of a copolymer obtained by radical-polymerizing a specific polyethylene oxide macromonomer with a specific hydrophobic monomer and a specific crosslinking monomer in a water/ethanol mixed solvent on the condition that: (A) the charge ratio of the polyethylene oxide macromonomer to the hydrophobic monomer is 1:10 to 1:250 by mole, (B) the charge of the crosslinking monomer is 0.1 to 1.5% by mass based on the charge of the hydrophobic monomer, and (C) the water/ethanol ratio of the mixed solvent is 90 to 30 : 10 to 70 by volume at 20˚C. The invention aims at providing a novel microgel swellable in organic solvents, a process for the production thereof, and cosmetics containing the copolymer constituting the microgel.

Description

Specification

Organic solvent swellable microgel and method for producing the same

Technical field

[0001] [Invention A, Invention B]

The present invention relates to a novel organic solvent swellable microgel and a method for producing the same. The organic solvent swellable microgel of the present invention is a corona-core type polymer microgel having a hydrophobic core and hydrophilic corona force, and various chemical products, for example, cosmetics, etc. in which the polymer microgel is blended. It is useful as a blending component.

[0002] [Invention C]

The present invention relates to cosmetics. More specifically, the present invention relates to a white turbid cosmetic material having excellent turbidity and excellent storage stability and usability.

[0003] [Invention D]

The present invention relates to an external preparation for skin. More specifically, the present invention relates to an external preparation for skin that is excellent in a moisturizing effect and an effect of improving rough skin, and excellent in touch.

[0004] [Invention E]

The present invention relates to a multilayer cosmetic. More specifically, the present invention relates to a cosmetic that has a clear layer boundary and also has a multi-layered composition having a water phase cloudy.

Background art

[0005] [Invention A, Invention B]

The technology for industrially synthesizing polymer fine particles (polymer emulsion) has been put into practical use since the 1930s, and in the general chemical industry such as rubber industry, paints, paper surface treatment, adhesives, etc., diagnostic agents, drug delivery formulations, etc. Applied in the medical field. Polymer emulsion can be synthesized and produced by a so-called emulsion polymerization method. The emulsion polymerization method is a method of polymerizing a desired monomer by preparing an emulsion composition using an appropriate dispersion stabilizer (Non-patent Document 1).

[0006] Also in the cosmetics industry, polymer emulsions produced by an emulsion polymerization method are applied to cosmetics. The present inventors have developed a core-shell type polymer emulsion with an aqueous beauty. The technology for producing organic solvent-free nail enamel has been put into practical use by blending it into nail materials (Patent Document 1). In addition, a technology for blending self-crosslinking polymer emulsion, which utilizes the crosslinking reaction of alkoxysilane, into cosmetic products has been put into practical use (Patent Documents 2 and 3).

[0007] On the other hand, a method for polymerizing corona core-type polymer fine particles of a polyethylene oxide macromonomer in a water / ethanol mixed solvent is known and described in Non-Patent Document 2. This technology is applied, for example, as an AIDS virus capture system (Non-patent Document 3).

[0008] Microgels are expected to be applied in the pharmaceutical and cosmetic industries by applying their swelling and shrinkage functions. There have been some reports on synthetic polymer microgels (Non-patent Document 4). These are all applications of polymer electrolytes such as polyacrylic acid, and their water dispersibility is not acid-resistant nor salt-resistant. However, when considering applications in the pharmaceutical and cosmetic industries, acid resistance and salt resistance are very important performances in order to adapt under physiological conditions.

[0009] On the other hand, there have been several reports on the polymer fine particle polymerization method based on the so-called macromonomer method using a macromonomer containing a water-soluble polymer structure (Non-patent Document 5). This method can be said to be an excellent method in that it can produce fine polymer particles having a uniform particle size without controlling the stirring conditions of the polymerization system, which is a problem in mass production of heterogeneous polymerization (non-patent literature). Five).

[0010] Patent Document 1: JP 2001-114650 A

Patent Document 2: Japanese Patent Laid-Open No. 2002-327019

Patent Document 3: Japanese Patent Laid-Open No. 2003-20314

^^ Special Reference 1: “Emmsion Polymerization and Emulsion Polymers J P.A. Lovell and M.S. E. Asser, John Wiley and son

Non-Patent Document 2: M.Q. Chen et al: J. Polym. Sci .: A: Polym. Chem., 38 1811-1817 (200 0)

Non-Patent Document 3: M. Akashi, M. Baba, et al: Bioconj. Chem., 9, 50-53 (1998) Non-Patent Document 4: MJ Snowden et al. Colloid Polym. Sci. 272, 1273 (1994)

Non-Patent Document 5: C. Wu, Macromolecules 27, 7099 (1944) [0011] [Invention c]

In recent years, cloudy cosmetics such as cloudy lotion have a cosmetic effect, such as moisturizing, moisturizing, and fuller skin, than transparent lotion due to the appearance characteristic of cloudiness. It is attracting attention because of For example, it is the same reason that the Shirahone hot springs in Nagano Prefecture are popular because they feel the effects of hot springs due to cloudiness.

[0012] Conventional white cloudy cosmetics include cosmetics in which an aqueous phase and an oil phase are emulsified and dispersed with a surfactant, and cosmetics in which a surfactant and an oily substance are dissolved in ethanol and dispersed in an aqueous phase. Fees are known.

However, there is a problem that it is difficult to select a surfactant to be used in order to obtain a cloudy cosmetic having a sufficient cloudiness and storage stability. In addition, there is a method of adding a water-soluble thickener to improve storage stability, but there are problems in that it is sticky in terms of use feeling and is unfamiliar.

[0014] In order to solve these problems, the white turbidity is excellent in stability, and the carbon chain of the fatty acid part or the alkyl part is unsaturated as it does not cause coloring or odor over time even under high temperature conditions. A cloudy cosmetic composition in which glycylglycine is mixed with a cloudy cosmetic composition using a nonionic and Z or anionic surfactant having a bond as an emulsifier has been developed (Patent Document 4).

[0015] Further, by dissolving a specific oily substance such as tocopherol or a derivative thereof, oryzanol and a nonionic surfactant in ethanol, and mixing with water, the white turbidity is good and the storage stability and feeling of use are improved. A white cloudy cosmetic is developed that is superior to the above (Patent Document 5).

[0016] Furthermore, tocopherol or a derivative thereof, parahydroxybenzoic acid alkyl ester, and a nonionic surfactant are dissolved in ethanol, and then mixed with water, so that the white turbidity is good and the storage stability and usability are improved. A white cloudy cosmetic material with excellent resistance has been developed (Patent Document 6) Patent Document 4: Japanese Patent Laid-Open No. 10-59838

Patent Document 5: JP-A-11 279043

Patent Document 6: Japanese Patent Laid-Open No. 11 269055

[0017] [Invention D] Moisture retention is indispensable for maintaining healthy skin, and many external preparations for moisturizing have been developed. In addition, as a feeling of use of the external preparation for the skin, there is a demand for a smooth and sticky feeling.

There are many studies on moisturizers. And glycerin is mentioned as a well-known moisturizing agent used for a lotion, a milky lotion, etc. (nonpatent literature 6). In addition to the moisturizing effect, this glycerin also has an effect of improving rough skin (Patent Document 7).

However, the amount of glycerin must be increased in order to increase the moisturizing effect and skin roughening effect. As a result, there are problems to be solved such as the system becomes unstable, the usability deteriorates, and when it is applied to the skin, it is repelled by sebum and becomes unfit to the skin.

On the other hand, polyhydric alcohols such as 1,3 butylene glycol, propylene glycol, polyethylene glycol, sorbitol, and xylitol are known as humectants other than glycerin (Patent Document 8).

However, these polyhydric alcohols are less sticky than glycerin, but have a low moisturizing effect and rough skin improving effect. In addition, as with glycerin, when applied to the skin, there were problems to be solved, such as being repelled by sebum and becoming less familiar to the skin.

[0019] In order to reduce the stickiness of the moisturizing agent, the formulation of powder is known! / Patent Document 7).

However, when blending the powder, it must be mixed in large quantities to reduce the stickiness. In addition, in the case of a topical skin preparation with a low viscosity, such as lotion, the powder settles, so it must be shaken and used, which is cumbersome and time-consuming. Furthermore, in the case of emulsions, there were problems when the powder melted depending on the process or the powder swelled depending on the preparation.

[0020] Non-Patent Document 6: New Cosmetic Science, Nanzan-do, p. 144

Patent Document 7: JP 2002-356416

Patent Document 8: JP-A-11 322575

[0021] [Invention E]

Multi-layer cosmetics, like powder Z water, powder Z oil, water Z oil, the appearance looks multilayer. Cosmetics. For example, in the case of water Z oil two-layer cosmetics, the upper layer is roughly divided into two types: oil alone or emulsified.

[0022] Multilayer cosmetics are useful for various cosmetics including multilayer skin lotions from the viewpoint of beauty of appearance and usability (Patent Documents 9 to 15).

[0023] The important point that the multi-layered cosmetic material exhibits a beautiful appearance is that it is necessary to keep its interface beautiful, but depending on the components forming the layer, the boundary between the upper layer and the lower layer is not good. There was a problem of clarity.

[0024] In particular, from the viewpoint of usability and multi-layer separation speed, blending with natural polymers (polysaccharides, etc.) and synthetic polymer thickeners, the tendency is strong. It was difficult to do.

[0025] Patent Document 9: JP-A-2005-281193

Patent Document 10: Japanese Patent Application Laid-Open No. 2004-203764

Patent Document 11: Japanese Patent Application Laid-Open No. 2004-10517

Patent Document 12: Japanese Unexamined Patent Application Publication No. 2002-234815

Patent Document 13: Japanese Patent Application Laid-Open No. 11 92356

Patent Document 14: Japanese Patent Application Laid-Open No. 11 71230

Patent Document 15: JP-A-10-182340

Disclosure of the invention

Problems to be solved by the invention

[Invention A, Invention B]

The present invention provides a novel polymer microgel and a method for producing the same. The microgel of the present invention has a narrow particle size distribution and excellent organic solvent swellability.

It is extremely useful as a microgel to be blended in various chemical products.

The microgel of the present invention is a microgel stabilized with a polyethylene oxide chain, which is a nonionic polymer, and its dispersion stability in water can be expected to have acid resistance and salt resistance. The microgel of the present invention is a novel organic solvent swellable microgel production method characterized by applying the macromonomer method described above to produce a core portion that has been reported so far as a microgel with a crosslinkable monomer. It is. [0027] [Invention C]

The present invention provides a cosmetic obtained by means fundamentally different from conventional cloudy cosmetics, and is obtained by polymerizing a specific polyethylene oxide macromonomer, a hydrophobic monomer, and a crosslinkable monomer. As a result of discovering that the obtained copolymer is dispersed in water, surprisingly, a cosmetic having good white turbidity and excellent storage stability and usability can be obtained.

[0028] The present invention is a cosmetic obtained by using a specific copolymer as a clouding agent and dispersing it in water.

[0029] [Invention D]

As a result of intensive studies by the present inventors in order to achieve the above object, when a microgel comprising a specific copolymer is used in combination with a humectant such as glycerin, the moisturizer does not impair the moisturizing effect of the moisturizing agent and the effect of improving skin roughness. It was found that the stickiness caused by the agent was remarkably improved.

[0030] An object of the present invention is to provide a cosmetic (external preparation for skin) that has a moisturizing effect and an effect of improving rough skin, as well as excellent use feeling.

[0031] [Invention E]

An object of the present invention is to provide a multi-layer cosmetic having a clear layer boundary. That is, it contains a specific copolymer and a liquid oil content of 5 to 40% by mass, does not substantially contain a surfactant, or even if it contains a surfactant, As a result of finding that the boundary between layers in the cosmetic composition constituting the multilayer composition is very clear, the weight ratio to the weight ratio is 0.8 or less.

Means for solving the problem

[Invention A: Claims 1 to 5]

That is, the present invention is obtained by polymerizing a polyethylene oxide macromonomer of the following formula (1), a hydrophobic monomer of the following formula (A-2), and a crosslinkable monomer of the following formula (A-3). A copolymer comprising the monomers (1) to (A-3) in a mixture of water and ethanol under the following conditions (A—A), (A—B), (A—C): Thus, an organic solvent swellable microgel comprising a copolymer obtained by radical polymerization is provided. (A-A) Polyethylene oxide macromonomer and hydrophobic monomer charge capacity Polyethylene oxide macromonomer: hydrophobic monomer = 1: 10 to 1: 250 (molar ratio)

(A-B) Feeding power of crosslinkable monomer To be 0.1 to 1.5 mass% with respect to the charged amount of hydrophobic monomer

(AC) Water-ethanol mixed solvent power Water: Ethanol = 90-30: 10-70 (volume ratio at 20)

[Chemical A- 13]

(1)

R represents alkyl having 1 to 3 carbon atoms, and n is a number from 20 to 200. X is H or C

1

Represents H.

Three

[Chemical A-14]

(A- 2)

R represents alkyl having 1 to 3 carbon atoms, R represents alkyl having 4 to 8 carbon atoms

[Chemical A-15]

(A-3)

R and R each independently represents alkyl having 1 to 3 carbon atoms, and m is a number from 0 to 2.

4 5

The

The present invention also provides a copolymer obtained by polymerizing a polyethylene oxide macromonomer represented by the following formula (1), a hydrophobic monomer represented by the following formula (A 2), and a crosslinkable monomer represented by the following formula (A-3). An organic solvent swellable microgel having a monodisperse particle force with a particle size of 50 to 300 nm is provided.

[Chemical A-16]

(1)

1

Represents H.

Three

[Chemical A-17]

(A- 2)

[Chemical A-18]

(A-3)

4 5

The

Furthermore, the present invention provides a copolymer obtained by polymerizing a polyethylene oxide macromonomer of the following formula (1), a hydrophobic monomer of the following formula (A-2), and a crosslinkable monomer of the following formula (A-3). The polymer particle size of the copolymer particles in water is d.

0

Copolymer in which benzene is stirred and saturated until it swells and saturated. When the particle size of the particles is d, the swelling ratio (dZd) ³ is 1 or more.

0

A gel is provided.

[Chemical A-19]

(1)

1

Represents H.

Three

[Chemical A-20]

(A- 2)

[Chemical A-21]

(A-3)

4 5

The

The present invention also provides a polyethylene oxide macromonomer represented by the following formula (1), a hydrophobic monomer represented by the following formula (A-2), and a crosslinkable monomer represented by the following formula (A-3): ), (A-B), (A-C), and a method for producing the above organic solvent-swellable microgel, characterized by radical polymerization in a water-ethanol mixed solvent. . (A-A) Polyethylene oxide macromonomer and hydrophobic monomer charge capacity Polyethylene oxide macromonomer: hydrophobic monomer = 1: 10 to 1: 250 (molar ratio)

(A-C) Water-ethanol mixed solvent is water: ethanol = 90-30: 10-70 (volume ratio at 20 ° C)

[Chemical A- 22]

(1)

1

Represents H.

Three

[Chemical A- 23]

(A- 2)

[Chemical A-24]

(A— 3)

4 5

The

Furthermore, the present invention provides a cosmetic comprising the organic solvent swellable microgel described above.

[0037] [Invention B: Claims 6 to 10]

That is, the present invention comprises a polyethylene oxide macromonomer of the following formula (1), a hydrophobic monomer of the following formulas (B-2) and (B-3), and a crosslinkable monomer of the following formula (B-4). A copolymer obtained by polymerization, wherein the above (1) to (B-4) are obtained under the following conditions (B—A), (B—B), (B—C), (B—D). The organic solvent swellable microgel comprising a copolymer obtained by radical polymerization of the monomer (1) in a water / ethanol mixed solvent.

(B—A) Hydrophobic monomer is a composition in which methyl methacrylate and a methacrylic acid derivative having an alkyl having 4 to 8 carbon atoms are mixed in 90-: LO: 10-90 (molar ratio) (BB) Polyethylene oxide macromonomer and hydrophobic monomer charge capacity Polyethylene oxide macromonomer: hydrophobic monomer = 1: 10 to 1: 250 (molar ratio) thing

(B- C) that the charged amount of the charged amount force hydrophobic monomer crosslinking monomer is from 0.1 to 1.5 mass ^_0/0

(BD) Water-ethanol mixed solvent power Water: Ethanol = 90-30: 10-70 (20 volume ratio)

[Chemical B-17]

(1)

R represents alkyl having 1 to 3 carbon atoms, and n is a number from 20 to 200. X represents H or C H.

Three

[Chemical B-18]

(B-2)

R represents alkyl having 1 to 3 carbon atoms,

2

[Chemical B- 19]

(B— 3)

R represents an alkyl having from 3 to 8 carbon atoms, and R represents an alkyl having 4 to 8 carbon atoms.

(B— 4)

5 6

The .

Further, the present invention polymerizes a polyethylene oxide macromonomer of the following formula (1), a hydrophobic monomer of the following formulas (B 2) and (B-3), and a crosslinkable monomer of the following formula (B-4). The copolymer thus obtained provides an organic solvent swellable microgel having a monodisperse particle force with a particle diameter of 50 to 300 nm.

[Chemical B-21]

(1)

1

Represents H.

Three

[Chemical B- 22]

(B-2) R represents alkyl having 1 to 3 carbon atoms.

2

[Chemical B- 23]

(B— 3)

3 4

. However, R may be the same as or different from R in the formula (B-2).

3 2

[Chemical B-24]

(B— 4)

5 6

The

Furthermore, the present invention provides a polyethylene oxide macromonomer represented by the following formula (1), a hydrophobic monomer represented by the following formulas (B-2) and (B-3), and a crosslinkable monomer represented by the following formula (B-4): A copolymer obtained by polymerization, wherein the particle size of the copolymer particles in water is d,

0

When a water-immiscible organic solvent in which the copolymer particles swell and saturate is mixed and stirred until the swell is saturated, the particle size of the copolymer particles is d, and the swelling ratio (dZd) ³ is 1 or more. so

0

An organic solvent swellable microgel is provided.

[Chemical B-25]

(1)

Represents H.

Three

[Chemical B-26]

(B— 2)

R represents alkyl having 1 to 3 carbon atoms,

[Chemical B-27]

(B— 3)

R. Represents alkyl having 1 to 3 carbon atoms, R represents alkyl having 4 to 8 carbon atoms

3 4

. However, R may be the same as or different from R in formula (B-2).

3 2

[Chemical B-28]

(B— 4)

Further, the present invention provides a polyethylene oxide macromonomer represented by the following formula (1) and the following formula (B 2) and the hydrophobic monomer of (B-3) and the crosslinkable monomer of the following formula (B-4) under the conditions of the following (BA), (BB), (BC) The present invention provides a method for producing an organic solvent swellable microgel characterized by radical polymerization in a water-ethanol mixed solvent.

(B-A) Feeding capacity of polyethylene oxide macromonomer and hydrophobic monomer Polyethylene oxide macromonomer: hydrophobic monomer = 1: 10 to 1: 250 (molar ratio)

(B—B) Feeding power of crosslinkable monomer 0.1 to 1.5% by weight with respect to the charged amount of hydrophobic monomer

(B- C) Water-ethanol mixed solvent power Water: Ethanol = 90-30: 10-70 (volume ratio of 20 ° ○)

[Chemical B-29]

(1)

1

Represents H.

Three

[Chemical B-30]

(B-2)

R represents alkyl having 1 to 3 carbon atoms.

2

[Chemical B- 31]

(B— 3)

3 4

. However, R may be the same as or different from R in the formula (B-2).

3 2

[Chemical B-32]

(B— 4)

5 6

The

[0041] Furthermore, the present invention provides a cosmetic comprising the organic solvent swellable microgel described above.

[0042] [Invention C: Claims 11 to 13]

That is, the present invention provides a copolymer obtained by polymerizing a polyethylene oxide macromonomer of the following formula (1), a hydrophobic monomer of the following formula (C 2), and a crosslinkable monomer of the following formula (C 3). The present invention provides a cosmetic characterized by containing a coalescence.

[C-C-4]

Represents an alkyl of 3, and n is a number from 20 to 200. X is H or C

(C-2)

R represents alkyl having 1 to 3 carbon atoms, R represents alkyl having 1 to 8 carbon atoms

(C 3)

4 5

The

In addition, the present invention provides the monomers (1;) to (C-3) as water under the following conditions (C—A), (C—B), (C—C), and (C—D). The present invention provides a cosmetic comprising a microgel comprising a copolymer obtained by radical polymerization in a mixed solvent of ethanol.

The (C A) hydrophobic monomer should have a composition in which one or more methacrylic acid derivatives having an alkyl having 1 to 8 carbon atoms are mixed.

(C—B) Polyethylene oxide macromonomer and hydrophobic monomer charge capacity Polyethylene oxide macromonomer: hydrophobic monomer = 1: 10 to 1: 250 (molar ratio)

(CC) Feeding power of crosslinkable monomer 0.1% to the charged amount of hydrophobic monomer ~ 1.5% by mass

(C-D) Water-ethanol mixed solvent should be water: ethanol = 90-30: 10-70 (20 ° C volume ratio)

[0044] Further, the present invention provides the cosmetic described above, wherein the particle size of the microgel is 50 to 300 nm.

[0045] [Invention D: Claims 14 to 15]

That is, the present invention provides a cosmetic characterized in that the cosmetic described above contains a moisturizing agent.

[0046] Furthermore, the present invention provides the above cosmetic, wherein the humectant is a polyhydric alcohol.

[0047] [Invention E: Claims 16 to 17]

That is, the present invention provides a multilayer cosmetic comprising 5 to 40% by mass of a liquid oil in the cosmetic and satisfying the following condition (a) or (b).

(a) substantially no surfactant

(b) When a surfactant is contained, the “surfactant content Z liquid oil content” is 0.8 or less by weight.

[0048] The present invention also provides the multilayer cosmetic described above, which further contains a thickener.

The invention's effect

[0049] [Invention A]

The microgel of the present invention is a core-corona type microgel in which a nonionic and water-soluble polyethylene oxide chain is grafted on the surface, and the core portion is a hydrophobic polymer crosslinked with a crosslinking monomer. By adjusting the monomer mixing ratio and the polarity of the polymerization solvent, the present microgel can easily produce microgel particles with a narrow particle size distribution without controlling particularly strict stirring conditions. This makes mass production easy and is advantageous for industrial applications.

[0050] The microgel of the present invention is a water-dispersible force. Since the dispersion is stabilized with a nonionic polymer, acid resistance and salt resistance are expected. This feature is in the pharmaceutical or cosmetic industry It is considered to be an excellent material that satisfies the requirement of stable dispersion under physiological conditions required for application in Japan.

[0051] A notable characteristic of the microgel of the present invention is the ability to swell with a water-immiscible organic solvent. This swelling ability has very high solvent selectivity. In addition, the swelling efficiency shows surprising results, and the organic solvent swells up to about 400 times its own volume.

In the present invention, in particular, by setting the alkyl group of the alkyl thiolate to 4 to 8 carbon atoms, the selectivity of the swellable solvent can be expanded as compared with the case where the carbon number power is 3 to 3. Be expected.

[0052] The microgel of the present invention is particularly useful as a cosmetic raw material.

[0053] [Invention

The microgel of the present invention is a core-corona type microgel in which a nonionic and water-soluble polyethylene oxide chain is grafted on the surface, and the core portion is a hydrophobic polymer crosslinked with a crosslinking monomer. By adjusting the monomer mixing ratio and the polarity of the polymerization solvent, this microgel can easily produce microgel particles with a narrow particle size distribution without controlling particularly strict stirring conditions. This is easy for mass production and is advantageous for industrial applications.

[0054] The microgel of the present invention is a water-dispersible force. Since the dispersion is stabilized with a nonionic polymer, acid resistance and salt resistance are expected. This feature is considered to be an excellent material that satisfies the requirement of stable dispersion under physiological conditions required for applications in the pharmaceutical or cosmetic industry.

[0055] Further, a notable characteristic of the microgel of the present invention is swelling ability with a water-immiscible organic solvent. This swelling ability has very high solvent selectivity. Its swelling efficiency shows surprising results, and it absorbs organic solvents up to 400 times its own volume and swells.

In the present invention, the alkyl group of alkylia talirate particularly has 1 carbon atom and 4

It is expected that the selectivity of the swelling solvent will be expanded by mixing -8 ones compared to the case where the number of carbon atoms is 1 to 3 alone.

[0056] The microgel of the present invention is particularly useful as a cosmetic raw material.

[0057] [Invention C] (C 1) The cosmetics of the present invention have extremely excellent white turbidity! Good turbidity can be obtained even if the amount of the copolymer is small.

(C-2) The cosmetic of the present invention is excellent in storage stability. In other words, the turbidity is stable even after long-term storage.

(C-3) The cosmetics of the present invention are excellent in the feeling of use. In other words, there is a feeling of stickiness. In addition, there is an effect of suppressing shine when applied to the skin with which familiarity is early.

[0058] [Invention D]

(D-1) The topical skin preparation of the present invention has a high moisturizing effect and also has an effect of improving rough skin.

(D-2) The external preparation for skin of the present invention is excellent in the feeling of use. In other words, it is smooth and has no stickiness. It is particularly useful for cosmetics containing glycerin where stickiness is a problem. (D-3) The external preparation for skin of the present invention gives an excellent feeling of moisturizing effect to the user.

[0059] [Invention E]

(E-1) In the multilayer cosmetic of the present invention, the boundary between layers is clear. When the multilayer cosmetic of the present invention filled in a container is shaken and mixed, the aqueous phase becomes cloudy and the cloudiness is extremely excellent. By standing again, the boundary surface of each layer is clearly separated, giving it a multi-layered appearance.

(E-2) The multilayer cosmetic of the present invention is excellent in storage stability and can maintain its multilayer appearance even after long-term storage.

(E-3) The multilayer cosmetic of the present invention is excellent in usability without impairing the beauty of the appearance, and the layer separation speed can be adjusted by further adding a thickener. . Brief Description of Drawings

[0060] FIG. 1 is a schematic diagram showing a mechanism for generating a core corona-type polymer nanosphere of a microgel of the present invention.

FIG. A-2 is a graph showing the swelling ratio of the microgel of the present invention by RA-PE408.

FIG. A-3 is a graph showing the swelling ratio of the microgel of the present invention by MCX.

FIG. A-4 is a graph showing the swelling rate of the microgel of the present invention by artificial sebum.

FIG. B-2 is a graph showing the swelling ratio of the microgel of the present invention by RA-PE408. FIG. B-3 is a graph showing the swelling ratio of the microgel of the present invention by MCX.

FIG. B-4 is a graph showing the swelling ratio of the microgel of the present invention by artificial sebum.

BEST MODE FOR CARRYING OUT THE INVENTION

[0061] Hereinafter, the present invention will be described in detail.

[0062] [Invention A, Invention B, Invention C, Invention D, Invention E]

As the polyethylene oxide macromonomer of the formula (1) used in the present invention, for example, a reagent commercially available from Aldrich or a blender (registered trademark) marketed by Nippon Oil & Fats can be used. The molecular weight (namely, the value of n) of the polyethylene oxide part of the formula (1) of these commercially available products can be widely used. The molecular weight of the polyethylene oxide portion is preferably n = 20-200. For example, Blemmer (registered trademark) PME1000 or Blemmer (registered trademark) PME4000 manufactured by Nippon Oil & Fats is suitable.

[0063] [Invention A]

The hydrophobic monomer of the formula (A-2) used in the present invention can be easily obtained as a general industrial raw material. The alkyl chain of R in formula (A-2) is an alkyl having 4 to 8 carbon atoms.

Three

In the formula (A-2), butyl methacrylate, hexyl methacrylate, and ethyl hexyl methacrylate are preferred.

[0064] The crosslinkable monomer of the formula (A-3) used in the present invention is a commercially available reagent! / Is available as an industrial raw material. This crosslinkable monomer is preferably hydrophobic. The value of m in the formula (A-3) is preferably 1 to 3. Specifically, ethylene glycol dimetatalylate sold by Aldrich and Bremer (registered trademark) PDE-50 manufactured by NOF Corporation are suitable.

[0065] The above monomers are prepared under the following conditions (A-A), (A-B), (A-C).

It can be obtained by radical polymerization of the monomer (3) in a water / ethanol mixed solvent.

(A-A) Polyethylene oxide macromonomer and hydrophobic monomer charge capacity Polyethylene oxide macromonomer: hydrophobic monomer = 1: 10 to 1: 250 (molar ratio)

(A-B) Feeding power of cross-linkable monomer 0.1% of hydrophobic monomer charge ~ 1.5% by mass

[0066] The charged amount of polyethylene oxide macromonomer and hydrophobic monomer of (AA) is polymerized in the range of polyethylene oxide macromonomer: hydrophobic monomer = 1:10 to 1: 250 (molar ratio). Is possible. When the charged amount of polyethylene oxide macromonomer exceeds 1/10 of the hydrophobic monomer by molar ratio, the polymerized polymer becomes water-soluble and no corona core polymer microgel is formed. When the amount of the hydrophobic monomer exceeds 250 times the molar amount of the polyethylene oxide macromonomer, the dispersion stability due to the polyethylene oxide macromonomer becomes incomplete, and the hydrophobic polymer due to the insoluble hydrophobic monomer aggregates and precipitates. The charging ratio of the polyethylene oxide macromonomer to the hydrophobic monomer is preferably in the range of 1:20 to 1: 200. More preferably, the range is 1:25 force to 1: 150.

[0067] By copolymerizing the crosslinkable monomer (A-B), a microgel in which the hydrophobic polymer in the core portion is crosslinked can be polymerized. If the charge amount of the crosslinkable monomer is less than 0.1% by weight of the charge amount of the hydrophobic monomer, this microgel having a low crosslink density will collapse upon swelling. On the other hand, when the content exceeds 1.5% by weight, the microgel particles are agglomerated with each other, and the particle size distribution is narrow, so that suitable microgel particles cannot be polymerized. Preferably, the amount of the crosslinkable monomer charged is 0.2 to 1.0, more preferably 0.2 to 0.8, and most preferably 0.2 to 0.5% by mass.

[0068] The mixing ratio of water / ethanol which is the polymerization solvent of (A—C) is that water: ethanol mixed solvent is water: ethanol = 90-30: 10-70 (volume ratio at 20). The polymerization solvent needs to cover ethanol in order to dissolve the hydrophobic monomer uniformly. The mixing ratio of ethanol is 10-60 volume ratio. When the mixing ratio of ethanol is lower than 10 volume ratio, it becomes difficult to dissolve the hydrophobic monomer, and the particle size distribution of the polymerized microgel particles becomes wide. When the mixing ratio of ethanol exceeds 60 volume ratio, the polymer to be polymerized is dissolved in the polymerization solvent, and microgel particles cannot be obtained. The preferred water / ethanol mixing ratio is water-ethanol mixed solvent power water: ethanol = 90-50: 10-50 (20 ° C volume ratio). More preferably, water: ethanol = 80 to 60: 20-40 (volume ratio at 20 ° C.).

[0069] As the polymerization initiator used in this polymerization system, a commercially available polymerization initiator used for usual water-soluble thermal radical polymerization can be used.

In this polymerization system, it is possible to obtain a very narrow particle size distribution of the microgel particles to be superposed even if polymerization is performed without strictly controlling the stirring conditions.

[0070] According to the production method described above, an organic solvent swellable microgel having a particle size of 50 to 300 nm and a degree of dispersion of less than 0.05 is obtained.

[0071] [Invention

The hydrophobic monomers of the formulas (B-2) and (B-3) used in the present invention can be easily obtained as general industrial raw materials. In formulas (B-2) and (B-3), the alkyl groups of R are the same,

2

May be different. In addition, the alkyl chain of R in formula (B-3) is a C 4-8 alkyl group.

Three

It is rukill.

In formula (B-2), methyl methacrylate is preferred. In formula (B-3), butyl methacrylate, hexyl methacrylate or ethyl hexyl methacrylate is preferred. Therefore, the hydrophobic monomer is preferably a combination of methyl methacrylate of the formula (B-2) and butyl methacrylate, hexyl methacrylate or ethyl hexyl methacrylate of the formula (B-3). is there

[0072] The crosslinkable monomer of the formula (B-4) used in the present invention is available as a commercially available reagent or an industrial raw material. This crosslinkable monomer is preferably hydrophobic. The value of m in the formula (B-4) is preferably 1 to 3. Specifically, ethylene glycol dimetatalylate sold by Aldrich and Bremer (registered trademark) PDE-50 manufactured by NOF Corporation are suitable.

[0073] The above monomers are the monomers (1) to (B-4) described above under the conditions (B-A), (BB), (BC), and (BD). Obtained by radical polymerization in water / ethanol mixed solvent

(B—A) Hydrophobic monomer has a composition in which methyl methacrylate and a methacrylic acid derivative having an alkyl having 4 to 8 carbon atoms are mixed at 90 to LO: 10-90 (molar ratio). (BB) Polyethylene oxide macromonomer and hydrophobic monomer charge capacity Polyethylene oxide macromonomer: hydrophobic monomer = 1: 10 to 1: 250 (molar ratio)

(B—C) Feeding capacity of crosslinkable monomer 0.1 to 1.5% by mass with respect to the charged quantity of hydrophobic monomer

(B—D) Water Ethanol mixed solvent must be water: ethanol = 90-30: 10-70 (volume ratio of 20 ° ○)

[0074] The charged amount of polyethylene oxide macromonomer and hydrophobic monomer of (BB) is polymerized in the range of polyethylene oxide macromonomer: hydrophobic monomer = 1:10 to 1: 250 (molar ratio). Is possible. When the charged amount of polyethylene oxide macromonomer exceeds 1/10 of the hydrophobic monomer by molar ratio, the polymerized polymer becomes water-soluble and no corona core polymer microgel is formed. When the amount of the hydrophobic monomer exceeds 250 times the molar amount of the polyethylene oxide macromonomer, the dispersion stability due to the polyethylene oxide macromonomer becomes incomplete, and the hydrophobic polymer due to the insoluble hydrophobic monomer aggregates and precipitates. The charging ratio of the polyethylene oxide macromonomer to the hydrophobic monomer is preferably in the range of 1:20 to 1: 200. More preferably, the range is 1:25 force to 1: 150.

[0075] By copolymerizing the crosslinkable monomer (B-C), it is possible to polymerize the microgel in which the hydrophobic polymer in the core portion is crosslinked. If the charge amount of the crosslinkable monomer is less than 0.1% by weight of the charge amount of the hydrophobic monomer, this microgel having a low crosslink density will collapse upon swelling. On the other hand, when the content exceeds 1.5% by weight, the microgel particles are agglomerated with each other, and the particle size distribution is narrow, so that suitable microgel particles cannot be polymerized. Preferably, the amount of the crosslinkable monomer charged is 0.2 to 1.0, more preferably 0.2 to 0.8, and most preferably 0.2 to 0.5% by mass.

[0076] The mixing ratio of water / ethanol which is the polymerization solvent of (B-D) is water: ethanol mixed solvent, water: ethanol = 90-30: 10-70 (volume ratio at 20). The polymerization solvent needs to cover ethanol in order to dissolve the hydrophobic monomer uniformly. The mixing ratio of ethanol is 10-60 volume ratio. Hydrophobic when ethanol mixing ratio is lower than 10 volume ratio It becomes difficult to dissolve soluble monomers, and the particle size distribution of the polymerized microgel particles becomes wide. When the mixing ratio of ethanol exceeds 60 volume ratio, the polymer to be polymerized is dissolved in the polymerization solvent, and microgel particles cannot be obtained. A preferable water / ethanol mixing ratio is water-ethanol mixed solvent power water: ethanol = 90-50: 10-50 (volume ratio of 20 ° C.). More preferably, water: ethanol = 80 to 60: 20-40 (volume ratio at 20 ° C.).

[0077] As the polymerization initiator used in this polymerization system, a commercially available polymerization initiator used for usual water-soluble thermal radical polymerization can be used.

[0078] By the above-described production method, an organic solvent-swellable microgel having a monodisperse particle force with a particle size of 50 to 300 nm is obtained.

[0079] [Invention C]

As the hydrophobic monomer of the formula (C-2), for example, a reagent sold by Aldrich or Tokyo Kasei can be used. The alkyl chain of R in formula (C-2) has 1 carbon atom.

Three

~ 8 alkyl. Formula (C-2) is methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, methyl methacrylate, ethyl methacrylate, methacryl Examples include propyl acid, butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate and octyl methacrylate. In particular, methyl methacrylate, butyl methacrylate, and octyl methacrylate are preferred. These hydrophobic monomers are general-purpose raw materials and can be easily obtained as general industrial raw materials.

[0080] The crosslinkable monomer represented by the formula (C-3) is available as a commercially available reagent or an industrial raw material. This crosslinkable monomer is preferably hydrophobic. The value of m in the formula (C-3) is preferably 0-2. Specifically, ethylene glycol dimetatalylate, which is also sold by Aldrich, and Bremer (registered trademark) PDE-50 manufactured by NOF are suitable.

[0081] The copolymer used in the present invention is a copolymer obtained by copolymerizing the above monomer by an arbitrary polymerization method. In particular, the following (C—A), (C—B), (C—C), (C-D) ;)-(C-3) is preferably a copolymer (microgel) obtained by radical polymerization in a water-ethanol mixed solvent.

(C A) Polyethylene oxide macromonomer and hydrophobic monomer charge capacity Polyethylene oxide macromonomer: hydrophobic monomer = 1: 10 to 1: 250 (molar ratio)

(C B) Feeding power of crosslinkable monomer To be 0.1 to 1.5% by weight with respect to the charged amount of hydrophobic monomer

(C-C) Water-ethanol mixed solvent power Water: Ethanol = 90-30: 10-70 (20 ° C volume ratio)

[0082] The charge amount of polyethylene oxide macromonomer and hydrophobic monomer of (CA) is within the range of polyethylene oxide macromonomer: hydrophobic monomer = 1:10 to 1: 250 (molar ratio), and the corona core type microgel can be polymerized. It is. When the charged amount of the polyethylene oxide macromonomer is less than 1/10 of the hydrophobic monomer by molar ratio, the polymerized polymer becomes water-soluble and no corona core polymer microgel is formed. When the amount of the hydrophobic monomer exceeds 250 times the molar amount of the polyethylene oxide macromonomer, the dispersion stability due to the polyethylene oxide macromonomer becomes incomplete, and the hydrophobic polymer due to the insoluble hydrophobic monomer aggregates and precipitates. The charging ratio of the polyethylene oxide macromonomer and the hydrophobic monomer is preferably in the range of 1:10 to 1: 200. More preferably, 1:25 force is also in the range of 1: 100.

[0083] By copolymerizing the crosslinkable monomer of (CB), it is possible to polymerize the microgel in which the hydrophobic polymer in the core portion is crosslinked. If the charge amount of the crosslinkable monomer is less than 0.1% by weight of the charge amount of the hydrophobic monomer, this microgel having a low crosslink density will collapse upon swelling. On the other hand, when the content exceeds 1.5% by weight, the microgel particles are agglomerated with each other, and the particle size distribution is narrow, so that suitable microgel particles cannot be polymerized. Preferably, the charge amount of the crosslinkable monomer is 0.2 to 1.0, more preferably 0.2 to 0.8, and most preferably 0.2 to 0.5% by weight. [0084] The mixing ratio of water / ethanol which is the polymerization solvent for (C—C) is water: ethanol mixed solvent, water: ethanol = 90-30: 10-70 (volume ratio at 20). The polymerization solvent needs to cover ethanol in order to dissolve the hydrophobic monomer uniformly. The mixing ratio of ethanol is 10-60 volume ratio. When the mixing ratio of ethanol is lower than 10 volume ratio, it becomes difficult to dissolve the hydrophobic monomer, and the particle size distribution of the polymerized microgel particles becomes wide. When the mixing ratio of ethanol exceeds 60 volume ratio, the polymer to be polymerized is dissolved in the polymerization solvent, and microgel particles cannot be obtained. A preferable water / ethanol mixing ratio is water ethanol mixed solvent power water: ethanol = 90-60: 10-40 (volume ratio of 20 ° C.). More preferably, water: ethanol = 80 to 70: 20-30 (volume ratio at 20 ° C.).

[0085] As the polymerization initiator used in this polymerization system, a commercially available polymerization initiator used for ordinary water-soluble thermal radical polymerization can be used.

[0086] According to the above production method, a microgel having a particle diameter of 50 to 300 nm and a dispersion degree of less than 0.01 is obtained. This microgel has the property of swelling in an organic solvent.

[0087] [Invention A, Invention B, Invention C, Invention D, Invention E]

In general, the particle diameter of so-called colloidal particles such as emulsified particles or polymer emulsions can be measured by a dynamic light scattering method or a photon correlation method. This measurement method irradiates a sample dispersion prepared to a sufficiently dilute concentration with laser light and measures the scattered light intensity scattered from the sample particles, thereby obtaining the translational diffusion coefficient (average value) of the sample particles. It is a method of measuring. The sample particles are constantly moving in Brownian motion in the dispersion. It is possible to analyze the movement speed of the particles by this Brownian motion, that is, the translational diffusion coefficient (average value) from the result of the temporal change of the scattered light intensity. The hydrodynamic size of the sample particles can be calculated from the translational diffusion coefficient (average value) thus obtained according to the Stokes-Suinstein equation (Equation 1).

[Number 1] D

••• (l)

Where D is the diffusion coefficient, k is the Boltzmann constant, T is the absolute temperature (Κ), η is the viscosity of the solvent, and r is the radius of the particle.

This measurement can be easily performed with a commercially available measuring apparatus. For example, DLS7 000 made by Otsuka Electronics, Autosizer 1700 made by Maverun, and Zetapulse made by Brooke Ibn can be used.

The above-mentioned commercially available measuring devices are equipped with data analysis software and can automatically analyze the measurement data. By using this analysis software, values of average particle size and degree of dispersion can be obtained. Here, the dispersity is a value indicating the dispersion of the average value of the particle diameter, and is a value obtained by standardizing the value of the secondary cumulant in the cumulant analysis, that is, the dispersion value. In general, if the degree of dispersion is 0.01 or less, the particle size distribution of the sample can be regarded as almost monodisperse.

[0088] Further, when the microgel polymerized by the above-described production method is dispersed in water, the particle diameter of the copolymer particles is d, and the mixed solvent is mixed with benzene that swells and saturates the copolymer particles.

0

Thus, an organic solvent swellable microgel having a swelling ratio (dZd) ³ of 20 to 450 is obtained, where d is the particle size of the copolymer particles when stirring until swelling saturation occurs.

0

[0089] "When the mixed solvent is mixed with an amount of benzene that swells and saturates the copolymer particles and stirred until the swelling and saturation", even when the amount of benzene and the stirring time are increased. The particle size swelling ratio (dZd) ^{3 of} the swollen microgel does not increase further.

0

It means that a gap is necessary.

For example, if microgels are dispersed in water and benzene with the same volume as this mixed solvent is added and stirred for 5 hours, it is sufficient to swell and saturate.

When the polymerization solvent is a mixed solvent of water: ethanol = 6: 4 (volume ratio of 20 ° C), the polymerization dispersion is sufficiently dialyzed against pure water after polymerization, and the dispersion is exchanged for pure water. This microgel aqueous dispersion is diluted with water to an appropriate concentration so that the concentration of the microgel is constant. It is sufficient to add the same volume of benzene as the measurement sample to the prepared sample and mix and stir for 5 hours.

The particle diameters d and d can be measured by the dynamic light scattering method. Measurement conditions are as follows

0

It is.

First, as a control value, that is, the value of d, the water in the microgel before adding the organic solvent.

0

Measure the particle size inside. This measurement can be easily performed using a commercially available dynamic light scattering measurement device. For example, it is possible to measure with Otsuka Electronics DLS7000, Maverun Autosizer 4 700, Brooke Ibn Zeta Pulse. These commercially available measuring devices are equipped with data analysis software, which can automatically obtain the average particle size and dispersion value. On the other hand, the particle size d after swelling with an organic solvent is processed by the following method. That is, an organic solvent such as benzene of the same volume is added to a microgel aqueous dispersion having a constant concentration, preferably about 0.01% by weight, and sealed in a covered sample tube. The sample tube is brought to room temperature and stirred for a certain time while gently stirring. A stirring time of about 5 hours is sufficient. After stirring, perform a light centrifuge operation of about 1000 X g together with the sample tube. Lift up the organic solvent and disperse the microgel. Collect the water phase part with a careful syringe. The average particle size and the degree of dispersion of this sample collected are measured in the same manner using the above-mentioned commercially available dynamic light scattering measuring device.

It is possible to calculate the value of the d and d value forces swelling rate (d / d) ³ obtained in this way.

0 0

come.

All of the conventional synthetic polymer microgels are made by applying a polymer electrolyte such as polyacrylic acid, and their water dispersibility is acid-resistant and salt-resistant. However, when considering application as a compounding ingredient for pharmaceuticals and cosmetics, acid resistance and salt resistance are very important performances for adaptation under physiological conditions. The microgel of the present invention is a microgel stabilized with a polyethylene oxide chain which is a nonionic polymer, and its dispersion stability in water can be expected to be salt resistant if it is acid resistant.

In addition, a polymer microparticle polymerization method based on a macromonomer method using a macromonomer containing a water-soluble polymer structure is known. By applying this method, the core portion is crosslinked with a crosslinkable monomer to form a microgel. The manufacturing method is known. The method for producing a microgel used in the present invention is a core in which an aqueous macromonomer and a hydrophobic monomer are ordered in a solvent as shown in FIG. 1, the particle diameter is almost constant, and the core part is crosslinked. It is thought that a corona-type polymer microgel is formed.

[0091] [Invention A, Invention B]

The microgel is useful as a cosmetic raw material. The cosmetic of the present invention can be produced by blending the above microgel into the cosmetic. That is, microgels and cosmetic ingredients (for example, powder ingredients, liquid fats and oils, solid fats and oils, waxes, hydrocarbon oils, higher fatty acids, higher alcohols, ester oils, silicone oils, ionic surfactants, cationic surfactants) , Amphoteric surfactants, nonionic surfactants, moisturizers, water-soluble polymers, thickeners, film agents, ultraviolet absorbers, sequestering agents, lower alcohols, polyhydric alcohols, sugars, amino acids, organic any Amin, polymer Emarujiyon, _P H adjusting agents, skin nutrients, vitamins, antioxidants, oxidation preventing aid, perfume, suitably blended with water or the like), by a conventional method depending on the dosage form for the purpose Of cosmetics.

[0092] The blending amount of the microgel is appropriately determined according to the cosmetic. It is desirable to blend in the range of 0.01 to 10% by mass.

[Invention C]

This core-corona polymer microgel is considered to function as an excellent turbidity agent.

[0094] The above is the description of the copolymer used in the present invention. The cosmetic of the present invention is produced by mixing and dispersing this copolymer in water (or an aqueous phase in which water-soluble cosmetic ingredients are dissolved) by a conventional method. That is, the cosmetic of the present invention is a cosmetic having an excellent commercial value that can be produced by a very simple manufacturing process.

[0095] The microgel used in the present invention preferably has a particle size in the range of 50 to 250 nm when dispersed in ion-exchanged water. If the particle size of the microgel is less than 50 nm, it is difficult to obtain a stable cloudy cosmetic. If the particle size exceeds 250 nm, it is preferable as a cosmetic for long-term storage under high temperature conditions. In addition, the feeling of use may become unfavorable.

[0096] The microgel used in the present invention is usually 0.01 to 5% by mass based on the total amount of the cosmetic ( In the following, it is desirable to blend in the range of simply indicated by%. When the blending amount of the microgel is less than 0.01%, it is difficult to obtain a stable cloudy cosmetic. When the blending amount exceeds 5%, it is preferable as a cosmetic for long-term storage under high temperature conditions. Or the feeling of use may not be preferred.

[0097] It can be visually confirmed that the microgel used in the present invention becomes cloudy only by adding 0.01% to water, and a Macbeth color difference meter with a compounding amount of 0.01% and 0.1%. If the measured L value (brightness) is 1 to 80, a white turbidity is obtained, which functions as an excellent turbidity agent. The conventional cloudy lotion technology using emulsification has been difficult to balance with stability and feeling of use because of the large amount of surfactant and oil.

[0098] In the present invention, the cloudy cosmetic means a cosmetic whose appearance can be recognized as visually cloudy. The cloudiness with the L value of 1 to 90 is preferred. More preferably, the turbidity is 1 to 60. Within this range, the significance of the present invention is high. This is because it is very difficult to adjust the balance between the surfactant and the oil content of white cloudy cosmetics having an L value of 1 to 60, and it is difficult to produce a stable cloudy cosmetic.

A translucent lotion prepared by the microemulsion method or the like is also a cloudy cosmetic of the present invention, and its L value is around 90.

[0099] The cosmetic of the present invention is particularly preferably used as a cloudy cosmetic such as a cloudy lotion or a cloudy cosmetic liquid.

[0100] The cosmetic of the present invention further includes a medicinal agent, a moisturizing component, an anti-inflammatory agent, a bactericidal agent, an antiseptic agent, an ultraviolet absorber, an antioxidant, an organic and inorganic agent that are usually used in cosmetics, pharmaceuticals, and the like. Powders, fragrances, pigments, etc. can be blended as necessary.

[0101] [Invention D]

The copolymer used in the present invention is the same as the copolymer of Invention C. The external preparation for skin of the present invention is produced by mixing and dispersing this copolymer in water (or an aqueous phase in which water-soluble cosmetic ingredients are dissolved) by a conventional method. That is, the external preparation for skin of the present invention is a cosmetic having excellent commercial value that can be produced by a very simple manufacturing process.

[0102] The microgel used in the present invention has a particle size of 250η when dispersed in ion-exchanged water. It is desirable to use m or less. In the case of a particle size exceeding 250 nm, the stability viewpoint may be unfavorable as a cosmetic material during long-term storage under high-temperature conditions, or the feeling of use may be unfavorable.

[0103] The microgel used in the present invention is preferably blended in a range of usually 0.001% by mass or more based on the total amount of the external preparation for skin. If the amount of the microgel is less than 0.001% by mass, it is difficult to improve the feeling of use.

[0104] The microgel used in the present invention can be confirmed to reduce the characteristic stickiness of the moisturizer only by adding 0.001% by mass in water, and functions as a usability improver by mixing. It is. With the conventional technology, it has been difficult to suppress the stickiness of the skin at the time of application and after drying while maintaining the moisturizing effect due to the high formulation of the moisturizing agent.

[0105] The external preparation for skin of the present invention is preferably a cosmetic preparation in which the above microgel and humectant are blended simultaneously. This is because cosmetics containing a moisturizing agent are very difficult to adjust the balance between the moisturizing effect and the feeling of use with conventional techniques, and it is difficult to produce cosmetics that emphasize the feeling of use.

The blending amount of the moisturizer is preferably 0.1% by mass or more and less than 40% by mass with respect to the total amount of the external preparation for skin.

[0106] The humectant used in the present invention is preferably a polyhydric alcohol. In particular, glycerin is preferable, and as humectants other than glycerin, polyethylene glycol, 1,3-butylene glycol, erythritol, dipropylene glycol, betaine, sonorebitole, xylitol, maltitol, mucopolysaccharide, hyaluronic acid, chondroitin sulfate, chitin , Chitosan and the like.

[0107] The external preparation for skin of the present invention can be used for skin care products, makeup products, and hair care products. Lotion, milky lotion, serum, cream, impregnation mask, body lotion, facial cleansing, etc., especially preferred for use as skin care products.

[0108] The topical skin preparation of the present invention further includes a medicinal agent, a moisturizing component, an anti-inflammatory agent, a bactericidal agent, an antiseptic agent, an ultraviolet absorber, an antioxidant, an organic and an organic agent commonly used in cosmetics, pharmaceuticals and the like. Inorganic powders, fragrances, pigments and the like can be blended as necessary.

[0109] The external preparation for skin of the present invention comprises an oil, an oil-soluble drug that dissolves in the oil, and Z or fragrance. Even if it is used in cosmetics containing a cosmetic, it can provide an external preparation for skin with excellent moisturizing effect and usability. In this case as well, as described above, the moisturizing amount is based on the total amount of the external preparation for skin.

Less than 0.01% by mass is preferable.

[0110] [Invention C, Invention D]

The oily component to be blended in the system may be any of a liquid oil, a solid oil, a semi-solid oil, or a substance hardly soluble in water. Among these, it is most preferable to blend a liquid polar oil.

[0111] [Invention E]

The copolymer used in the present invention is the same as the copolymer of Invention C. The multilayer cosmetic of the present invention is produced by mixing and dispersing this copolymer in water (or an aqueous phase in which water-soluble cosmetic ingredients are dissolved) by a conventional method. That is, the multilayer cosmetic of the present invention is a composition having an excellent commercial value that can be produced by an extremely simple manufacturing process.

[0112] The microgel used in the present invention is preferably 250 or less when dispersed in ion-exchanged water. In the case of a particle size exceeding 250 nm, it may be preferable as a multilayer composition from the viewpoint of stability in long-term storage under high temperature conditions.

[0113] The microgel used in the present invention is desirably blended in the range of usually 0.001 to 90% by mass based on the total amount of the multilayer cosmetic, and more preferably 0.01 to 50% by mass. It is difficult to obtain a stable multi-layered composition if the blending amount of the Miku Mouth gel is less than 0.001% by mass. There are cases.

[0114] It can be visually confirmed that the microgel used in the present invention becomes cloudy only by adding 0.01 mass% to water. A layer boundary with a clear layer boundary is obtained with a blending amount of 0.01% by mass, and functions as an excellent clouding agent. In the conventional technique for clarifying the layer boundary by the activator, it is difficult to clarify the layer boundary, and there is no one in which the aqueous phase is cloudy.

[0115] The multilayer cosmetic of the present invention contains 540 mass% of a liquid oil. The liquid oil is exemplified below. Even when oil-soluble chemicals and fragrances are dissolved in liquid oil, the layer boundary is clear. Layered cosmetics can be provided. In addition, 5 to 40% by mass of the content of the liquid oil means the content including oil such as solid, semi-solid oil, oil-soluble drug, oil-soluble fragrance, etc. that dissolves in the liquid oil of the base. .

[0116] The liquid oil used in the present invention is not limited as long as it is a liquid oil at room temperature (15 ° C).

[0117] It is a condition that the multilayer cosmetic of the present invention having a clear layer boundary is substantially free of a surfactant. When a surfactant is added, an emulsification phenomenon may occur, and it may be difficult to form a clear boundary. In addition, a stable and uniform emulsion composition is generated and can be separated even if left standing. In some cases, the multi-layered appearance does not occur.

However, when a surfactant is blended, it is necessary to at least make the blending amount 0.8 or less in terms of the weight composition with respect to the blending amount of the liquid oil in order to produce a multilayer cosmetic.

[0118] Any surfactant that can be added in a weight composition with respect to the liquid oil with a blending amount of 0.8 or less is not limited. (

[0119] When the multilayer cosmetic of the present invention is blended with a thickener of a natural polymer or a synthetic polymer, the usability and the separation rate of the multilayer can be adjusted. In the present invention, when such a thickener is blended, the boundary in an ordinary multilayer cosmetic becomes unclear, but in the present invention, a clear and beautiful multilayer cosmetic can be provided. The amount of thickener is not limited, but is preferably 0.01 to LO mass% with respect to the total amount of the multilayer cosmetic.

[0120] The thickener that can be blended in the multilayer cosmetic of the present invention is not limited to either a natural water-soluble polymer or a semi-synthetic synthetic water-soluble polymer.

[0121] The multi-layer cosmetic of the present invention includes a medicinal agent, a moisturizing component, an anti-inflammatory agent, a bactericide, an antiseptic, an ultraviolet absorber, an antioxidant, an organic and inorganic powder, and a fragrance that are commonly used in cosmetics. , Pigments and the like can be blended as necessary.

[0122] The product type of the multilayer cosmetic of the present invention is not limited. The most preferred product is multi-layered lotion, but it can also be applied to cosmetics such as liquid hair cosmetics and liquid baths. The

Example

[0123] Hereinafter, the present invention will be described more specifically with reference to Examples. The present invention is not limited to these examples. The blending amount is mass% unless otherwise specified.

[0124] [Invention A]

"Monomers and reagents used in the examples"

Polyethylene oxide macromonomer (polyethyleneglycololemethinoreethenore methacrylate; Nippon Oil & Fats Bremer PME-4000), n-butyl methacrylate (abbreviated as C4MA; made by Aldrich), 2-ethylhexyl methacrylate (C8MA; Aldrich), dodecyl methacrylate (abbreviated as C12MA; manufactured by Tokyo Chemical Industry) and ethylene glycol dimethacrylate (abbreviated as EGDM; manufactured by Aldrich) were used as monomers. As a polymerization initiator, 2,2, azobis (2-methylpropionamidine dihydrochloride) (manufactured by Aldrich) was used. As the water, ion exchange water was used. Other organic solvents used are as follows. Ethyl alcohol (Aldrich), benzene (Aldrich) and hexane (Aldrich).

[0125] Example A— 1

The polymerization of the microgel was carried out by the following method. A 200 mL three-necked flask equipped with a reflux tube and a nitrogen inlet tube is mixed with water and ethanol (water: ethanol = 40:60 volume ratio) 50 mL with PME-4000 (219.5 mg) and n-butyl methacrylate (C4MA) 780 Dissolve 5 mg and ethylene glycol dimetatalylate 2. Omg. After sufficient dissolution, add 2, 2, azobis (2-methylpropionamidine dihydrochloride) at a ratio of lmol% with respect to the total amount of monomers and further dissolve. The completely homogenized polymerization solution is purged with nitrogen for 20 minutes to remove dissolved oxygen, and then stirred for 8 hours in an oil bath at 65 to 70 ° C while stirring with a magnetic stirrer. After completion of the polymerization, the polymerization solution is returned to room temperature, and then the polymerization solution is dialyzed against water for 5 days to remove residual monomers, and at the same time, the dispersion is replaced with water. The sample obtained here is PMG 1.

[0126] Example A-2

The polymerization of the microgel was carried out by the following method. A 200 mL three-necked flask equipped with a reflux tube and a nitrogen inlet tube is mixed with water and ethanol (water: ethanol = 60:40 volume ratio) 50 mL Dissolve 167.8 mg of PME-4000, 832.2 mg of 2-ethylhexylmetatalylate (C8MA) and 1.5 mg of ethylene glycol dimetatalate. After sufficient dissolution, 2,2′azobis (2-methylpropionamidine dihydrochloride) is added at a ratio of 1 mol% with respect to the total amount of monomers and further dissolved. The completely homogenized polymerization solution is purged with nitrogen for 20 minutes to remove dissolved oxygen, and then stirred for 8 hours in an oil bath at 65 to 70 ° C while stirring with a magnetic stirrer. After completion of the polymerization, the polymerization solution is returned to room temperature, and then the polymerization solution is dialyzed against water for 5 days to remove residual monomers, and at the same time, the dispersion is replaced with water. The sample obtained here is PMG2.

[0127] Comparative Example A— 1

The polymerization of the microgel was carried out by the following method. In a 200 mL three-necked flask equipped with a reflux tube and a nitrogen inlet tube, water ethanol mixed solvent (water: ethanol = 30:70 volume ratio) 50 mL PME-4000 136. lmg, dodecylmetatalylate (C12MA) 863.9 mg And Dissolve 1.2 mg of ethylene glycol dimetatalylate. After sufficient dissolution, add 2,2′azobis (2-methylpropionamidine dihydrochloride) at a ratio of 1 mol% with respect to the total amount of monomer and further dissolve. The completely homogenized polymerization solution is purged with nitrogen for 20 minutes to remove dissolved oxygen, and then stirred for 8 hours in an oil bath at 65 to 70 ° C while stirring with a magnetic stirrer. After completion of the polymerization, the polymerization solution is returned to room temperature, and then the polymerization solution is dialyzed against water for 5 days to remove residual monomers, and at the same time, the dispersion is replaced with water. The sample obtained here is PMG3.

[0128] Comparative Example A-2

The polymerization of the microgel was carried out by the following method. In a 200 mL three-necked flask equipped with a reflux tube and a nitrogen introduction tube, 280 mg of PME-4000 and 853.2.2 mg of methyl metatalylate (C IMA) and 50 mL of water / ethanol mixed solvent (water: ethanol = 30:70 volume ratio) Dissolve 2. mg of ethylene glycol dimetatalylate. After sufficient dissolution, add 2,2'azobis (2-methylpropionamidine dihydrochloride) at a rate of lmol% with respect to the total amount of monomer and further dissolve. The completely homogenized polymerization solution is purged with nitrogen for 20 minutes to remove dissolved oxygen, and then stirred for 8 hours at 65 to 70 ° C in an oil bath while stirring with a magnetic stirrer. After the polymerization, the polymerization solution is returned to room temperature, Dialyze for 5 days to remove residual monomer and simultaneously replace the dispersion with water. The sample obtained here is PMG4.

[0129] The polymerization results are shown in "Table A-1."

Sample numbers PMG1 and PMG2 are the microgels of the present invention.

PMG3 and PMG4 both have an alkyl chain length (R) of the hydrophobic monomer of formula (A-2)

This is a comparative example when the condition of 3 is not satisfied. That is, Comparative Example A-1 (PMG3) uses dodecylmetatalylate, which is a hydrophobic monomer with a large number of R carbon atoms.

Three

The Comparative Example A-2 (PMG4) uses methylmetatalate, which has R carbon atoms

Three

A small, hydrophobic monomer.

PMG3 was transparent in the polymerization solution at the end of polymerization and did not take the form of a microgel. Due to the high content of ethanol, the polymer appears to be dissolved in ethanol. Further, when the alcohol content of the mixed solvent was decreased, the hydrophobic monomer was not sufficiently dissolved, and the reaction solution before the polymerization reaction became cloudy.

[0130] [Table A-1]

* Crosslinking rate (%) is mass% of EGDM with respect to the total mass of PME4000 and hydrophobic monomer.

Next, the characteristics of the microgel obtained above were examined. The measurement method is shown below.

"Measurement method of particle size and degree of dispersion"

The microgel particle size was measured using a zeta plus manufactured by Ichibun Co., Ltd. in Brook. Prepare a measurement sample by adjusting the microgel concentration of the microgel dispersion to approximately 0.1%, remove dust with a 0.45 micrometer filter, and then determine the scattering intensity at 25 ° C at a scattering angle of 90 °. The average particle size and the degree of dispersion were calculated using analysis software installed in the measuring device. The particle size is analyzed by cumulant analysis, and the degree of dispersion is obtained by cumulant analysis. This is a numerical value obtained by standardizing the value of the second-order cumulant. This degree of dispersion is a commonly used parameter and can be automatically prayed by using a commercially available dynamic light scattering measurement device. As the viscosity of the solvent necessary for the particle size analysis, the viscosity of pure water at 25 ° C., that is, a value of 0.89 mPas was used.

The measurement was performed 10 times for each sample and the average value was taken.

As a control value, measure the particle size of untreated microgel in water and use this as the d value.

0.

[0132] "Measurement method of swelling degree"

The degree of swelling with an organic solvent was measured by the following method. RA-PE408 and MCX! /, Which are oils commonly used in cosmetics, used artificial sebum.

Take 20 mL of a microgel aqueous dispersion with a microgel concentration adjusted to 0.1% in a 50 mL glass lidded sample tube, and add 0.2 mL of each water-immiscible solvent (oil). The sample tube was stirred at room temperature for 8 hours with an overturning stirrer. After stirring, the mixture was lightly centrifuged to allow excess organic solvent to float, and the aqueous phase of the sample solution was carefully aspirated using a syringe to obtain a measurement sample. The measurement sample measured the average particle diameter and dispersion degree at 25 degreeC by the said method. The particle diameter after the swelling treatment measured here is defined as d, and the ratio with d described above is defined as

The value obtained by taking 0 and raising this to the third power was taken as the degree of swelling (dZd 0) ³ .

[0133] "Results and discussion"

The characteristic values of the microgel polymerized by the present invention are shown in “Table A-2”.

Samples of PMG1, 2, and 4 had a particle size of about 50 to 150 nm, the dispersities were both less than 0.05, and the particle size distribution was relatively narrow.

[0134] [Table A-2]

[0135] Samples of PMG1 to 4 Swelled by RA—PE408, MCX and artificial sebum The degree was measured. The results are shown in “Table A-3”.

[0136] [Table A-3]

[0137] The swelling rates of PMG1 to 4 by RA-PE408, MCX, and artificial sebum are shown in the graphs of Figure A-2, Figure A-3, and Figure A-4. The vertical axis of the graph indicates the degree of swelling.

[0138] In contrast to polar oils such as RA-PE408 and MCX, which are widely used as cosmetic raw materials, and human sebum, PMG4 did not swell at all, but only PMG1 and 2 swelled. This is because the length of the alkyl chain in the core part of the mouth-opening gel becomes bulky, and the glass transition temperature decreases, so the range of solvents that can be swollen with high flexibility is widened. It is done.

[0139] Examples of cosmetics containing the microgel of the present invention are shown below.

[0140] "Example A-3 lotion"

One nore

(2) Glycerin

(3) 1,3-Butyleneglycanol

(4) Polyoxyethylene poly enore

0.2

(5) Sodium hexametaphosphate 0.03

(6) Trimethinoreglicin

(7) Sodium polyaspartate 0.1

(8) a-Tocopherol 2-L-ascorbic acid potassium phosphate diester

0.1

(9) Chotaurine 0.1

(10) Green tea extract 0.1

(11) Western Heart Force Extract 0.1 (12) Sodium HEDTA3 0.1

(13) Microgel (PMG1) 0.1

(14) Carboxybule polymer 0.05

(15) Potassium hydroxide 0.02

(16) Appropriate amount of phenoxyethanol

(17) Purified water residue

(18) Perfume appropriate amount

Production method

(13), (16) and (18) are mixed uniformly in (1) and dissolved uniformly. This mixed solution was homogenized by placing it in a solution in which (2) to (12) were uniformly mixed in (17), and then (14) and (15) were added to obtain a lotion.

“Example A—4 Moisturizing Cream”

(1) Liquid paraffin 10

(2) Dimethylpolysiloxane 2

(3) Glycerin 10

(4) 1,3-Butyleneglycolole 2

(5) Erythritol 1

(6) Polyethylene glycol 1500 5

(7) Sukuran 15

(8) Tetra 2-ethylhexanoic acid pentaerythrit 5

(9) Potassium hydroxide 0.1

(10) Sodium hexametaphosphate 0.05

(11) Tokovol acetate acetate 0.05

(12) Appropriate amount of paraoxybenzoate

(13) Hydroxypropyl methylcellulose 0.2

(14) Microgel (PMG2) 0.1

(15) Polybulal alcohol 0.1

(16) Carboxyvinyl polymer 0.2 (17) Acrylic acid / alkyl methacrylate copolymer (Pemulene TR-2)

0.1

(18) Purified water residue

Production method

Dissolve (3) to (6) and (8) to (17) in (18), add the mixture of (1), (2) and (7), mix and cool the mixture to cool the moisturizing cream. Obtained.

Example A-5 Sunscreen "

1) Decamethylcyclopentasiloxane 20

2) Ethanol 5

3) Isostearyl alcohol 2

4) Dipropylene glycol 3

5) Isostearic acid 2

6) Tri-2-Ethylhexanoic acid glyceryl 5

7) 2-Ethinorehexanoic acid cetinole 2

8) Dextrin fatty acid ester coated fine particle titanium oxide (40nm) 2

9) Sodium chloride 2

10) edetic acid trisodium appropriate amount

11) Ubinar T-150 (BASF) 1

12) 4-t-Butyl-4, -methoxydibenzoylmethane 1

13) 2-Methylhexyl paramethoxycinnamate 7.5

14) Carboxymethylcellulose Na 0.4

15) Microgel (PMG1) 0.1

16) Ethylcellulose 1

17) Spherical acrylic resin powder 5

18) Purified water residue

19) Perfume appropriate amount

Production method

(4), (9), (10), (15) is dissolved in (18), and other components are melt mixed The resulting liquid was added to obtain a sunscreen.

[0143] "Example A-6 Cleansing Genore"

(1) Polyoxyethylene 'methyl polysiloxane copolymer 5

(2) Dipropylene glycolate 3

(3) 1,3-Butylene glycol 10

(4) Polyethylene glycol 1500 1

(5) Polyoxyethylene methyl darcoside 1

(6) Microgel (PMG1) 0.05

(7) Polyethylene glycol diisostearate 5

(8) Dipotassium glycyrrhizinate 0.1

(9) Cola 'De' Cavallo extract 0.1

(10) edetic acid tri-Na 0.01

(11) Hydroxypropyl methylcellulose 0.8

(12) Carboxybule polymer potassium 0.35

(13) Paraxybenzoic acid ester

(14) Purified water residue

Production method

(11) and (12) were dissolved in (14) and mixed with other ingredients to obtain a cleansing jewel.

[0144] "Example A—7 Latex"

(1) Dimethylolene polysiloxane 3

(2) Decamethylcyclopentasiloxane 4

(3) Ethanore 5

(4) Glycerin 6

(5) 1,3-Butylene glycol 5

(6) Polyoxyethylene methyl darcoside 3

(7) Castor oil 1

(8) Skullan 2 (9) Potassium hydroxide 0.1

(10) Sodium hexametaphosphate 0.05

(11) Hydroxypropyl mono-β-cyclodextrin 0.1

(12) Dipotassium glycyrrhizinate 0.05

(13) Bi-leaf extract 0.1

(14) L-Sodium glutamate 0.05

(15) Wikiyou extract 0.1

(16) Yeast extract 0.1

(17) Lavender oil 0.1

(18) Zio Extract 0.1

(19) Dimorpholinopyridazinone 0.1

(20) Xanthan gum 0.1

(21) Microgel (PMG2) 0.1

(22) Acrylic acid 'alkyl methacrylate copolymer (Pemulene TR-1)

0.1

(23) Bengala appropriate amount

(24) Yellow iron oxide appropriate amount

(25) Paraben appropriate amount

(26) Purified water residue

Production method

A mixed solution obtained by dissolving (9) to (12) and (20) to (22) in (26) was added to a solution obtained by melting and mixing other components to obtain an emulsion.

“Example Α-8 Shampoo”

(1) Ethylene glycol distearate 1.5

(2) Palm oil fatty acid ethanolamide 5.5

(3) Palm oil fatty acid sodium methyl taurine 8

(4) Palm oil fatty acid amidopropyl betaine 5

(5) Polymer JR—400 (Union Carbide) 0.4 (6) Microgel (PMG1) 0.1

0.5

(8) Salty sodium 1.2

(9) Bi-leaf extract 0.1

(10) Phenoxyethanol 0.1

(11) Sodium benzoate appropriate amount

(12) edetate disodium appropriate amount

(13) Purified water residue

(14) Appropriate amount of perfume

Production method

The components (1) to (12) were stirred in (13), and (14) was added to obtain a shampoo. Example A-9 Conditioner "

1) Highly polymerized dimethylsiloxane 'methyl (aminopropyl) siloxane copolymer

0.2

2) Hardened rapeseed oil alcohol 3

3) Glycerin 3.5

4) 3-Methyl-1,3-butanediol 5

5) Hydroxystearic acid 0.5

6) 2-Ethinorehexanoic acid cetinole 1

7) Isononanoic acid isonol 0.5

8) Sensormer CI-50 (Nalco) 0.2

9) Dimethylaminopropylamide stearate 1

10) Marcote 550 (Calgon) 1

11) Microgel (PMG1) 0.1

12) L-glutamic acid 0.5

13) Phenoxyethanol 0.4

14) Lecithin 0.1

15) Water remaining (16) Appropriate perfume

(17) Dye proper amount

Production method

A liquid obtained by melting and mixing (1), (2) and (7) was stirred and mixed with other components at a high temperature, and cooled to obtain a conditioner.

Example A-10 Face Wash Foam "

1) Glycerin 35

2)

0.5

3) Maltitol hydroxyalkyl (12, 14) ether solution 0.5

4) Ethylene glycol distearate 1

5) N coconut oil fatty acid oil 15

6) Dodecane-1, 2 diol sodium acetate ether 1

7) Arginine Palm oil fatty acid 1

8) N Lauroyl L L Sodium glutamate 2

9) Palm oil fatty acid amidopropyl betaine 1.5

10) Microgel (PMG2) 0.05

1

12) Aubata extract 0.05

13) L-Menthol 0.1

14) Granule * 1

15) Purified water

16) Fragrance

* [Granule composition]

Zinc oxide

Talc

Magnesium aluminate metasilicate 10

Polyethylene powder 75

Ethino Resenorelose Production method

All ingredients were stirred in (15) at high temperature and cooled to obtain a face-wash foam. Example A-11 Body Soap "

1) Propylene glycolate 5

2) Polyoxypropylene glyceryl ether 0.5

3) Isostearic acid 1

(4) Lauric acid 10

: 5) Palm fatty acid 9

(6) Myristic acid 1

7) Ethylene glycol distearate 2

(8) Palm oil fatty acid diethanolamide 1

9) Sodium polyoxyethylene lauryl ether sulfate 1.5

: 10) Palm oil fatty acid methyl taurine sodium 0.3

: 11) Taurine sodium laurate 0.3

: 12) 2—Anolequinole-N-canoleboxoxymethinole-hydroxyethinoreidomidori Tyne 2

13) Marcote 100 (Calgon) 0.1

14) Potassium hydroxide 5

15) Hydroxypropyl methylcellulose 0.3

16) Microgel (PMG1) 0.1

17) Bi-leaf extract

18) edetic acid disodium

19) Purified water

: 20) Perfume appropriate amount

Production method

After (3) to (8) were melted and stirred in (19), other components were added and a body one soap was obtained by stirring and mixing.

“Example A—12 Liquid Foundation” (1) Ethanol 10.0

(2) Glycerin 10.0

(3) 1, 3-Butylene glycol 7.0

(4) Silica coated acid titanium 8.0

(5) Synthetic phlogopite 3.0

(6) Spherical caustic anhydride 5.0

(7) Bengala coated mica titanium (color rendering pearl G) 2.0

(8) Salty sodium 0.3

(9) Hydroxypropyl mono-β-cyclodextrin 0.1

(10) Green tea extract 0.1

(11) Lily extract 0.1

(12) Bengala 0.1

(13) Jielan gum 0.1

(14) Microgel (PMG2) 0.1

(15) Porous spherical cellulose 0.1

(16) Lavender extract 0.1

(17) Purified water residue

Production method

(2), (3), (8), (9), (13), (14) were mixed with (17), and other components were added to the mixed liquid, and a liquid foundation was obtained by stirring.

“Example Α—13 makeup base”

(1) Dimethylolene polysiloxane

(2) Decamethylcyclopentasiloxane

(3) Ethanol

(4) Behe-Norano Recone

(5) Batyl alcohol

(6) Dipropylene glycol

(7) 1,3-Butyleneglycanol (8) Polyethylene glycol 1500 4

(9) Plant squalene 0.1

(10) Polyoxyethylene glyceryl isostearate 0.3

(11) Titanium 'Bengara Coated Mica 0.3

(12) Titanium mica 0.3

(13) Potassium hydroxide 0.2

(14) Sodium hexametaphosphate 0.05

(15) Tokovol acetate 0.1

(16) Appropriate amount of paraoxybenzoate

(17) Lithium cobalt titanate appropriate amount

(18) Porous spherical cellulose powder 0.5

(19) Microgel (PMG1) 0.2

(20) Carboxybule polymer 0.2

(21) Acrylic acid / alkyl methacrylate copolymer 0.2

(22) Purified water residue

Production method

(19) to (21) were dissolved in (22), and then added to the melted mixture of other components and stirred to obtain a makeup base.

“Example A—14 Mascara”

(1) Ethanol 5

(2) 1, 3-Butylene glycol 4

(3) Polyethylene terephthalate 'polymethylmetatalate laminated film powder

0.1

(4) Potassium hydroxide 0.1

(5) Sodium hexametaphosphate appropriate amount

(6) Appropriate amount of paraoxybenzoate

(7) Acid Red 0.1

(8) Tartrazine 0.1 (9) Brilliant Bull FCF 0.1

(10) Dextrin 30

(11) Microgel (PMG2) 0.2

(12) Carboxybule polymer 1

(13) Remaining amount of purified water

Production method

All components were melted and stirred to obtain mascara.

“Example A—15 Eyeliner”

(1) Liquid paraffin 5

(2) Methyl polysiloxane emulsion suitable!

(3) Glycerin 3

(4) 1,3-Butyleneglycolanol 6

(5) Polyoxyethylene sorbitan monolaurate (20E.O.)

(6) Isobutylene / sodium maleate copolymer solution

(7) Titanium oxide appropriate amount

(8) Plate-shaped barium sulfate appropriate amount

(9) Kaolin 8

(10) Titanium black mite-coated mica titanium (pearl)

(11) Black iron oxide 9

(12) Acetic acid DL- α-tocopherol 0.1

(13) Paraxybenzoic acid ester Suitable

(14) Bentonite 1

(15) Carboxymethylcellulose sodium 1.

(16) Alkyl acrylate copolymer emulsion

(17) Microgel (PMG2) 0.5

(18) Purified water remaining

Production method

Melt and stir the mixture of (3) and (4) dissolved in (18) and the other ingredients to remove the eyeliner Obtained.

[0153] [Invention

"Monomers and reagents used in the examples"

Polyethylene oxide macromonomer (polyethyleneglycololemethinoreethenore methacrylate; Nippon Oil & Fats Bremer PME-4000), methyl methacrylate (abbreviated as C1MA; manufactured by Aldrich), n-butyl methacrylate (abbreviated as C4MA; Aldrich) ), 2-ethyl hexamethyl methacrylate (abbreviated as C8MA; manufactured by Aldrich) and ethylene glycol dimethacrylate (abbreviated as EGDM; manufactured by Aldrich) were used as monomers. As the polymerization initiator, 2,2, azobis (2-methylpropionamidine dihydrochloride) (manufactured by Aldrich) was used. Water used was ion exchange water. Other organic solvents used are as follows. Ethyl alcohol (Aldrich), benzene (Aldrich) and hexane (Aldrich).

[0154] Example B— 1

The polymerization of the microgel was carried out by the following method. A 200 mL three-necked flask equipped with a reflux tube and a nitrogen inlet tube is mixed with water ethanol mixed solvent (water: ethanol = 40:60 volume ratio) 50 mL with PME-4000 267. Omg ゝ methylmetatalylate (C1MA) 303.0 mg ゝ-Dissolve 428. lmg butynole metatalylate (C4MA) and 2. lm g ethylene glycol dimetatalate. After sufficient dissolution, 2,2′azobis (2-methylpropionamidine dihydrochloride) is added at a ratio of 1 mol% with respect to the total amount of monomers and further dissolved. The completely homogenized polymerization solution is purged with nitrogen for 20 minutes to remove dissolved oxygen, and then stirred in a magnetic stirrer and kept in an oil bath at 65 to 70 ° C for 8 hours for polymerization. After completion of the polymerization, the polymerization solution is returned to room temperature, and then the polymerization solution is dialyzed against water for 5 days to remove residual monomers, and at the same time, the dispersion is replaced with water. The sample obtained here is PMG1.

[0155] Example B-2

The polymerization of the microgel was carried out by the following method. A 200 mL three-necked flask equipped with a reflux tube and a nitrogen inlet tube is mixed with water ethanol mixed solvent (water: ethanol = 60:40 volume ratio) 50 mL with 218.0 mg of PME-4000, methylmetatalylate (C1MA) 261.8 mg ゝ 2 Dissolve 502. lmg of hexylmethacrylate (C8MA) and 1.5mg of ethylene glycol dimethacrylate. 2, 2'azobis (2-methylpropionamidine) Dihydrochloride) is added at a rate of 1 mol% with respect to the total monomer amount and further dissolved. The completely homogenized polymerization solution is purged with nitrogen for 20 minutes to remove dissolved oxygen, and then stirred in a magnetic stirrer and kept in an oil bath at 65 to 70 ° C for 8 hours for polymerization. After completion of the polymerization, the polymerization solution is returned to room temperature, and then the polymerization solution is dialyzed against water for 5 days to remove residual monomers, and at the same time, the dispersion is replaced with water. The sample obtained here is PMG2.

[0156] Example B-3

The polymerization of the microgel was carried out by the following method. A 200 mL three-necked flask equipped with a reflux tube and a nitrogen inlet tube is mixed with water. Ethanol mixed solvent (water: ethanol = 40:60 volume ratio) 50 mL with PME-4000 267. Omg ゝ methylmetatalylate (ClMA) -Dissolve 171.5mg butynole metatalylate (C4MA) and 2.lm g ethylene glycol dimetatalylate. After sufficient dissolution, 2,2′azobis (2-methylpropionamidine dihydrochloride) is added at a ratio of 1 mol% with respect to the total amount of monomers and further dissolved. The completely homogenized polymerization solution is purged with nitrogen for 20 minutes to remove dissolved oxygen, and then stirred in a magnetic stirrer and kept in an oil bath at 65 to 70 ° C for 8 hours for polymerization. After completion of the polymerization, the polymerization solution is returned to room temperature, and then the polymerization solution is dialyzed against water for 5 days to remove residual monomers, and at the same time, the dispersion is replaced with water. The sample obtained here is PMG3.

[0157] Example B— 4

The polymerization of the microgel was carried out by the following method. In a 200 mL three-necked flask equipped with a reflux tube and a nitrogen introduction tube, water and ethanol mixed solvent (water: ethanol = 40:60 volume ratio) 50 mL to PME—4000 267. Omg, methylmetatalylate (C1MA) 120.3 mg, n -Dissolve 685.7mg of butyl metatalylate (C4MA) and 2.lmg of ethylene glycol dimetatalylate. After sufficient dissolution, 2,2′azobis (2-methylpropionamidine dihydrochloride) is added at a ratio of 1 mol% with respect to the total amount of monomers and further dissolved. The completely homogenized polymerization solution is purged with nitrogen for 20 minutes to remove dissolved oxygen, and then stirred in a magnetic stirrer and kept in an oil bath at 65 to 70 ° C for 8 hours for polymerization. After completion of the polymerization, the polymerization solution is returned to room temperature, and then the polymerization solution is dialyzed against water for 5 days to remove residual monomers, and at the same time, the dispersion is replaced with water. The sample obtained here is PMG4. [0158] Comparative Example B— 1

The polymerization of the microgel was carried out by the following method. In a 200 mL three-necked flask equipped with a reflux tube and a nitrogen introduction tube, 280 mg of PME-4000 and 853.2.2 mg of methyl metatalylate (C IMA) Dissolve 2. mg of ethylene glycol dimetatalylate. After sufficient dissolution, add 2,2'azobis (2-methylpropionamidine dihydrochloride) at a rate of lmol% with respect to the total amount of monomer and further dissolve. The completely homogenized polymerization solution is purged with nitrogen for 20 minutes to remove dissolved oxygen, and then stirred for 8 hours at 65 to 70 ° C in an oil bath while stirring with a magnetic stirrer. After completion of the polymerization, the polymerization solution is returned to room temperature, and the polymerization solution is dialyzed against water for 5 days to remove residual monomers, and at the same time, the dispersion is replaced with water. The sample obtained here is PMG5.

[0159] The polymerization results are shown in Table B-1.

Sample numbers PMG1, 2, 3, and 4 are the microgels of the present invention. PMG5 is a comparative example in which only the hydrophobic monomer of formula (B-2) is used without using the hydrophobic monomer of formula (B-3). Each sample had a cloudy color at the end of the reaction.

[Table B-1]

However crosslinking ratio (%) is the mass ^_0/0 of EGD M to the total mass of PME4000 and hydrophobic monomers.

Next, the characteristics of the microgel obtained above were examined. The measurement method is shown below. "Measurement method of particle size and degree of dispersion"

The microgel particle size was measured using a zeta plus manufactured by Ichibun Co., Ltd. in Brook. Prepare a measurement sample by adjusting the microgel concentration of the microgel dispersion to about 0.1%. After removing dust with a micrometer filter, the scattering intensity at 25 ° C was measured at a scattering angle of 90 °, and the average particle size and degree of dispersion were calculated with the analysis software installed in the measuring device. The particle size is analyzed by the cumulant analysis method, and the degree of dispersion is a numerical value obtained by standardizing the value of the secondary cumulant obtained by the cumulant analysis. This degree of dispersion is a commonly used parameter and can be automatically prayed by using a commercially available dynamic light scattering measurement device. As the viscosity of the solvent necessary for the particle size analysis, the viscosity of pure water at 25 ° C., that is, a value of 0.89 mPas was used.

0.

[0161] "Method for measuring degree of swelling"

The degree of swelling with an organic solvent was measured by the following method. In the microgel of the present invention, polymethacrylalkyl forms a core portion. The solvent used was benzene, which is a good solvent, and hexane, which is a poor solvent, for polymethacrylic methyl. Also, RA-PE408, MCX or artificial sebum, which is a common oil used in cosmetics, was used.

[0162] "Results and discussion"

The characteristic values of the microgel polymerized by the present invention are shown in “Table B-2”.

The sample particle size was about 50-150 nm. Although the degree of dispersion of the microgel of the present invention was higher than that of PMG5, monodisperse particles having a degree of dispersion of less than 0.10 were obtained.

[Table B-2] Sample d (nm) Dispersion

PMG1 105.1 0.092

PMG2 73.3 0.096

PMG3 58.0 0.061

PMG4 1 14.5 0.082

PMG5 145.7 0.005

The PMG1-5 samples were measured for swelling degree by RA-PE408, MCX and artificial sebum. The results are shown in “Table B-3”.

[Table B-3]

[0164] The swelling rates of PMG1 to 5 with RA-PE408, MCX, and artificial sebum are shown in the graphs in Figure B-2, Figure B-3, and Figure B-4. The vertical axis of the graph indicates the degree of swelling.

[0165] PMG5 does not swell at all for polar oils such as RA-PE408 and MCX and human sebum, which are widely used as cosmetic raw materials, and a monomer having several alkyl chain lengths is mixed with a hydrophobic monomer As a result, it swelled with respect to these oils. This is because the length of the alkyl chain in the core part of the mouth-opening gel becomes bulky, and the glass transition temperature decreases, so the range of solvents that can be swollen with high flexibility is widened. It is done.

[0166] Examples of cosmetics containing the microgel of the present invention are shown below.

[0167] "Example B-5 lotion"

Ethyl alcohol 5% by mass

Glycerin 1 1, 3—Butyleneglycanol 5

Polyoxyethylene polyoxypropylene decyl tetradecyl ether

0.2

Sodium hexametaphosphate 0.03 Trimethylglycine 1

Sodium polyaspartate 0.1 a-tocopherol 2- L-ascorbic acid potassium phosphate diester

0.1

Cheotaurine 0.1

Green tea extract 0.1

Western Heart Force Extract 0.1

HEDTA3 Sodium 0.1 Microgel (PMG1) 0.1

Canoleboxyvininole polymer 0.05 Potassium hydroxide 0.02

Suitable amount of phenoxyethanol

Purified water residue

Perfume

"Example B-6 moisturizing cream"

Liquid paraffin 10

Dimethinorepolysiloxane 2

Glycerin 10

1, 3—Butyleneglycanol 2

Erythritol 1

Posiethylene glycol nore 1500 5

Skullan 15

Tetra 2-ethylhexanoic acid pentaerythritol 5 Potassium hydroxide 0.1 Sodium hexametaphosphate 0.05 Tocofenol acetate 0.05 Noroxybenzoic acid ester Suitable amount Hydroxypropylmethylcellulose 0.2 Microgel (PMG2) 0.1 Polybulal alcohol 0.1 Canoleboxini vinyle polymer 0.2 Acrylic acid 'alkyl methacrylate copolymer (Pemulene TR-2)

0.1 Purified water residue “Example B-7 Sunscreen”

Decamethylcyclopentasiloxane 20 Ethanol 5 Isostearyl alcohol 2 Dipropylene glycol 3 Isostearic acid 2 Tri 2-Ethylhexanoic acid glyceryl 5 2-Ethylhexanoic acid cetyl 2 Dextrin fatty acid ester-coated fine particle acid-titanium (40) Chloride Sodium 2 edetic acid 3 sodium proper amount ubinal T-150 (manufactured by BASF) 1 4-tert-butyl-4'-methoxydibenzoylmethane 1 paramethoxycinnamic acid 2-ethylhexyl 7.5 carboxymethylcellulose Na 0.4 microgel (PMG4) 0.1 ethino Resenorelose 1 Spherical acrylic resin powder 5 Purified water Residue Fragrance Appropriate amount

[0170] "Example B—8 Cleansing Genore"

Polyoxyethylene 'methylpolysiloxane copolymer 5 Dipropylene glycol 3

1,3-Butyleneglycolanol 10 Posiethyleneglycolole 1500 1 Polyoxyethylene methyl darcoside 1 Microgenole (PMG4) 0.05 Polyethylene glycol diisostearate 5 Dipotassium glycyrrhizinate 0.1 Cora 'de' cabaro extract 0.1 Tride acid tri Na 0.01 Hydroxypropylmethylcellulose 0.8 Carboxybule polymer potassium 0.35 Noroxybenzoate Suitable amount Purified water Residual

[0171] "Example B-9 emulsion"

Dimethylol polysiloxane 3 Decamethylcyclopentasiloxane 4 Ethanol 5 Glycerin 6

1,3-Butyleneglycolanol 5 Polyoxyethylene methyl darcoside 3 Castor oil 1 Squalane 2 Potassium hydroxide 0.1 Hexametaphosphate 0.05 Hydroxypropyl mono-β-cyclodextrin 0.1 Dipotassium glycyrrhizinate 0.05 Bi-leaf extract 0.1

L-sodium glutamate 0.05 Wikiweed extract 0.1 Yeast extract 0.1 Lavender oil 0.1 Zio extract 0.1 Dimonoreforinopyridazinone 0.1 Xanthan gum 0.1 Microgel (PMG3) 0.1 Acrylic acid / alkyl methacrylate copolymer (Pemulene TR-1)

0.1 Bengala appropriate amount Yellow iron oxide appropriate amount Noraben appropriate amount Purified water residue “Example Β—10 Shampoo”

Ethylene glycol distearate 1.5 Coconut oil fatty acid ethanolamide 5.5 Coconut oil fatty acid methyl taurine sodium 8 Coconut oil fatty acid amidopropyl betaine 5 Polymer JR-400 (manufactured by Union Carbide) 0.4 Microgel (PMG3) 0.1 Quenic acid 0.5 Sodium chloride 1.2 Bi Leaf extract 0.1 Phenoxyethanol 0.1 Sodium benzoate appropriate amount edetate disodium appropriate amount

Purified water residue

Perfume

[0173] "Example B—11 Conditioner"

Highly polymerized dimethylsiloxane 'methyl (aminopropyl) siloxane copolymer

0.2

Hardened rapeseed oil alcohol 3

Glycerin 3.5

3-Methyl-1, 3-butanediol 5

Hydroxystearic acid 0.5

2-Ethylhexanoic acid cetyl 1

Isononanoic acid isonol 0.5

Sensormer CI-50 (Nalco) 0.2

Stearic acid dimethylaminopropylamide 1

Marcote 550 (Calgon) 1

Microgel (PMG3) 0.1

L-glutamic acid 0.5

Phenoxyethanol 0.4

Lecithin 0.1

Purified water remaining

Perfume

Colorant

[0174] "Example B—12 facial cleansing foam"

Glycerin 35

Positive ethylene IJn—Nore 20000 0.5

Maltitol hydroxyalkyl (12, 14) ether solution 0.5 Ethylene glycol distearate 1 N Palm oil fatty acid sodium acylglycine 15 Dodecane-1, 2 Sodium diol acetate 1 Arginine Palm oil fatty acid 1

N-Lauroy L L-Sodium glutamate 2 Palm oil fatty acid amidopropyl betaine 1.5 Microgenole (PMG3) 0.05 Chenate 1 Ovata extract 0.05 L-Mentoren 0.1 Granulated water 1 Purified water Residue Fragrance Appropriate amount Water [granular composition]

Zinc oxide 5 Tanorek 5

Magnesium aluminate metasilicate 10 Polyethylene powder 75 Ethenoresenorelose 5 "Example B-13 Body soap"

Propylene glycol 5 Polyoxypropylene glyceryl ether 0.5 Isostearic acid 1 Lauric acid 10 Palm fatty acid 9 Myristic acid 1 Ethylene glycol distearate 2 Palm oil fatty acid diethanolamide 1 Sodium polyoxyethylene lauryl ether sulfate 1.5 Palm oil fatty acid sodium methyl taurine 0.3 Sodium taurine laurate 0.3

2-anolequinole -N-canoleboxoxymethinole -N-hydroxyethyl imidazoli

2

Marcote 100 (Calgon) 0.1

Potassium hydroxide 5

Hydroxypropyl methylcellulose 0.3 Microgel (PMG1) 0.1

Bi-leaf extract appropriate amount

Edetic acid disodium

Purified water residue

Perfume

“Example B—14 Liquid Foundation”

Ethanol 10.0

Glycerin 10.0

1,3-Butyleneglycolanol 7.0

Silica-coated acid titanium 8.0

Synthetic phlogopite 3.0

Spherical Caustic Acid 5.0

Bengala-coated mica titanium (color rendering pearl G) 2.0 Sodium chloride 0.3

Hydroxypropyl mono-β-cyclodextrin 0.1 Green tea extract 0.1

Lily extract 0.1

Bengala 0.1

The Langham 0.1

Microgel (PMG2) 0.1

Porous spherical cellulose 0.1 Lavender extract 0.1 Purified water Residual

[0177] "Example B-15 Makeup Base"

Dimethylolene polysiloxane 2 Decamethylcyclopentasiloxane 5 Ethanol 3 Be = Reinoreconolele 0.1 Notinorenoreconolele 0.1 Dipropylene glycol 5 1,3-Butyleneglycol / Le 3 Posiethylene gucco / re 1500 4 Plant squalene 0.1 Polyoxyethylene glyceryl isostearate 0.3 Titanium oxide 'Bengara-coated mica 0.3 Mica titanium 0.3 Potassium hydroxide 0.2 Hexametaphosphate 0.05 Tocopherol acetate 0.1 Noroxybenzoic acid ester Suitable amount Lithium cobalt titanate Suitable amount Porous spherical cellulose powder 0.5 Microgel (PMG2 ) 0.2 Canolepoxy bis / repolymer 0.2 Acrylic acid 'alkyl methacrylate copolymer 0.2 Purified water Residual

[0178] "Example B—16 mascara"

Ethanore 5

1,3-Butyleneglycol / Le 4 Polyethylene terephthalate · Polymethylmethalate laminated film powder

0.1

Potassium hydroxide 0.1 Sodium hexametaphosphate appropriate amount Paraoxybenzoate Suitable acid red 0.1

Tartrazine 0.1

Brilliant bull, FCF 0.1 dextrin 30

Microgel (PMG4) 0.2

Canoleboxyvininore polymer 1 Purified water Remaining

“Example B—17 Eyeliner”

Liquid paraffin 5

Suitable for methylpolysiloxane emulsion! Glycerin 3

1,3-Butyleneglycolanol 6 Polyoxyethylene sorbitan monolaurate (20E.O.)

Isobutylene 'sodium maleate copolymer liquid

Titanium oxide Appropriate amount Plate-like barium sulfate Appropriate amount Kaolin 8

Black iron oxide coated mica titanium (pearl agent)

Black iron oxide 9

Acetic acid DL—j8—Tocopherol 0.1 Paraoxybenzoate Suitable Bentonite 1

Sodium carboxymethylcellulose 1 Alkyl acrylate copolymer emulsion

Microgel (PMG4)

purified water

[Invention C]

First, production examples of the copolymer (microgel) used in the examples are shown.

[0181] "Production example of microgel"

The polymerization of the microgel was carried out by the following method. A 200 mL three-necked flask equipped with a reflux tube and a nitrogen inlet tube is mixed with water. Ethanol mixed solvent (water: ethanol = 40:60 volume ratio) 50 mL with PME—4000, methyl metatalylate (MMA), butyl metatalylate (nBMA) Dissolve 2-ethylhexylmetatalylate (EHMA) and ethylene glycol dimetatalylate (E GDMA). After sufficient dissolution, 2,2′azobis (2-methylpropionamidine dihydrochloride) is added at a ratio of 1 mol% with respect to the total amount of monomers and further dissolved. The completely homogenized polymerization solution is purged with nitrogen for 20 minutes to remove dissolved oxygen, and then stirred in a magnetic stirrer and kept in an oil bath at 65 to 70 ° C for 8 hours for polymerization. After completion of the polymerization, the polymerization solution is returned to room temperature, and then the polymerization solution is dialyzed against water for 5 days to remove the residual monomer, and at the same time, the dispersion is replaced with water.

The amount of monomer used (g) is shown in “Table C-1”.

[0182] [Table C-1] Monomer PME4000 隱 nB A EHMA EGD A

Formula (1) Formula (2) Formula (2) Formula (2) Formula (3) Production Example 1 0. 267 0. 603 ― 0.002 Production Example 2 0. 267 ― 0. 857 ― 0.002 Production Example 3 0. 218 ― ― 1. 195 0. 002 Production Example 4 0. 267 0. 303 0. 428 ― 0. 002 Production Example 5 0. 267 0. 303 0. 428 ― 0. 003 Production Example 6 0. 267 0 303 0. 428 ― 0. 006 Production Example 7 0. 218 0. 303 ― 0. 597 0. 002 Production Example 8 0. 218 0. 303 ― 0. 597 0. 003 Production Example 9 0. 218 0. 303 ― 0. 597 0. 006 Production example 1 0 0. 267 0. 482 0. 1 71 ― 0. 002 Production example 1 1 0. 267 0. 120 0. 685 ― 0. 002

[0183] "Microgel particle size and degree of dispersion" The particle size and degree of dispersion of the obtained microgel are shown in “Table C 2”.

[Table C-2] Particle size (nm) Dispersion

Production Example 1 145.7 0.005

Production Example 2 179.2 0.055

Production Example 3 246.5 0.021

Production Example 4 105.1 0.312

Production Example 5 134.5 0.117

Production Example 6 164.5 0.181

Production Example 7 73.3 0.223

Production Example 8 153.6 0.020

Production Example 9 91.0 0.235

Production example 1 0 58.0 0.061

Production example 1 1 114.5 0.082

[0184] "Method of measuring turbidity"

The white turbidity was evaluated based on the straightness (brightness) obtained by measuring the microgel-containing lotion with a Macbeth color difference meter.

[0185] "Evaluation method of storage stability"

— 5 ° C, 0 ° C, RT, 37 ° C, 50 ° C and MlCy (change from 5 to 45 ° C, 2 hours dwell at 5 ° C and 45 ° C for 2 cycles a day) The microgel compounded lotion water was stored in a thermostatic bath, and the L value after one month was measured.

The following evaluation was performed based on the difference in the initial value force of the L value.

○: Change from the initial value is less than ± 5

X: Variation from the initial value is ± 5 or more

[0186] "Evaluation of use"

Ten professional panelists evaluated the quality of use (“no stickiness”, “feel”, “familiarity”, “feeling of shine”) according to the following criteria.

◎: More than 7 out of 10 responded that they were “good” and “actual”.

〇: More than 5 out of 10 answered “good” or “real”.

Δ: Three or more out of 10 responded that they were “good” and “can feel”.

X: Less than 2 out of 10 answered “good” or “can feel”. "Production of Examples C1-C11 and Comparative Example C1"

The following cloudy lotion (moisturizing lotion) was prepared by the following production method. In addition, the lotion of Comparative Example c 1 is a transparent lotion without blending the polymer of Production Example.

(A) Mix and dissolve each component uniformly. Ingredients (B) in “Table C 3” and “Table C 4” are mixed and dissolved uniformly. Add (B) to (A) with stirring to obtain each cloudy moisturizing lotion. This was used as a sample and evaluated according to the above evaluation method.

(A) Ion-exchanged water 73.5 quality

Echino-leano reconorre 10

Glycerin 0.5

Dipropylene glycol 5.

Positive ethylene glycolate 1000 1. 0

Polyoxyethylene polyoxypropylene 2-decyl tetradecyl ester

8.5

Button extract 0. 01

Raspberry extract 0. 01

Yukinoshita extract 0. 01

1 Menthol JP 0. 002

Chenic acid (food) 0. 02

Sodium quenate 0.08

Hexametaphosphate sodium salt 0. 03

Phenoxyethanol 0.3

New fragrance 0. 05

(B) Copolymer dispersion aqueous solution

[Table C-3] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Manufacturing Example 1 0.1-----Manufacturing Example 2-0. 1---Manufacturing Example 3--0. 1--- Production Example 4 ― ― ― 0.1.

Production Example 5 ― ― ― ― 0.1-Production Example 6 ― ― ― ― ― 0.1 Ion-exchanged water 8. 89 8. 89 8. 89 8. 89 8. 89 8. 89

[Table C-4]

[0190] "Evaluation of storage stability"

As shown in “Table C 5” and “Table C 6” below, the above-described cloudy lotion was excellent in long-term stability.

[Table C-5]

[Table C-6]

[0191] "Evaluation of use"

As shown in “Table C 7” and “Table C 8” below, the cloudy lotion of each example is particularly It is a lotion that improves the stickiness derived from the surfactants of conventional cloudy lotions, and that also has a feeling of richness, quick familiarity, and shine control.

[Table C-7]

[Table C-8]

The other cloudy cosmetics of the present invention are listed below.

The present invention can provide an excellent cloudy cosmetic, not only for cosmetic raw material oils but also for cosmetics containing an oil-soluble drug and Z or a fragrance.

"Example C 12 whitening lotion"

Copolymer of Production Example 4 0.3

Ethanore 10

Dipropylene glycol 1

Polyethylene glycol 1000 1

Polyoxyethylene methyl darcoside 1

Glyceryl tri-2-ethyl hexylate0.1

Polyoxyethylene hydrogenated castor oil 0.2

Polyglyceryl diisostearate 0.15

N-stearoyl- L sodium glutamate 0.1

Cuenic acid 0.05

Sodium quenate 0.2

Potassium hydroxide 0.4 Dipotassium glycyrrhizinate 0.1 Arginine hydrochloride 0.1 Oyster extract 0.1 Tranexamic acid 2

Potassium 4-methoxysalicylate 1 Trisodium edetate 0.05 Paramethoxycinnamate 2 Ethylhexyl 0.01 Dibutylhydroxytoluene Appropriate amount Noraben Appropriate Deep sea water 3 Purified water Residual material Appearance “Example C 13 Whitening moisturizing lotion”

Copolymer of Production Example 6 0.5 Glycerin 1

Dipropylene glycol 12 Ethanol 8

POE methyldanolecoside 3

POE (24) POP (13) Decinoletetradecyl ether 0.5 Chenic acid 0.02 Sodium quenate 0.08 Hydroxypropyl mono; 3-cyclodextrin 0.5 Thiotaurine 0.1 Adenosine Triphosphate disodium 0.1 Sodium hyaluronate 0.01 EDTA3 sodium 0.01 Hydroxyethylol Senorelose 0.1

L-Ascorbic acid 2—Dalcoside 2 Anolebutin 0.05

Noraben appropriate amount

Purified water residue

Perfume

[0195] "Example C-14 non-alcohol lotion"

Copolymer of Production Example 1 0.3

Glycerin 2.0

1,3-Butyleneglycolanol 4.0

Erythritol 1.0

Polyoxyethylene methyl darcoside 1.0

Polyoxyethylene hydrogenated castor oil 0.5

Chenic acid 0.02

Sodium quenate 0.08

Suitable amount of phenoxyethanol

Methinorepolysiloxane 0.02

N-coconut oil fatty acid acyl L-arginine cetyl DL-pyrrolidone carboxylic acid

0. 1

Purified water residue

[0196] [Invention D]

Initially, the copolymer used in the present invention is the same as that of invention C.

[0197] Next, examples in which a microgel is blended with an external preparation for skin will be described.

Prior to the description of the examples of the present invention, an evaluation method is shown below.

"Test method by conductance measurement"

Skin conductance was measured before and 120 minutes after application using the forearm of 10 panelists, and the moisturizing effect was evaluated from the rate of change. In addition, it is possible to examine the effect of the stratum corneum on the water absorption and water retention capacity by the skin conductance increase rate. .

[0198] Evaluation criteria of "Evaluation (1) Test by conductance measurement" are as follows. ◎ · · · Panel 10 conductance increase average force 0% or more

〇･･ The average increase in conductance of 10 panelists is 25% or more and less than 40%

△ · · 'The average increase in conductance of 10 panelists is 10% or more and less than 25%

X.. 'The average increase in conductance of 10 panelists is less than 10%

[0199] "Evaluation (2): Smooth skin"

An actual use test was conducted by 10 expert panelists on the smoothness of the skin during and after use. The evaluation criteria are as follows.

◎… More than 8 professional panelists recognized that the skin was smooth during and after use. 〇… Special panelists More than 6 people and less than 8 people recognized that the skin was smooth during and after use.

△… Special panelists More than 3 people and less than 6 people recognized that the skin was smooth during and after use.

X · · · Specialized panelists Less than 3 people recognized that the skin was smooth during and after use.

[0200] "Evaluation (3): No stickiness on the skin"

An actual use test was conducted by 10 expert panelists on the non-stickiness of the skin during and after use. The evaluation criteria are as follows.

◎… More than 8 professional panelists recognized that there was no stickiness on the skin during and after use. ○ · · · Special panelists 6 or more and less than 8 recognized that there was no stickiness on the skin during and after use.

△… Special panelists 3 or more and less than 6 people recognized that there was no stickiness on the skin during and after use.

X · · · Specialist panelists recognized that there was no stickiness on the skin during and after use.

[0201] "Evaluation (4): Moisturizing effect"

An actual use test was conducted by 10 expert panelists to determine whether there was a moisturizing effect after 120 minutes of use. The evaluation criteria are as follows.

◎… 8 or more professional panelists recognized that there was a moisturizing effect.

○ · · · Special panelists 6 or more and less than 8 people recognized that there was a moisturizing effect.

△ · · · 3 panelists and less than 6 panelists recognized the moisturizing effect. X · · · Specialist panelists recognized that there were moisturizing effects.

[0202] "Evaluation (5): Skin roughness improvement effect test"

A rough skin improvement effect test was conducted with a panel of 10 people who had rough skin on their face (part: wrinkles). In the test method, different lotions were applied to the left and right eyelids for 1 week, and the determination was made the next day after the period. The evaluation criteria are as follows.

◎ · · · Panel 8 people or more power It was recognized that rough skin was improved.

〇 ··· Panel 6 or more and less than 8 persons We recognized that rough skin was improved.

△ · · · Panel 3 or more, but less than 6 people Recognized that rough skin was improved.

X · · · Panel Less than 3 people Power recognized as rough skin.

[0203] "Influence of microgel composition"

Evaluation as a skin external preparation was performed using the following basic composition for test. Ion exchange water to 100 quality

Ethyl alcohol 10

Production Example 1-7 Microgel (A) 0.1

Glycerin 8.0

Quenic acid

Sodium quenate

Hexametaphosphate sodium

Suitable amount of phenoxyethanol

Perfume

[0204] (A)

[Table D-1] Examples Examples Examples Examples Examples Examples Examples Examples Examples Comparative Examples

1 2 3 4 5 6 7 1 Microgel of Production Example 1 0.1 ― ― ― ― ― ― ― Microgel of Production Example 2 ― 0.1 1 ― ― ― ― ― Microgel of Production Example 3 ― ― 0.1 ― ― ― ― ― Production Example 4 Microgel of Production Example 5----0.1---Microgel of Production Example 6-----0.1--Microgel of Production Example 7-One---0.1-

(1) Conductance

(4) Moisturizing effect ◎ ◎ ◎ ◎ ◎ ◎ ◎ X

(5) Skin roughening effect ◎ ◎ ◎ ◎ ◎ ◎ ◎ X

[0205] As shown in Table D-1 above, a topical skin preparation containing copolymers of various compositions is excellent in all of conductance measurement, smoothness, stickiness, feeling of moisturizing effect, and improvement of rough skin. ing.

[0206] "Effect of compounding amount of microgel"

Echino-leano reconorre 10

Microgel from Production Example 4 (B)

Glycerin 8.0

Quenic acid

Sodium quenate

Hexametaphosphate sodium

Suitable amount of phenoxyethanol

Fragrance

[0207] (B)

[Table D-2] Examples Examples Examples Examples Examples Examples Examples Examples Examples Comparative Examples

8 9 1 0 1 1 1 2 1 3 1 4 1 Microgel of Production Example 4 0.001 0.01 0.1 5.0 10.0 15.0 20.0 ―

(1) Conductance

○ ◎ ◎ © ©

Measurement (3 Omin) ◎ ◎ 〇

(1) Conductance

(5) Rough skin improvement effect △ ◎ ◎ @ ◎ ◎ ◎ X

[0208] As shown in Table D-2 above, the blending amount of the copolymer in the external preparation for skin is preferably 0.01 to 20 mass%, particularly preferably 0.1 to 1.0 mass%.

[0209] "Effects of humectant content"

Evaluation as a skin external preparation was performed using the following basic composition for test. Ion exchange water to 100

Ethyl alcohol 10

Microgel of Production Example 4 0.1

Moisturizer (C)

Quenic acid (food) appropriate amount

Sodium quenate

Hexametaphosphate sodium

Suitable amount of phenoxyethanol

Perfume

(C)

[Table D-3] Examples Examples Examples Examples Examples Examples Examples Examples Examples Comparative Examples

1 5 1 6 1 7 1 8 1 9 20 2 1 2 Glycerin 0.01 0.1 1 10 15 5 5 ―

1.3-Butylene----

Coal ― 5 15 ― Dipropylene glycol ― ― ― ― ― ― 10 ―

(1) Conductance

○ ○ ◎ ◎ ◎ ◎ ◎ X measurement (3 Omin)

(1) Conductance

Δ 〇

(1) Conductance

Measurement (1 2 Omin) △ 〇 ◎ ◎ ◎ ◎ ◎ X

(2) Smoothness 〇 ◎ ◎ ◎ ◎ ◎ X

(3) Stickiness ◎ ◎ ◎ ◎ ◎ 〇 X

(5) Rough skin improvement effect Δ 〇 ◎ ◎ ◎ ◎ ◎ X

[0211] As shown in Table D-3 above, the moisturizing agent content is preferably 0.1 to 30 mass%.

15% by mass is particularly preferred.

[0212] Other skin external preparations of the present invention are listed below.

The present invention can provide an excellent external preparation for skin, not only for cosmetic raw material oils, but also for cosmetics containing an oil-soluble drug and Z or a fragrance.

[0213] "Example D—22 Latex"

Microgel from Production Example 1

Dimethylol polysiloxane

Decamethylcyclopentasiloxane

Echinorea noreconole

Glycerin

1,3-Butyleneglycolanol

Polyoxyethylene methyl darcoside

POE (14) POP (7) Dimethyl ether

Ascorbic acid darcoside

Castor oil

Skulang

Potassium hydroxide Sodium hexametaphosphate 0.05 Hydroxypropyl mono-β-cyclodextrin 0.1 Dipotassium glycyrrhizinate 0.05 Bi-leaf extract 0.1 L Sodium glutamate 0.05 Wikki extract 0.1 Yeast extract 0.1 Lavender oil 0.1 Diole extract 0.1 Dimonoreforinopyridazinone 0.1 Xanthan gum 0.1 Canolevo Xyvininole polymer 0.1 Acrylic acid / alkyl methacrylate copolymer (Pemulene TR-1)

0.1

Bengala Appropriate amount Yellow iron oxide Appropriate amount Noraben Appropriate amount Purified water Residue “Example D— 23 Eye Cream”

Microgel of Production Example 5 1.0 Decamethylcyclopentasiloxane 15 Trimethylsiloxy keysan Otamethylcyclotetrasiloxane

7.5

Polyoxyethylene 'methylpolysiloxane copolymer 2.0 Glycerin 15

1, 3 Butylene glyconole 3.0 Manoletotonole solution 2.0 Macadamia nut oil 0.5 School Run 1.0

Cholesteryl hydroxystearate 0.1

2-Ethylhexanoic acid cetyl ester 2.0

L-ascorbic acid sulfate disodium 0.01 DL- a tocopherol 2-L ascorbic acid phosphate diester

0.02

Acetic acid DL—α Tocopherolol 0.05 Succi-Luuterocollagen solution 0.4 Sodium hyaluronate 0.002 ρ Oxybenzoate 0.15 Edetate 3Na 0.02 Diparamethoxykelic acid mono 2-Ethylhexylate glyceryl 0.02 Canolemin cate Magnesium 0.3 Purified water Residual

“Example D—24 Impregnation Mask”

Microgel of Production Example 1 0.1 Glycerin 1.0

1, 3 Butylene Glycolanol 8.0 Xylit 2.0

Polyethylene glycol 1500 2.0 Rosemary oil 0.01 Sage oil 0.1

Cubic acid 0.02 Sodium citrate 0.08 Sodium hexametaphosphate 0.01 Hydroxypropyl mono β-cyclodextrin 0.1 Tranexamic acid 2.0 Vitamin E Acetate 1.0 Aloe Extract 0.1 Burcheskis 0.1 Lavender Oil 0.01 Xanthan Gum 0.05 Canoleboxyvininole Polymer 0.15 Noroxybenzoic Acid Equivalent Purified Water Residue “Example D—25 Cream Foundation”

Production Example 3 Microgel 0.1 Behe-Norenoreconole 0.5 Dipropylene Glycolol 6.0 Stearic Acid 1.0 Glycerol Monostearate 1.0 Potassium Hydroxide 0.2 Triesteranolamine 0.8 Acetic Acid DL- α-Tocopherol 0.1 Noroxybenzoic Acid Equivalent Yellow iron oxide 1.0 a-olefin oligomer 3.0 Dimethylol polysiloxane (6 mPa.s) 2.0 Dimethylpolysiloxane (lOOmPa. S) 5.0 Nethyl alcohol 0.5 Isostearic acid 1.0 Behenic acid 0.5

Cetyl 2-ethylhexanoate 10 Polyoxyethylene glycerol monostearate 1.0 Titanium oxide 3.0 Mica titanium 'polyalkyl acrylate composite powder 0.5

Surface-treated titanium oxide (MT—062) 10

Polyalkyl talate-coated mica titanium 0.5

Black iron oxide coated mica titanium 0.5

Keiic anhydride 6.0

2-Methoxyhexyl p-methoxycinnamate 2.0

Bengala appropriate amount

Ultramarine blue

Black iron oxide

Legal dye Appropriate amount

Xanthan gum 0.1

Bentonite 1

Sodium carboxymethylcellulose 0.1

Purified water residue

Perfume

[0217] [Invention E]

The copolymer used in the present invention is the same as the copolymer of Invention C.

[0218] "Evaluation method of storage stability"

Ten specialist panelists confirmed the appearance of the multi-layered cosmetics containing microgels stored at room temperature for 1 month compared with the state immediately after that. The change in appearance is evaluated as follows.

◎: All 10 out of 10 respondents could not confirm the change from the state immediately after!

○: More than 7 out of 10 people confirmed that the change from the immediately following state was not confirmed.

Δ: More than 5 out of 10 respondents confirmed that they had not changed since the last time.

X: Less than 4 out of 10 people could not confirm the change in state power immediately after that.

[0219] "Evaluation of use"

A panel of 10 specialists gave us a feeling of use (“no stickiness”, “richness”, “familiar speed”, “shine” The quality of the “suppression feeling” was evaluated according to the following criteria.

〇: More than 5 out of 10 answered “good” or “real”.

X: Less than 2 out of 10 answered “good” or “can feel”.

[0220] The following two-layer cosmetic was prepared by the following production method. The multilayer cosmetic of Comparative Example 1 is a two-layer cosmetic that does not contain the polymer of Production Example and has a transparent aqueous phase. <Production method>

Each component of (A) is uniformly mixed and dissolved. Mix and dissolve the components (C) in “Table E-3” and “Table E-4” uniformly. (B) and (C) were added to (A) with stirring, and a two-layer cosmetic was obtained while stirring (D), which was uniformly mixed. This was used as a sample and evaluated according to the above evaluation method.

[0221]

(A) Purified water residue

Hexametaphosphate sodium salt 0. 03

Quenic acid (food) 0. 05

Sodium quenate 0.05

(B) Glycerin 12

Xanthan gum 0.12

(C) Copolymer dispersion aqueous solution The composition shown in [Table E-3] and [Table E-4] below

(D) Scran 5.

Cetyl octanoate 2.0

[Table E-3]

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Production Example 1 0.1 ― ― ― ― One Production Example 2 ― 0.1 ― 1

Production Example 3 ― ― 0. 1 ― ― ― Production Example 4 ― ― 0. 1 ― ― Production Example 5 ― ― ― 1 0, 1 ― Production Example 6 ― ― ― ― ― 0.1 Ion-exchanged water 8. 89 8 89 8. 89 8. 89 8. 89 8. 89 [0223] [Table E-4]

[0224] "Evaluation of storage stability"

As shown in “Table E-5” and “Table E-6” below, the multilayer cosmetic of the present invention was excellent in storage stability. That is, the multilayer cosmetic of the present invention can maintain a clear boundary even when stored for a long time.

[0225] [Table E-5]

[0226] [Table E-6]

[0227] "Evaluation of use"

As shown in “Table E-7” and “Table E-8” below, the multi-layered cosmetic of the present invention has a feeling that the stickiness has been reduced particularly compared to the conventional multi-layered cosmetic. it can.

[0228] [Table E-7]

[0229] [Table E-8]

[0230] Other multilayer cosmetics of the present invention are listed below.

[0231] "Example E-12, three-layer cleansing oil"

Copolymer of Production Example 4 0.3 quality ” Liquid paraffin 20. 0

2-Ethylhexyl palmitate 5. 0 Silicone oil 5. 0 Antioxidant Suitable amount Preservative Suitable amount Fragrance Suitable amount Hexylene glycol 30. 0 Polyoxyethylene (5 monore) oleinoreethenore 3.0 Salt 3.0 Purified water Residual

[0232] "Example E—13 Three-layer lotion"

Copolymer of Production Example 6 0.5 quality squalene 5. 0 Silicone oil 5. 0 Antioxidant Appropriate Preservative Appropriate Perfume Appropriate Propylene glycol 10. 0 Sorbitan monooleate 3.0 Salt (Pharmacopoeia) 5.0 Purification Water residue

[0233] "Example E-14: Sunscreen lotion"

A. Water phase

Purified water residue Dipropylene glycol 5. 0 heavy! Diglycerin 3.0 Sodium lactate 1.0 Ethanol 10.0 Polyethylene glycol monooleate (10) 0.3

Methylparaben 0.

Kaolin 2.0

B. Oil phase

Otamethoxycinnamate 8.0

Decamethylcyclopentasiloxane 5.0

Otamethylcyclotetrasiloxane 10.0

Tocopherol acetate 0.1

Industrial applicability

[Invention A, Invention B]

Since the microgel of the present invention is water-dispersible and non-ionic polymer is dispersed and stabilized, acid resistance and salt resistance are expected. This feature is considered to be an excellent material that satisfies the requirement of stable dispersion under physiological conditions required for applications in the pharmaceutical or cosmetic industry. A notable characteristic of the microgel of the present invention is the ability to swell with a water-immiscible organic solvent. This swelling ability is extremely high in solvent selectivity. Its swelling efficiency shows surprising results, absorbing up to 400 times the organic solvent up to its own volume and swelling.

From the above characteristics, the microgel according to the present invention is expected to be applied in a wide range of industrial fields.

[0235] [Invention C]

ADVANTAGE OF THE INVENTION According to this invention, the cosmetics which are excellent in white turbidity, and excellent in storage stability and a feeling of use can be provided. The cosmetic of the present invention is a useful cloudy cosmetic that can effectively appeal the impression of the cosmetic effect to consumers due to its excellent cloudiness.

[0236] [Invention D]

ADVANTAGE OF THE INVENTION According to this invention, the skin external preparation which has a moisturizing effect and a rough skin improvement effect, and was excellent in the usability | use_condition can be provided.

When the external preparation for skin of the present invention is a cosmetic, it is a useful cosmetic that can appeal the impression of the cosmetic effect to the user very effectively from its excellent feeling of use.

[0237] [Invention E]

The multilayer cosmetic of the present invention can provide a multilayer cosmetic that has a clear boundary between layers and a stable and beautiful appearance. In addition, it is possible to provide a multi-layered cosmetic with a white aqueous phase. The multilayer type cosmetic of the present invention can be blended with various thickeners to improve its usability, and is useful for various cosmetics including multilayer type lotions.

Claims

Claims A copolymer obtained by polymerizing a polyethylene oxide macromonomer of the following formula (1), a hydrophobic monomer of the following formula (A-2), and a crosslinkable monomer of the following formula (A-3) In the following conditions (A-A), (A-B), (A-C), the monomers (1) to (A-3) are radically polymerized in a water / ethanol mixed solvent. The organic solvent swellable microgel which becomes the copolymer power obtained. (AA) Polyethylene oxide macromonomer and hydrophobic monomer charge capacity Polyethylene oxide macromonomer: Hydrophobic monomer = 1: 10 to 1: 250 (molar ratio) (A—B) Crosslinkable monomer charge capacity Hydrophobic (AC) Water-ethanol mixed solvent is water: ethanol = 90-30: 10-70 (volume ratio at 20 ° C) [Chemical Formula A-1] (1) R represents alkyl having 1 to 3 carbon atoms, and n is a number of 20 to 200. X represents H or C1 H. 3 [Chemical A-2] (A-2) R represents alkyl having 1 to 3 carbon atoms, R represents alkyl having 4 to 8 carbon atoms (A-3) R and R are each independently carbon. Represents an alkyl having 3 atoms, and m is a number from 0 to 2. A copolymer obtained by polymerizing a polyethylene oxide macromonomer of the following formula (1), a hydrophobic monomer of the following formula (A-2), and a crosslinkable monomer of the following formula (A-3): An organic solvent swellable microgel comprising monodisperse particles having a particle size of 50 to 300 nm. [Chemical Formula A-4] (1) R represents alkyl having 3 carbon atoms, and n is a number of 20 to 200. X represents H or C1 H. (A-2) R represents alkyl having 1 to 3 carbon atoms, R represents alkyl having 4 to 8 carbon atoms (A-3) R and R each independently represents alkyl having 3 carbon atoms. M is a number from 0 to 2. A copolymer obtained by polymerizing a polyethylene oxide macromonomer of the following formula (1), a hydrophobic monomer of the following formula (A-2), and a crosslinkable monomer of the following formula (A-3): The particle size of the copolymer particles in water is d, and the water in which the copolymer particles swell and saturate is mixed in this water. An organic solvent swellable microgel having a swelling ratio (dZd) 3 of 1 or more when the particle diameter is d. 0 [Chemical A-7] (1) R represents alkyl having 3 carbon atoms, and n is a number of 20 to 200. X represents H or C1 H. [Chemical A-8] (A-2) R represents alkyl having 1 to 3 carbon atoms, R represents alkyl having 4 to 8 carbon atoms [Chemical A-9] (A-3) R and R Each independently represents alkyl having 1 to 3 carbon atoms, and m is a number from 0 to 2. A polyethylene oxide macromonomer represented by the following formula (1), a hydrophobic monomer represented by the following formula (A-2), and a crosslinkable monomer represented by the following formula (A-3) are represented by the following (A—A), (A— 4. The method for producing an organic solvent swellable microgel according to claim 1, wherein radical polymerization is carried out in a mixed solvent of water and ethanol under the conditions of B) and (AC). (AA) Polyethylene oxide macromonomer and hydrophobic monomer charge capacity Polyethylene oxide macromonomer: Hydrophobic monomer = 1: 10 to 1: 250 (molar ratio) (A—B) Crosslinkable monomer charge capacity Hydrophobic (AC) Water-ethanol mixed solvent is water: ethanol = 90-30: 10-70 (volume ratio at 20 ° C) [Chemical A-10] R represents alkyl having 1 to 3 carbon atoms, and n is a number of 20 to 200. X represents H or CH. 3 [Chemical A-11] (A-2) R represents alkyl having 1 to 3 carbon atoms, R represents alkyl having 4 to 8 carbon atoms [Chemical A-12] (A-3) Each R independently represents alkyl having 1 to 3 carbon atoms, and m is a number from 0 to 2. [5] A cosmetic comprising the organic solvent swellable microgel according to any one of claims 1 to 4. [6] A polyethylene oxide macromonomer of the following formula (1), a hydrophobic monomer of the following formulas (B-2) and (B-3), and a crosslinkable monomer of the following formula (B-4) are polymerized. It is a copolymer to be obtained, and the monomers (1) to (B4) are prepared under the following conditions (B—A), (B—B), (B—C), (B—D). Water An organic solvent swellable microgel obtained by radical polymerization in an ethanol mixed solvent. (B—A) Hydrophobic monomer is a composition in which methyl methacrylate and a methacrylic acid derivative having an alkyl having 4 to 8 carbon atoms are mixed in 90-: LO: 10-90 (molar ratio) (BB) Polyethylene oxide macromonomer and hydrophobic monomer charge capacity Polyethylene oxide macromonomer: Hydrophobic monomer = 1: 10 to 1: 250 (molar ratio) (B—C) Crosslinkable monomer charge capacity of hydrophobic monomer 0.1 to 1.5 mass 0/0 with respect to the charged amount (B—D) Water-ethanol mixed solvent power Water: Ethanol = 90-30: 10-70 (volume ratio at 20) [Chemical B-1]

(1)

Three

[Chemical B-2]

(B— 2)

R represents an alkyl having from 3 to 3 carbon atoms,

2

[Chemical B- 3]

(B-3)

R represents alkyl having 1 to 3 carbon atoms, R represents alkyl having 4 to 8 carbon atoms . However, it may be the same as or different from R in RJ formula (B-2)

[Chemical B- 4]

(B— 4)

5 6

The

A copolymer obtained by polymerizing a polyethylene oxide macromonomer of the following formula (1), a hydrophobic monomer of the following formulas (B-2) and (B-3), and a crosslinkable monomer of the following formula (B-4). Organic solvent swellable micronole which is a polymer and has a monodisperse particle force with a particle size of 50 to 300 nm.

[Chemical B-5]

(1)

R represents alkyl having 3 carbon atoms, and n is a number from 20 to 200. X is H or C

1

Represents H.

Three

[Chemical B-6]

(B-2) R represents alkyl having 1 to 3 carbon atoms.

2

[Chemical B-7]

(B— 3)

3 4

. However, R may be the same as or different from R in the formula (B-2).

3 2

[Chemical B-8]

(B— 4)

5 6

The

A copolymer obtained by polymerizing a polyethylene oxide macromonomer of the following formula (1), a hydrophobic monomer of the following formulas (B-2) and (B-3), and a crosslinkable monomer of the following formula (B-4). The diameter of the copolymer particles in water is d, and the copolymer particles are swollen in this water.

0

Swelling rate of organic solvent with dwell ratio (dZd) ³ of 1 or more, where d is the particle size of copolymer particles when mixed with water-immiscible organic solvent which is saturated and swollen until saturated

0

Microgel.

[Chemical B-9]

(1)

Represents alkyl having 1 to 3 carbon atoms, and n is a number of 20 to 200. X is H or C

Represents H.

Three

[Chemical B-10]

(B— 2)

R represents alkyl having 1 to 3 carbon atoms,

[Chemical B-11]

(B— 3)

3 4

. However, R may be the same as or different from R in the formula (B-2).

3 2

[Chemical B-12]

(B— 4)

R and R each independently represents alkyl having 1 to 3 carbon atoms, m is a number of 0 to 2 a 6

The

Polyethylene oxide macromonomer of the following formula (1) and the following formulas (B-2) and (B-3) And a crosslinking monomer represented by the following formula (B-4) in a water-ethanol mixed solvent under the following conditions (B—A), (BB), (B—C) 9. The method for producing an organic solvent swellable microgel according to claim 6, 7 or 8, wherein polymerization is performed.

[Chemical B—13]

(1)

1

Represents H.

Three

[Chemical B- 14]

(B-2)

R represents alkyl having 1 to 3 carbon atoms.

2

[Chemical B—15]

(B— 3)

3 4

. However, R may be the same as or different from R in the formula (B-2).

3 2

[Chemical B-16]

(B— 4)

5 6

The

[10] A cosmetic comprising the organic solvent swellable microgel according to any one of claims 6 to 9.

[11] Contains a copolymer obtained by polymerizing a polyethylene oxide macromonomer of the following formula (1), a hydrophobic monomer of the following formula (C2), and a crosslinkable monomer of the following formula (C3) Cosmetics characterized by

[C-C-1]

(1)

1

Represents H. [C-C-2]

(C-2)

[C-C-3]

(C 3)

4 5

The

Under the following conditions (C-A), (C-B), (C-C), and (C-D), the monomers (1) to (C-3) are placed in a water-ethanol mixed solvent. A cosmetic comprising a microgel having a copolymer power obtained by radical polymerization.

(C C) Feeding power of crosslinkable monomer To be 0.1 to 1.5% by weight with respect to the charged amount of hydrophobic monomer

(CD) Water-ethanol mixed solvent is water: ethanol = 90-30: 10-70 (volume ratio of 20 ° C) 13. The cosmetic according to claim 12, wherein the microgel has a particle size of 50 to 300 nm.

[14] The cosmetic according to claim 11, 12 or 13, comprising a humectant.

15. The cosmetic according to claim 14, wherein the humectant is a polyhydric alcohol.

[16] The multilayer cosmetic according to claim 11, 12 or 13, which contains 5 to 40% by mass of a liquid oil and satisfies the following condition (a) or (b).

(a) substantially no surfactant

17. The multilayer cosmetic according to claim 16, further comprising a thickener.