JP2018100250A - External composition for skin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an external composition for skin excellent in ultraviolet absorbency.SOLUTION: There is provided an external composition for skin which comprises (A) an urethane-(meth)acrylic composite resin and (B) at least one selected from an ultraviolet absorber and an ultraviolet scattering agent. There is provided an external composition for skin in which the outer layer part of the component (A) is an urethane resin and the inner layer part of the is a (meth)acrylic resin. There is provided an external composition for skin in which the urethane resin preferably is a carboxyl group-containing polyurethane and the (meth)acrylic resin preferably is an alkyl acrylate copolymer. There is provided the external composition for skin which is a sunscreen composition. There is provided an external composition for skin in which the composition has ability of enhancing an ultraviolet absorption spectrum and has a good use feeling.SELECTED DRAWING: None

Description

  The present invention relates to an external composition for skin.

  Ultraviolet rays include ultraviolet A waves (UV-A, 315 to 400 nm), ultraviolet B waves (UV-B, 280 to 315 nm), and others. Of these, UV-A is less likely to cause sunburn, but recent studies have shown that it is greatly involved in the formation of spots and wrinkles. That is, UV-A has a long wavelength and reaches deep into the skin, and has an effect of, for example, denaturing collagen.

  UV-B has a short wavelength and is blocked by the ozone layer and clouds as compared with UV-A, and the amount reaching the ground is a small amount of about 10% of the total amount of ultraviolet rays. However, UV-B is strong in energy and damages cells on the skin surface or causes inflammation, which may cause skin cancer and spots.

  Thus, as the influence of ultraviolet rays on the skin becomes clear, there is an increasing demand for sunscreen compositions with a high ultraviolet blocking effect, and various skin external compositions have been proposed (Patent Document 1).

JP2015-17080 A

  An object of this invention is to provide the skin external composition which has ultraviolet-ray absorption ability.

  As a result of intensive studies to solve this problem, the present inventors have at least one selected from the group consisting of (A) a urethane- (meth) acrylic composite resin, (B) an ultraviolet absorber, and an ultraviolet scattering agent. By using the seed, it was found that a composition for external use having a high ultraviolet absorption spectrum enhancing ability was obtained, and the present invention was completed.

That is, the present invention provides the following external composition for skin.
Item 1.
(A) urethane- (meth) acrylic composite resin;
(B) at least one selected from the group consisting of ultraviolet absorbers and ultraviolet scattering agents,
A composition for external use on the skin, comprising:
Item 2.
Item 2. The external composition for skin according to Item 1, wherein the outer layer portion of the component (A) is formed of a urethane resin matrix, and the inner layer portion of the composite resin is formed of a (meth) acrylic resin matrix.
Item 3.
Item 3. The external composition for skin according to Item 1 or 2, wherein the outer layer portion of the component (A) is a urethane resin, and the inner layer portion of the composite resin is a (meth) acrylic resin.
Item 4.
Item 4. The external composition for skin according to any one of Items 1 to 3, wherein the urethane resin in the component (A) is a carboxyl group-containing polyurethane.
Item 5.
Item 5. The external composition for skin according to any one of Items 1 to 4, wherein the (meth) acrylic resin in the component (A) is an alkyl acrylate copolymer.
Item 6.
Item 6. The external composition for skin according to any one of Items 1 to 5, wherein the component (A) has an average particle size of 5 nm to 2000 nm.
Item 7.
Item 7. The external composition for skin according to any one of Items 1 to 6, further comprising (C) an ester oil having three or more ester groups in the molecule.
Item 8.
Item 8. The external composition for skin according to any one of Items 1 to 7, wherein the (B) ultraviolet absorber is an oil-soluble ultraviolet absorber.
Item 9.
Item 10. The external composition for skin according to any one of Items 1 to 8, wherein the content of the component (B) is 0.01 to 50 w / w% with respect to the total amount of the composition.
Item 10.
Item 10. The external composition for skin according to any one of Items 1 to 9, which is a sunscreen composition.

  INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide an external composition for skin that has an ability to enhance an ultraviolet absorption spectrum and has a good feeling of use.

FIG. 1 is a graph showing the results of an ultraviolet protective effect test of the composition for external skin of the present invention and the composition for external skin of a comparative example. FIG. 2 is a measurement result of an ultraviolet absorption spectrum of the composition for external skin of the present invention and the composition for external skin of a comparative example. The unit of the vertical axis is Absorbance (Abs.). FIG. 3 is a graph showing the results of the ultraviolet protective effect test of the composition for external use of the present invention and the composition for external use of the comparative example. FIG. 4 is a graph showing the results of the ultraviolet protective effect test of the composition for external use of the present invention and the composition for external use of the comparative example. FIG. 5 is a measurement result of an ultraviolet absorption spectrum of the composition for external skin of the present invention and the composition for external skin of a comparative example. The unit of the vertical axis is Absorbance (Abs.). FIG. 6 is a graph showing the results of the ultraviolet protective effect test of the composition for external use of the present invention and the composition for external use of the comparative example. FIG. 7 shows the measurement results of the ultraviolet absorption spectrum of the composition for external use of the present invention and the composition for external use of the comparative example. The unit of the vertical axis is Absorbance (Abs.). FIG. 8 is a graph showing the results of a residual test after water treatment for the external composition for skin of the present invention and the external composition for comparison. FIG. 9 is a graph showing the results of a secondary adhesion evaluation test for the composition for external skin of the present invention and the composition for external skin of a comparative example.

  In the present specification, the unit of content “w / w%” is synonymous with w / w% of “g / 100 g”.

  In this specification, “oil-soluble” means that the solubility in water is 1 w / w% or less, and “water-soluble” means that the solubility in water is greater than 1 w / w%.

  As used herein, the “skin external composition” refers to an external composition that can be applied to the skin. Although not particularly limited, the composition for external use includes a sunscreen composition having an ability to absorb ultraviolet rays. Here, the “sunscreen composition” includes, for example, a form that clearly shows sunscreen in a product, but if it is a composition for external use for skin having such a function even if there is no indication, it is referred to in this specification. Included in “sunscreen composition”.

  The external composition for skin of the present invention contains (A) a urethane- (meth) acrylic composite resin and (B) at least one selected from the group consisting of an ultraviolet absorber and an ultraviolet scattering agent, It is a composition.

[(A) Urethane- (meth) acrylic composite resin]
In this specification, (A) urethane- (meth) acrylic composite resin refers to a composite resin (component) composed of a urethane resin and a (meth) acrylic resin. In this specification, when the component (A) is in the form of particles such as an emulsion, the outer layer portion refers to the outside (surface layer side) portion (outer shell portion, etc.) of the particle and the like in the core-shell structure. It may be a shell part. In the present specification, the inner layer portion means the inner portion (center layer side) portion (inner shell portion, etc.) of the particle or the like when the component (A) is in the form of particles such as an emulsion. It may be a core part in the structure.

  In the present specification, “(meth) acryl” means “acryl or methacryl”.

  (A) As a urethane- (meth) acrylic composite resin, the outer layer portion of the component (A) is formed of a urethane resin matrix, and the inner layer portion of the composite resin is formed of a (meth) acrylic resin matrix. Those are preferred. The urethane resin matrix refers to a layer in which a urethane resin component is present as a main component, and may include a case where another resin (for example, (meth) acrylic resin) is partially mixed. . Moreover, the sea part in the case where the urethane resin component forms a sea-island type phase separation structure may be used. The (meth) acrylic resin matrix refers to a layer in which a (meth) acrylic resin component is present as a main component, including a case where a part of other resin (for example, urethane resin) is mixed. May be. Moreover, the sea part in the case where the (meth) acrylic resin component forms a sea-island type phase separation structure may be used.

  In the specification of the present application, “existing as a main component” means, for example, that it is contained in an amount of 50% by weight or more, even if it is contained in an amount of 60% by weight or more. It may be 70% by weight or more, 80% by weight or more, 90% by weight or more, 95% by weight or more. It may be included 98% by weight or more, or 99% by weight or more. Moreover, when using 3 or more types of resin, the thing with the largest usage-amount is said.

  The (A) urethane- (meth) acrylic composite resin is preferably one in which the outer layer part of the component (A) is a urethane resin and the inner layer part of the composite resin is a (meth) acrylic resin. Further, the outer layer portion and the inner layer portion may be continuous, and may further have a single layer or a plurality of layers therebetween. Moreover, in the (A) urethane- (meth) acrylic composite resin, the urethane resin part and the (meth) acrylic resin part are, for example, intermolecular force, hydrophobic / hydrophilic action, ionic bond, etc. The composite resin may be formed by a non-covalent bond, or both may be bonded by a covalent bond.

  Examples of the (A) urethane- (meth) acrylic composite resin include an emulsion polymer, a composite resin obtained by previously polymerizing a urethane resin and a (meth) acrylic resin, and a dendrimer. The component (A) is preferably an emulsion polymer.

  As the (A) urethane- (meth) acrylic composite resin in the present invention, for example, a urethane- (meth) acrylic composite resin emulsion is preferably used. When a urethane- (meth) acrylic composite resin emulsion is used as the component (A), it is preferably prepared or used as a urethane- (meth) acrylic composite resin aqueous dispersion.

  When the urethane- (meth) acrylic composite resin aqueous dispersion is used, for example, a raw material emulsion in which one or more kinds of (meth) acrylic monomers are dispersed in advance is sequentially added into a reaction vessel in which an aqueous medium is present. Or by adding continuously, it can obtain by carrying out emulsion polymerization of the said 1 type or multiple types of (meth) acrylic-type monomer in presence of a urethane resin.

  The (meth) acrylic monomer is a monomer having a (meth) acrylic group. Especially, as a monomer used as a main component, it is preferable to use the monofunctional monomer which has a well-known (meth) acryl group.

  In addition, the main component regarding a monomer means the thing with the largest usage-amount among the usage-amount exceeding 50% of the total monomer amount, or when using 3 or more types of monomers.

  Among the above (meth) acrylic monomers, examples of the (meth) acrylic acid alkyl ester include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, ( (Meth) butyl acrylate, (meth) acrylate isobutyl, (meth) acrylate s-butyl, (meth) acrylate t-butyl, (meth) acrylate pentyl, (meth) acrylate s-pentyl, (meth) 1-ethylpropyl acrylate, 2-methylbutyl (meth) acrylate, isopentyl (meth) acrylate, t-pentyl (meth) acrylate, 3-methylbutyl (meth) acrylate, neopentyl (meth) acrylate, (meta ) Hexyl acrylate, 2-methylpentyl (meth) acrylate, (meth) acrylic 4-methylpentyl, 2-ethylbutyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) acrylate, 2-heptyl (meth) acrylate, (meth) acrylic acid 3 -Heptyl, octyl (meth) acrylate, 2-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, 3,3 (meth) acrylate , 5-trimethylhexyl, decyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, eicosyl (meth) acrylate, (meth ) Docosyl acrylate, Tetracosyl (meth) acrylate, (Meth) Ac Le methyl cyclohexyl, (meth) acrylic acid isobornyl (meth) norbornyl acrylate, (meth) acrylate, benzyl (meth) phenethyl acrylate and the like. Among them, (meth) acrylic acid alkyl esters having 1 to 24 carbon atoms in the alkyl group, particularly (meth) acrylic acid alkyl esters having 1 to 8 carbon atoms in the alkyl group are preferred. it can.

  These monomers may be used alone or in combination of two or more.

  In addition to the (meth) acrylic monomer, the raw material emulsion containing the (meth) acrylic monomer may contain another monomer having a polymerizable double bond. Examples of the other monomers include ester group-containing vinyl monomers, styrene derivatives, and vinyl ether monomers.

  Examples of the ester group-containing vinyl monomer include hydrophobicity such as (meth) acrylic acid lower alkyl esters having 1 to 8 carbon atoms, vinyl acetate, diethyl maleate, dibutyl maleate, and vinyl (meth) acrylate. Examples thereof include vinyl monomers, fluoroalkyl esters of (meth) acrylic acid, and unsaturated group-containing macromonomers such as radically polymerizable unsaturated group-containing silicon macromonomers.

  Examples of the styrene derivative include styrene, α-methylstyrene, p-methylstyrene, vinyltoluene and the like. Furthermore, examples of the vinyl ether monomer include vinyl methyl ether and vinyl cyclohexyl ether.

  The (meth) acrylic monomer is preferably selected so that the glass transition temperature (Tg) of the polymer obtained from the (meth) acrylic monomer to be used is -80 ° C or higher. It is more preferable to select so as to be above, it is still more preferable to select to be -40 ° C or higher, even more preferable to select to be -20 ° C or higher, so as to be 0 ° C or higher. It is particularly preferred to select. On the other hand, the upper limit of the glass transition temperature (Tg) is preferably 70 ° C. or lower, more preferably 60 ° C. or lower, still more preferably 50 ° C. or lower, still more preferably 30 ° C. or lower, and particularly preferably 10 ° C. or lower. By setting it to the glass transition temperature or lower, it is possible to enhance the ultraviolet absorption ability more effectively, increase the residual rate after water treatment, and / or suppress secondary adhesion. The glass transition temperature (Tg) can be measured using a differential scanning calorimeter as shown in the test examples described later.

  The urethane resin is a polymer obtained by reacting a diol component and a polyvalent isocyanate compound, has an average particle size and molecular weight that can be mixed with the (meth) acrylic monomer, and is water-dispersible. Is preferred.

  A known polyurethane resin can be used as the urethane resin. Examples of the urethane resin include polyurethane-1, polyurethane-4, polyurethane-2, polyurethane-6, polyurethane-7, polyurethane-8, polyurethane-9, polyurethane-10, polyurethane-11, polyurethane-14, and polyurethane-15. , Polyurethane-21, polyurethane-23, polyurethane-24, polyurethane-26, polyurethane-27, polyurethane-32, polyurethane-33, polyurethane-34, polyurethane-35, polyurethane-39, polyurethane-40, polyurethane-42, polyurethane -43, polyurethane-44, polyurethane-45, polyurethane-46, polyurethane-48, polyurethane-51, polyurethane-59, polyurethane-62, polyurethane-64, etc. It is possible. Polyurethane-1 is known as a copolymer composed of isophthalic acid, adipic acid, hexylene glycol, neopentyl glycol, dimethylolpropionic acid, and isophorone diisocyanate. Polyurethane-4 is known as a copolymer comprising PPG-17, PPG-34, isophorone diisocyanate, and dimethylolpropionic acid. The urethane resin as described above may be synthesized and used, or a commercially available product (for example, a commercially available urethane aqueous emulsion) may be used as it is. The said urethane resin may be used independently, and may mix and use 2 or more types.

  The blending ratio of the diol component and the polyvalent isocyanate compound in the urethane resin is not particularly limited, but the equivalent ratio is diol component: polyvalent isocyanate compound = 1: 0.5 to 2.5. It is preferable that the ratio is 1: 1 to 2.

  Although the weight average molecular weight of the said urethane resin is not specifically limited, For example, it is preferable that it is 500 or more, and it is more preferable that it is 1000 or more. The upper limit of the weight average molecular weight is not particularly limited, for example, preferably 500,000 or less, and more preferably 100,000 or less.

  For example, by dispersing the urethane resin in an aqueous medium to be described later to produce a urethane resin emulsion, when the (meth) acrylic monomer mixture is added to the system, it is suitably used as an aqueous dispersion. Can do. The aqueous dispersion can be supplied as it is to the emulsion polymerization reaction of the (meth) acrylic monomer, and the reaction system during the emulsion polymerization can be further stabilized, and the stabilized urethane- (meth) acrylic system. A dispersion of the composite resin emulsion can be obtained.

  When producing the urethane resin emulsion, it is preferable to introduce a carboxyl group into the urethane resin. Thus, by introducing a carboxyl group into a urethane resin, the effect of the present invention can be achieved more effectively. If necessary, an emulsifier can be used to further stabilize the emulsion.

  As the emulsifier, anionic, cationic, nonionic, and amphoteric surfactants can be used. These may be used singly or in combination of two or more. Although the addition amount in the case of using an emulsifier is not specifically limited, As an example, it can be 0.01 to 10 weight%, Preferably it can be about 0.1 to 5 weight%.

  The average particle size of the aqueous dispersion of the urethane resin emulsion is preferably 5 nm or more, may be 30 nm or more, and may be 50 nm or more. When the thickness is less than 5 nm, the viscosity of the aqueous dispersion increases, and the fluidity may decrease. On the other hand, it is preferably 2000 nm or less, and may be 1500 nm or less, or 1000 nm or less. If it exceeds 2000 nm, the average particle size of the resulting urethane- (meth) acrylic composite resin increases, and there is a risk of separation / sedimentation during storage. Examples of the urethane resin emulsion include the above-described commercially available water-dispersible urethane resins.

  As the aqueous medium, water or a mixed solution of water and an organic solvent compatible with water such as methanol or ethanol can be used. Of these, water is preferably used.

  Although the solid content rate of the said urethane resin emulsion is not specifically limited, For example, it is preferable that it is 10 weight% or more, and it is more preferable that it is 25 weight% or more. If the amount is less than 10% by weight, the concentration of the dispersion with the (meth) acrylic monomer is lowered, and the concentration of the resulting composite resin dispersion may be lowered. The upper limit is not particularly limited as long as the effect of the present invention is exhibited, but it is preferably 70% by weight or less, and more preferably 60% by weight or less. If it exceeds 70% by weight, the viscosity of the dispersion liquid tends to increase, and the handling and usability on the preparation tends to be poor.

  In addition, when the production | generation of the said urethane resin is performed in organic solvent environment, it is preferable to carry out phase inversion from the organic solvent to the said aqueous medium, and to remove an organic solvent.

  For example, as described above, the aqueous urethane- (meth) acrylic composite resin dispersion can be added in the presence of the urethane resin by sequentially or continuously adding the raw emulsion to a reaction vessel in which an aqueous medium is present. Can be obtained by emulsion polymerization of one or more (meth) acrylic monomers.

  Examples of the raw material emulsion include an emulsion of a (meth) acrylic monomer obtained by emulsifying and dispersing one or more kinds of (meth) acrylic monomers in an aqueous medium. The raw material emulsion first added to the reactor contains a urethane resin. By using the raw material dispersion as an emulsion, it is possible to more easily disperse the (meth) acrylic monomer in the aqueous medium in the emulsion polymerization reaction described below, and to stabilize the dispersion.

  When the above dispersion is performed, an emulsifier can be used in order to improve dispersibility, but it may be performed without using an emulsifier as appropriate. As the emulsifier, an emulsifier similar to the above-mentioned emulsifier can be used.

  It is preferable to add an emulsifier in the aqueous medium in advance, because the emulsion polymerization reaction system can be stabilized. As the emulsifier used here, the same ones as described above can be used.

  The amount of the emulsifier contained in the aqueous medium in the reaction vessel is not particularly limited, but is preferably 0.05% by weight, preferably 0.1% by weight or more based on the (meth) acrylic monomer. It is more preferable. The upper limit of the amount of the emulsifier contained in the aqueous medium in the reaction vessel is also not particularly limited, but is preferably 10% by weight or less and preferably 5% by weight or less with respect to the (meth) acrylic monomer. It is more preferable.

  In the emulsion polymerization reaction, it is preferable from the viewpoint of reaction efficiency to use a polymerization initiator. Examples of the polymerization initiator include azo initiators such as azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyanovaleric acid, and persulfuric acid such as sodium persulfate, potassium persulfate, and ammonium persulfate. Use of organic peroxide initiators such as salt initiators, t-butyl hydroperoxide, dilauroyl peroxide, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxypivalate, etc. it can. Redox initiators obtained by combining these peroxide initiators (including persulfate initiators) and reducing agents are also preferred because they have good reactivity at low temperatures. Examples of the reducing agent include ascorbic acid, erythorbic acid, thiourea dioxide, Rongalite, or metal sulfite. The amount of the polymerization initiator used is about 0.01 to 5% by weight, preferably about 0.1 to 2% by weight, based on the total amount of the (meth) acrylic monomer and the other monomers. Can do.

  The polymerization initiator can be added by the various methods described above, and the polymerization initiator is preferably added continuously over a certain period of the reaction. For example, it is preferably added continuously for at least 50% or more of the reaction period, and more preferably continuously added for 70% or more. Thus, by adding continuously over a fixed period, a polymerization reaction can be advanced stably.

  The temperature of the reaction system in the emulsion polymerization is not particularly limited. As an example, the temperature of the reaction system in the emulsion polymerization can be 10 to 80 ° C, preferably 20 to 75 ° C, and more preferably 30 to 70 ° C. The above polymerization is usually almost completed by maintaining the temperature at about 40 to 70 ° C. for about 30 minutes to 3 hours after the end of heat generation. Thereby, the aqueous dispersion of urethane- (meth) acrylic composite resin is obtained.

  The content of the urethane resin contained in the composite resin in the urethane- (meth) acrylic composite resin aqueous dispersion is, for example, preferably 5% by weight or more, and preferably 10% by weight or more. Although the upper limit of the said content is not specifically limited, 85 weight% or less is preferable and 80 weight% or less is more preferable.

  The average particle size of the composite resin in the urethane- (meth) acrylic composite resin aqueous dispersion is preferably 5 nm or more, may be 30 nm or more, and may be 50 nm or more. If it is less than 5 nm, the emulsion has a high viscosity, and the stability and usability of the preparation tend to be poor. On the other hand, the upper limit of the average particle diameter is preferably 2000 nm (2.0 μm), may be 1500 nm or less, and may be 1000 nm or less. When it is larger than 1500 nm, the stability of the resulting composite resin aqueous dispersion may be lowered.

  In addition, the measurement of the said average particle diameter measurement can be performed as follows, for example. The aqueous urethane- (meth) acrylic composite resin dispersion is diluted 10,000 times with ion-exchanged water filtered through a filter (manufactured by Advantech: DISMIC-25cs). It can be obtained by filling the cell for measurement and measuring the average particle size by a dynamic light scattering method (Otsuka Electronics Co., Ltd .: DLS-8000 is used). In addition, the average particle size of the urethane aqueous dispersion can be determined by the same method.

  The urethane- (meth) acrylic composite resin emulsion is preferably an anionic ionomer emulsion.

  Moreover, it is preferable that the urethane resin in the said (A) component is a carboxyl group-containing polyurethane.

  Further, the (meth) acrylic resin in the component (A) is preferably an alkyl acrylate copolymer (also referred to as an alkyl acrylate copolymer).

  As the urethane- (meth) acrylic composite resin, for example, an aqueous urethane emulsion product may be used as it is. Examples of the urethane aqueous emulsion include products such as Rikabond FS-1000, Ricabond FHT-2000, and Ricabond SS-3000 manufactured by Japan Coating Resin Co., Ltd.

  In the external composition for skin of the present invention, the total content of the component (A) relative to the total amount of the external composition for skin is appropriately set depending on the balance with other components. The total content of component (A) is preferably 0.001 w / w% or more, more preferably 0.01 w / w% or more, still more preferably 0.1 w with respect to the total amount of the composition for external use on the skin. / W% or more, most preferably 0.2 w / w% or more. The total content of the component (A) is preferably 20 w / w% or less, more preferably 10 w / w% or less, still more preferably 5 w / w% or less, most preferably with respect to the total amount of the composition for external use on the skin. Is 3 w / w% or less. The total content of the component (A) is preferably 0.001 w / w% to 20 w / w%, more preferably 0.01 w / w% to 10 w / w%, based on the total amount of the composition for external use on the skin. More preferably, it is 0.1 w / w%-5 w / w%, Most preferably, it is 0.2 w / w%-3 w / w%.

[(B) UV absorber or UV scattering agent]
In this specification, an ultraviolet absorber means a compound (component) having a property of absorbing ultraviolet rays.

As the ultraviolet absorber, for example,
(A) 2-ethylhexyl paramethoxycinnamate (also called ethyl hexyl methoxycinnamate), isopropyl methoxycinnamate, 2-ethylhexyl α-cyano-β-phenylcinnamate (octocrylene), diisopropyl methylcinnamate, trimethoxysilica Methyl bis (trimethylsiloxy) silylisopentyl cinnamate, methyl 2,5-diisopropylcinnamate, diparamethoxycinnamate mono-2-ethylhexanoate glyceryl, cinoxalate, DEA methoxycinnamate, ferulic acid, and methoxycinnamon Cinnamic acid derivatives such as isoamyl acid;
(B) Para-aminobenzoic acid (hereinafter abbreviated as “PABA”), ethyl PABA, ethyl-dihydroxypropyl PABA, ethylhexyl-dimethyl PABA, glyceryl PABA, PEG-25PABA, paradimethylaminobenzoic acid amyl, paradimethylamino Benzoic acid derivatives such as 2-ethylhexyl benzoate and 2- [4- (diethylamino) -2-hydroxybenzoyl] benzoic acid hexyl ester (also referred to as diethylaminohydroxybenzoyl hexyl benzoate);
(C) salicylic acid derivatives such as homosalate, ethylhexyl salicylate, TEA salicylate, ethylene glycol salicylate, and dipropylene glycol salicylate;
(D) Dihydroxybenzophenone (benzophenone-1), tetrahydroxybenzophenone (benzophenone-2), 2-hydroxy-4-methoxybenzophenone (benzophenone-3), hydroxymethoxybenzophenonesulfonic acid (benzophenone-4), dihydroxydimethoxybenzophenone (benzophenone) -5), dihydroxydimethoxybenzophenone (benzophenone-6), 2,2'-dihydroxy-4-methoxybenzophenone (benzophenone-8), and 3,3'-carbonylbis [4-hydroxy-6-methoxybenzenesulfonic acid Benzophenone derivatives such as disodium (benzophenone-9);
(E) benzylidene camphor derivatives such as 3-benzylidene camphor, 4-methyl benzylidene camphor, benzylidene camphor sulfonic acid, terephthalidene di camphor sulfonic acid, camphor benzalkonium methosulfate, and polyacrylamide methyl benzylidene camphor;
(F) Anisotriazine, diethylhexylbutamide triazone, 2,4,6-tris (diisobutyl-4′-aminobenzalmalonate) -s-triazine, 2,4-bis-[{4- (2- Ethylhexyloxy) -2-hydroxy} -phenyl] -6- (4-methoxyphenyl) -1,3,5-triazine (also known as bisethylhexyloxyphenol methoxyphenyl triazine), and 2,4,6 -Triazine derivatives such as tris [4- (2-ethylhexyloxycarbonyl) anilino] -1,3,5-triazine;
(G) phenylbenzimidazole derivatives such as phenylbenzimidazolesulfonic acid and disodium phenyldibenzimidazole tetrasulfonate;
(H) Drometrizol trisiloxane and 2,2′-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol] Phenylbenzotriazole derivatives;
(I) anthranyl derivatives such as menthyl anthranilate;
(J) imidazolidine derivatives such as 2-methoxyhexyl dimethoxybenzylidene oxoimidazolidine propionate;
(K) benzalmalonate derivatives such as dimethicodiethylbenzalmalonate;
(L) 4,4-diarylbutadiene derivatives such as 1,1-dicarboxy (2,2′-dimethylpropyl) -4,4-diphenylbutadiene; and (m) 4-tert-butyl-4′-methoxydi Dibenzoylmethane derivatives such as benzoylmethane;
Etc.

  In the present invention, the ultraviolet absorber is preferably an oil-soluble ultraviolet absorber. By using an oil-soluble ultraviolet absorber, the composition for external use of the skin of the present invention is resistant to sweat, prevents the sunscreen from falling off after application, and is well-suited for sebum in combination with other ingredients. The composition exhibits an excellent effect of easily forming a uniform film.

Here, as an oil-soluble ultraviolet absorber,
(A) 2-ethylhexyl paramethoxycinnamate, isopropyl methoxycinnamate, α-cyano-β-phenylcinnamate 2-ethylhexyl (octocrylene), diisopropyl methylcinnamate, methylbis (trimethylsiloxy) silylisopentyl trimethoxycinnamate, Methyl 2,5-diisopropylcinnamate, diparamethoxycinnamate mono-2-ethylhexanoate glyceryl, synoxate, DEA methoxycinnamate, ferulic acid, and isoamyl methoxycinnamate;
(B) PABA, ethyl PABA, ethyl-dihydroxypropyl PABA, ethylhexyl-dimethyl PABA, glyceryl PABA, PEG-25PABA, amyl paradimethylaminobenzoate, 2-ethylhexyl paradimethylaminobenzoate, and 2- [4- ( Diethylamino) -2-hydroxybenzoyl] benzoic acid hexyl ester;
(C) ethylhexyl salicylate, TEA salicylate, and dipropylene glycol salicylate;
(D) dihydroxydimethoxybenzophenone (benzophenone-6), (e) polyacrylamide methylbenzylidene camphor;
(F) Anisotriazine, diethylhexylbutamide triazone, 2,4,6-tris (diisobutyl-4′-aminobenzalmalonate) -s-triazine, 2,4-bis-[{4- (2- Ethylhexyloxy) -2-hydroxy} -phenyl] -6- (4-methoxyphenyl) -1,3,5-triazine and 2,4,6-tris [4- (2-ethylhexyloxycarbonyl) anilino] -1,3,5-triazine;
(H) Drometrizol trisiloxane;
(I) menthyl anthranilate;
(J) 2-ethylhexyl dimethoxybenzylideneoxoimidazolidinepropionate;
(K) Dimethicodiethylbenzalmalonate;
(L) 1,1-dicarboxy (2,2′-dimethylpropyl) -4,4-diphenylbutadiene; and (m) 4-tert-butyl-4′-methoxydibenzoylmethane;
Etc.

  These ultraviolet absorbers may be used alone or in combination of two or more. The ultraviolet absorber can be synthesized and used, or a commercially available product can be used as it is.

  In the composition for external use of the skin of the present invention, as an ultraviolet absorber, one or two or more of the above ultraviolet absorbers are used in order to reduce irritation and odor, or improve the feeling of use and solubility. A raw material to which a formulation modification such as inclusion in a capsule is added can also be used. Specifically, a UV absorber is encapsulated in a shell substantially composed of a polymer component composed of poly (ethylene glycol dimethacrylate), ethylene glycol dimethacrylate / divinylbenzene copolymer, or poly (divinylbenzene), Microcapsules (ultraviolet absorber-containing capsules) with an average particle size of 0.4 to 10 μm, or microcapsules (for example Eusolex) in which t-butylmethoxydibenzoylmethane is encapsulated in sol-gel silica glass and dispersed in water. UV-Pearls OB-S (trade name), Eusolex UV-Pearls OB-S2 (trade name); manufactured by Merck & Co., Inc.) and ethyl hexyl methoxycinnamate in sol-gel silica glass and dispersed in water Capsules (eg Eusolex U -Pearls 2292 (trade name), Eusolex UV-Pearls OMC (trade name); manufactured by Merck & Co., Ltd., and UV absorbers (octocrylene, diethylaminohydroxybenzoylbenzoic acid, ethylhexyl methoxycinnamate, paramethoxycinnamate 2- Ethylhexyl, t-butyl-methoxydibenzoylmethane, etc.) are encapsulated in silicone-resinized hydrolyzed silk (polysilicone-14) to form microcapsules with an average particle size of 2 μm and dispersed in water (for example, Silomasoma (registered) Trademark) ME, Siloma MEA, Siloma MEA (S), Siloma MEA (V), Siloma MEA (L), Siloma MFA (S), Siloma MFA (LS), Silazo a EP (S), Silasoma series (trade name) such as Silasoma REA (S); Seiwa Kasei Co., Ltd.), and others. These raw materials may be used alone or in combination of two or more.

  In the external composition for skin of the present invention, the total content of the ultraviolet absorber relative to the total amount of the external composition for skin is appropriately set depending on the balance with other components. The total content of the ultraviolet absorber is preferably 0.01 w / w% or more, more preferably 0.1 w / w% or more, and further preferably 0.5 w / w with respect to the total amount of the composition for external use on the skin. % Or more, even more preferably 1.0 w / w% or more, and most preferably 3.0 w / w% or more. Further, the total content of the component (B) is preferably 25 w / w% or less, more preferably 20 w / w% or less, and further preferably 15 w / w% or less with respect to the total amount of the composition for external use on the skin. . The total content of component (B) is preferably 0.01 w / w% to 25 w / w%, more preferably 0.1 w / w% to 20 w / w%, based on the total amount of the composition for external use on the skin. More preferably, it is 0.5 w / w%-15 w / w%.

  The ultraviolet scattering agent in the present invention refers to a compound (component) having a property of scattering ultraviolet rays. Examples of the ultraviolet scattering agent include metal oxide powder and clay particles. For example, metal oxides such as zinc oxide, titanium oxide, iron oxide, cerium oxide, and zirconium oxide; silicate metals such as titanium silicate, zinc silicate, and cerium silicate; anhydrous silicic acid, and hydrous silica Examples thereof include silicic acids such as acids; inorganic compounds such as metals such as titanium, zinc and iron. Also, those inorganic compounds whose surfaces are coated with inorganic powders such as hydrous silicic acid, aluminum hydroxide, mica or talc, and those inorganic compounds are resin powders such as polyamide, polyethylene, polyester, polystyrene or nylon Examples thereof include those which are complexed with a body or whose surface is coated with them, and those whose inorganic compounds are treated with silicone oil or fatty acid aluminum salts or whose surfaces are coated with these. Although not limited, as the ultraviolet scattering agent, fine particle inorganic powder is preferably used, fine particle metal oxide is more preferable, and fine particle titanium oxide or fine particle zinc oxide is still more preferable. Furthermore, those fine particle inorganic powders whose surfaces are coated with inorganic powders such as hydrous silicic acid, aluminum hydroxide, mica or talc, or those fine particle inorganic powders with silicone oil or fatty acid aluminum salts, etc. What processed or coat | covered the surface and gave the hydrophobic treatment is preferable.

  The average particle diameter of the ultraviolet scattering agent is not particularly limited, but is preferably about 1 to 500 nm. Among these, the average particle diameter of the ultraviolet light scattering agent is preferably about 2 to 200 nm, more preferably about 3 to 100 nm, and further preferably about 5 to 50 nm, which are fine particles.

  These ultraviolet scattering agents may be used alone or in combination of two or more. The ultraviolet scattering agent can be synthesized and used, or a commercially available product can be used as it is.

  In the external composition for skin of the present invention, the total content of the ultraviolet light scattering agent with respect to the total amount of the external composition for skin can be, for example, 0.1 to 40 w / w%. 5 w / w% or more and 35 w / w% or less may be sufficient, and 1.0 w / w% or more and 30 w / w% or less may be sufficient.

  In the present invention, an ultraviolet absorber and an ultraviolet scattering agent can be used in combination. The composition for external use of the skin of the present invention preferably contains at least one ultraviolet absorber as the component (B) from the viewpoint that a higher ultraviolet absorption function can be expected, and both the ultraviolet absorber and the ultraviolet scattering agent are included. More preferably.

  Moreover, in this invention, an ultraviolet A wave (UV-A, 315-400 nm) absorber and a scattering agent, and an ultraviolet B wave (UV-B, 280-315 nm) absorber and a scattering agent by having the said structure. In any of these, a high ultraviolet absorption function and / or an ultraviolet scattering function can be exhibited, and a particularly high ultraviolet absorption function can be exhibited.

  In the external composition for skin of the present invention, the total content of the component (B) relative to the total amount of the external composition for skin can be, for example, a content of 0.01 w / w% to 50 w / w%, .1w / w% or more and 45w / w% or less may be sufficient and 1w / w% or more and 40w / w% or less may be sufficient.

  In the composition for external use of the skin of the present invention, the ratio of the blending amount of the (B) component to the (A) component is such that the total content of the (B) component is 0 to 1 part by weight of the total content of the (A) component .0005 to 25000 parts by weight is preferred, 0.01 to 2000 parts by weight is more preferred, 0.1 to 150 parts by weight is further preferred, and 0.5 to 50 parts by weight is most preferred.

  By containing the component (A) and the component (B), the external composition for skin of the present invention can exhibit a high ultraviolet absorption function and / or ultraviolet scattering function, and can exhibit a particularly high ultraviolet absorption function. The ultraviolet absorptivity can be evaluated by measuring the ultraviolet absorption spectrum by a method as described in a test example described later. That is, specifically, the composition for external use of the skin of the present invention can have an ultraviolet absorbing ability enhanced more than the value exhibited by (B) the ultraviolet absorber and / or the ultraviolet scattering agent alone. Furthermore, the external composition for skin of the present invention can be well retained even in water such as seawater with high sweat and salt concentration. Here, the salt is, but is not limited to, chloride or sulfate. Examples of the chloride or sulfate include sodium chloride, magnesium chloride, potassium chloride, calcium chloride, magnesium sulfate, and calcium sulfate. In addition, the composition for external use of the skin of the present invention effectively suppresses secondary adhesion, and therefore, when the moisture such as sweat is wiped with tissue paper, handkerchief, towel, etc., or it is rubbed with clothes. However, it can remain on the skin and can retain its UV absorption ability well.

  The external composition for skin of the present invention may optionally contain components other than the above components (A) and (B). As such a component, for example, (C) an ester oil having 3 or more ester groups in the molecule and / or (D) a thickener is preferable.

[(C) Ester oil]
It is preferable that the composition for external use of the present invention further contains (C) an ester oil having three or more ester groups in the molecule. By including the ester oil, it is possible to keep the components (A) and (B) of the present invention in a state where the effects are more easily exhibited. In the present specification, (C) an ester oil having three or more ester groups in a molecule refers to an ester oil (component) having three or more ester bonds in the same molecule. Preferably, it is liquid at 25 ° C.

  (C) As ester oil which has three or more ester groups in a molecule | numerator, polyester oil, such as triester oil, tetraester oil, pentaester oil, hexaester oil, heptaester oil, can be mention | raise | lifted, for example. Preferably, a triester oil, a tetraester oil, a pentaester oil or the like is preferable, and a triester oil or a tetraester oil is more preferable. In addition, the monoester oil and the diester oil may be suitably contained in the range which does not impair the effect of this invention.

  The triester oil refers to an ester oil having three ester groups in the molecule, for example, an ester oil obtained from a polyhydric alcohol having three hydroxyl groups in the molecule and a monobasic acid. Triester oils include, for example, triethylhexanoin, triethylhexyl trimellitate, trimethylolpropane triisostearate, trimethylolpropane tri-2-ethylhexanoate, trimethylolpropane trioctanoate, glyceryl tri-2-ethylhexanoate, triisostearic acid Examples thereof include diglyceryl, decaglyceryl triisostearate, glyceryl triisopalmitate, glyceryl tricaprylate, tri (caprylic / capric) glycerin, triethylhexyl citrate and the like.

  The tetraester oil refers to an ester oil having four ester groups in the molecule, for example, an ester oil obtained from a polyhydric alcohol having four hydroxyl groups in the molecule and a monobasic acid. Examples of the tetraester oil include pentaerythrityl tetraethylhexanoate, pentaerythrityl tetraisostearate, pentaerythritol tetra-2-ethylhexanoate, decaglyceryl tetra-2-ethylhexanoate, and the like.

  Examples of the polyester oil having a plurality of ester groups (for example, 5 or more) in the molecule include polyglyceryl-2 isostearate, polyglyceryl-2 diisostearate, polyglyceryl-2 triisostearate, and polyglyceryl tetraisostearate which are polyglycerin fatty acid esters. -2, polyglyceryl-3 diisostearate, polyglyceryl-6 octacaprate, and the like.

  These (C) ester oils having 3 or more ester groups in the molecule may be used alone or in combination of two or more. When these ester oils are used, it is possible to prepare an external composition for skin that can exhibit a more excellent ability to enhance the ultraviolet absorption spectrum.

  Also, these are commercially available products such as Neosolue-MCT, IOTG, NS-308, NS-408 (manufactured by Nippon Seika Co., Ltd.), NIKKOL Trifat S-308, NIKKOL Triester F-810, NIKKOL TOC, NIKKOL DGTIS ( Manufactured by Nikko Chemicals Co., Ltd.) I. O, O.I. D. O, Saracos 6318V, Saracos 5408, Saracos 5418V, Saracos HG-8, Cosmol 43V, Cosmol 43N, Cosmol 44V (Nisshin Oilio Group), TOG, KAK TTO, KAK TTI, KAK PTI, TCG-M, Risolex PGIS21 Risolex PGIS22, Risolex PGIS23, Risolex PGIS32 (manufactured by Higher Alcohol Industry Co., Ltd.), SR Crodamol TOTM, Kurodamol PTIS (Croda Japan).

  In the external composition for skin of the present invention, the content of the ester oil having 3 or more ester groups in the molecule (C) relative to the total amount of the external composition for skin is preferably 0.00001 w / w% or more. Preferably, it is 0.0001 w / w% or more, more preferably 0.001 w / w% or more, and most preferably 0.1 w / w% or more. The total content of the component (C) is preferably 20 w / w% or less, more preferably 15 w / w% or less, still more preferably 10 w / w% or less, particularly with respect to the total amount of the external composition for skin. Preferably it is 7 w / w% or less. The total content of the component (C) is preferably 0.00001 w / w% to 20 w / w%, more preferably 0.0001 w / w% to 15 w / w% with respect to the total amount of the composition for external use on the skin. More preferably, it is 0.001 w / w% to 10 w / w%, and most preferably 0.1 w / w% to 7 w / w%.

  In the composition for external use of the skin of the present invention, the ratio of the component (C) to the component (A) is such that the total content of the component (C) is 0 with respect to 1 part by weight of the total content of the component (A). 0.0001 to 500 parts by weight is preferable, 0.0001 to 200 parts by weight is more preferable, 0.001 to 100 parts by weight is further preferable, and 0.01 to 25 parts by weight is most preferable.

[(D) Thickener]
It is preferable that the composition for external use of the present invention further contains a thickener. When preparing the skin external composition of the present invention as an oil-in-water (O / W type) emulsion composition, the stability of the emulsion composition is enhanced by including the thickener in this way. The components (A) and (B) of the invention can be kept in a state where the effects are more easily exhibited. In the present specification, the (D) thickener refers to a drug (component) having a property of increasing the viscosity of the added composition. Preferably, the thickener is a water-soluble thickener that is soluble in water.

  Water-soluble thickener is water-soluble anionic polymer thickener, acrylic acid thickener, cellulose thickener, mucopolysaccharide thickener, amino acid thickener, seaweed thickener, A microbial-derived thickener, a polyethylene glycol thickener, or a starch thickener is preferred.

Specific examples of the water-soluble thickener include (a) acrylic acid / alkyl methacrylate copolymer, hydroxyethyl acrylate / acryloyldimethyltaurine salt copolymer, polyacrylic acid, and salts thereof. Acrylic acid thickener;
(B) Cellulosic thickeners such as methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxymethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose, carboxyethylcellulose, stearoxyhydroxypropylmethylcellulose;
(C) mucopolysaccharide thickeners such as hyaluronic acid, hyaluronic acid derivatives and salts thereof, chondroitin sodium sulfate;
(D) an amino acid thickener such as collagen;
(E) Carrageenan, alginate, propylene glycol alginate, seaweed thickener such as agar;
(F) Microbial derived thickeners such as xanthan gum, hydroxypropyl xanthan gum, dextran, sclerotium gum, gellan gum;
(G) Polyethylene glycol thickeners such as polyethylene glycol, polyethylene glycol distearate, (PEG-240 / decyltetredeces-20 / HDI) copolymer, glyceryl behenate and polyglyceryl-6 octastearate;
(H) starch-based thickeners such as hydroxypropyl starch phosphate and corn starch; and (i) a water-soluble anionic property containing a monomer having an anionic group such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group as a constituent unit. Polymer (including copolymers, homopolymers, crosspolymers) thickeners;
Is exemplified.

  In addition, other water-soluble polymers such as ethylene glycol triisostearate, polyoxyethylene (20) methyl glucoside triisostearate, bentonite, macrogol, sodium caseinate and the like can be mentioned.

  Examples of the (D) thickener preferably used in the present invention include acrylic thickeners. Particularly preferred as acrylic thickeners are (acrylates / alkyl acrylate (C10-30)) crosspolymers, (hydroxyethyl acrylate / sodium acryloyldimethyltaurate) copolymers, acrylamide / ammonium acrylate copolymers, (acrylates / (Beheneth methacrylate-25) crosspolymer sodium, polyacrylate-6, polyacrylate-13, (acrylic acid / acryloyldimethyltaurine / dimethylacrylamide) crosspolymer, (acrylates / steaconic acid steareth-20) copolymer, (acryloyldimethyltaurine ammonium) / Vinylpyrrolidone) copolymer, (sodium acrylate / acryloyldimethyltaurine / dimethylacrylamide) crosspolymer, Tearesu 10 allyl ether acrylated retaining clips polymer, it is at least one selected from the group consisting of carboxyvinyl polymers and polyacrylamides. Especially, it is preferable that (D) thickener used for this invention is an acrylic acid type thickener which is water-soluble anionic property.

  Examples of the (D) thickener preferably used in the present invention include acrylic thickeners. Particularly preferred as acrylic thickeners are (acrylates / alkyl acrylate (C10-30)) crosspolymers, (hydroxyethyl acrylate / sodium acryloyldimethyltaurate) copolymers, acrylamide / ammonium acrylate copolymers, (acrylates / (Beheneth methacrylate-25) crosspolymer sodium, polyacrylate-6, polyacrylate-13, (acrylic acid / acryloyldimethyltaurine / dimethylacrylamide) crosspolymer, (acrylates / steaconic acid steareth-20) copolymer, (acryloyldimethyltaurine ammonium) / VP) copolymer, (sodium acrylate / acryloyldimethyltaurine / dimethylacrylamide) crosspolymer, steareth- 0 allyl ether acrylated retaining clips polymer, it is at least one selected from the group consisting of carboxyvinyl polymers and polyacrylamides.

  In addition, hydroxyethylcellulose, hydroxypropylmethylcellulose, polyethylene glycol, polyvinyl alcohol, xanthan gum, hydroxypropyl starch phosphate, sodium hyaluronate, hyaluronic acid derivatives or salts thereof, collagen, agar, xanthan gum, hydroxypropyl starch phosphate, macrogol Etc. are also preferred.

  These (D) thickeners may be used alone or in combination of two or more. When these thickeners are used, it is possible to create gel preparations with a lot of water feeling, making it possible to produce light gel preparations with appropriate film feeling and formulation stability and good feeling to use. it can.

  In addition, these are commercially available products such as PEMULEN (trademark) TR-1 and TR-2 (manufactured by Lubrizol Advanced Materials); Carbopol (trademark) ETD2020, Ultraz20 Polymer, Ultrez21 Polymer, Ultrez10 Polymer ) 2001 (manufactured by Akzo Nobel), Aristoflex (trademark) AVC, HMB (manufactured by Clariant Japan) or the like can be used. Examples of the polyvinyl alcohol include commercially available Gohsenol (trademark) EG-05 and EG-40 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.). Moreover, you may use as a mixture mixed with oil agents, such as squalane, a nonionic surfactant, and water. Specific examples of such a mixture include, for example, SIMULGEL (trademark) FL, NS (manufactured by Sepic), which is a commercial product containing hydroxyethyl acrylate / sodium acryloyldimethyltaurate copolymer; sodium acrylate / acryloyl SIMULGEL (trademark) EG (manufactured by Sepic), SIMULGEL (trademark) EPG (manufactured by Sepic), which is a commercial product containing a dimethyltaurine copolymer, and a commercial product containing steareth-10 allyl ether / acrylate copolymer. A certain SALCARE ™ SC80 (manufactured by Ciba Specialty Chemicals); a commercially available product, SALCARE ™ SC, containing sodium acrylate, sodium acrylate, sodium methacrylate alkyl methacrylate copolymer 1 (manufactured by Ciba Specialty Chemicals); (Nacryacrylate / acryloyldimethyltaurine / dimethylacrylamide) SEPINOV (trademark) P88 (manufactured by Sepic) and Adecanol (trademark) GT-700, which are commercial products containing a crosspolymer. (Manufactured by Asahi Denka Kogyo Co., Ltd.); and SEPIGEL (trademark) 305 (Seiwa Kasei), which is a commercial product containing polyacrylamide. As said polyacrylic acid amide, commercially available SEPIGEL (trademark) 305 (made by Seiwa Kasei Co., Ltd.) etc. can be used, for example. Examples of the carboxyvinyl polymer include Carbopol (trademark) 940, 941, 980, 981, ETD2050, Ultraz10 Polymer, (manufactured by Lubrizol Advanced Materials); Sinteralene K Syntalen L (manufactured by 3V SIGMA); , HV-504E, HV-505E (manufactured by Sumitomo Seika Co., Ltd.); Hibiswako 103, 104, 105 (manufactured by Wako Pure Chemical Industries, Ltd.); Junron PW-110 (manufactured by Nippon Seiyaku Co., Ltd.), Aristoflex AVC (Clariant Japan) Can be used.

  In addition, as a commercial product containing (PEG-240 / decyltetradeces-20 / HDI) copolymer, Adecanol (trademark) GT-700 (manufactured by Asahi Denka Kogyo Co., Ltd.), the starch thickener, for example, Examples thereof include STRUCTURE (trademark) XL (manufactured by Akzo Nobel), which is a commercial product containing hydroxypropyl starch phosphate.

  In the external composition for skin of the present invention, the content of the (D) thickener with respect to the total amount of the external composition for skin is preferably 0.00001 w / w% or more, more preferably 0.0001 w / w%. As mentioned above, More preferably, it is 0.001 w / w% or more, Most preferably, it is 0.1 w / w% or more. The total content of component (D) is preferably 20 w / w% or less, more preferably 10 w / w% or less, and even more preferably 5 w / w% or less with respect to the total amount of the composition for external use on the skin. . The total content of component (D) is preferably 0.00001 w / w% to 20 w / w%, more preferably 0.0001 w / w% to 10 w / w% with respect to the total amount of the composition for external use on the skin. More preferably, it is 0.001 w / w% to 5 w / w%, and most preferably 0.1 w / w% to 5 w / w%.

  In the composition for external use of the skin of the present invention, the ratio of the amount of the component (D) to the component (A) is such that the total content of the component (D) is 0 with respect to 1 part by weight of the total content of the component (A). 0.00000 to 20000 parts by weight is preferable, 0.000001 to 2000 parts by weight is more preferable, 0.00002 to 100 parts by weight is further preferable, and 0.0005 to 25 parts by weight is most preferable.

  As long as the composition for external use of the skin of the present invention does not interfere with the effects of the present invention, in addition to the above components (A) to (D), for example, antioxidants, whitening active ingredients, various pharmacologically active ingredients and physiological activities An appropriate amount may be contained in combination.

[Antioxidant]
As the antioxidant (antioxidant component) in the present invention, a known antioxidant can be used as long as the effects of the present invention are not impaired. In the present invention, the antioxidant (antioxidant component, antioxidant component) refers to a drug (component) having a property of inhibiting, reducing, or suppressing oxidation by reactive oxygen species.

As the antioxidant, for example,
(A) Tocopherols and derivatives thereof or salts thereof (for example, α-tocopherol, δ-tocopherol, acetic acid-α-tocopherol, tocotrienol), pyrroloquinoline quinone and derivatives thereof or salts thereof, ubiquinones and derivatives thereof or them Vitamin antioxidants, such as salts, retinols and derivatives thereof or salts thereof, pantothenic acid and derivatives or salts thereof, erythorbic acid or salts thereof;
(B) thiotaurine, cysteine, homocysteine, acetylcysteine, methionine, thioglycerol, sodium sulfite, sodium metabisulfite, sodium thiosulfate, sodium pyrosulfite, thioredoxin, dithiothreitol, alpha lipoic acid, ergothioneine, glutathione, glutathione peroxidase, Sulfur-containing antioxidants such as glutathione-S-transferase;
(C) phenols such as dibutylhydroxytoluene, dibutylhydroxyanisole, bisethylhexylhydroxydimethoxybenzyl malonate, diethylhexylsyringylidene malonate, gallic acid and its derivatives or their salts, chlorogenic acid and its derivatives or their salts Antioxidants;
(D) components derived from plants (eg, grapes, ginseng, comfrey, etc.) (eg, grape seed extract, grape leaf extract, ginseng extract, comfrey leaf extract, etc.); proanthocyanidins, hesperidins, glucosyl hesperidins, flavonoids And polyphenol antioxidants. These may be used singly or in combination of two or more.

  In the external composition for skin of the present invention, the antioxidant is bisethylhexyl hydroxydimethoxybenzyl malonate and derivatives thereof, malonic acid and derivatives thereof, pyrroloquinoline quinone and derivatives thereof, tocopherols and derivatives thereof, thiotaurine and derivatives thereof, Dibutylhydroxytoluene and derivatives thereof, gallic acid or derivatives thereof, chlorogenic acid and derivatives thereof, hesperidin and derivatives thereof, glucosyl hesperidin and derivatives thereof, ergothioneine and derivatives thereof, flavonoids and derivatives thereof, or dibutylhydroxyanisole and derivatives thereof, And when it can take the form of a salt, it is preferable that they are the salt of any one of the said compounds, the salt of any of the said derivatives, etc. Among them, bisethylhexyl hydroxydimethoxybenzyl malonate, pyrroloquinoline quinone and derivatives thereof or salts thereof, tocopherols and derivatives thereof or salts thereof, thiotaurine, dibutylhydroxytoluene, gallic acid and derivatives thereof or salts thereof, chlorogenic acid And its derivatives or their salts, or dibutylhydroxyanisole is more preferred. In addition, bisethylhexyl hydroxydimethoxybenzyl malonate, diethylhexyl syringylidene malonate, pyrroloquinoline quinone and its derivatives or their salts, tocopherol and its derivatives or their salts, thiotaurine, dibutylhydroxytoluene, or gallic acid and its Even more preferred are derivatives or their salts.

  In the external composition for skin of the present invention, the content of the antioxidant relative to the total amount of the external composition for skin can be 0.00001 w / w% or more and 20 w / w% or less, 0.0001 w / W% or more and 10 w / w% or less, 0.001 w / w% or more and 7 w / w% or less, 0.05 w / w% or more and 5 w / w% or less 0.03 w / w% to 3 w / w%, 0.02 w / w% to 1 w / w%, 0.01 w / w% to 0.5 w / w% It may be the following.

[Whitening active ingredient]
As the whitening active ingredient (whitening agent) in the present invention, a known whitening active ingredient can be used as long as the effects of the present invention are not impaired. In the present invention, the whitening active ingredient (whitening agent) is an improvement, suppression / reduction / prevention, prevention of skin pigmentation due to melanin pigment particularly related to dullness and itching of the skin, liver spots, etc. Or it refers to a drug (component) having the property of delaying.

As the whitening active ingredient, for example,
(A) hydroquinone and derivatives thereof or salts thereof (for example, α-arbutin, β-arbutin); kojic acid; ellagic acid; phytic acid; lucinol; ascorbic acid and its derivatives or salts thereof (for example, ascorbic acid phosphate ester) Sodium, magnesium ascorbate phosphate, ascorbyl tetraisopalmitate (ascorbyl tetra-2-hexyldecanoate), 2-O-ethylascorbic acid, 3-O-ethylascorbic acid, ascorbic acid glucoside, etc.), potassium 4-methoxysalicylate Tyrosinase inhibitors such as salts, tranexamic acid and derivatives thereof or salts thereof;
(B) an endothelin-1 receptor inhibitor such as chamomile ET;
(C) a tyrosinase proteolytic promoter such as free linoleic acid;
(D) a melanin excretion enhancer such as adenosine monophosphate disodium salt;
(E) a melanin transport inhibitor such as niacinamide;
(F) Other plant components having a whitening effect (for example, plant extracts and essential oils);
Can give. These may be used singly or in combination of two or more.

  In the external composition for skin of the present invention, the whitening active ingredient is hydroquinone and derivatives thereof or salts thereof, ascorbic acid and derivatives thereof or salts thereof, tranexamic acid and derivatives thereof or salts thereof, ellagic acid, niacinamide, etc. It is preferable that Among them, hydroquinone, arbutin, sodium ascorbate phosphate, ascorbic acid, magnesium ascorbate phosphate, ascorbyl tetraisopalmitate (ascorbyl tetra-2-hexyldecanoate), 3-O-ethylascorbic acid, ascorbic acid glucoside, More preferred is tranexamic acid.

  In the external composition for skin of the present invention, the content of the whitening active ingredient relative to the total amount of the external composition for skin can be 0.00001 w / w% or more and 20 w / w% or less, 0.00001 w / W% or more and 10 w / w% or less, 0.001 w / w% or more and 7 w / w% or less, 0.05 w / w% or more and 5 w / w% or less 0.03 w / w% to 3 w / w%, 0.02 w / w% to 1 w / w%, 0.01 w / w% to 0.5 w / w% It may be the following.

[Anti-inflammatory ingredients]
As the anti-inflammatory component (anti-inflammatory agent) in the present invention, a known anti-inflammatory component can be used as long as the effects of the present invention are not impaired. In addition, in this invention, an anti-inflammatory component (anti-inflammatory agent) means the chemical | medical agent (component) which has a property which inhibits, reduces, and suppresses inflammation of cells, such as epidermis.

  Examples of the anti-inflammatory component include components derived from plants (eg, comfrey leaf extract); allantoin, calamine, glycyrrhizic acid and derivatives thereof or salts thereof (dipotassium glycyrrhizinate, sodium glycyrrhizinate, etc.), glycyrrhetic acid And derivatives thereof or salts thereof (stearyl glycyrrhetinate, 18α-hydroxyglycyrrhetinic acid, etc.), guaiazulene, pyridoxine hydrochloride, menthol, camphor, turpentine oil, indomethacin, salicylic acid, and derivatives thereof. These may be used singly or in combination of two or more.

  In the external composition for skin of the present invention, the anti-inflammatory component is allantoin, glycyrrhizic acid and derivatives thereof or salts thereof, glycyrrhetinic acid and derivatives or salts thereof, guaiazulene, pyridoxine hydrochloride, menthol, camphor, turpentine oil, indomethacin Or salicylic acid and its derivatives or salts thereof are preferred. Of these, allantoin, glycyrrhizic acid, dipotassium glycyrrhizinate, glycyrrhetinic acid, stearyl glycyrrhetinate, menthol, camphor, indomethacin, and salicylic acid are more preferable.

  In the external composition for skin of the present invention, the content of the anti-inflammatory component relative to the total amount of the external composition for skin can be 0.00001 w / w% or more and 20 w / w% or less. It may be 0001 w / w% or more and 10 w / w% or less, may be 0.001 w / w% or more and 5 w / w% or less, or may be 0.05 w / w% or more and 3 w / w% or less. It may be 0.03 w / w% or more and 1 w / w% or less, 0.02 w / w% or more and 0.5 w / w% or less, 0.01 w / w% or more and 0.1 w / W% or less may be sufficient.

[Other bases or carriers]
The external composition for skin of the present invention can contain a known base or carrier used for cosmetics and quasi-drugs as long as the effects of the present invention are not impaired. A base or a carrier can be used singly or in combination of two or more.

  Bases or carriers include paraffin, liquid paraffin, squalane, white wax, gelled hydrocarbons (plastibase, etc.), ozokerite, ceresin, petrolatum, hard fat, microcrystalline wax, α-olefin oligomer, light liquid paraffin, etc. Hydrocarbons; fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, isostearic acid; such as glyceryl tri-2-ethylhexanoate (trioctanoin), tri (caprylic acid / capric acid) glyceryl Tri-fatty acid glycerides; higher alcohols such as cetanol, stearyl alcohol, behenyl alcohol; methyl polysiloxane, didemethylcyclopentasiloxane, decamethylcyclopentasiloxane, methylsiloxane network weight , Silicones such as methyl hydrogen polysiloxane, dimethicone; isopropyl myristate, octyldodecyl myristate, isopropyl palmitate, cetyl palmitate, isononyl isononanoate, pentaerythritol tetra-2-ethylhexanoate, triethylhexyl trimellitate Esters such as dextrin and maltodextrin; lower alcohols such as ethanol and isopropanol; glycol ethers such as ethylene glycol monoethyl ether; and water-based bases such as water.

  Especially, it is preferable that the external composition for skin of this invention shall contain water and / or a lower alcohol, and it is more preferable to contain water. The skin external composition of the present invention is not limited, but the content of water relative to the total amount of the skin external composition is preferably 30 w / w% or more and 99 w / w% or less, and 40 w / w% or more and 95 w / w% or less. Is more preferable, and 50 w / w% or more and 90 w / w% or less is still more preferable. The external composition for skin of the present invention is most preferably an O / W type composition containing 50 w / w% or more of water.

[Additive]
To the skin external composition of the present invention, known additives that are added to cosmetics and quasi drugs, for example, surfactants, preservatives, pH adjusters, chelating agents, as long as the effects of the present invention are not impaired. Stabilizers, irritation reducers, preservatives, colorants and the like can be added. An additive can be used individually by 1 type or in combination of 2 or more types.

  Examples of the surfactant include sorbitan monoisostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, diglycerol sorbitan penta-2-ethylhexylate, and diglycerol sorbitan tetra-2-ethylhexylate. Sorbitan fatty acid esters; glyceryl fatty acids such as glyceryl monostearate and glyceryl monostearate; polyglyceryl fatty acids such as polyglyceryl monostearate, polyglyceryl monoisostearate and polyglyceryl diisostearate; propylene glycol monostearate Propylene glycol fatty acid esters such as: polyoxyethylene hydrogenated castor oil 40 (PEG-40 hydrogenated castor oil, HCO-40) Polyoxyethylene hydrogenated castor oil 50 (PEG-50 hydrogenated castor oil, HCO-50), polyoxyethylene hydrogenated castor oil 60 (PEG-60 hydrogenated castor oil, HCO-60), polyoxyethylene hydrogenated castor oil 80 ( Hardened castor oil derivatives such as PEG-80 hydrogenated castor oil, HCO-80); polyoxyethylene (20) sorbitan (polysorbate 20) monolaurate, polyoxyethylene (20) sorbitan monostearate (polysorbate 60), mono Polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene (20) sorbitan oleate (polysorbate 80), polyoxyethylene (20) sorbitan isostearate; polyoxyethylene monococonut oil fatty acid glyceryl; glycerin alkyl ether; Kill glucoside; polyoxyalkylene alkyl ether such as polyoxyethylene cetyl ether; amines such as stearylamine and oleylamine; polyoxyethylene methylpolysiloxane copolymer, lauryl PEG-9 polydimethylsiloxyethyl dimethicone, PEG- 9 Silicone surfactants such as polydimethylsiloxyethyl dimethicone, dimethyl silicone oil, polyglycerin modified silicone (including polyglycerin / alkyl co-modified silicones such as lauryl polyglyceryl-3 polydimethylsiloxyethyl dimethicone) I can give you.

  Among them, glycerin fatty acids (particularly glyceryl monostearate), polyglycerin fatty acids (particularly polyglyceryl monostearate, polyglyceryl pentaisostearate), hydrogenated castor oil derivative (particularly polyoxyethylene hydrogenated castor oil 50 (PEG- 50 hydrogenated castor oil, HCO-50), polyoxyethylene hydrogenated castor oil 60 (PEG-60 hydrogenated castor oil, HCO-60)), polyoxyethylene sorbitan fatty acid esters (particularly polyoxyethylene isostearate (20 ) Sorbitan, polyoxyethylene monostearate (20) sorbitan (polysorbate 60)), polyoxyalkylene alkyl ether (particularly polyoxyethylene cetyl ether), silicone surfactant (particularly polyoxyethylene Chill polysiloxane copolymer, lauryl PEG-9 polydimethylsiloxyethyl dimethicone, PEG-9 polydimethylsiloxyethyl dimethicone, dimethyl silicone oil, lauryl polyglyceryl-3 polydimethylsiloxyethyl dimethicone) is preferred.

  Preservatives and preservatives include benzoic acid, sodium benzoate, dehydroacetic acid, sodium dehydroacetate, isobutyl paraoxybenzoate, isopropyl paraoxybenzoate, butyl paraoxybenzoate, ethyl paraoxybenzoate, propyl paraoxybenzoate, paraoxybenzoic acid Examples thereof include benzyl, methyl paraoxybenzoate, and phenoxyethanol. Of these, methyl paraoxybenzoate, propyl paraoxybenzoate, and phenoxyethanol are preferable.

  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, sodium succinate, Oxalic acid, gluconic acid, fumaric acid, propionic acid, acetic acid, aspartic acid, ε-aminocaproic acid, glutamic acid, aminoethylsulfonic acid, etc.), gluconolactone, ammonium acetate, inorganic base (sodium bicarbonate, sodium carbonate, hydroxylation) And potassium (sodium hydroxide, calcium hydroxide, magnesium hydroxide, etc.), organic bases (monoethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, lysine, etc.). Of these, succinic acid, sodium succinate, citric acid, sodium citrate, triethanolamine, potassium hydroxide, and sodium hydroxide are preferable.

  Chelating agents include ethylenediaminetetraacetic acid (edetic acid), ethylenediaminetetraacetic acid salt (sodium salt (sodium edetate: Japanese Pharmacopoeia, EDTA-2Na, etc.), potassium salt, etc.), phytic acid, gluconic acid, polyphosphoric acid, metalin Acids can be raised. Of these, sodium edetate is preferred.

  Examples of the stabilizer include butylhydroxyanisole.

  Examples of the irritation reducing agent include licorice extract, sodium alginate, 2-methacryloyloxyethyl phosphorylcholine and the like.

  Examples of the colorant include inorganic pigments and natural pigments.

  Usability improvers include polystyrene, polymethyl methacrylate, acrylates copolymer, acrylates cross polymer, (butyl acrylate / dimethacrylate glycol) cross polymer, methyl methacrylate cross polymer, (methyl methacrylate / dimethacrylic acid) Glycol) crosspolymer, (styrene / divinylbenzene) crosspolymer, lauroyl lysine, nylon-12.

[Other active ingredients]
In the present invention, the composition for external use of skin is an anti-wrinkle / anti-aging ingredient, a keratin softening ingredient, a cell activation ingredient, vitamins, a moisturizing ingredient, prevention of DNA damage, and so long as the effects of the present invention are not hindered. Other active ingredients that can be added to cosmetics and quasi-drugs, such as components having a restorative action, antibacterial components, and astringent components, can be blended. Other active ingredients can be used singly or in combination of two or more.

  Anti-wrinkle and anti-aging components include hydrolyzed soy protein, retinoids (retinol and derivatives thereof, retinoic acid, retinal, etc.), pangamic acid, kinetin, ursolic acid, turmeric extract, sphingosine derivatives, silicon, silicic acid, N-methyl -L-serine, mevalonolactone and the like can be mentioned. Of these, artemia extract, hydrolyzed soy protein, retinol, retinol acetate, and retinol palmitate are preferred.

  Examples of the keratin soft component include lanolin, urea, α-hydroxy acid (phytic acid, lactic acid, lactate, glycolic acid, salicylic acid, malic acid, etc.), citric acid, and the like. Of these, lactic acid, sodium lactate, glycolic acid, salicylic acid, and phytic acid are preferable.

  Cell activation components include components derived from plants (for example, bilberry); amino acids such as γ-aminobutyric acid and ε-aminoproic acid; α-hydroxy acids such as glycolic acid and lactic acid; tannins, flavonoids, saponins, and allantoins And photosensitive element 301. Of these, bilberry leaf extract is preferred.

  Vitamins include retinol, retinol acetate, retinol palmitate, etc., retinal, retinoic acid, methyl retinoic acid, ethyl retinoic acid, retinol retinoic acid, d-δ-tocopheryl retinoate, α-tocopheryl retinoate Vitamins such as β-tocopheryl retinoate; provitamins A such as β-carotene, α-carotene, γ-carotene, δ-carotene, lycopene, zeaxanthin, cryptoxanthin, echinone; δ-tocopherol, α- Vitamin Es such as tocopherol, β-tocopherol, dl-α-tocopherol succinate, dl-α-tocopherol calcium succinate, δ-tocopherol, tocopherol nicotinate; riboflavin, flavin mononucleotide, Vitamin B2 such as rabin adenine dinucleotide, riboflavin butyrate, riboflavin tetrabutyrate, sodium riboflavin 5′-phosphate, riboflavin tetranicotinate; nicotinic acids such as methyl nicotinate, nicotinic acid, nicotinamide; stearin Vitamins C such as ascorbyl acid, L-ascorbyl dipalmitate, ascorbyl tetraisopalmitate (ascorbyl tetra-2-hexyldecanoate); vitamin Ds such as methyl hesperidin, ergocalciferol, cholecalciferol; phylloquinone, farnoquinone, etc. Vitamin K of dibenzoyl thiamine, dibenzoyl thiamine hydrochloride, thiamine hydrochloride, thiamine cetyl hydrochloride, thiamine thiocyanate, thiamine Uril hydrochloride, thiamine nitrate, thiamine monophosphate, thiamine lysine salt, thiamine triphosphate, thiamine monophosphate phosphate, thiamine monophosphate, thiamine diphosphate, thiamine diphosphate hydrochloride, thiamine triphosphate Vitamin B1 such as thiamine triphosphate monophosphate; vitamin B6 such as pyridoxine hydrochloride, pyridoxine acetate, pyridoxal hydrochloride, 5′-phosphate pyridoxal hydrochloride, pyridoxamine hydrochloride, vitamins such as cyanocobalamin, hydroxocobalamin, deoxyadenosylcobalamin B12 types; Folic acids such as folic acid and pteroylglutamic acid; pantothenic acid, calcium pantothenate, pantothenyl alcohol (panthenol), D-pantethein, D-pante Pantothenic acids such as acetylene, coenzyme A, and pantothenyl ethyl ether; biotins such as biotin and biocytin; and other vitamin-like agents such as carnitine, ferulic acid, α-lipoic acid, orotic acid, and γ-oryzanol be able to.

  Among them, vitamin A such as retinol, retinol acetate, and retinol palmitate; sodium ascorbate phosphate, magnesium ascorbate phosphate, ascorbyl tetraisopalmitate (ascorbyl tetra-2-hexyldecanoate), 2-O-ethyl Vitamin Cs such as ascorbic acid and 3-O-ethylascorbic acid; Vitamin Es such as δ-tocopherol and tocopherol nicotinate; and nicotinic acids such as nicotinamide are preferable.

  Moisturizing ingredients include ingredients derived from plants (eg, Tigaya); amino acids such as alanine, serine, leucine, isoleucine, threonine, glycine, proline, hydroxyproline, glucosamine, theanine and derivatives thereof; collagen, gelatin, elastin Such proteins and peptides, hydrolysates thereof; polyhydric alcohols such as glycerin, 1,3-butylene glycol, propylene glycol, dipropylene glycol, diglycerin; sugar alcohols such as sorbitol; lecithin, hydrogenated lecithin, etc. Phospholipids; NMF-derived components such as lactic acid, sodium pyrrolidonecarboxylate, urea; polyglutamic acid; polymers having phospholipid polar groups such as MPC polymers (for example, LIPIDURE ™); Cypropylene methyl glucoside; PPG-10 methyl glucose (for example, Macbiobride MG (trademark) series (manufactured by NOF Corporation), etc.), PEG / PPG / polybutylene glycol-8 / 5/3 glycerin (for example, Wilbride) (Trademark) S-753 (manufactured by NOF Corporation)); trimethylglycine (betaine); hydroxyethylurea; acrylic acid / acrylamide / dimethyldiallylammonium chloride copolymer; sorbitol and the like. Among them, hydrolyzed collagen, hydrolyzed elastin, MPC polymer glycerin, 1,3-butylene glycol, dipropylene glycol, diglycerin, polyoxypropylene methylglucoside, trimethylglycine (betaine), hydroxyethylurea, hydrogenated lecithin, sorbitol Is preferred.

  Components having a preventive and / or repairing action on DNA damage include components derived from animals (eg, Artemia); components derived from plants (eg, cat's claw); DNA, DNA salts, RNA, RNA salts, etc. Of the nucleic acid component. Of these, artemia extract and DNA-Na are preferable.

  Antibacterial components include chlorhexidine, salicylic acid, benzalkonium chloride, acrinol, ethanol, benzethonium chloride, cresol, gluconic acid and its derivatives, popidone iodine, potassium iodide, iodine, isopropylmethylphenol, triclocarban, triclosan, photosensitizer 101 Photosensitive element 201, paraben, phenoxyethanol, 1,2-pentanediol, alkyldiaminoglycine hydrochloride, and the like. Among them, benzalkonium chloride, benzethonium chloride, gluconic acid and derivatives thereof, isopropylmethylphenol, triclocarban, triclosan, photosensitizer 101, photosensitizer 201, paraben, phenoxyethanol, 1,2-pentanediol, alkyldiamino hydrochloride Glycine is preferred, and benzalkonium chloride, gluconic acid and its derivatives, benzethonium chloride, and isopropylmethylphenol are more preferred.

  Examples of the astringent component include metal salts such as alum, chlorohydroxyaluminum, aluminum chloride, allantoin aluminum salt, zinc sulfate, and aluminum potassium sulfate; organic acids such as tannic acid, citric acid, lactic acid, and succinic acid. Of these, alum, chlorohydroxyaluminum, aluminum chloride, allantoin aluminum salt, potassium aluminum sulfate, and tannic acid are preferable.

[Formulation]
In addition, the external composition for skin in the present invention can be prepared by mixing and stirring each component according to a conventional method, for example.

  The form of the drug for the external composition for skin in the present invention is not particularly limited, and can take a form known as a cosmetic or quasi-drug form. Among such known forms, for example, sheets of liquids, suspensions, emulsions, creams, gels, liniments, lotions, aerosols, powders, poultices, non-woven fabrics, etc. were impregnated with chemicals. Examples thereof include a sheet agent and a lip emulsion. Among these, a liquid agent, a suspension agent, an emulsion, a cream agent, a gel agent, and a lotion agent are preferable in terms of good usability. The external composition for skin of the present invention may be an oil-in-water (O / W) composition or a water-in-oil (W / O) composition. Here, the O / W type composition means an emulsified composition in which the aqueous component is a continuous phase and the oil component is a dispersed phase. The W / O type composition means an emulsified composition in which the oil component is a continuous phase and the aqueous component is a dispersed phase. When the external composition for skin of the present invention is an oil-in-water (O / W) composition, an aqueous emulsion, aqueous gel, or aqueous lotion formulation is preferred. Moreover, when the composition for external use of skin of this invention is a water-in-oil (W / O) composition, the formulation form of an emulsion and a cream is suitable. When the external composition for skin of the present invention is an emulsified composition, it may be either an O / W type or W / O type emulsified composition, but a viewpoint that an even higher UV absorption enhancing effect can be obtained. Therefore, among these, an O / W type emulsion composition is preferable.

  The composition for external use of the skin of the present invention can be preferably used in the form of a basic cosmetic product such as a lip emulsion, emulsion, emulsified lotion or body lotion. The external composition for skin of the present invention can also be used in the form of makeup cosmetics such as foundation, lipstick, blusher, eye makeup, funny, nail polish, pedicure and the like.

  Since the ultraviolet absorption function can be enhanced by the present invention, the composition for external use of the skin of the present invention has a value of SPF (Sun Protection Factor) which is a protection index against ultraviolet B wave (UV-B), ultraviolet A wave ( It can be set as the external composition for skin with the high value of PA (Protection Grade of UVA) which is a protection index with respect to UV-A). For example, the composition for external use of the present invention may have an SPF value of SPF 10 or more, preferably SPF 20 or more, more preferably SPF 30 or more, still more preferably SPF 40 or more, and particularly preferably SPF 50 or more. For example, the composition for external use of the skin of the present invention may have a PA value of PA +, preferably PA ++, more preferably PA ++, and still more preferably PA ++++.

  EXAMPLES Next, the present invention will be specifically described with reference to examples, but the present invention is not limited to the following examples. In addition, the unit of each component amount in Tables 1 to 6 is w / w%.

  The external composition for skin of the composition shown in Tables 1-6 was prepared according to a conventional method. Specifically, each of the oil phase component and the water phase component was weighed and dissolved by heating as necessary. Thereafter, in the case of the O / W type composition, the oil phase was charged into the aqueous phase and stirred to prepare a uniform O / W type composition (Tables 1 and 5). In the case of the W / O type composition, the aqueous phase was added to the oil phase and stirred to prepare a uniform W / O type composition (Tables 2 to 4 and Table 6). Moreover, if necessary, a neutralizing agent was added after stirring to prepare a uniform composition.

Each external composition for skin according to Test Example 1 UV protective effect test Table 1 to Table 4, was uniformly applied so as to 1.3 mg / cm ² on a plate made of polymethyl methacrylate (PMMA), a dark After being allowed to stand at the place for 15 minutes to dry, the ultraviolet absorption spectrum was measured using an ultraviolet-visible spectrophotometer (UV-2450: manufactured by Shimadzu Corporation). The increase rate (enhancement effect) of the ultraviolet absorption spectrum was calculated by comparing the area under the absorbance curve (AUC) at 290 to 400 nm with that of the blank formulation (prescription not including the component (A)). The calculation formula is as follows:
[Formula 1]
Increase rate of ultraviolet absorption spectrum = [(each AUC in Examples) / (each AUC in Comparative Examples)] × 100 (%)
In addition, the ultraviolet absorption spectrum measured five different points in the same PMMA board, and took those average values. For the component (A) used in this test example (* 1 raw material, * 2 raw material in Table 1), the glass transition temperature (Tg) of the alkyl acrylate copolymer was measured using a differential scanning calorimeter (DSC823e device, METTLER Measured by Toledo). Specifically, about 30 mg of a sample after loss on drying was prepared and measured by increasing the temperature from −40 ° C. to 40 ° C. at a rate of temperature increase of 10 ° C./min. In the obtained DSC curve, The midpoint between the start point (onset) and the end point (offset) was determined as the glass transition temperature (Tg). As a result, it was confirmed that the glass transition temperatures (Tg) of the alkyl acrylate copolymer portions of the * 1 raw material and the * 2 raw material were both in the range of 0 to 10 ° C.

In the table, the raw material name of * 1 is Rikabond FS-1000 (manufactured by Japan Coating Resin), and the raw material name of * 2 is Ricabond SS-3000 (manufactured by Japan Coating Resin).

The raw material name of * 1 in the table is Rikabond SS-3000, and the raw material name of * 2 is Ricabond FS-1000.

The raw material name of * 1 in the table is Rikabond SS-3000, and the raw material name of * 2 is Ricabond FS-1000.

The raw material name of * 1 in the table is Rikabond SS-3000, and the raw material name of * 2 is Ricabond FS-1000.

The raw material name of * 1 in the table is Simulgel NS (manufactured by Sepic), and the component name of * 2 is Rikabond SS-3000.

The raw material name of * 1 in the table is Rikabond SS-3000.

  The result of the test example 1 by prescription of Table 1 is shown to FIGS. It was confirmed that the ultraviolet absorption spectrum increased in Example 1 and Example 2 containing the component (A) and the component (B) as compared with Comparative Example 1 containing only the component (B).

  The results of Test Example 1 with the formulations shown in Tables 2 to 4 are shown in FIG. (B) Compared to Comparative Example 4-1 and Comparative Example 5-1 with only the component, Example 4-1 including Example (A) and Component (B), Example 4-2, Example 5-1, In Example 5-2, Example 6-1 and Example 6-2, it was confirmed that the ultraviolet absorption spectrum increased. In addition, Examples 1-1, 2-1, 3-1, and 3-2 using monoester oil or diester oil were compared to Examples 4-1 and Examples using triester oil or tetraester oil. As for 4-2, Example 5-1, Example 5-2, Example 6-1 and Example 6-2, it was confirmed that an ultraviolet absorption spectrum increases more notably.

  The results of Test Example 1 with the formulations shown in Table 5 are shown in FIGS. It was confirmed that the ultraviolet absorption spectrum of Example 3 containing the component (A) and the component (B) was increased as compared with Comparative Example 2 containing only the component (B).

  The results of Test Example 1 with the formulations shown in Table 6 are shown in FIGS. It was confirmed that the ultraviolet absorption spectrum of Example 4 containing the component (A) and the component (B) was increased as compared with Comparative Example 3 containing only the component (B).

[Test Example 2] Residual test after water treatment For the composition for external use shown in Table 1, after measuring the ultraviolet absorption spectrum in Test Example 1, it was treated with water, and again the ultraviolet absorption spectrum in the same manner. Was measured, and the area under the absorbance curve (AUC) at 290 to 400 nm before and after water treatment was compared to calculate the residual rate. The calculation formula is as follows.
Residual rate after water treatment = [(AUC after water treatment) / (AUC before water treatment)] × 100 (%)
In this test example, the water treatment means that a PMMA plate coated with the composition is attached to one end of a stirring blade of a water bath and immersed in a water bath (tap water) at 20 to 25 ° C. for 5 minutes. The PMMA plate is then slowly removed and left in the dark for 30 minutes to dry.
Moreover, the ultraviolet absorption spectrum measured five different points in the same PMMA board, and took those average values.

  The results of Test Example 2 are shown in FIG. Compared with the comparative example only of (B) component, Example 1 and Example 2 containing (A) component have a favorable residual rate after a water treatment.

[Test Example 3] Secondary Adhesion Evaluation Test Each of the external compositions for skin (samples) of Examples 1-2 and Comparative Example 1 in Table 1 was uniformly applied to a PMMA plate at 2 mg / cm ² and dried. I let you. After drying the sample, the ultraviolet absorption spectrum of each PMMA plate was measured with an ultraviolet-visible spectrophotometer (UV-2450; manufactured by Shimadzu Corporation), and the area under the absorbance curve (AUC) at 290 to 400 nm was determined. After that, the PMMA plate is applied on the tissue paper with the coated surface facing down, and a 500 g load is applied to the tissue paper over 10 minutes from the top of the PMMA plate. Then, the ultraviolet absorption spectrum is measured again, and 290-400 nm. The residual ratio of the ultraviolet absorptivity was calculated by obtaining the AUC at and comparing the difference in AUC before and after the adhesion. The calculation formula is as shown in Formula 2.
[Formula 2]
Residual rate of UV absorbing ability = [(each AUC after adhesion) / (each AUC before adhesion)] × 100 (%)
In addition, the ultraviolet absorption spectrum measured five different points in the same PMMA board, and took those average values.
The result is shown in FIG. It was confirmed that the external composition for skin of the present invention hardly adheres secondary.

[Formulation example]
The formulations described in Table 7 and Table 8 below are prepared. Formulation Examples 1 to 8 are all O / W gel external compositions for skin, and Formulation Examples 9 to 16 are all W / O emulsion external compositions for skin.

  In Table 7, the raw material name of * 1 is Ricabond SS-3000, the raw material name of * 2 is Ricabond FS-1000, the raw material name of * 3 is Simulgel NS, and the raw material name of * 4 Is Aristoflex AVC.

In Table 8, the raw material name of * 1 is Rikabond FS-1000, and the raw material name of * 2 is Ricabond SS-3000.

Claims (10)

(A) urethane- (meth) acrylic composite resin;
(B) at least one selected from the group consisting of ultraviolet absorbers and ultraviolet scattering agents,
A composition for external use on the skin, comprising:   The external composition for skin according to claim 1, wherein the outer layer part of the component (A) is formed of a urethane resin matrix, and the inner layer part of the composite resin is formed of a (meth) acrylic resin matrix.   The external composition for skin according to claim 1 or 2, wherein the outer layer part of the component (A) is a urethane resin, and the inner layer part of the composite resin is a (meth) acrylic resin.   The external composition for skin according to any one of claims 1 to 3, wherein the urethane resin in the component (A) is a carboxyl group-containing polyurethane.   The external composition for skin according to any one of claims 1 to 4, wherein the (meth) acrylic resin in the component (A) is an alkyl acrylate copolymer.   The composition for external use according to any one of claims 1 to 5, wherein the average particle size of the component (A) is 5 nm to 2000 nm.   Furthermore, the composition for external use of the skin in any one of Claims 1-6 containing (C) ester oil which has three or more ester groups in a molecule | numerator.   The external composition for skin according to any one of claims 1 to 7, wherein the (B) ultraviolet absorber is an oil-soluble ultraviolet absorber.   The external composition for skin according to any one of claims 1 to 8, wherein the content of the component (B) is 0.01 to 50 w / w% based on the total amount of the composition. The external composition for skin according to any one of claims 1 to 9, which is a sunscreen composition.