JP2014058513A - External skin composition comprising hollow polymer particle - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an external composition comprising hollow polymer particles, which allows a component having an ionic functional group and being used in production of this composition to sufficiently exhibit its action, is excellent in stability, and also can be made neutral to weakly acidic suitable for skin, mucosa, lips, and body-hair such as head-hair.SOLUTION: An external composition comprises hollow polymer particles, where this polymer is obtained by polymerization of a monomer having an ionic functional group and the monomer has a ratio of 5 mol% or less.

Description

  The present invention relates to a composition for external use suitable for uses such as temperature shielding, ultraviolet shielding, and makeup, hollow polymer particles, and uses thereof.

  Hollow particles are used in various fields. For example, it is used in the industrial field as a heat insulating material, a high-temperature stable inkjet ink, a white pigment, a paint, a light weight reducing material, a light scattering improving material, and the like. Also, it has been proposed to use it in the cosmetic field as a sunscreen using light scattering.

  For example, Patent Document 1 discloses that an unsaturated carboxylic acid is polymerized in a medium by emulsion polymerization to produce a core particle, and then the surface of this particle is covered with an ethylenically unsaturated monomer to form a sheath, Disclosed is a method of producing a dispersion of particles having a large number of pores inside by swelling the core by neutralizing the particles with a water-soluble volatile base such as ammonia or amine after polymerization. .

  Patent Document 2 discloses that a latex obtained by copolymerizing an unsaturated carboxylic acid is swollen by neutralizing at least a part of the constituting carboxyl groups with a base and then acid-treated to adjust the pH of the latex. 7 or less, a method for producing a dispersion of particles having a large number of pores therein is disclosed.

  In Patent Document 3, a latex of a copolymer containing amino groups is treated with an acid to neutralize at least a part of the amino groups in the copolymer, and then a base is added to adjust the pH of the latex to 7. Thus, a method for producing a dispersion of particles having a large number of pores therein is disclosed.

  In preparing the composition for external use, it is desired that the preparation can be prepared in a wide pH range without being restricted by positively or negatively charged components. However, some external preparations have a positive or negative charge, and when an external preparation is prepared by blending components with opposite charges, stability of the preparation may occur due to aggregation or the like. May affect the effectiveness of active ingredients.

  For example, the hollow particles produced by the method of Patent Document 1 or 2 ionize the carboxylic acid with an alkali to make the particle surface a negative charge of a carboxylate. Therefore, when a component having a positive charge is added, a salt is formed. The blended component is adhered or fixed to the particle surface, and the action of the component is not exhibited. In addition, when a compound having a positive charge is used in the production process of the preparation containing particles, problems such as unstable preparation occur. Examples of such a component include a cationic surfactant, and the cationic surfactant and the carboxylate on the particle surface may form an ion pair and cannot be emulsified.

  In addition, when the particle surface has a positive charge as in the hollow particles of Patent Document 3, a component having a negative charge forms a salt with the positive charge and is fixed to the surface of the fine particles, and the action of the component is not exhibited. There is a case. Examples of such a component include an anionic surfactant.

  In addition, since the pH of healthy skin is weakly acidic, preparations that are applied directly to the skin, such as pharmaceutical agents, quasi-drugs, cosmetics, and miscellaneous products, should be neutral to weakly acidic. Is desired. In addition, neutral to slightly acidic preparations are preferable for mucous membranes, lips, hair, eyelashes, eyebrows, and the like. However, since the hollow particles produced by the method of Patent Document 1 or 2 are carboxylated by ionizing the carboxylic acid on the surface of the hollow particles with an alkali, the pH of the preparation that can keep the particles stable is neutral. ~ Alkaline is limited. On the contrary, the latex of the copolymer containing an amino group or the like produced by the method of Patent Document 3 is not preferable as a preparation to be applied to the skin because it is acidic by the addition of an acid. Furthermore, when there are many portions where the hollow particle surface is not ionized with alkali or acid, the presence of a large number of carboxyl groups or amino groups on the particle surface makes the carboxyl group on the particle surface neutral, or the amino group is medium alkaline. And is not desirable as a direct application to the skin.

JP 56-32513 A Japanese Patent Publication No. 7-21011 Japanese Patent No. 3608303

  The present invention is a composition for external use containing hollow polymer particles. When a component having an ionic functional group is used in the production of this composition, the effect of the component can be sufficiently exerted and the stability can be improved. The main object is to provide a composition for external use which is excellent and can be made neutral to slightly acidic, which is preferable for body hair such as skin, mucous membranes, lips and hair.

In order to solve the above-mentioned problems, the present inventors have conducted research and obtained the following knowledge.
(i) An external preparation containing hollow particles produced by polymerization of a monomer having a ratio of the monomer having an ionic functional group of 5 mol% or less exhibits its function sufficiently when it contains a component having an ionic functional group And can be neutral to slightly acidic, which is preferable for skin, mucous membranes, lips, hair, eyelashes, and eyebrows.
(ii) The polymer particles having a hollow structure (i) have a high temperature shielding effect.
(iii) The polymer particles having a hollow structure of (i) enhance the ultraviolet blocking effect by being combined with an ultraviolet absorber and / or an ultraviolet scattering agent. As a result, the protection index (SPF (Sun Protection Factor) or PA (Protection Grade of UVA)) of the composition containing the ultraviolet absorber and / or the ultraviolet scattering agent is enhanced.
(iv) The polymer particles having a hollow structure (i) can hide skin irregularities, spots, pores and the like while giving the skin a sense of transparency.

The present invention has been completed based on this finding, and provides the following external composition and the like.
Item 1. A composition for external use comprising hollow polymer particles, the hollow polymer particles being obtained by polymerization of a monomer in which the ratio of the monomer having an ionic functional group is 5 mol% or less.
Item 2. Item 2. The external composition according to Item 1, wherein the polymer constituting the hollow polymer particle is a polymer or copolymer of at least one monomer selected from the group consisting of a monovinyl aromatic monomer and a (meth) acrylic acid ester monomer. object.
Item 3. Item 3. The external composition according to Item 1 or 2, wherein the hollow polymer particles have an average particle size of 10 to 30000 nm.
Item 4. Item 4. The external composition according to any one of Items 1 to 3, wherein the content of the hollow polymer particles is 0.05 to 50% by weight based on the total amount of the composition.
Item 5. Furthermore, the external composition in any one of claim | item 1 -4 containing the component which has an ionic functional group.
Item 6. Item 6. The external composition according to any one of Items 1 to 5, further comprising at least one ultraviolet shielding agent selected from the group consisting of an organic ultraviolet absorber and an inorganic ultraviolet scattering agent.

Item 7. Item 7. The composition for external use according to any one of Items 1 to 6, which is for temperature shielding.
Item 8. Item 7. The composition for external use according to any one of Items 1 to 6, which is for ultraviolet shielding.
Item 9. Item 7. The composition for external use according to any one of Items 1 to 6, which is for makeup.

Item 10. A temperature shielding agent comprising hollow polymer particles.
Item 11. Item 11. The temperature shielding agent according to Item 10, wherein the polymer of the hollow polymer particles is obtained by polymerization of a monomer having a ionic functional group-containing monomer ratio of 5 mol% or less.
Item 12. A makeup agent comprising hollow polymer particles.
Item 13. Item 13. The makeup agent according to Item 12, wherein the polymer of the hollow polymer particles is obtained by polymerization of a monomer having a ratio of the monomer having an ionic functional group of 5 mol% or less.
Item 14. An ultraviolet shielding effect enhancer comprising hollow polymer particles.
Item 15. Item 15. The ultraviolet shielding effect enhancer according to Item 14, wherein the polymer of the hollow polymer particles is obtained by polymerization of a monomer having a proportion of a monomer having an ionic functional group of 5 mol% or less.

Item 16. A temperature at which an external composition comprising hollow polymer particles, which is obtained by polymerization of a monomer in which the ratio of the monomer having an ionic functional group is 5 mol% or less, is applied to the skin. Or a heat shielding method or a temperature control method.
Item 17. Applying to the skin an external composition comprising hollow polymer particles, the polymer comprising hollow polymer particles obtained by polymerization of a monomer in which the ratio of the monomer having an ionic functional group is 5 mol% or less. How to give a feeling of feeling or cooling.
Item 18. An external composition comprising hollow polymer particles, which is obtained by polymerization of a monomer in which the ratio of the monomer having an ionic functional group is 5 mol% or less, is applied to the skin. Sweat way.
Item 19. An ultraviolet ray for applying to the skin an external composition comprising hollow polymer particles, the hollow polymer particles being obtained by polymerization of a monomer in which the ratio of the monomer having an ionic functional group is 5 mol% or less. Shielding method.
Item 20. Applying to the skin an external composition comprising hollow polymer particles, the hollow polymer particles being obtained by polymerization of a monomer in which the polymer has an ionic functional group-containing monomer ratio of 5 mol% or less. A method of concealing irregularities, spots, or pores of skin, a method of brightening skin color, or a method of imparting a transparent feeling to the skin.

Item 21. A method for enhancing the ultraviolet shielding effect of this composition, wherein hollow polymer particles are blended with an external composition containing an ultraviolet absorber and / or an ultraviolet scattering agent.
Item 22. A method of imparting temperature or heat shielding action or temperature control action to the composition by blending the hollow polymer particles into the composition for external use.
Item 23. By blending the hollow polymer particles into the composition for external use, the composition has an effect of concealing unevenness, spots or pores of the skin, an effect of soft focus, an effect of brightening the skin color, or an effect of imparting transparency to the skin. How to grant.

Item 24. Use of hollow polymer particles as an ultraviolet shielding effect enhancer.
Item 25. Use of hollow polymer particles as temperature or heat shielding agent or temperature control agent.
Item 26. Use of the hollow polymer particles as a skin unevenness, stain or pore concealing agent, soft focus agent, skin color brightness improving agent, or skin transparency imparting agent.

Item 27. Use of hollow polymer particles for the production of a UV-screening agent.
Item 28. Use of hollow polymer particles for the production of temperature or heat shielding agents or temperature control agents.
Item 29. Use of hollow polymer particles for the production of a skin unevenness, stain or pore concealing agent, soft focus agent, skin color brightness improving agent, or skin transparency imparting agent.

External Composition The external composition of the present invention contains hollow polymer particles, and this polymer is obtained by polymerization of a monomer having a ratio of the monomer having an ionic functional group of 5 mol% or less. Therefore, unlike the case of including conventional hollow polymer particles having a large number of ionic functional groups such as carboxyl groups, the composition for external use of the present invention is preferably neutral to weak for skin, mucous membranes, lips, hair, eyelashes, and eyebrows. Even if acidic, the dispersibility of the particles in the composition can be kept stable without changing the chemical properties of the particles. Moreover, even if the composition for external use of this invention is neutral-weakly acidic, the composition itself is kept stable. Moreover, even when the composition for external use of this invention contains the component which has an ionic functional group, the effect | action of the component can fully be exhibited.

Hollow polymer particles
<Temperature shielding effect>
The ideal temperature on the skin surface is said to be 32 ° C to 34 ° C. Keeping the skin surface temperature constant is one means of keeping the skin condition stable. Skin surface temperature is subtly affected by external heat stimulation. Even if the skin changes by 1 ° C., it is sensitive to heat or cold. Therefore, if the outside temperature can be shielded even at several degrees Celsius, an appropriate cooling feeling or warm feeling can be obtained and the skin can be kept at an ideal surface temperature.
Since the hollow polymer particles have single or plural voids inside, they have a temperature or heat shielding effect due to the presence of the air layer. For this reason, the composition for external use of the present invention containing these hollow particles has a temperature or heat shielding action.
Also, to protect yourself from changes in environmental temperature, the action on the skin tissue is also important. By blocking the TRPV3 sensor in keratinside (keratinocytes), it is possible to suppress the effect of temperature changes on the skin. (Sogabe et al., Pfluger Archiv. Eur. J. Physiol. 458: 1093-1102, 2009.) Hollow polymer particles can also protect the skin from temperature changes by blocking the TRPV3 sensor.

In general, pepper extract (the active ingredient is capsaicin), nonyl acid vanillylamide, or the like which gives warmth to the skin is used as a warming agent. Capsicum extract and nonylic acid vanillylamide are expected to dilate local blood vessels, increase the blood flow in the affected area, accelerate repair of damaged tissue, and reduce pain due to muscle blood flow disturbance. However, these warming agents have strong skin irritation and may have side effects such as redness and rash, and the application site may hurt during bathing.
Moreover, as a cooling agent, refreshing agents, such as menthol and camphor, are used. Some refreshing agents can prevent local fever due to inflammation and the expansion of the inflamed site, and some have analgesic action. However, these cooling sensates, when used at high concentrations, are highly irritating to the skin and may cause sensory paralysis.
Since the hollow polymer particles have a temperature shielding action, they have a warm feeling action when the outside temperature is low, and have a cooling feeling action when the outside temperature is high. Moreover, since there is no skin irritation | stimulation like the conventional warming sensation agent or cooling sensation agent, it can mix | blend with a composition for external use in large quantities. Therefore, the external composition containing the hollow polymer particles is useful as a warm and cool sensation agent that is safe and has a good feeling of use.

<Enhancement effect of UV shielding effect>
Conventionally, ultraviolet absorbers or ultraviolet scattering or reflecting agents have been used for sunscreens. The former may be added in a large amount for the purpose of enhancing the ultraviolet blocking effect (protection index). However, it is difficult to repeatedly apply cosmetics to the skin from the viewpoint of tolerability, and it may give a sticky feeling and impair the feeling of use. Further, when a sunscreen containing the latter at a high concentration is applied to the skin, a so-called white residue is generated, and the skin cannot be given a sense of transparency.
In this regard, the hollow polymer particles enhance the ultraviolet shielding effect by the ultraviolet absorber or the ultraviolet scattering agent with respect to both UV-A and UV-B. Therefore, the amount of the ultraviolet absorber and / or the ultraviolet scattering agent can be reduced by blending the hollow polymer particles into the sunscreen.
Since the hollow polymer particles have a safe and good feeling of use without causing trouble or stickiness to the skin, the sunscreen containing the hollow polymer particles has a safe and good feeling of use. .

<Makeup effect>
2. Description of the Related Art Conventionally, cosmetics have been devised to give the skin a feeling of skin or transparency, or to make the skin or lips look fresh. For this reason, attempts have been made to blend inorganic powders such as par pigments or inorganic composites into cosmetics. However, cosmetics blended with these cannot provide a practically sufficient transparency, There are drawbacks such as glare and the effect of reflection angle dependence.
In this respect, the hollow polymer particles cause the light to be greatly refracted, reflected, or scattered due to the presence of the hollow, so that the skin can be provided with a sufficient transparency or fresh appearance. In addition, since the reflection angle dependency is small, the skin or lips are brightly shining from any angle. Moreover, since it is a polymer particle, there are few glare and roughness. In particular, particles that are spherical and have a single hollow have high effects.
In addition, the hollow polymer particles have a soft focus effect that blurs and shows unevenness, spots, pores, etc. on the surface of the skin or lips. Thus, the hollow polymer particles are highly valuable as a cosmetic ingredient in that the skin or the unevenness of the lips, spots, pores and the like can be concealed without impairing the transparency of the skin.

It is a figure which shows the temperature shielding effect of a hollow polymer particle. It is a figure which shows the ultraviolet-ray shielding enhancement effect of a hollow polymer particle. It is a figure which shows the soft focus effect of a hollow polymer particle. It is a figure which shows the angle dependence of the light-scattering effect of a hollow polymer particle. 2 is a photograph of hollow particles of Example 1. 2 is a photograph of hollow particles of Example 2.

Hereinafter, the present invention will be described in detail.
(I) Composition for external use
(1) Hollow particles
(1-1) Polymer The polymer of the hollow polymer particles contained in the composition for external use of the present invention is a monomer polymerization in which the ratio of the monomer having an ionic functional group is 5 mol% or less with respect to the total amount of the monomer Is obtained. The ratio of the monomer having an ionic functional group is preferably 5 mol% or less, more preferably 2 mol% or less, and even more preferably 1 mol% or less with respect to the total amount of monomers. Most preferably, the polymer of the hollow particles is obtained by polymerizing only a monomer having no ionic functional group.

  The type of the polymer is not particularly limited as long as the ratio of the monomer having an ionic functional group is within the above range, but a polymer or copolymer of a vinyl monofunctional monomer, a polymer or copolymer of a vinyl polyfunctional monomer, or the like. Polymers and copolymers of vinyl monofunctional monomers and vinyl polyfunctional monomers are preferred.

Vinyl polyfunctional monomer The vinyl polyfunctional monomer is a polyfunctional monomer having two or more polymerizable double bonds (for example, C = C bond) (particularly, 2 to 4). Examples of such monomers include, but are not limited to, divinylbenzene, divinylbiphenyl, divinylnaphthalene, diallyl phthalate, triallyl cyanurate, ethylene glycol dimethacrylate, and tetraethylene glycol dimethacrylate. In particular, divinylbenzene and ethylene glycol dimethacrylate are preferred.
A vinyl type polyfunctional monomer can be used individually by 1 type or in combination of 2 or more types.

Vinyl monofunctional monomers Vinyl monofunctional monomers include, but are not limited to, monovinyl aromatic monomers, acrylic monomers (including methacrylic monomers), vinyl ester monomers, vinyl ether monomers, etc. Is mentioned. A vinyl type monofunctional monomer can be used individually by 1 type or in combination of 2 or more types.

Examples of the monovinyl aromatic monomer include, but are not limited to, for example, vinylbiphenyl optionally substituted with a monovinyl aromatic hydrocarbon represented by the following general formula (1) or a lower (1 to 4 carbon) alkyl group. And vinyl naphthalene which may be substituted with a lower (1 to 4 carbon atoms) alkyl group.
[In the formula, R ¹ represents a hydrogen atom, a lower (1-4 carbon atoms) alkyl group, or a halogen atom, R ² is a hydrogen atom, a lower (1-4 carbon atoms) alkyl group, a halogen atom, - SO ₃ Na group, —SO ₃ H group, hydroxyl group, ω-hydroxyalkyl group, lower (1 to 4 carbon atoms) alkoxy group, amino group, or carboxyl group is shown. ]
In the general formula (1), R ¹ is preferably a hydrogen atom, a methyl group, or a chlorine atom, and R ² is preferably a hydrogen atom, a chlorine atom, a methyl group, or an ω-hydroxyalkyl group.

  Specific examples of the monovinyl aromatic hydrocarbon represented by the general formula (1) include, but are not limited to, styrene, vinyl toluene (o-methylstyrene, m-methylstyrene, p-methylstyrene), o -Chlorostyrene, m-chlorostyrene, p-chlorostyrene, p-hydroxymethylstyrene, o-hydroxymethylstyrene and the like.

  Furthermore, vinyl biphenyl which may be substituted with a lower alkyl group, and vinyl naphthalene which may be substituted with a lower alkyl group include vinyl biphenyl substituted with a lower alkyl group such as vinyl biphenyl, methyl group and ethyl group. , Vinyl naphthalene, and vinyl naphthalene substituted with a lower alkyl group such as a methyl group or an ethyl group.

Examples of the acrylic monomer include, but are not limited to, an acrylic monomer (including a methacrylic monomer) represented by the following general formula (2).
Wherein, R ³ is a hydrogen atom, or a lower an alkyl group (1 to 4 carbon atoms), R ⁴ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group, having 1 to 6 carbon atoms A hydroxyalkyl group, a lower (1 to 4 carbon atoms) aminoalkyl group or a di (C ₁ -C ₄ alkyl) amino- (C ₁ -C ₄ ) alkyl group, or an ethylene dihydroxyphosphate group is shown. ]
In General Formula (2), R ³ is preferably a hydrogen atom or a methyl group, and R ⁴ is an alkyl group having 1 to 8 carbon atoms, a phenyl group, or a lower (1 to 4 carbon atoms) hydroxyalkyl group. preferable.

  Specific examples of acrylic monomers include, but are not limited to, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, acrylic Phenyl acid, β-hydroxyethyl acrylate, γ-hydroxypropyl acrylate, δ-hydroxybutyl acrylate, γ-aminopropyl acrylate, γ-N, N-dimethylaminopropyl acrylate, γ-N, N acrylic acid Acrylic esters such as diethylaminopropyl; methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, 2,2-dihydroxypropyl methacrylate, methacrylate Methacrylic acid esters such as glycidyl phosphate, β-hydroxyethyl methacrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl methacrylate, β-aminoethyl methacrylate; dimethyl itaconate, diethyl itaconate, dipropyl itaconate, And particularly preferred are methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, and methacrylic acid. Examples include propyl, butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, dimethyl itaconate, and diethyl itaconate.

Examples of the vinyl ester monomer include, but are not limited to, those represented by the following general formula (3).
[Wherein, R ⁵ represents a hydrogen atom, a lower (C1 to C4) alkyl group, a phenyl group, or a phenylalkyl group having a C1 to C4 alkyl group. ]
Specific examples of the vinyl ester monomer include, but are not limited to, vinyl formate, vinyl acetate, vinyl propionate, vinyl benzoate, and vinyl vinyl acetate.

Although not limited to it as a vinyl ether type monomer, For example, the vinyl ether type monomer represented by following General formula (4) is mentioned.
[R ⁶ represents an alkyl group having 1 to 12 carbon atoms, a phenyl group, or a cyclohexyl group. ]
Specific examples of the vinyl ether monomer include, but are not limited to, for example, vinyl methyl ether, vinyl ethyl ether, vinyl n-propyl ether, vinyl iso-propyl ether, vinyl n-butyl ether, vinyl phenyl ether, vinyl cyclohexyl ether, And vinyl benzyl ether.

  As the vinyl monofunctional monomer, a monovinyl aromatic monomer, a methacrylic acid ester monomer, and an acrylic acid ester monomer are preferable, and among them, styrene, methyl acrylate, butyl acrylate, methyl methacrylate, butyl methacrylate, methacrylic acid. Acid-2,3-dihydroxypropyl, β-hydroxyethyl methacrylate, and glycidyl methacrylate are more preferred, styrene and methyl methacrylate are even more preferred, and styrene is most preferred.

Preferred polymer
(a) Preferred Polymer of Polyfunctional Monomer A polymer or copolymer of vinyl-based polyfunctional monomer is preferred because it has high strength and is not easily crushed.
Preferred polymers of multifunctional monomers include, but are not limited to, polydivinylbenzene and polyethylene glycol dimethacrylate. Moreover, as a preferable copolymer of a polyfunctional monomer, although it is not limited to it, For example, an ethylene glycol dimethacrylate / divinylbenzene copolymer is mentioned.
(b) Preferred Polymer of Monofunctional Monomer A polymer or copolymer of a vinyl monofunctional monomer is preferred in that a soft feeling of use is obtained.
Preferred polymers of monofunctional monomers include, but are not limited to, for example, polymers of monovinyl aromatic monomers, polymers of methacrylic acid ester monomers, and polymers of acrylate ester monomers. Methyl acrylate, polybutyl acrylate, polymethyl methacrylate, polybutyl methacrylate, poly 2,3-dihydroxypropyl methacrylate, and polyglycidyl methacrylate are preferred.
Further, preferred copolymers of monofunctional monomers include, but are not limited to, copolymers of monomers selected from monovinyl aromatic monomers, methacrylic acid ester monomers, and acrylic acid ester monomers, Among them, poly (styrene-methyl methacrylate), poly (styrene-butyl methacrylate), poly (styrene-methacrylic acid 2,3-dihydroxypropyl), poly (methyl methacrylate-butyl methacrylate), and poly (methacrylic acid) Methyl-methacrylic acid 2,3-dihydroxypropyl) and the like.

(c) Preferred Copolymer of Polyfunctional Monomer and Monofunctional Monomer A copolymer of a vinyl polyfunctional monomer and a vinyl monofunctional monomer is preferred in that it has both advantages.
In the copolymer of a vinyl polyfunctional monomer and a vinyl monofunctional monomer, each of the vinyl polyfunctional monomer and the vinyl monofunctional monomer is used alone or in combination of two or more. Can be used.

(i) As a preferable copolymer of a two-component polyfunctional monomer and a monofunctional monomer, a two-component system is not limited thereto. For example, ethylene glycol dimethacrylate / methyl methacrylate copolymer, ethylene Glycol dimethacrylate / butyl methacrylate copolymer, ethylene glycol dimethacrylate / methyl acrylate copolymer, ethylene glycol dimethacrylate / butyl acrylate copolymer, ethylene glycol dimethacrylate / methacrylic acid 2,3-dihydroxypropyl copolymer Polymers, ethylene glycol dimethacrylate / styrene copolymers, and ethylene glycol dimethacrylate / glycidyl methacrylate polymers;
Divinylbenzene / methyl methacrylate copolymer, divinylbenzene / butyl methacrylate copolymer, divinylbenzene / methyl acrylate copolymer, divinylbenzene / butyl acrylate copolymer, divinylbenzene / 2,3-dihydroxy methacrylate Examples include propyl copolymers, divinylbenzene / styrene copolymers, and divinylbenzene / glycidyl methacrylate polymers.
Among them, ethylene glycol dimethacrylate / methyl methacrylate copolymer, ethylene glycol dimethacrylate / butyl methacrylate copolymer, ethylene glycol dimethacrylate / methyl acrylate copolymer, in terms of good usability and low cost, Ethylene glycol dimethacrylate / butyl acrylate copolymer, divinylbenzene / methyl methacrylate copolymer, divinylbenzene / butyl methacrylate copolymer, divinylbenzene / methyl acrylate copolymer, and divinylbenzene / butyl acrylate copolymer Polymers are preferred.
In addition, ethylene glycol dimethacrylate / methyl methacrylate copolymer, and divinylbenzene / methyl methacrylate copolymer are cost effective while maintaining the same strength and durability as when only polyfunctional monomers are used. Is also preferable in that it can be greatly reduced.

(ii) Three component system
In a three-component system, for example, but not limited to, ethylene glycol dimethacrylate / methyl methacrylate / itaconic acid copolymer, ethylene glycol dimethacrylate / methyl methacrylate / methacrylic acid copolymer, ethylene glycol Rudimethacrylate / methyl methacrylate / β-carboxyethyl methacrylate copolymer, ethylene glycol dimethacrylate / butyl methacrylate / methacrylic acid copolymer, ethylene glycol dimethacrylate / methyl acrylate / methacrylic acid copolymer, ethylene glycol Dimethacrylate / butyl acrylate / methacrylic acid copolymer, divinylbenzene / methyl methacrylate / methacrylic acid copolymer, divinylbenzene / butyl methacrylate / methacrylic acid copolymer, divinylbenze / Methyl acrylate / methacrylic acid copolymer, divinylbenzene / butyl acrylate / methacrylic acid copolymer, ethylene glycol dimethacrylate / methyl methacrylate / methacrylic acid β-N, N-dimethylaminoethyl copolymer, ethylene glycol -Ludimethacrylate / methyl methacrylate / β-aminoethyl methacrylate copolymer, ethylene glycol dimethacrylate / butyl methacrylate / β-N, N-dimethylaminoethyl methacrylate copolymer, divinylbenzene / methyl methacrylate / Β-N, N-dimethylaminoethyl methacrylate copolymer, divinylbenzene / butyl methacrylate / β-aminoethyl methacrylate copolymer, and divinylbenzene / methyl acrylate / γ-aminopropyl acrylate copolymer, ethylene Recall dimethacrylate / methyl methacrylate / styrene copolymer, ethylene glycol dimethacrylate / butyl methacrylate / methyl methacrylate copolymer, ethylene glycol dimethacrylate / methyl acrylate / styrene copolymer, ethylene glycol dimethacrylate / acrylic acid Butyl / methyl methacrylate copolymer, ethylene glycol dimethacrylate / methacrylic acid 2,3-dihydroxypropyl / methyl methacrylate copolymer, and ethylene glycol dimethacrylate / glycidyl methacrylate / styrene polymer;
Divinylbenzene / methyl methacrylate / styrene copolymer, divinylbenzene / butyl methacrylate / methyl methacrylate copolymer, divinylbenzene / methyl acrylate / styrene copolymer, divinylbenzene / butyl acrylate / styrene copolymer, Examples include divinylbenzene / 2,3-dihydroxypropyl methacrylate / methyl methacrylate copolymer, and divinylbenzene / glycidyl methacrylate / methyl methacrylate polymer.
Among these, ethylene glycol dimethacrylate / methyl methacrylate / butyl methacrylate copolymer, ethylene glycol dimethacrylate / methyl methacrylate / styrene copolymer, ethylene glycol dimethacrylate / methacrylic are preferred because of good usability and low cost. Butyl acid / styrene copolymer, ethylene glycol dimethacrylate / methyl acrylate / butyl acrylate copolymer, divinylbenzene / methyl methacrylate / butyl methacrylate copolymer, divinylbenzene / methyl acrylate / styrene copolymer, And divinylbenzene / butyl acrylate / styrene are preferred,
Ethylene glycol dimethacrylate / methyl methacrylate / styrene copolymer, ethylene glycol dimethacrylate / butyl methacrylate / methyl methacrylate copolymer, ethylene glycol dimethacrylate / butyl acrylate / methyl methacrylate copolymer, divinylbenzene / methacrylic More preferred are methyl acrylate / styrene copolymer, divinylbenzene / butyl methacrylate / methyl methacrylate copolymer, divinylbenzene / methyl acrylate / styrene copolymer,
Ethylene glycol dimethacrylate / butyl methacrylate / methyl methacrylate copolymer, ethylene glycol dimethacrylate / butyl acrylate / methyl methacrylate copolymer, divinylbenzene / methyl methacrylate / styrene copolymer, divinylbenzene / butyl methacrylate / Methyl methacrylate copolymer, divinylbenzene / butyl methacrylate / styrene copolymer are even more preferred.

(d) When the copolymerization ratio polymer contains a polyfunctional monomer, the capsule strength of the particles can be improved. As a method for forming a shell by polymerization of monomers, there are two methods, an emulsion polymerization method (a method described in Japanese Patent No. 4884053) and a SaPSeP method by suspension emulsification (a method described in Japanese Patent No. 3785440). Depending on the, the possible blending ratios of polyfunctional monomers and monofunctional monomers are different.
When the polymer is a copolymer of a polyfunctional monomer and a monofunctional monomer, the ratio of the polyfunctional monomer to the monofunctional monomer is as follows. In the case of the emulsion polymerization method, it is preferably about 10% by weight or less, more preferably about 5% by weight or less, still more preferably about 2% by weight or less, and most preferably about 0% by weight as long as the capsule strength is secured.
The copolymerization ratio can be adjusted by adjusting the use ratio of the polyfunctional monomer and the monofunctional monomer when producing the microcapsules.
If it is the said range, since particle | grain hardness will become high too much and will not prevent taking in of the water to microparticles | fine-particles when forming a hollow particle, expansion | swelling of particle | grains will become easy. In this sense, it is most preferable to polymerize only a monofunctional monomer.
Further, the ratio of the polyfunctional monomer to the whole monomer is preferably about 1 to 99% by weight, more preferably about 30 to 99% by weight, more preferably about 60 to 99% by weight, in the case of the SaPSeP method. About 99% by weight is even more preferable. More preferably, it is about 85 to 99% by weight. Thus, capsule strength can be secured by increasing the ratio of the polyfunctional monomer. The copolymerization ratio can be adjusted by adjusting the use ratio of the polyfunctional monomer and the monofunctional monomer when producing the microcapsules. If it is the said range, a hollow particle can be easily formed, without giving a big hindrance to formation of the capsule of a hollow particle.

(e) Other polymers Vinyl-based monomers and other monomers copolymerized and / or polymers other than vinyl-based polymers may be contained in the shell.

(1-2) Properties of hollow particles
The shape hollow particles may have a spherical shape or a substantially spherical shape, and are preferably spherical.
The hollow portion may be a single hollow or a multi-hollow. When it is multi-hollow, the number of hollow portions observed in the maximum area cross section of the particles is preferably about 1 to 50, more preferably about 1 to 20, and about 1 to 5 Even more preferred. Within this range, the interfacial area between the shell and the voids in the particles is sufficient, and as a result, the effect of adding hollow particles to the external preparation, that is, the temperature or heat shielding effect, the ultraviolet shielding enhancement effect And a makeup effect (soft focus effect including an effect of hiding spots and the like, an effect of imparting a transparent feeling to the skin) can be sufficiently obtained.

The average particle size of an average particle diameter of the hollow particles is preferably at least 1 nm, more preferably at least 10 nm, even more preferably more than 50nm. It can also be 100 nm or more. Moreover, 30000 nm or less is preferable, 10000 nm or less is more preferable, and 2000 nm or less is still more preferable. If it is the said range, when apply | coating to skin etc. and using it, there is no rough feeling and the effect of this invention can be exhibited effectively.
In the present invention, the average particle diameter is a value measured by a laser diffraction scattering method, and specifically, a value measured by the method described in Examples.

Hollow ratio The hollow ratio of the hollow particles is preferably 10% or more, more preferably 15% or more, still more preferably 20% or more, and even more preferably 30% or more. Moreover, it can also be made 40% or more, and can also be made 60% or more. If it is the said range, the effect by adding a hollow particle to an external composition will fully be acquired.
Further, the hollow ratio of the hollow particles is preferably 90% or less, more preferably 85% or less, and even more preferably 80% or less. If it is the said range, a particle | grain will not be destroyed when a hollow particle is mix | blended with an external composition.
In the present invention, the hollow ratio is the particle diameter of single hollow particles and multi-hollow particles, which are hollow particles (HP), and solid particles (DP) in which the hollow portion disappears by sufficiently heat-treating the hollow particles (HP). Was measured using a transmission electron microscope, and each particle volume (V _HP , V _DP ) and hollow volume (V _HP −V _DP ) were calculated from each average value, and 100 × [(V _HP −V _DP ) / V _HP ], specifically, a value measured by the method described in the examples.
In addition, as described in the item of the examples, in the case of single hollow particles having one hollow portion inside, the outer diameter and the hollow diameter are measured with a transmission electron microscope, and the hollow ratio is calculated from these values. However, it agrees well with the hollowness determined by the above method.
In the present invention, a gas such as air and / or a liquid such as water usually exists in the hollow portion. It is preferable that the hollow portion of the hollow particles contained in the external composition does not contain a liquid, thereby improving the effect of adding the hollow particles to the external composition.

(1-3) Method for producing hollow particles The method for producing the hollow polymer particles used in the present invention is not particularly limited, but when hollow particles are obtained by polymerizing a monofunctional monomer such as a monofunctional vinyl monomer. In the case where a polyfunctional monomer is contained but the ratio is extremely small, for example, an emulsion polymerization method (the method of Japanese Patent No. 4884053) can be employed. Briefly describing this method, a first step of obtaining a fine particle containing a polymer by emulsion polymerization of a monofunctional vinyl monomer in water containing a persulfate as an initiator, and a second step of drying the resulting fine polymer particle. And a step of setting the temperature of the reaction system to be equal to or higher than the glass transition temperature of the fine particles between the first step and the second step.
In the first step, the weight average molecular weight is not limited thereto, but is preferably about 1000 to 2000000, more preferably about 2000 to 1000000, and particularly preferably about 3000 to 500000. If it is this weight average weight molecular weight, the hollow particle which show | plays the effect of this invention can be manufactured.

Moreover, when polymerizing a monomer containing a large amount of a multifunctional vinyl monomer to obtain hollow particles, for example, the SaPSeP method (the method of Japanese Patent No. 3785440) can be mentioned. This method can also be used when hollow particles are obtained by polymerizing only the polyfunctional monomer.
Briefly describing this method, a mixture containing a water-insoluble organic solvent, the following monomer component, the following auxiliary polymer (SPA) and an initiator is dispersed as fine droplets in an aqueous dispersion stabilizer solution, and suspension polymerization is performed. It is a method to do.
Monomer component: monomer component auxiliary polymer (SPA) containing 100 to 0% by weight of polyfunctional monomer and 0 to 100% by weight of monofunctional monomer: polymer (PA) obtained by polymerizing or copolymerizing monomer components The interfacial tension between the auxiliary polymer (SPA) and water (γ ^x ) (mN / m) and the interfacial tension between the polymer (PA) and water (γ ^y ) (mN / m), after obtaining hollow polymer particles satisfying the condition of γ ^x ≧ γ ^y , the organic solvent may be removed by drying.

(2) Content of hollow particles The content of the hollow polymer particles in the composition for external use of the present invention is preferably about 0.05% by weight or more, more preferably about 1% by weight or more, and even more preferably about 2% by weight or more. Preferably, about 3 wt% or more is even more preferred. It can also be about 5% by weight or more. If it is this range, an effect is fully acquired by adding a hollow polymer particle to an external composition.
The content of the hollow polymer particles in the external composition of the present invention is preferably about 50% by weight or less, more preferably about 30% by weight or less, and still more preferably about 20% by weight or less. If it is this range, the effect of invention of a hollow polymer particle can be utilized with appropriate cost, and a usability | use_condition will not worsen.

(3) Formulation The composition for external use of the present invention is a pharmaceutically or physiologically acceptable base or carrier that can use the above-described hollow polymer particles in cosmetics, quasi drugs, or pharmaceuticals, and necessary. Depending on cosmetics, quasi-drugs, or pharmaceutical additives, and active ingredients other than hollow polymer particles (physiologically active ingredients or pharmacologically active ingredients) It can be used as an external preparation.

The pharmaceutical preparation for external use can be, for example, a liquid, fluid, or semisolid preparation. For example, it is a liquid, suspension, emulsion, cream, ointment, gel, liniment, lotion. Agents, aerosol agents, and poultices. These preparations can be manufactured according to the method described in the 16th revised Japanese Pharmacopoeia General Rules for Preparations.
In the case of quasi-drugs and cosmetics, the same form as that of the above-mentioned pharmaceuticals can be used. In addition, a sheet agent obtained by impregnating a non-woven fabric with a chemical solution can be used.
Specific uses for quasi-drugs and cosmetics include lotions, emulsions, gels, creams, serums, sunscreen cosmetics (sunscreens), packs, masks, hand creams, body lotions, And basic cosmetics such as body creams; cleansing cosmetics such as facial cleansers, makeup removers, body shampoos, shampoos, rinses and treatments; makeup cosmetics such as foundations and various colors; and antiperspirants Is mentioned.

Bases or carriers Bases or carriers include, but are not limited to, hydrocarbons such as paraffin, squalane, white wax, ceresin, petrolatum, microcrystalline wax, α-olefin oligomers, and light liquid paraffin; Fatty acids such as acid, myristic acid, palmitic acid, stearic acid, behenic acid, and isostearic acid; tri-fatty acids such as glyceryl tri-2-ethylhexanoate (trioctanoin) and glyceryl tri (caprylic / capric acid) Glycerides; higher alcohols such as cetanol, stearyl alcohol, and behenyl alcohol; silicone oils such as methylpolysiloxane and dimethylpolysiloxane; hydroxypropylcellulose, and hydroxypropylmethylcellulose Such as cellulose derivatives; polyvinyl pyrrolidone; carrageenan; polyvinyl butyrate; polyethylene glycol; Examples include esters; polysaccharides such as dextrin and maltodextrin; lower alcohols such as ethanol and isopropanol; and aqueous bases such as water.

Among them, hydrocarbons (especially α-olefin oligomers, squalane and light liquid paraffin), trifatty acid glycerides (especially glyceryl tri-2-ethylhexanoate, and tri (caprylic / capric) glyceryl), higher alcohols (especially , Cetanol, stearyl alcohol, and behenyl alcohol), silicone oils (especially methylpolysiloxane and dimethylpolysiloxane), esters (especially isononyl isononanoate and pentaerythritol tetra-2-ethylhexanoate), polysaccharides (especially , Dextrin, and maltodextrin), and water.
A base or a support | carrier can be used individually by 1 type or in combination of 2 or more types.

Additives In the composition for external use of the present invention, additives that can be added to cosmetics, quasi drugs, or pharmaceuticals, for example, surfactants, thickeners, preservatives, as long as the effects of the present invention are not impaired. A pH adjuster, a chelating agent, a stabilizer, an antiseptic, a colorant, a dispersant, a fragrance, a pearly luster imparting agent, and the like can be added.
An additive can be used individually by 1 type or in combination of 2 or more types.

  Surfactants include, for example, sorbitan fatty acid esters such as sorbitan monoisostearate, sorbitan monolaurate, sorbitan monopalmitate, and sorbitan monostearate; glycerin fatty acids such as glyceryl monostearate; monostearin Polyglyceryl fatty acids such as polyglyceryl acid, polyglyceryl monoisostearate, and polyglyceryl diisostearate; polyoxyethylene hydrogenated castor oil 40 (HCO-40), polyoxyethylene hydrogenated castor oil 50 (HCO-50), polyoxyethylene hydrogenated Castor oil 60 (HCO-60), and hydrogenated castor oil derivatives such as polyoxyethylene hydrogenated castor oil 80; polyoxyethylene (20) sorbitan monolaurate (polysorbate 20), Polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene (20) sorbitan nostearate (polysorbate 60), polyoxyethylene monooxylate (20) sorbitan (polysorbate 80), and polyoxyethylene (20) sorbitan isostearate Polyoxyalkylene alkyl ethers such as polyoxyethylene cetyl ether; and silicone-based surfactants such as lauryl PEG-9 polydimethylsiloxyethyl dimethicone.

  Among them, glycerin fatty acids (particularly glyceryl monostearate), polyglycerin fatty acids (particularly polyglyceryl monostearate), hardened castor oil derivatives (particularly polyoxyethylene hardened castor oil 50 (HCO-50), polyoxyethylene) Hydrogenated castor oil 60 (HCO-60)), polyoxyethylene sorbitan fatty acid esters (particularly polyoxyethylene (20) sorbitan isostearate and polyoxyethylene (20) sorbitan monostearate (polysorbate 60)), polyoxy Alkylene alkyl ethers (particularly polyoxyethylene cetyl ether) and silicone surfactants (particularly PEG-9 polydimethylsiloxyethyl dimethicone) are preferred.

Examples of thickeners include guar gum, locust bean gum, carrageenan, xanthan gum, dextran, methylcellulose, ethylcellulose, carboxymethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, sodium alginate, propylene glycol alginate, polyvinyl Alcohol, polyvinyl pyrrolidone, polyvinyl methyl ether, carboxy vinyl polymer, acrylic acid / alkyl methacrylate copolymer, sodium polyacrylate, polyethylene glycol, bentonite, dextrin fatty acid ester, pectin, (hydroxyethyl acrylate / acryloyldimethyltaurine Na) Copolymer, Methyl distearyl ammonium hectorite, (ammonium acryloyldimethyltaurate / vinylpyrrolidone) copolymer, polyethylene glycol distearate, triisostearate, ethylene glycol, and triisostearate, polyoxyethylene (20) and the like methyl glucoside.
Among them, xanthan gum, acrylic acid / alkyl methacrylate copolymer, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methylcellulose, polyethylene glycol, carboxyvinyl polymer, (hydroxyethyl acrylate / acryloyldimethyltaurine Na) copolymer, dimethyl distearyl ammonium hect Wright, (acryloyldimethyltauronium ammonium / vinyl pyrrolidone) copolymer, polyethylene glycol distearate, ethylene glycol triisostearate, and polyoxyethylene (20) methyl glucoside triisostearate are preferred.

  Examples of preservatives or preservatives include benzoic acid, sodium benzoate, dehydroacetic acid, sodium dehydroacetate, isobutyl paraoxybenzoate, isopropyl paraoxybenzoate, butyl paraoxybenzoate, ethyl paraoxybenzoate, propyl paraoxybenzoate, Examples include benzyl paraoxybenzoate, methyl paraoxybenzoate, and phenoxyethanol. Of these, methyl paraoxybenzoate, propyl paraoxybenzoate, and phenoxyethanol are preferred.

  Examples of pH adjusters include inorganic acids (hydrochloric acid, sulfuric acid, phosphoric acid, polyphosphoric acid, boric acid, etc.), organic acids (lactic acid, acetic acid, citric acid, sodium citrate, tartaric acid, malic acid, succinic acid, succinic acid, etc. Acid sodium, oxalic acid, gluconic acid, fumaric acid, propionic acid, acetic acid, aspartic acid, epsilon-aminocaproic acid, glutamic acid, and aminoethylsulfonic acid), gluconolactone, ammonium acetate, inorganic base (sodium bicarbonate, carbonic acid) Sodium, potassium hydroxide, sodium hydroxide, calcium hydroxide, and magnesium hydroxide), and organic bases (such as monoethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, and lysine). Among these, succinic acid, sodium succinate, citric acid, sodium citrate, triethanolamine, potassium hydroxide, and sodium hydroxide are preferable.

Examples of the chelating agent include ethylenediaminetetraacetic acid (edetic acid), ethylenediaminetetraacetic acid salt (sodium salt (sodium edetate: Japanese Pharmacopoeia, EDTA-2Na, etc.), potassium salt, etc.), phytic acid, gluconic acid, polyphosphorus An acid, metaphosphoric acid, etc. are mentioned. Of these, sodium edetate is preferable.
Examples of the stabilizer include sodium polyacrylate, dibutylhydroxytoluene, and butylhydroxyanisole.

Examples of the colorant include inorganic pigments and natural pigments.
Examples of the pearl luster imparting agent include ethylene glycol distearate, ethylene glycol monostearate, and triethylene glycol distearate. Of these, ethylene glycol distearate is preferable.

Active ingredients other than hollow polymer particles (bioactive ingredients or pharmacologically active ingredients)
The composition for external use of the present invention can contain various physiologically active ingredients or pharmacologically active ingredients as long as the effects of the present invention are not impaired. Specific examples of such components include, for example, antioxidant components, anti-aging components, anti-inflammatory components, whitening components, vitamins, blood circulation promoting components, warming components, organic UV absorbing components, inorganic UV scattering components, and cleaning components. , Antibacterial components, and refreshing agents.
A physiologically active ingredient or a pharmacologically active ingredient can be used individually by 1 type or in combination of 2 or more types.

  Examples of the antioxidant component include components derived from plants (eg, grape, ginseng, or comfrey); proanthocyanidins, tocopherols and derivatives thereof, ascorbic acid and derivatives thereof, hesperidin, glucosyl hesperidin, ergothioneine, hydrogen sulfite Examples thereof include sodium, erythorbic acid and salts thereof, flavonoids, glutathione, glutathione peroxidase, glutathione-S-transferase, catalase, superoxide dismutase, thioredoxin, taurine, thiotaurine, ubiquinone, α-lipoic acid, and hypotaurine. Among them, grape seed extract, grape leaf extract, ginseng extract, comfrey leaf extract, proanthocyanidins, tocopherol and its derivatives (particularly δ-tocopherol and α-tocopherol), ascorbic acid and its derivatives (particularly ascorbic acid, ascorbine) Sodium acid phosphate, magnesium ascorbate, and ascorbyl tetraisopalmitate (ascorbyl tetra-2-hexyldecanoate), hesperidin, glucosyl hesperidin, ubiquinone, α-lipoic acid, and ergothioneine are preferred.

  Antiaging components include, for example, hydrolyzed soy protein, retinoid (retinol and its derivatives, retinoic acid, retinal, etc.), pangamic acid, kinetin, ursolic acid, turmeric extract, sphingosine derivative, silicon, silicic acid, N-methyl -L-serine, pyrroloquinoline quinone, mevalonolactone and the like. Among these, artemia extract, hydrolyzed soy protein, retinol, retinol acetate, pyrroloquinoline quinone, and retinol palmitate are preferable.

  Anti-inflammatory components include, for example, components derived from plants (eg, Comfrey); allantoin, calamine, glycyrrhizic acid or derivatives thereof, glycyrrhetinic acid or derivatives thereof, zinc oxide, guaiazulene, pyridoxine hydrochloride, menthol, camphor, turpentine oil , Indomethacin, and salicylic acid or derivatives thereof. Of these, Comfrey leaf extract, allantoin, dipotassium glycyrrhizinate, and stearyl glycyrrhetinate are preferable.

  Examples of the whitening component include arbutin, hydroquinone, kojic acid, ellagic acid, phytic acid, lucinol, chamomile ET, ascorbic acid or a derivative thereof, vitamin E or a derivative thereof, pantothenic acid or a derivative thereof, tranexamic acid, and a whitening action. Examples thereof include plant components (for example, plant extracts or essential oils). Among them, arbutin, hydroquinone, kojic acid, ascorbic acid, sodium ascorbate phosphate, magnesium ascorbate phosphate, ascorbyl tetraisopalmitate (ascorbyl tetra-2-hexyldecanoate), lucinol, and tranexamic acid are preferable.

  As vitamins, vitamin A such as retinol, retinol acetate, and retinol palmitate; ascorbic acid, sodium ascorbate phosphate, magnesium ascorbate phosphate, and ascorbyl tetraisopalmitate (ascorbyl tetra-2-hexyldecanoate) Vitamin Cs such as δ-tocopherol and tocopherol nicotinate; and nicotinic acids such as nicotinamide.

  Examples of the circulation promoting component include red pepper extract and nonylic acid vanillylamide.

  Examples of UV absorbing components include cinnamic acid derivatives, benzalmalonate derivatives, triazine derivatives, dibenzoylmethane derivatives, benzoic acid derivatives, salicylic acid derivatives, benzophenone derivatives, benzylidene camphor derivatives, phenylbenzoylimidazole derivatives, anthranyl derivatives, imidazoline derivatives, etc. The organic ultraviolet absorber is mentioned.

  Examples of cinnamic acid derivatives include methoxycinnamic acid-2-ethylhexyl (Ubinal MC80, BASF Japan; Pulsol MCX, DSM Nutrition Japan), isoamyl methoxycinnamate (Neohelipan TS, Hermand Raymer), methoxy Isopropyl cinnamate, cinnoxate, DEA methoxycinnamate, diisopropyl methyl cinnamate, methyl bis (trimethylsilon) silylisopentyl trimethoxycinnamate, methyl 2,5-diisopropyl cinnamate, mono-2 diparamethoxy cinnamate -Glyceryl ethylhexanoate etc. are mentioned.

  Examples of the benzalmalonate derivative include dimethicodiethylbenzalmalonate (Pulsol SLX, DSM Nutrition Japan).

  Examples of triazine derivatives include bisethylhexyloxyphenol methoxyphenyl triazine (Tinosolve S, BASF Japan), methylenebisbenzotriazolyltetramethylbutylphenol (Tinosolv M, BASF Japan), 2,4,6-Tris [4 -(2-Ethylhexyloxycarbonyl) anilino] -1,3,5-triazine (Ubinal T150, BASF Japan), diethylhexylbutamide triazoline (Yubasorb HEB, Sigma 3V) and the like.

  Examples of the dibenzoylmethane derivatives include t-butylmethoxydibenzoylmethane (Pulsol 1789, DSM Nutrition Japan), 4-isopropyldibenzoylmethane (Usolex 8020, Merck) and the like.

  Examples of benzoic acid derivatives include 2-[-4- (diethylamino) -2-hydroxybenzoyl] benzoic acid hexyl ester (Ubinal A plus, BASF Japan Ltd.), paradimethylaminobenzoic acid amyl, paradimethylaminobenzoic acid- Examples include 2-ethylhexyl, paraaminobenzoic acid (PABA), glyceryl PABA, ethyl PABA, ethyl-dihydroxypropyl PABA, and ethylhexyl-dimethyl PABA.

  Examples of salicylic acid derivatives include homosalate (Pulsol HMS, DSM Nutrition Japan), ethylhexyl salicylate (Neohelipan OS, Herman and Reimer), dipropylene glycol salicylate (Dipisar, Skell), TEA salilate (Neohelipan TS, Herman and Reimer) and ethylene glycol salicylate.

  Examples of benzophenone derivatives include benzophenone-1 (Ubinal 400, BASF Japan), benzophenone-2 (Ubinal D50, BASF Japan), benzophenone-3 (Ubinal M40, BASF Japan), benzophenone-4 (Ubinal MS40, BASF Japan), benzophenone-5 (Helisorb 11, Norquay), benzophenone-8 (Spectrasorb, American Cyanamide), benzophenone-9 (Ubinal DS49, BASF Japan) and the like.

  Examples of benzylidene camphor derivatives include 3-benzylidene camphor (Megizolyl SD, Simex), benzylidene camphor sulfonic acid (Megizolyl SL, Simex), methosulfate camphor benzalkonium (Megizolyl SO, Simex), terephthalidene Examples include camphor sulfonic acid (Megizolyl SX, Simex), polyacrylamide methylbenzylidene camphor (Megizolyl SW, Simex).

  Examples of phenylbenzoylimidazole derivatives include phenylbenzimidazolesulfonic acid (Pulsol HS, DSM Nutrition Japan), disodium phenyldibenzimidazoletetrasulfonate (Neohelipan AP, Herman and Reimer), and the like.

  Examples of anthranyl derivatives include menthyl anthranilate.

  Examples of imidazoline derivatives include 2-methoxyhexyl dimethoxybenzylideneoxoimidazolidine propionate.

Among the ultraviolet absorbers, cinnamic acid derivatives, benzalmalonate derivatives, triazine derivatives, dibenzoylmethane derivatives, and benzoic acid derivatives are preferable. Among them, methoxycinnamic acid-2-ethylhexyl, dimethicodiethylbenzalmalonate, 2,4,6-tris [4- (2-ethylhexyloxycarbonyl) anilino] -1,3,5-triazine, bisethylhexyloxyphenol methoxyphenyl triazine, methylenebisbenzotriazolyl tetramethylbutylphenol, t-butylmethoxy Dibenzoylmethane, 2-[-4- (diethylamino) -2-hydroxybenzoyl] benzoic acid hexyl ester is particularly preferred.
An ultraviolet absorber can be used individually by 1 type or in combination of 2 or more types.

The content of the ultraviolet absorber in the external composition is preferably 0.01% by weight or more, more preferably 0.05% by weight or more, and still more preferably 0.1% by weight or more based on the total amount of the composition. . Within this range, the ultraviolet blocking effect (SPF or PA) can be enhanced.
Moreover, 30 weight% or less is preferable with respect to the whole quantity of a composition, as for content of the ultraviolet absorber in an external composition, 25 weight% or less is more preferable, and 20 weight% or less is still more preferable. If it is the said range, a favorable usability | use_condition will be obtained.

Further, the ratio of the content of the ultraviolet absorber to the content of the hollow particles is preferably 0.01 parts by weight or more, more preferably 0.1 parts by weight or more, with respect to 1 part by weight of the hollow particles. Is even more preferred. Within this range, the ultraviolet blocking effect can be enhanced, and the ultraviolet protection index can be enhanced.
In addition, the ratio of the content of the ultraviolet absorber to the content of the hollow particles is preferably 300 parts by weight or less, more preferably 100 parts by weight or less, and even more preferably 50 parts by weight or less with respect to 1 part by weight of the hollow particles. . If it is the said range, a favorable usability | use_condition will be obtained.

Examples of the inorganic ultraviolet scattering component include metal oxides such as zinc oxide, titanium oxide, iron oxide, cerium oxide, and zirconium oxide; metal silicates such as titanium silicate, zinc silicate, and cerium silicate; Examples thereof include silicic anhydride and silicic acid such as hydrous silicic acid; and inorganic compounds such as metals such as titanium, zinc and iron.
Also, those inorganic compounds coated with an inorganic powder such as hydrous silicate, aluminum hydroxide, mica, or talc, and those inorganic compounds as resin powders such as polyamide, polyethylene, polyester, polystyrene, or nylon Examples include those which are combined or coated with these, and those which are treated with or coated with a silicone oil or a fatty acid aluminum salt.
An ultraviolet absorber can be used individually by 1 type or in combination of 2 or more types.
The average particle size of the inorganic ultraviolet scattering component is preferably about 5 to 500 nm, and more preferably 5 to 20 nm.

Further, the ratio of the content of the inorganic ultraviolet scattering component to the content of the hollow particles is preferably 0.1 parts by weight or more, more preferably 1 part by weight or more, and more preferably 5 parts by weight or more with respect to 1 part by weight of the hollow particles. Even more preferred. Within this range, the ultraviolet blocking effect can be enhanced.
Further, the ratio of the content of the inorganic ultraviolet scattering component to the content of the hollow particles is preferably 40 parts by weight or less, more preferably 35 parts by weight or less, and even more preferably 30 parts by weight or less with respect to 1 part by weight of the hollow particles. preferable. If it is the said range, a favorable usability | use_condition will be obtained.

  Examples of the cleaning component include polyoxyalkylene alkyl (or alkenyl) ether sulfate, alkyl (or alkenyl) sulfate, higher fatty acid salt, ether carboxylate, amide ether carboxylate, alkyl phosphate ester salt, N- Anionic surfactants such as acyl amino acid salts, polyoxyalkylene fatty acid amide ether sulfates, acylated isethionates, and acylated taurates; amine oxides, glycerin fatty acid esters, sorbitan fatty acid esters, alkyl saccharides, polyoxyalkylene alkyl ethers, Nonionic surfactants such as fatty acid alkanolamides and polyoxyalkylene hydrogenated castor oil; mono- or di-long chains optionally having alkylene oxide attached thereto and having straight-chain or branched long-chain alkyl groups Alkyl cationic surfactants such as quaternary ammonium salts; carboxymethyl betaine, sulfobetaine, imidazolinium betaine, and amphoteric surfactants such as amide betaine.

  Antibacterial components include, for example, chlorhexidine, salicylic acid, benzalkonium chloride, acrinol, ethanol, benzethonium chloride, gluconic acid and its derivatives, isopropylmethylphenol, phenoxyethanol, 1,2-pentanediol, and alkyldiaminoglycine hydrochloride. It is done. Among them, benzalkonium chloride, benzethonium chloride, gluconic acid and derivatives thereof, isopropylmethylphenol, triclocarban, phenoxyethanol, 1,2-pentanediol, and alkyldiaminoglycine hydrochloride are preferable, benzalkonium chloride, gluconic acid and derivatives thereof More preferred are benzethonium chloride, and isopropylmethylphenol.

  Examples of the refreshing agent include camphor, borneol, menthol, mint water, anethole, eugenol, geraniol, limonene, essential oils (such as mint oil, peppermint oil, eucalyptus oil, bergamot oil, and rose oil).

  As described above, the hollow particles in the present invention have a suppressed interaction with components having an ionic functional group. Therefore, as a component mix | blended with the external composition of this invention, the component (cation component, anion component, or amphoteric component) which has an ionic functional group is suitable. Typically, cationic, anionic, or amphoteric surfactants can be mentioned.

The composition for external use of this invention can be conveniently used as a composition containing the compound (cationic compound, anionic compound, and amphoteric compound) which has an ionic functional group. Typical examples of the compound having an ionic functional group include a cationic surfactant, an anionic surfactant, and an amphoteric surfactant.
Moreover, since the hollow polymer particle demonstrated above has the effect | action of an ultraviolet-ray shielding effect, it is preferable that the external composition of this invention contains an organic ultraviolet absorber and / or an inorganic ultraviolet scattering agent.

Specific examples of formulations
<Temperature shielding agent>
Since the hollow polymer particles have single or plural voids inside, the hollow polymer particles have a temperature or heat shielding effect due to the presence of the air layer. Therefore, the composition for external use of the present invention containing hollow polymer particles can be used as a temperature shielding agent, a heat shielding agent, or a temperature control agent.
When the composition for external use of the present invention is a temperature shielding agent, the content of the hollow particles is preferably 0.05% by weight or more, more preferably 1% by weight or more, more preferably 2% by weight based on the total amount of the temperature shielding agent. The above is even more preferable, and 3% by weight or more is even more preferable. Moreover, it can also be 5 weight% or more. Thereby, the effect of hollow particle blending is sufficiently obtained. The content of the hollow particles is preferably 50% by weight or less, more preferably 30% by weight or less, and still more preferably 20% by weight or less, based on the total amount of the temperature shielding agent. Thereby, the stability of the preparation is not adversely affected and the feeling of use is not deteriorated.

  The present invention includes a temperature or heat shielding method or a temperature control method for applying (applying, sticking, spraying, etc.) the above-described external composition of the present invention to the skin.

<Heat / cooling agent>
Since the hollow polymer particles have a heat shielding action, the composition for external use of the present invention can maintain or enhance the thermal effect or the cool feeling effect. Therefore, the composition for external use of the present invention can be suitably used as a warming sensation agent or a cooling sensation agent. The form of the preparation is not particularly limited, but a warm patch, warm spray, cool patch, or cool spray that is a general-purpose formulation is suitable.
The warm patch contains active ingredients such as nonylic acid vanillyl amide and red pepper extract. It is expected to reduce pain. Further, the warming spray is a spray obtained by dissolving and dispersing the above components in an aqueous alcohol. Mist can be produced in the same manner.
In addition, the cooling sensation poultice is intended to obtain a cooling effect by including an essential oil component having a local stimulating action such as menthol and camphor. The cold patch is used for the purpose of suppressing local fever by cooling the inflamed area and preventing the inflamed area from expanding. Further, the cooling sensation spray is obtained by dissolving and dispersing the above components in an aqueous alcohol. Mist can be produced in the same manner.
When the external composition of the present invention is a thermal agent or a cooling agent, the content of the hollow polymer particles is preferably 0.05% by weight or more, more preferably 1% by weight or more, based on the total amount of the preparation. 2% by weight or more is even more preferred, and 3% by weight or more is even more preferred. Moreover, it can also be 5 weight% or more. Thereby, the effect of hollow particle blending is sufficiently obtained. Further, the content of the hollow particles is preferably 50% by weight or less, more preferably 30% by weight or less, and still more preferably 20% by weight or less with respect to the total amount of the preparation.
The thermal agent can further include, for example, one or more of the warming components exemplified above, and the cooling agent can further include, for example, one or more of the refreshing agents exemplified above.

  The present invention includes a method for imparting a feeling of warmth or coolness by applying (applying, sticking, spraying, etc.) the above-described external composition of the present invention to the skin.

<Antiperspirant>
Antiperspirants contain an astringent such as chlorohydroxyaluminum as an active ingredient. By blending the above-described hollow polymer particles with the antiperspirant, when the outside is hot, the heat from the outside can be shielded to keep the body surface temperature low and the antiperspirant effect can be enhanced. Therefore, the composition for external use of the present invention can be suitably used as an antiperspirant.
When the composition for external use of the present invention is an antiperspirant, the content of the hollow particles is preferably 0.05% by weight or more, more preferably 1% by weight or more, more preferably 2% by weight with respect to the total amount of the antiperspirant. The above is even more preferable, and 3% by weight or more is even more preferable. Moreover, it can also be 5 weight% or more. Thereby, the effect of hollow particle blending is sufficiently obtained. Further, the content of the hollow particles is preferably 50% by weight or less, more preferably 30% by weight or less, and still more preferably 20% by weight or less based on the total amount of the antiperspirant.
The antiperspirant can further include one or more of the astringent components exemplified above.

  The present invention includes an antiperspirant method in which the above-described external composition of the present invention is applied (applied, affixed, or sprayed) to the skin.

<Sunscreen>
Since the hollow polymer particles described above have an effect of enhancing ultraviolet shielding, the external composition of the present invention can be suitably used as a sunscreen (ultraviolet shielding agent).
In this case, the amount of the hollow particles varies depending on the amount of the other ultraviolet absorbing component or ultraviolet scattering component, but is preferably 0.05% by weight or more, more preferably 1% by weight or more based on the total amount of the sunscreen, 2% by weight or more is even more preferred, and 3% by weight or more is even more preferred. Moreover, it can also be 5 weight% or more. If it is this range, the effect of hollow particle mixing will be sufficiently obtained.
Moreover, 50 weight% or less is preferable with respect to the whole quantity of a sunscreen, 30 weight% or less is more preferable, and 20 weight% or less is more preferable. If it is this range, stability of a formulation will not be impaired and a usability | use_condition will not be worsened.
The sunscreen may further contain at least one ultraviolet shielding agent selected from the group consisting of the organic ultraviolet absorbing component and the inorganic ultraviolet scattering component exemplified above.

  The present invention includes an ultraviolet shielding method for applying (applying, sticking, spraying, etc.) the above-described external composition of the present invention to the skin.

<Makeup agent>
Since the hollow polymer particles described above have a concealing effect such as a stain and an effect of brightening the skin color, the composition for external use of the present invention can be suitably used as a makeup agent such as a foundation. The makeup agent can be a makeup agent for concealing skin irregularities, spots, pores, etc., or a makeup agent for imparting transparency or brightness to the skin.
In this case, the amount of hollow particles varies depending on the amount of other components, but is preferably 0.05% by weight or more, more preferably 1% by weight or more, and more preferably 2% by weight or more based on the total amount of the makeup agent. Is more preferable, and 3% by weight or more is even more preferable. Moreover, it can also be 5 weight% or more. If it is this range, the effect of hollow particle mixing will be sufficiently obtained.
Moreover, 50 weight% or less is preferable with respect to the whole quantity of a makeup agent, 30 weight% or less is more preferable, and 20 weight% or less is still more preferable. If it is this range, stability of a formulation will not be impaired and a usability | use_condition will not be worsened.
The makeup agent can further contain, for example, one or more of the above-described whitening agents and anti-aging agents.

  The present invention includes a makeup method for applying (applying, sticking, spraying, etc.) the above-described external composition of the present invention to the skin. Specifically, the present invention applies the above-described external composition of the present invention to the skin, a method for concealing skin irregularities, spots, or pores, a method for imparting transparency to the skin, and a method for brightening the skin color. Is included.

Method of use The method of using the composition for external use of the present invention varies depending on the use of the composition and the health condition, skin condition, age, gender, etc. of the subject of use, but may be the normal method of use for each use .
In the case of a heat, a cooling sensation agent or an antiperspirant, for example, 0.05 to 2 g may be applied or affixed to the skin at a frequency of 1 to 4 times a day. Can be given a warm feeling or a cold feeling. The period of use may be until the symptoms are alleviated, and may be, for example, 1 day to 1 year.
The target of use of the heat agent is preferably a healthy person, a person with coldness, a person with pain, a person with chills, and the like. The target of use of the cooling sensation agent is preferably a healthy person, a person with heat stroke, a person with fever, a person with bruise or bruise, and the like.
In the case of a sunscreen, 0.05 to 2 g may be applied to the skin at a frequency of 1 to 4 times a day, thereby shielding ultraviolet rays that reach the skin. .
In the case of a makeup agent, 0.05 to 2 g may be applied to the skin at a frequency of 1 to 4 times a day, thereby concealing discoloration such as spots and pores. Can give a clear feeling to the skin.

(II) Use of hollow polymer particles
(1) Applications As described above, the hollow polymer particles are useful as an active ingredient of an ultraviolet shielding effect enhancer because the ultraviolet shielding effect by the ultraviolet absorber or ultraviolet scattering agent is enhanced (booster effect).
Moreover, since the hollow polymer particle has a temperature shielding effect, it is useful as an active ingredient of a temperature or a heat shielding agent or a temperature control agent.
In addition, the hollow polymer particles are useful as an active ingredient of a makeup agent because they conceal skin irregularities, spots, pores, etc., and give the skin a sense of transparency or brightness. Furthermore, it is useful as an active ingredient of a makeup agent for concealing skin irregularities, spots, or pores, and is useful as an active ingredient of a makeup agent for imparting transparency or brightness to the skin.

Therefore, the present invention includes a method for enhancing the ultraviolet shielding effect of the composition, in which the hollow polymer particles are blended with an external composition containing an ultraviolet absorber and / or an ultraviolet scattering agent.
The present invention also includes a method of imparting temperature or heat shielding action or temperature control action to the composition by blending the hollow polymer particles into the composition for external use.
In addition, the present invention can be obtained by blending the hollow polymer particles in the composition for external use, thereby providing the composition with a soft focus action such as an action for concealing skin irregularities, spots, or pores, an action for brightening the skin color, or It includes a method of imparting an action of imparting a transparent feeling to the skin.

(2) Polymer
(2-1) The monomer hollow polymer particles constituting the polymer may be polymer particles having a hollow structure.
The type of polymer is not particularly limited, but a polymer or copolymer of a vinyl monofunctional monomer, a polymer or copolymer of a vinyl polyfunctional monomer, and a vinyl monofunctional monomer and a vinyl polyfunctional Copolymers with monomers are preferred.

(2-1-1) Vinyl-based multifunctional monomer The vinyl-based multifunctional monomer is not limited thereto, but examples thereof include divinylbenzene, divinylbiphenyl, divinylnaphthalene, diallyl phthalate, triallyl cyanurate, and ethylene glycol diester. Examples include methacrylate and tetraethylene glycol dimethacrylate. In particular, divinylbenzene and ethylene glycol dimethacrylate are preferred.
A vinyl type polyfunctional monomer can be used individually by 1 type or in combination of 2 or more types.

(2-1-2) Vinyl-based monofunctional monomer The vinyl-based monofunctional monomer is not limited thereto, but examples thereof include monovinyl aromatic monomers, acrylic monomers (including methacrylic monomers), and vinyl ester-based monomers. Examples thereof include monomers and vinyl ether monomers. A vinyl type monofunctional monomer can be used individually by 1 type or in combination of 2 or more types.

Examples of the monovinyl aromatic monomer include, but are not limited to, for example, vinylbiphenyl optionally substituted with a monovinyl aromatic hydrocarbon represented by the following general formula (5) or a lower (1 to 4 carbon) alkyl group. And vinyl naphthalene which may be substituted with a lower (1 to 4 carbon atoms) alkyl group.
Wherein, ^{R 7} is a hydrogen atom, a lower (1-4 carbon atoms) alkyl group, or a halogen atom, ^{R 8} is a hydrogen atom, a lower (1-4 carbon atoms) alkyl group, a halogen atom, - SO ₃ Na group, —SO ₃ H group, hydroxyl group, ω-hydroxyalkyl group, lower (C 1-4) alkoxy group, amino group, or carboxyl group is shown. ]
In the above general formula (5), R ⁷ is preferably a hydrogen atom, a methyl group or a chlorine atom, and R ⁸ is preferably a hydrogen atom, a chlorine atom, a methyl group, a —SO ₃ Na group or a —SO ₃ H group. Or an ω-hydroxyalkyl group.

  Specific examples of the monovinyl aromatic hydrocarbon represented by the general formula (5) include, but are not limited to, styrene, vinyl toluene (o-methylstyrene, m-methylstyrene, p-methylstyrene), o -Chlorostyrene, m-chlorostyrene, p-chlorostyrene, sodium styrenesulfonate, p-hydroxymethylstyrene, o-hydroxymethylstyrene, and the like.

  Furthermore, vinyl biphenyl which may be substituted with a lower alkyl group, and vinyl naphthalene which may be substituted with a lower alkyl group include vinyl biphenyl substituted with a lower alkyl group such as vinyl biphenyl, methyl group and ethyl group. , Vinyl naphthalene, and vinyl naphthalene substituted with a lower alkyl group such as a methyl group or an ethyl group.

In addition, the acrylic monomer is not limited thereto, and examples thereof include an acrylic monomer (including a methacrylic monomer) represented by the following general formula (6).
[Wherein, R ⁹ represents a hydrogen atom or a lower (1 to 4 carbon atoms) alkyl group, and R ¹⁰ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group, or a C 1 to 6 carbon atom. A hydroxyalkyl group, a lower (1 to 4 carbon atoms) aminoalkyl group or a di (C ₁ -C ₄ alkyl) amino- (C ₁ -C ₄ ) alkyl group, or an ethylene dihydroxyphosphate group is shown. ]
In General Formula (6), R ⁹ is preferably a hydrogen atom or a methyl group, and R ¹⁰ is preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a phenyl group, or lower (1 to 4 carbon atoms) hydroxy. An alkyl group, a lower (1 to 4 carbon atoms) aminoalkyl group, or an ethylenedihydroxyphosphate group is preferred.

  Specific examples of the acrylic monomer include, but are not limited to, acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate. Cyclohexyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, β-hydroxyethyl acrylate, γ-hydroxybutyl acrylate, acrylic Acid δ-hydroxybutyl, methacrylate-2,3-dihydroxypropyl, glycidyl methacrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl methacrylate, γ-aminopropyl acrylate, meta Β-aminoethyl acrylate, γ-N, N-dimethylaminopropyl acrylate, γ-N, N-diethylaminopropyl acrylate, β-N, N-dimethylaminoethyl methacrylate, itaconic acid, dimethyl itaconate, itacon Examples include diethyl acid, dipropyl itaconate, and dibutyl itaconate.

Examples of the vinyl ester monomer include, but are not limited to, those represented by the following general formula (7).
[Wherein, R ¹¹ represents a hydrogen atom, a lower (C1-4) alkyl group, a phenyl group, or a phenylalkyl group having a C1-4 alkyl group. ]
Specific examples of the vinyl ester monomer include, but are not limited to, vinyl formate, vinyl acetate, vinyl propionate, vinyl benzoate, and vinyl vinyl acetate.

Although not limited to it as a vinyl ether type monomer, For example, the vinyl ether type monomer represented by following General formula (8) is mentioned.
[R ¹² represents an alkyl group having 1 to 12 carbon atoms, a phenyl group, or a cyclohexyl group. ]
Specific examples of vinyl ether monomers include, but are not limited to, vinyl methyl ether, vinyl ethyl ether, vinyl n-propyl ether, vinyl iso-propyl ether vinyl, vinyl n-butyl ether, vinyl phenyl ether, vinyl cyclohexyl ether. And vinyl benzyl ether.

(2-2) Preferred monomer Preferred monomers are the same as those of the hollow polymer particles used in the external composition of the present invention.

(2-3) Preferred polymer
(a) Preferred polymer of polyfunctional monomer The preferred polymer of the polyfunctional monomer is the same as that of the hollow polymer particles used in the composition for external use of the present invention.

(b) Preferred polymer of monofunctional monomer The preferred polymer of the monofunctional monomer is the same as that of the hollow polymer particles used in the composition for external use of the present invention.

(c) Preferred copolymer of polyfunctional monomer and monofunctional monomer Preferred copolymer of polyfunctional monomer and monofunctional monomer is the case of hollow polymer particles used in the composition for external use of the present invention. Is the same.

(d) Copolymerization ratio
The copolymerization ratio of the polyfunctional monomer and the monofunctional monomer is the same as that of the hollow polymer particles used in the composition for external use of the present invention.

  The ratio of the ionic functional group in the monomer is not particularly limited, but is preferably 5 mol% or less, more preferably less than 5 mol%, still more preferably 2 mol% or less, and even more preferably 1 mol based on the total amount of monomers. % Or less is even more preferable. The polymer of the hollow particles is most preferably obtained by polymerizing only a monomer having no ionic functional group. If it is the said range, when adding to a skin external preparation, even if it makes a formulation neutral-weakly acidic, it is hard to impair the stability of a hollow particle. In addition, it is difficult to inhibit the action of other components.

(e) Other polymers Vinyl-based monomers and other monomers copolymerized and / or polymers other than vinyl-based polymers may be contained in the shell.

(3) Properties of hollow particles
(3-1) The shape hollow particles may have a spherical shape or a substantially spherical shape, and are preferably spherical.
The hollow portion may be a single hollow or a multi-hollow. When it is multi-hollow, the number of hollow portions observed in the maximum area cross section of the particles is preferably about 1 to 50, more preferably about 1 to 20, and about 1 to 5 Even more preferred. Within this range, the interfacial area between the shell and the voids in the particles will be sufficient, and the temperature or heat shielding effect, the ultraviolet shielding enhancement effect, and the makeup effect (stain hiding effect, etc., the skin will be transparent) Effect) is sufficiently obtained.

(3-2) Average particle size of an average particle diameter of the hollow particles is preferably at least 1 nm, more preferably at least 10 nm, even more preferably more than 50nm. It can also be 100 nm or more. If it is the said range, the space | gap (air layer) which can exhibit the effect (the ultraviolet shielding enhancement effect, the temperature shielding effect, and the makeup effect) of this invention on the skin surface is securable.
The average particle diameter of the hollow particles is preferably 30000 nm or less, more preferably 10,000 nm or less, and even more preferably 2000 nm or less. If it is the said range, when apply | coating to skin etc. and using it, there is no rough feeling and the effect of this invention can be exhibited effectively.

(3-3) Hollow ratio The hollow ratio of the hollow particles is preferably 10% or more, more preferably 15% or more, still more preferably 20% or more, and even more preferably 30% or more. Moreover, it can also be made 40% or more, and can also be made 60% or more. If it is the said range, intensity | strength sufficient practically will be obtained. Further, the thermal conductivity is lowered, and a sufficient temperature shielding effect is obtained. In addition, the ultraviolet shielding enhancement effect and the makeup effect are sufficient.
The void ratio of the hollow particles is preferably 90% or less, more preferably 85% or less, and even more preferably 80% or less. If it is the said range, it will become the durable particle | grains strong against an impact.

  In the space in the shell of the hollow particles, a gas such as air and / or a liquid such as water is usually present. The space inside the shell of the hollow particles is preferably free of liquids, so that the temperature or heat shielding effect, the ultraviolet shielding enhancement effect, and the makeup effect (scrubbing effect, skin transparency, brightness, etc.) Effect).

  The hollow polymer particles are preferably hollow polymer particles in the above-described external composition of the present invention.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated more concretely, this invention is not limited to these.
(1) Production of hollow particles
Hollow particles 1 (Example 1)
Nonionic surfactant Emulgen 150 (Kao Chemical) (cloud point: 100 ° C or higher) 1.0 g, Emulgen 109P (Kao Chemical) (cloud point: 83 ° C) 10 g, styrene 100 g, potassium persulfate 1 g and ion-exchanged water 350 g were put into a four-necked separable flask equipped with a reflux condenser and reacted at 70 ° C. for 16 hours with stirring at 600 rpm under a nitrogen gas stream.
The polymerization solution was centrifuged at 15000 rpm for 40 minutes to collect a precipitate (fine particles). Water twice as much as the precipitate was added, the precipitate was well dispersed, centrifuged again at 15000 rpm for 40 minutes, the upper phase was discarded, and the precipitate (fine particles) was collected. Four times as much water as the precipitate was added, the precipitate was well dispersed, sealed in a pressure-resistant bottle and heat-treated at 120 ° C. for 1 hour.
When the heat-treated polymer fine particles were observed with a transmission electron micrograph, most of them were single hollow particles, and multi-hollow particles having 2 to 5 hollow portions of several% or less of the whole were included.
Further, the heat treatment liquid was centrifuged at 15000 rpm for 40 minutes to collect a precipitate (fine particles), and dried under reduced pressure under heating at 50 ° C. When the produced particles were dispersed in the aqueous surfactant solution, it was found that a hollow structure was formed because the particles floated in water. In addition, it was confirmed that the polymer fine particles before drying under reduced pressure were precipitated under heating at 50 ° C.
A photograph of the hollow particles of Example 1 is shown in FIG.

Hollow particle 2 (Example 2)
A nonionic surfactant, Emulgen 911 (manufactured by Kao Chemical) (cloud point: 74 ° C.) 10 g, styrene 50 g, methyl methacrylate 50 g, potassium persulfate 1 g, and ion-exchanged water 350 g were provided with a reflux condenser. The mixture was placed in a one-necked separable flask and reacted at 70 ° C. for 16 hours with stirring at 600 rpm under a nitrogen gas stream.
The polymerization solution was centrifuged at 15000 rpm for 40 minutes to collect precipitates (fine particles). Water twice as much as the precipitate was added and well dispersed, and centrifuged again at 15000 rpm for 40 minutes, the upper phase was discarded, and the precipitate (fine particles) was collected. Four times as much water as the precipitate was added, well dispersed, sealed in a pressure-resistant bottle and heat-treated at 120 ° C. for 1 hour.
The treatment liquid was centrifuged at 15000 rpm for 40 minutes to collect a precipitate (fine particles), and dried under reduced pressure under heating at 50 ° C. Since the produced particle floated in water, it turns out that it has a hollow structure. In addition, it was confirmed that the polymer fine particles before drying under reduced pressure were precipitated under heating at 50 ° C.
A photograph of the hollow particles of Example 2 is shown in FIG.

Hollow particles 3 (Example 3)
A nonionic surfactant, Emulgen 911 (manufactured by Kao Chemical) (cloud point: 74 ° C.), 10 g of methyl methacrylate, 100 g of methyl methacrylate, 1 g of potassium persulfate, 350 g of ion-exchanged water, The mixture was placed in a separable flask and reacted at 70 ° C. for 16 hours with stirring at 600 rpm under a nitrogen gas stream.
The polymerization solution is centrifuged at 15000 rpm for 40 minutes to collect a precipitate (fine particles). Water twice as much as the precipitate was added and well dispersed, and centrifuged again at 15000 rpm for 40 minutes, the upper phase was discarded, and the precipitate (fine particles) was collected. Four times as much water as the precipitate was added, well dispersed, sealed in a pressure-resistant bottle and heat-treated at 120 ° C. for 1 hour.
The treatment liquid was centrifuged at 15000 rpm for 40 minutes to collect a precipitate (fine particles), and dried under reduced pressure under heating at 50 ° C. Since the produced particle floated in water, it turns out that it has a hollow structure. In addition, it was confirmed that the polymer fine particles before drying under reduced pressure were precipitated under heating at 50 ° C.

Hollow particles 4 (Example 4)
Nonionic surfactant Emulgen 150 (manufactured by Kao Chemical) (cloud point: 100 ° C or higher) 1.0g, Emulgen 109P (manufactured by Kao Chemical) (cloud point: 83 ° C) 10g, styrene 100g, 35% peroxide Hydrogen water 360mg, sodium ascorbate 733mg (half amount of 1466mg in total) and ion-exchanged water 350g were placed in a four-necked separable flask equipped with a reflux condenser and stirred at 50 ° C under nitrogen gas flow at 600 ° C. The reaction was continued for a period of time, 733 mg of sodium ascorbate was added, and the reaction was continued under the same conditions for another 10 hours.
The polymerization solution was centrifuged at 15000 rpm for 40 minutes to collect a precipitate (fine particles). Water twice as much as the precipitate was added and well dispersed, and centrifuged again at 15000 rpm for 40 minutes, the upper phase was discarded, and the precipitate (fine particles) was collected. Four times as much water as the precipitate was added, well dispersed, sealed in a pressure-resistant bottle and heat-treated at 120 ° C. for 1 hour.
When the heat-treated polymer fine particles were observed with a transmission electron micrograph, most of the particles were single hollow particles although very few multi-hollow particles having 2 to 5 cavities were observed.
The treatment liquid was centrifuged at 15000 rpm for 40 minutes to collect a precipitate (fine particles), and dried under reduced pressure under heating at 50 ° C. When the produced particles are put in water, it is understood that the particles have a hollow structure because they float. In addition, it was confirmed that the polymer fine particles before drying under reduced pressure were precipitated under heating at 50 ° C.

Hollow particles 5 (Example 5)
To a solution obtained by dissolving 1.8 g of polyvinyl alcohol in 180 g of water, 9 g of toluene, 9 g of a crosslinkable ethylene glycol dimethacrylate as a monomer component, 0.9 g of polystyrene as an auxiliary polymer, and as a polymerization initiator A solution obtained by uniformly mixing 0.036 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was suspended. The suspension was performed using a homomixer (TKROBOMICS, manufactured by PRIMIX) at a stirring speed of 7000 rpm for 5 minutes and at a stirring speed of 10000 rpm for 10 minutes at room temperature.
Next, the suspension was placed in a separable flask and subjected to suspension polymerization at 50 ° C. for 18 hours and then at 80 ° C. for 6 hours with stirring at 120 rpm in a nitrogen gas atmosphere.
After completion of the polymerization, the mixture was centrifuged at 1500 rpm for 10 minutes to collect toluene-encapsulated microcapsules. The collected toluene-encapsulated microcapsules were washed with 500 mL of water three times, and dried under reduced pressure under heating at 50 ° C. When confirmed with a microscope (VHX-1000 Digital Microscope manufactured by Keyence Co., Ltd.), it was found that all were single hollow particles. The produced dry particles floated without being settled in a 1% aqueous solution of a surfactant, indicating that they have a hollow structure.

Hollow particles 6 (Example 6)
Nonionic surfactant, Emulgen 150 (manufactured by Kao Chemical) (cloud point: 100 ° C or higher) 1.0 g, Emulgen 109P (manufactured by Kao Chemical) (cloud point: 83 ° C) 10 g, styrene 97 g, methacrylic acid 3 g, 1 g of potassium persulfate and 350 g of ion-exchanged water were placed in a four-necked separable flask equipped with a reflux condenser and reacted at 70 ° C. for 16 hours with stirring at 600 rpm under a nitrogen gas stream.
The polymerization solution was centrifuged at 15000 rpm for 40 minutes to collect a precipitate (fine particles). Water twice as much as the precipitate was added, the precipitate was well dispersed, centrifuged again at 15000 rpm for 40 minutes, the upper phase was discarded, and the precipitate (fine particles) was collected. Four times as much water as the precipitate was added, the precipitate was well dispersed, sealed in a pressure-resistant bottle and heat-treated at 120 ° C. for 1 hour.
When the heat-treated polymer fine particles were observed with a transmission electron micrograph, most of the particles were single hollow particles, and multi-hollow particles having 2 to 5 hollow portions of several% or less of the whole were included.
The treatment liquid was centrifuged at 15000 rpm for 40 minutes to collect a precipitate (fine particles), and dried under reduced pressure under heating at 50 ° C. When the produced particles are put in water, it is understood that the particles have a hollow structure because they float. In addition, it was confirmed that the polymer fine particles before drying under reduced pressure were precipitated under heating at 50 ° C.

Hollow particle 7
(Example 7)
Nonionic surfactant Emulgen 150 (Kao Chemical) (cloud point: 100 ° C or higher) 1.0g, Emulgen 109P (Kao Chemical) (cloud point: 83 ° C) 10g, styrene 97g, ethylene glycol dimethacrylate -3 g of potassium, 1 g of potassium persulfate, and 350 g of ion-exchanged water were placed in a four-necked separable flask equipped with a reflux condenser, and reacted at 70 ° C for 14 hours while stirring at 600 rpm under a nitrogen gas stream.
The polymerization solution was centrifuged at 15000 rpm for 40 minutes to collect a precipitate (fine particles). Water twice as much as the precipitate was added, the precipitate was well dispersed, centrifuged again at 15000 rpm for 40 minutes, the upper phase was discarded, and the precipitate (fine particles) was collected. Four times as much water as the precipitate was added, the precipitate was well dispersed, sealed in a pressure-resistant bottle and heat-treated at 120 ° C. for 2 hours.
The heat-treated solution was centrifuged at 15000 rpm for 40 minutes to collect a precipitate (fine particles), and dried under reduced pressure under heating at 50 ° C. When the produced particles were put into water, it was found that a hollow structure was formed from the fact that they floated in water. In addition, it was confirmed that the polymer fine particles before drying under reduced pressure were precipitated under heating at 50 ° C.

Hollow particles containing water in the hollow part (Example 8)
Styrene was polymerized in the same manner as in the production example of the hollow particles 1. That is, 1.0 g of Emulgen 150 (manufactured by Kao Chemical) (cloud point: 100 ° C. or higher), 10 g of Emulgen 109P (manufactured by Kao Chemical) (cloud point: 83 ° C.), which is a nonionic surfactant, 100 g of styrene 1 g of potassium sulfate and 350 g of ion-exchanged water were placed in a four-necked separable flask equipped with a reflux condenser and reacted at 70 ° C. for 16 hours while stirring at 600 rpm under a nitrogen gas stream.
The polymerization solution was centrifuged at 15000 rpm for 40 minutes to collect a precipitate (fine particles). Water twice as much as the precipitate was added, the precipitate was well dispersed, centrifuged again at 15000 rpm for 40 minutes, the upper phase was discarded, and the precipitate (fine particles) was collected. Four times as much water as the precipitate was added, the precipitate was well dispersed, sealed in a pressure-resistant bottle and heat-treated at 120 ° C. for 1 hour.
Furthermore, the heat-treated liquid was centrifuged at 14000 rpm for 40 minutes, and the resulting precipitate (particles) was air-dried at room temperature for 2 hours.

Solid particles not having a hollow structure (Comparative Example 1)
Styrene was polymerized in the same manner as in the production example of the hollow particles 1. That is, 1.0 g of Emulgen 150 (manufactured by Kao Chemical) (cloud point: 100 ° C. or higher), 10 g of Emulgen 109P (manufactured by Kao Chemical) (cloud point: 83 ° C.), which is a nonionic surfactant, 100 g of styrene 1 g of potassium sulfate and 350 g of ion-exchanged water were placed in a four-necked separable flask equipped with a reflux condenser and reacted at 70 ° C. for 16 hours while stirring at 600 rpm under a nitrogen gas stream.
The polymerization solution was centrifuged at 15000 rpm for 40 minutes to collect a precipitate (fine particles). Water twice as much as the precipitate was added, the precipitate was well dispersed, centrifuged again at 15000 rpm for 40 minutes, the upper phase was discarded, and the precipitate (fine particles) was collected. The precipitate (fine particles) was dried under reduced pressure with heating at 50 ° C. to obtain solid particles.

(2) Characteristics of Hollow Particles The average particle diameter and hollow ratio of the above hollow particles 1 to 7 (Examples 1 to 7) were measured.

Average particle size The average particle size is determined by the average particle size laser diffraction scattering method (device name: Fiber-Optics Particle Analyzer, model number FPAR-1000, Otsuka Electronics Co., Ltd.) or the average particle laser scattering method (device name: Laser). Scattering Particle size Distribution Analyzer, HORIBA, Ltd.). For the value of the average particle diameter, the number was adopted on the basis of the particle diameter.

The hollow ratio (%) of the hollow ratio single hollow particles and the multi-hollow particles is the hollow particles (HP) and solid particles (DP) particles in which the hollow portions disappeared by sufficiently heat-treating them. The diameter was measured by an average particle diameter laser diffraction scattering method or an average particle laser scattering method using a Fiber-Optics Particle Analyzer (model number FPAR-1000, Otsuka Electronics Co., Ltd.). The particle volume (V _HP , V _DP ) and the hollow volume (V _HP −V _DP ) are calculated from the average value (measured three times) of the measured values, and 100 × [(V _HP −V _DP ) / V _HP ]. Furthermore, the average value of 100 × [(V _HP −V _DP ) / V _HP ] of the five particles was defined as the hollow ratio (%) in the present invention.
For single hollow particles having one hollow portion inside, the outer diameter and the hollow diameter were measured with a transmission electron microscope, and the particle volume of the single hollow particles (V _HP ) and the hollow volume could be calculated from the hollow volume (average value of 5 grains), which agreed well with the hollow ratio obtained by the above method.

The results are shown in Table 1 below.
* 1: Average particle diameter laser diffraction scattering method (device name: Fiber-Optics Particle Analyzer,
Measured with model number FPAR-1000, Otsuka Electronics Co., Ltd.
* 2: Average particle laser scattering method (device name: Laser Scattering Particle size
Measured with Distribution Analyzer, HORIBA, Ltd.

(3) Evaluation of temperature shielding effect
<Base 1>
A phase A was prepared by thoroughly mixing 67.9 g of purified water, 0.1 g of benzalkonium chloride, 2.0 g of chlorohydroxyaluminum, and 5.0 g of concentrated glycerin. Separately, 10.0 g of decamethylcyclopentasiloxane was added to 5.0 g of polyoxyethylene hydrogenated castor oil and stirred well to prepare Phase B. Phase A was added to phase B, and the mixture was well stirred with a homogenizer and emulsified. Further, 5.0 g of silylated silicic acid and 5 g of polyalkyl acrylate were added thereto, and the mixture was stirred with a homogenizer to make a base 1.
This base is a base for antiperspirants.

  Formulation in which hollow particles 1 (Example 1) are mixed with Base 1 so that the final concentrations are 3% by weight, 4% by weight, 5% by weight, 5.5% by weight, 6% by weight, and 7.5% by weight, respectively. Were prepared (Examples 9 to 14). Base 1 was set as Comparative Example 2. Moreover, the formulation which mixed the solid particle | grains (comparative example 1) which is not hollow with the base material 1 so that it might become final concentration of 5 weight% was produced (comparative example 3).

  The temperature shielding effect was evaluated by the difference between the hot plate surface temperature measured as follows and the temperature of the preparation surface applied on the aluminum plate placed on the hot plate. That is, each preparation was applied to an aluminum plate with a width of 1 cm × 1 cm to a thickness of 0.18 mm, and each product was placed on a hot plate (Tech Jam Co., Ltd., Micro Heat Plate MP-10DMFH-PG). An aluminum plate coated with the preparation was placed. Thereafter, the plate surface temperature was set to automatically increase from 30 ° C. to 50 ° C. over about 8 minutes (temperature increased at a rate of about 2.5 ° C./min). After the start of temperature increase, the surface temperature of the hot plate was read from the temperature indicated on the instrument, and the surface temperature of the coating applied with the preparation was measured with a non-contact thermometer (HORIBA HORIBA, IT-545, radiation thermometer). Specifically, an aluminum plate coated with the example preparation (Examples 9 to 14) and the comparative example preparation (Comparative Examples 2 and 3) was placed on a hot plate, and the plate temperatures shown in Table 2 below were obtained. The temperature of the preparation application surface at that time was measured. The results are shown in Table 2 below and FIG. The numerical value in parentheses in the table is a temperature difference due to temperature shielding.

  As is apparent from Table 2 and FIG. 1, the difference between the hot plate surface temperature and the preparation surface temperature when the hot plate surface temperature was 33 to 37 ° C. was calculated. This formulation showed a temperature shielding effect in a dose-dependent manner. However, the temperature shielding effect was not observed in the preparation of Comparative Example 3 containing solid particles.

(4) Evaluation of makeup effect
<Base 2>
While stirring with a homogenizer, 29.35 g of water was slowly added dropwise to a mixed solution of 1.7 g of polyglycerol-3-disiloxy dimethicone, 10 g of diglycerin, 10 g of dimethylpolysiloxane, and 0.8 g of PCA dimethicone. While stirring 0.05 g of acrylic acid-alkyl methacrylate copolymer powder swollen with 5 g of water, 0.05 g of disodium ethylenediaminetetraacetate, 2 g of 1,2-pentanediol, and 0.05 g of triethanolamine with a homogenizer, Base 2 was added.
This base is a base that can be used for many purposes.

The hollow particles 1 mixed with the base 2 so as to have a final concentration of 5% by weight (Example 15) were applied to the right cheek of a 59-year-old man so as to be ² μL / cm ² . In addition, the hollow particles 2 mixed with the base 2 so as to have a final concentration of 5% by weight (Example 16) were applied to the left cheek of this 59-year-old man so as to be ² μL / cm ^2. did. Before and after application, use VISIA (made by CANFIELD) to measure the number of spots (index value), the number of ultraviolet spots (index value), the number of red parts (index value), and the number of pores (index value) did.
On the next day, the base 2 (Comparative Example 4) was also treated with the male right cheek and left cheek (Examples 14 and 15 on the previous day) in the same manner as in the preparations of Examples 15 and 16. The same evaluation item before and after application was measured.
The results are shown in Tables 3 and 4 below.

As is apparent from Tables 3 and 4, the preparations of Example 15 and Example 16 have a make-up effect that makes the skin look beautiful by making spots, UV spots, red parts, and pores inconspicuous. It was.

(5) Evaluation of Color Difference of Hollow Particles Hollow particle 1 and hollow particle 2 and hollow particles containing water in the hollow part (Example 8) were mixed with base 2 so that the final concentration was 5% by weight, respectively. The preparations of Example 15, Example 16, and Example 17 were prepared.
The preparations of Example 15, Example 16, Example 17, and Comparative Example 4 (Base 2) were applied to BioSkinPlate (FR40: Burrax Co., Ltd.) so as to be ² μL / cm ² , respectively. ΔE, ΔL, Δa, Δb were determined using a meter (Minolta CR-221).
The L value (ΔL) is a value related to bidirectionality between black and white, and is a value used as an index of the whitening effect. In addition, the a value (Δa) is a value related to bidirectionality between red and green, and the b value (Δb) is a value related to bidirectionality between yellow and blue.
ΔE is a value calculated from ΔL, Δa, and Δb according to the following formula, and is considered to be an index indicating the effect of makeup.
ΔE = X ^1/2 (where X = ΔL ² + Δa ² + Δb ² )
The results are shown in Table 5 below. The numerical values in Table 5 are average values measured three times (n = 3).

The closer the ΔL value is to 0, the more black it is, and the closer it is to 100, the white the color is.
Δa indicates that the larger the negative value (−), the more greenish, and the larger the positive value (+), the more reddish.
Further, Δb indicates that the greater the negative value (−), the more bluish, and the greater the positive value (+), the more yellowish.
The ΔL value represents the lightness (brightness, fairness) of the skin as the value increases. The Δa value represents that the smaller the value, the less reddish skin (white). Further, the Δb value represents the skin color of a person with a sense of transparency as the numerical value is smaller.

As is apparent from Table 5, in BioSkinPlate to which the preparations of Example 15 and Example 16 were applied, the skin color was light (ΔL> 0), less red (Δa <0), and transparent (Δb <0> A result was obtained.
In addition, the BioSkinPlate to which the preparation of Example 17 was applied was less effective in all factors than the BioSkinPlate to which the preparations of Example 15 and Example 16 were applied, but Δb <0, and it is clear that the BioSkinPlate has a transparency. became. On the other hand, BioSkinPlate to which the preparation of Comparative Example 4 (Base 2) was applied had Δb> 0 and a skin state with a low transparency.
From this, it has been clarified that the hollow particles have the effect of brightening the skin, making the skin light-skinned, and imparting a transparency to the skin.

(6) Evaluation of UV protection ability of hollow particles Commercially available sunscreen preparation (Rohto Pharmaceutical Co., Skin Aqua SPF + 24) using an applicator (manufactured by Nippon Cedars Service) on a quartz plate. PA2 + and the ultraviolet absorbers incorporated in the preparation were ethyl hexyl methoxycinnamate, ethyl hexyl triazone, and hexyl diethylaminohydroxybenzoyl benzoate) at a thickness of 8 μm to prepare a coating film.
In addition, preparations were prepared by blending hollow particles 1 in the above-mentioned commercially available sunscreen preparations to final concentrations of 1% by weight, 5% by weight, and 10% by weight, respectively, and an applicator (Japan) Using a seeder service, a coating film was produced at a thickness of 8 μm.
As a reference example, a preparation in which the hollow particles 1 were blended with the base 2 so as to have a final concentration of 5% by weight was also prepared, and a coating film was similarly prepared.
The ultraviolet transmittance of each film was measured using a UV-VIS spectrometer (Shimadzu UV-2450 UV-VIS Spectrometer). The results are shown in FIG.
As shown in FIG. 2, the UV transmittance was reduced in a dose-dependent manner by blending the hollow particles 1 with a commercial screen in the wavelength range of 290 to 350 nm including UVA and UVB. On the other hand, what mixed the hollow particle 1 with the base material 2 which does not contain a ultraviolet absorber or a ultraviolet-ray scattering agent had very high UV transmittance.
Therefore, by blending hollow particles with a sunscreen agent containing an ultraviolet absorber and / or an ultraviolet scattering agent, the light transmission is attenuated, and the protection factor (SPF (Sun Protection Factor) or PA of the composition is reduced. (Protection Grade of UVA)) is significantly enhanced (Buster effect).

(7) Evaluation of Soft Focus Effect of Hollow Particles The preparations of Example 15 and Comparative Example 4 were applied to artificial skin (manufactured by Idemitsu Techno Fine Co., Ltd., trade name: Technofan), respectively, and a microscope ( The artificial skin surface was photographed using a VHX-1000 digital microscope (manufactured by Keyence Corporation).
The results are shown in FIG. As apparent from FIG. 3, the unevenness on the surface of the artificial skin became inconspicuous by blending the hollow particles. It is considered that the fine particles enter the recesses and the soft focus effect of the fine particles.

(8) Evaluation of angle dependency of light scattering effect of hollow particles The preparations of Example 15, Example 16, and Comparative Example 4 were respectively applied to artificial skin (trade name: Technofan, manufactured by Idemitsu Technofine Co., Ltd.). Then, using a microscope, the artificial skin surface was photographed from an angle of 60 degrees with respect to the artificial skin surface, that is, a direction inclined by 30 degrees from the light irradiation direction.
The results are shown in FIG. As is clear from FIG. 4, the surface of the skin coated with the preparation of Comparative Example 4 (Base 2) became dark when tilted 30 degrees from the light irradiation direction. On the other hand, the skin to which the preparations of Example 15 and Example 16 were applied suppressed the decrease in surface brightness even when observed from a direction inclined 30 degrees from the light irradiation direction.

(9) Formulation example Commercially available sunscreen agent (manufactured by Rohto Pharmaceutical Co., Ltd., Skin Aqua SPF + 24, PA2 +, UV absorber blended in the preparation is ethylhexyl methoxycinnamate, ethylhexyltriazone, hexyl diethylaminohydroxybenzoylbenzoate) In this manner, 0.1 g of the hollow particles 1 was thoroughly kneaded into 1.9 g to prepare a sunscreen agent containing 5% by weight of the hollow particles at a final concentration.
Similarly, a sunscreen agent containing 1% by weight or 10% by weight of hollow particles was prepared.

(10) Stability Evaluation of Formulation Containing Hollow Particles In base 2, hollow particles 1 and a commercially available weakly acidic cation exchange resin (amberlite IRC76 having —COONa in which the hydrogen of the carboxyl group is replaced with sodium) The preparations of Example 15 and Comparative Example 5 were prepared by mixing the organocore combination)) to a final concentration of 20% by weight.
The viscosity of the base 2 and the viscosity of the preparation immediately after mixing the hollow particle 1 or Amberlite IRC76 with the base 2 were measured using a rotational viscometer (RD-80L, rotor No. M-2, Toyo Sangyo Co., Ltd.) (Measured 1 minute after the start of measurement). Viscosity change rate by particle | grain mixing | blending was computed according to the following formula.

Viscosity change rate (%)
= [(Viscosity of formulation after blending particles) / (Viscosity of base 2)] x 100

The results are shown in Table 6. Formulation of the hollow particles 1 increased the viscosity of the preparation (Example 15). This is a result of a physical action due to the blending of hollow particles that are powders, and is a phenomenon that occurs regardless of the base used. On the other hand, the viscosity of the preparation was significantly reduced in a short time by the incorporation of Amberlite IRC76 (Comparative Example 5).
From this, when a component having an ionic functional group on the polymer surface is blended with a preparation containing a cationic component or an anionic component, the viscosity decreases due to the formation of a salt, making it impossible to prepare a desired formulation. It was found that even when hollow particles having no ionic functional group were added to the molecular surface, the viscosity of the preparation was not lowered. Thus, in preparing a preparation containing a cationic component or an anionic component and hollow particles, a stable preparation can be prepared by using the hollow particles of the present invention.

Since the composition for external use of this invention contains the hollow polymer particle which hardly has an ionic functional group derived from a monomer, it can be made into a weak acidic area | region preferable as an external preparation. Moreover, the component which has an ionic functional group can be mix | blended without a restriction | limiting.
In addition, since the hollow polymer particles exert a heat shielding effect, an ultraviolet shielding enhancement effect, a skin hiding effect, and an effect of imparting transparency to the skin without giving irritation to the skin, It is suitable for blending into pharmaceuticals, quasi drugs and other miscellaneous goods.

Claims (15)

  A composition for external use comprising hollow polymer particles, the hollow polymer particles being obtained by polymerization of a monomer in which the ratio of the monomer having an ionic functional group is 5 mol% or less.   The external use according to claim 1, wherein the polymer constituting the hollow polymer particles is a polymer or copolymer of at least one monomer selected from the group consisting of a monovinyl aromatic monomer and a (meth) acrylic acid ester monomer. Composition.   The external composition according to claim 1 or 2, wherein the hollow polymer particles have an average particle size of 10 to 30000 nm.   The composition for external use according to any one of claims 1 to 3, wherein the content of the hollow polymer particles is 0.05 to 50% by weight based on the total amount of the composition.   Furthermore, the composition for external use in any one of Claims 1-4 containing the component which has an ionic functional group.   Furthermore, the external composition in any one of Claims 1-5 containing the at least 1 sort (s) of ultraviolet-ray shielding agent chosen from the group which consists of an organic ultraviolet absorber and an inorganic ultraviolet scattering agent.   It is an object for temperature shielding, The composition for external use in any one of Claims 1-6.   The composition for external use according to any one of claims 1 to 6, which is for ultraviolet shielding.   The composition for external use according to any one of claims 1 to 6, which is for makeup.   A temperature shielding agent comprising hollow polymer particles.   The temperature shielding agent according to claim 10, wherein the polymer of the hollow polymer particles is obtained by polymerization of a monomer having a proportion of a monomer having an ionic functional group of 5 mol% or less.   A makeup agent comprising hollow polymer particles.   The makeup agent according to claim 12, wherein the polymer of the hollow polymer particles is obtained by polymerization of a monomer having a ionic functional group-containing monomer ratio of 5 mol% or less.   An ultraviolet shielding effect enhancer comprising hollow polymer particles.   15. The ultraviolet shielding effect enhancer according to claim 14, wherein the polymer of the hollow polymer particles is obtained by polymerization of a monomer having a ratio of the monomer having an ionic functional group of 5 mol% or less.