JPWO2020032246A1 - Sunscreen effect enhancer - Google Patents

Abstract

An object of the present invention is to develop an additive that enables the provision of an ideal sunscreen cosmetic whose UV protection ability is improved by being heated. Additives for enhancing the UV protection effect of sunscreen cosmetics by heating, which comprises at least one selected from the group consisting of amphipathic substances or moisturizers having an IOB value of 5.0 or less. .. The amphipathic substance or moisturizer is preferably a polyoxyalkylene / polyoxyethylene copolymer dialkyl ether and / or a polyhydric alcohol. [Selection diagram] None

Description

The present invention relates to additives for enhancing the sunscreen effect. More specifically, when added to a sunscreen cosmetic containing an ultraviolet absorber or an ultraviolet scattering agent, it can be added to a sunscreen cosmetic that can impart a new property that the ultraviolet protection effect is improved by heating. Regarding agents.

Cosmetics that have a sunscreen effect have an adverse effect on the skin by reducing the amount of ultraviolet rays that reach the skin to which the cosmetics are applied by the action of the ultraviolet absorbers and ultraviolet scattering agents contained in the cosmetics. Suppress.

The Sun Protection Factor (SPF) is the most widely known index of the UV protection effect of sunscreen cosmetics, and the UV protection effect is displayed as an SPF value (for example, "SPF30"). NS. In Japan, PFA (Protection Factor of UVA) or UVAPF (UVA Protection factor of product) is used for ultraviolet rays in the UVA region, and the degree of UVA protection effect of the product is PA (Protection grade of) based on the value of PFA or UVAPF. It is displayed by UVA) classification ("PA ++", etc.). In the United States, a critical wavelength (CW) is used, which indicates the balance between the protective effects of UVA and UVB.

In recent years, in order to suppress the adverse effects of ultraviolet rays on the skin, cosmetics that exert a high ultraviolet protection effect in a wide wavelength range from UVA to UVB have been required. The appealing sunscreen products have come to the market.

The UV protection effect of sunscreen products is exerted by the UV absorbers and UV scatterers that are included, but while some UV absorbers reduce their UV absorption capacity due to light irradiation, they are combined with moisture. Contact may cause UV absorbers and scattering agents to flow out and reduce the protective ability.

Many devices for suppressing photodegradation of the UV protection effect have been proposed (Patent Document 1), and regarding water resistance, the UV protection effect does not decrease even if it comes into contact with moisture, and conversely, the protection effect is improved. Cosmetics having an innovative performance of improving have been developed (Patent Document 2).

On the other hand, as with light and moisture, the decrease in UV protection effect due to heat cannot be ignored. In general, when heat is applied to a cosmetic applied to the skin, the ultraviolet absorber and other components contained in the cosmetic are deteriorated, and the ultraviolet protection effect is reduced. However, regarding heat, for example, there are examples of examining the effect of heat on the emulsification stability of emulsified cosmetics including cosmetics (Patent Document 3), but changes in the UV protection effect due to heating are the subject of consideration to date. It has never been said.

JP-A-2010-150172 WO2016 / 068300 Japanese Patent No. 4397286

Generally, it is said that the amount of ultraviolet rays reaching the surface of the earth begins to increase around April and reaches its maximum from early summer (May) to midsummer (August). During the above period when the amount of ultraviolet rays is maximum, the skin is heated by radiant heat from the sun or radiant heat from the ground. Therefore, the presence of sunscreen cosmetics whose UV protection is improved by the addition of heat is ideal for protecting the skin from strong UV rays. Therefore, it is an object of the present invention to develop a sunscreen cosmetic whose ultraviolet protection ability is improved by heating, particularly an additive capable of providing such a sunscreen cosmetic.

As a result of diligent studies to solve the above-mentioned problems, the present inventors have selected at least a sunscreen cosmetic containing an ultraviolet protective agent from a parent-mediated substance or a moisturizer having a specific IOB. It has been found that when an additive containing one kind is blended, a special effect that the ultraviolet protection effect of the sunscreen cosmetic is improved (enhanced) by heating is obtained, and the present invention has been completed.

That is, the present invention enhances the UV protection effect of sunscreen cosmetics by heating, which comprises at least one selected from amphipathic substances or moisturizers having an IOB value of 5.0 or less. To provide an additive for.

By blending the additive of the present invention with a sunscreen cosmetic, the UV protection ability after heat is applied can be remarkably improved as compared with immediately after the cosmetic is applied to the skin. That is, the sunscreen cosmetic containing the additive of the present invention is a new and innovative sunscreen cosmetic in which the ultraviolet protection ability is improved by heat, which has been conventionally considered to be a cause of deterioration.

It is explanatory drawing which shows the outline of the evaluation method which can be used in this invention.

The present invention is an additive for enhancing the ultraviolet protection effect of sunscreen cosmetics by heating, and can also be referred to as an agent for enhancing the ultraviolet protection effect or sunscreen effect of sunscreen cosmetics by heating.

The additive for enhancing the ultraviolet protection effect of the sunscreen cosmetic according to the present invention by heating (also simply referred to as "additive" in the present specification) is an amphipathic substance having an IOB value of 5.0 or less. Alternatively, it is characterized by containing at least one selected from moisturizers.

"IOB" is an abbreviation for "Inorganic / Organic Balance" and is defined as IOB value = inorganic value / organic value. The organic value and the inorganic value are unique values given to atoms, functional groups, etc. in the organic conceptual diagram. The organic conceptual diagram is a good representation of the properties of organic substances having relatively complicated interactions. , Especially widely used in the fields of environmental chemistry and pharmacochemistry. For details, refer to, for example, Yoshio Koda, "Organic Conceptual Diagram-Basics and Applications-", Sankyo Publishing, 1984.

The additives of the present invention include amphipathic substances or moisturizers having an IOB value of 5.0 or less, more preferably 3.0 or less, even more preferably 2.5 or less. If the IOB value exceeds 5.0, the effect of improving the UV protection ability by heat may not be sufficiently obtained. The lower limit of the IOB value is not particularly limited (0 or more, for example, 0.0001 or more, 0.001 or more, 0.01 or more, etc.).

The amphipathic substance or moisturizer having an IOB value of 5.0 or less in the present invention preferably has an ether bond in the molecule. Above all, the following formula (I):
R ₁ O-[(AO) _m (EO) _n ] -R ₂ (I)
(In the above formula (I), AO represents an oxyalkylene group having 3 to 4 carbon atoms, EO represents an oxyethylene group, and R ₁ and R ₂ are independently hydrocarbons having 1 to 4 carbon atoms. A polyoxyalkylene polyoxyethylene copolymer dialkyl ether showing a hydrogen group or a hydrogen atom and represented by 1 ≦ m ≦ 70, 1 ≦ n ≦ 70), and the following formula (II):
HO (RO) _p H (II)
(In the formula, RO represents an oxyalkylene group having 2 to 4 carbon atoms, and p is 3 to 500.)
Polyalkylene glycol represented by, and polyhydric alcohol selected from butylene glycol, dipropylene glycol, diglycerin, propanediol, erythritol, xylitol, methylgluces-10, and sorbitol.
It is preferable to select from the group consisting of.

In the polyoxyalkylene / polyoxyethylene copolymer dialkyl ether represented by the above formula (I) (hereinafter, abbreviated as “POA / POE alkyl ether”), AO contains an oxyalkylene group having 3 to 4 carbon atoms. show. Specific examples thereof include an oxypropylene group, an oxybutylene group, an oxyisobutylene group, an oxytrimethylene group and an oxytetramethylene group. Preferred examples include an oxypropylene group and an oxybutylene group. EO represents an oxyethylene group.

M in the formula (I) is the average number of moles of AO added in one molecule, and is 1 ≦ m ≦ 70, preferably 1 ≦ m ≦ 30, and more preferably 1 ≦ m ≦ 20. n is the average number of moles of EO added in one molecule, which is 1 ≦ n ≦ 70, preferably 1 ≦ n ≦ 30, and more preferably 1 ≦ n ≦ 20. In the present invention, POA / POE alkyl ethers having m + n of 40 or less, preferably 25 or less, and more preferably 20 or less are used.

The order of addition of AO and EO in the POA / POE alkyl ether used in the present invention is not particularly limited. AO and EO may be block copolymers added in a block shape, or random copolymers added randomly. The block copolymer includes not only a two-stage block but also a copolymer containing three or more stages of blocks. Random copolymers are preferably used.

The molecular weight of the POA / POE alkyl ether represented by the formula (I) is preferably 100 to 10000, more preferably 200 to 5000, and further preferably 300 to 2000. The ratio of EO to the total of AO and EO in one molecule [EO / (AO + EO)] is preferably in the range of 20 to 80% by mass.

_{R 1} and R ₂ in the formula (I) independently represent a hydrocarbon group or a hydrogen atom having 1 to 4 carbon atoms. Examples of the hydrocarbon group include an alkyl group, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group and the like. It is preferably a methyl group or an ethyl group.

_{R 1} and R _{2 in} one molecule of POA / POE alkyl ether may be one kind of hydrocarbon group which is the same as each other, or a hydrocarbon group and a hydrogen atom may be mixed, and the number of carbon atoms is different. A plurality of hydrocarbon groups may be mixed. However, _{for each of R 1} and R _2, the ratio of the number of hydrogen atoms (Y) to the number of hydrocarbon groups (X) (Y / X) is 0.15 as the abundance ratio of hydrocarbon groups and hydrogen atoms. It is preferably less than or equal to, more preferably 0.06 or less.

Specific examples of the POA / POE alkyl ether preferably used in the present invention include, but are not limited to, the following.
PEG / PPG-9 / 2 dimethyl ether PEG / PPG-17 / 4 dimethyl ether PEG / PPG-14 / 7 dimethyl ether PEG / PPG-11 / 9 dimethyl ether PEG / PPG-55 / 28 dimethyl ether PEG / PPG-36 / 41 dimethyl ether PEG / PPG-6 / 3 dimethyl ether PEG / PPG-8 / 4 dimethyl ether PEG / PPG-6 / 11 dimethyl ether PEG / PPG-14 / 27 dimethyl ether

The alkylene oxide derivative having a relatively small molecular weight tends to be more effective in improving the UV protection ability due to heat. Therefore, among the polyoxypropylene / polyoxyethylene copolymer dimethyl ethers listed above, PEG / PPG-9 / 2 dimethyl ether shows the highest effect.

On the other hand, examples of the polyhydric alcohol include polyalkylene glycol of the formula (II) described later, butylene glycol, dipropylene glycol, diglycerin, propanediol, erythritol, xylitol, methylgluces-10, sorbitol and the like.

Here, the polyalkylene glycol is represented by the following formula (II) :.
HO (RO) _p H (II)
(In the formula, RO represents an oxyalkylene group having 2 to 4 carbon atoms, and p is 3 to 500.)
It is represented by.
Specifically, it can be used for external skin preparations such as cosmetics such as polyethylene glycol (also referred to as "PEG"), polypropylene glycol (also referred to as "PPG") and polybutylene glycol (also referred to as "PBG"). It is selected from the ones.

Among them, in the above formula (II), polyethylene glycol in which RO is an oxyethylene group and p is in the range of 3 to 500, more preferably 3 to 60 is preferable. The average molecular weight of the preferred polyethylene glycol is in the range of 150 to 23000, more preferably 150 to 3000. Specific examples thereof include polyethylene glycol 300, polyethylene glycol 400, polyethylene glycol 1500, and polyethylene glycol 20000.

The smaller the molecular weight of the polyalkylene glycol, the more excellent the effect of improving the ultraviolet protection ability due to heat tends to be. Therefore, among the polyethylene glycols listed above, the use of polyethylene glycol 300 or polyethylene glycol 400 is particularly effective.

The additive of the present invention may contain one type of amphipathic substance or moisturizer having an IOB value of 5.0 or less alone, or may contain two or more types in combination. For example, an additive containing at least one POA / POE alkyl ether of formula (I) and at least one polyalkylene glycol of formula (II) is a good example. The combination of PEG / PPG-9 / 2 dimethyl ether and polyethylene glycol 300 is a particularly preferred example.

The additive of the present invention may consist only of an amphipathic substance or a moisturizer having an IOB value of 5.0 or less, or may contain other components. For example, an embodiment in which an amphipathic substance or a moisturizer is dissolved in an aqueous medium such as water or alcohol, an embodiment in which an amphipathic substance or a moisturizer or an aqueous solution thereof is dispersed in oil, and the like can be mentioned.

The additive of the present invention is not particularly limited, but the amount of the amphoteric substance or moisturizer is 0.1% by mass or more, for example 0.1 to 25% by mass, preferably 0.1% by mass, based on the total amount of the sunscreen cosmetics. Is preferably blended in an amount of 1.0 to 20% by mass. If the blending amount is less than 0.1% by mass, the effect of improving the UV protection ability due to heat may not be sufficiently obtained, and if the blending amount exceeds 25% by mass, the stability and usability of the sunscreen cosmetics may not be obtained. May affect.

The amphipathic substance or moisturizer having an IOB value of 5.0 or less, particularly the POA / POE alkyl ether of the formula (I) and the polyalkylene glycol of the formula (II), which constitute the additive of the present invention, have been conventionally used in cosmetics. It is an ingredient used from. Therefore, there are also sunscreen cosmetics containing these. For example, WO2017 / 057676 can be used as an additive of the present invention in sunscreen cosmetics containing a combination of a specific UV absorber, 4-tert-butyl-4'-methoxydibenzoylmethane and ethylhexyl methoxycinnamate. It is disclosed that the deterioration of the ultraviolet protection effect due to light can be suppressed by blending the corresponding benzoyl substance or moisturizer. However, in WO2017 / 057676, the cosmetics are irradiated with ultraviolet rays to visible rays by a suntest machine whose wavelength is set to 300 to 800 nm, and infrared rays that give heat are not irradiated. As a result, although the conventional photodegradation is effectively suppressed, the UV protection effect after light irradiation is lower than that before irradiation. That is, no improvement in UV protection ability by heating has been observed.

The amphipathic substance or moisturizer having an IOB value of 5.0 or less constituting the additive of the present invention partially overlaps with the amphipathic substance described in WO2017 / 057676, but does not completely match. For example, it has been confirmed that glycerin (IOB = 6.0), which has an effect of suppressing photodegradation in WO2017 / 057676, does not show the effect of improving the ultraviolet protection ability due to heat of the present invention.

The additive of the present invention exerts its effect when blended in a sunscreen cosmetic. The sunscreen cosmetic containing the additive of the present invention is not particularly limited, and any cosmetic containing at least an ultraviolet absorber and / or an ultraviolet protective agent such as an ultraviolet scattering agent may be used.

The ultraviolet absorber is not particularly limited, and an ultraviolet absorber generally used for cosmetics can be widely mentioned. For example, benzoic acid derivative, salicylic acid derivative, silicic acid derivative, dibenzoylmethane derivative, β, β-diphenyl acrylate derivative, benzophenone derivative, benzilidenshonow derivative, phenylbenzoimidazole derivative, triazine derivative, phenylbenzotriazole derivative, anthranil derivative, imidazoline Derivatives, benzalmalonate derivatives, 4,4-diarylbutadiene derivatives and the like are exemplified. Specific examples and product names are listed below, but the present invention is not limited to these.

Examples of the benzoic acid derivative include para-aminobenzoic acid (PABA) ethyl, ethyl-dihydroxypropyl PABA, ethylhexyl-dimethyl PABA (for example, "Escalol 507"; ISP), glyceryl PABA, and PEG-25-PABA (for example, "ubinal"). P25 ”; BASF), hexyl diethylaminohydroxybenzoylbenzoate (eg,“ Ubinal A Plus ”; BASF) and the like are exemplified.

Salicylic acid derivatives include homosalate (“Eusolex HMS”; Lona / EM Industries), ethylhexyl salicylate (eg, “NeoHeliopan OS”; Harman & Reimer), dipropylene glycol. Examples include salicylate (eg, "Dipsal"; Skel), TEA salicylate (eg, "Neo Heliopan TS"; Harman and Reimer).

Examples of the silicic acid derivative include octylmethoxycinnamate or ethylhexyl methoxycinnamate (eg, "Pulsol MCX"; Hoffmann-La Roche), isopropyl methoxycinnamate, isoamyl methoxycinnamate (eg, "Neo Heliopan E1000"; Herman. And Reimer), cinnoxate, DEA methoxycinnamate, diisopropyl methylsilicate, glyceryl-ethylhexanoate-dimethoxycinnamate, di- (2-ethylhexyl) -4'-methoxybenzalmalonate and the like.

As the dibenzoylmethane derivative, 4-tert-butyl-4'-methoxydibenzoylmethane (sometimes abbreviated as "t-butylmethoxydibenzoylmethane") (for example, "Palsol 1789"; Hoffmann-la Roche) ) Etc. are exemplified.

Examples of the β, β-diphenylacrylate derivative include octocrylene (for example, “Ubinal N539T”; BASF).

Examples of the benzophenone derivative include benzophenone-1 (eg, "Ubinal 400"; BASF), benzophenone-2 (eg, "Ubinal D50"; BASF), benzophenone-3 or oxybenzone-3 (eg, "Ubinal M40"; BASF). , Benzophenone-4 (eg, "Ubinal MS40"; BASF), Benzophenone-5, Benzophenone-6 (eg, "Helisorb 11"; Norquay), Benzophenone-8 (eg, "Spectra-Sorb"). UV-24 ”; American Cyanamide), benzophenone-9 (eg,“ Ubinal DS-49 ”; BASF), benzophenone-12 and the like are exemplified.

Benzylidene camphor derivatives include 3-benzylene camphor (eg, "Mexoryl SD"; Simex), 4-methylbenzylene camphor, benzylidene camphor sulfonic acid (eg, "Megisolyl SL"; Simex), camphor benzalco methosulfate. Examples include nium (eg, "Megisolyl SO"; Simex), terephthalilidene dicamphorsulfonic acid (eg, "Megizolyl SX"; Simex), polyacrylamide methylbenzylene camphor (eg, "Megisolyl SW"; Simex), and the like. ..

Examples of the phenylbenzimidazole derivative include phenylbenzimidazole sulfonic acid (for example, "Usolex 232"; Merck), phenyldivene imidazole disodium tetrasulfonate (for example, "Neo Heliopan AP"; Herman & Reimer), etc. Is exemplified.

Examples of triazine derivatives include bisethylhexyloxyphenol methoxyphenyl triazine (for example, "Tinosorb S"; Ciba Specialty Chemicals), ethylhexyltriazone (for example, "Ubinal T150"; BASF), and diethylhexylbutamidtri. Azone (eg, "Uvasorb HEB"; Sigma 3V), 2,4,6-tris (diisobutyl-4'-aminobenzalmaronate) -s-triazine, 2,4,6-tris [4] -(2-Ethylhexyloxycarbonyl) anilino] -1,3,5-triazine and the like are exemplified.

Phenylbenzotriazole derivatives include drometrizoletrisiloxane (eg, "Silatrizole"; Rhodia Shimmy), methylenebis (benzotriazolyltetramethylbutylphenol) (eg, "Tinosorb M" (Ciba Specialty). Chemicals)), etc. are exemplified.

Examples of the anthranil derivative include menthyl anthranilate (for example, "Neo Heliopan MA"; Harman & Reimer).

Examples of the imidazoline derivative include ethylhexyldimethoxybenzylidenedioxoimidazoline propionate.

Examples of the benzalmalonate derivative include polyorganosiloxane having a benzalmalonate functional group (for example, polysilicone-15 (dimethicodiethylbenzalmalonate); "Pulsol SLX"; DSM Nutrition Japan Co., Ltd.). NS.

Examples of the 4,4-diarylbutadiene derivative include 1,1-dicarboxy (2,2'-dimethylpropyl) -4,4-diphenylbutadiene.

Particularly preferred examples are, but are not limited to, ethylhexyl methoxycinnamate, octocrylene, dimethicodiethylbenzalmalonate, polyvinyl-15, t-butylmethoxydibenzoylmethane, ethylhexyltriazone, hexyl diethylaminohydroxybenzoyl benzoate, bis. Ethylhexyloxyphenol Methoxyphenyltriazine, oxybenzon-3, methylenebis (benzotriazolyltetramethylbutylphenol), phenylbenzimidazole sulfonic acid, 3- (4'-methylbenzylene) -d, l-campar, 3-benzylene-d, Examples thereof include organic ultraviolet absorbers such as l-phenyl, homosalate, and ethylhexyl salicylate.

The ultraviolet scattering agent is not particularly limited, and specific examples thereof include fine metal oxides such as zinc oxide, titanium oxide, iron oxide, cerium oxide, and tungsten oxide.

The ultraviolet scattering agent may be one that has not been surface-treated or one that has been subjected to various hydrophobic surface treatments, but those that have been subjected to hydrophobic surface treatment are preferably used. Surface treatment agents are widely used in the cosmetics field, for example, silicones such as dimethicone and alkyl-modified silicones, alkoxysilanes such as octylriethoxysilane, dextrin fatty acid esters such as dextrin palmitate, and fatty acids such as stearic acid. Can be used.

The UV protection agent may be any of a mode consisting of only a UV absorber, a mode consisting of only a UV scatterer, and a mode containing both a UV absorber and a UV scatterer.
The amount of the UV protection agent to be blended in the sunscreen cosmetics is not particularly limited, but is usually 5% by mass or more, for example, 5 to 40% by mass, preferably 6 to 40% by mass, more preferably 7 with respect to the total amount of the cosmetics. ~ 30% by mass. If the blending amount of the UV protection agent is less than 5% by mass, it is difficult to obtain a sufficient UV protection effect, and even if it is blended in excess of 40% by mass, an increase in the UV protection effect commensurate with the blending amount cannot be expected, and the stability is improved. It is not preferable because it becomes worse.

When t-butylmethoxydibenzoylmethane is blended as an ultraviolet absorber, it is preferable that the blending amount is small. For example, it is preferably less than 0.5% by mass with respect to the total amount of cosmetics, or 10% by mass or less with respect to the total amount of UV protective agents. This is because t-butylmethoxydibenzoylmethane tends to hinder the improvement of the ultraviolet protection effect by heating when the additive of the present invention is blended, so that it is difficult to realize the enhancement of the ultraviolet protection effect by heat.

In addition to the ultraviolet protective agent, sunscreen cosmetics may contain ingredients usually used in cosmetics as long as the effects of the present invention are not impaired. For example, pH adjusters, chelating agents, preservatives, antioxidants, oily activators, surfactants, aqueous phase thickeners, alcohols, powder components, coloring agents, pigments, chemicals, etc. are appropriately blended as necessary. can do. Examples of the drug include ascorbic acid (vitamin C), tranexamic acid, kodiic acid, ellagic acid, arbutin, alkoxysalicylic acid, nicotinic acid amide, glycyrrhizinic acid, tocopherol, retinol and salts or derivatives thereof (for example, L-ascorbic acid). Sodium, L-ascorbic acid ester magnesium salt, L-ascorbic acid glucoside, 2-O-ethyl-L-ascorbic acid, 3-O-ethyl-L-ascorbic acid, 4-methoxysalicylic acid sodium salt, 4-methoxysalicylate potassium Examples thereof include salts, dipotassium glycyrrhizinate, stearyl glycyrrhizinate, tocopherol acetate, retinol acetate, retinol palmitate, etc. Further, a moisturizing agent having an IOB value of more than 5.0 such as glycerin does not inhibit the effect of the present invention. It can be blended in a range.

The sunscreen cosmetics may be in the form of oil-based cosmetics, water-in-oil emulsified cosmetics, oil-in-water emulsified cosmetics, polyphasic emulsified cosmetics, or water-based cosmetics, and are not particularly limited. In the case of an emulsified cosmetic, by blending 5% by mass or more of alcohol with respect to the total amount of the cosmetic, a smooth feeling of use and improvement in elongation can be obtained. However, if the amount of alcohol blended is too large, the emulsification stability may be inferior. Therefore, it is preferably 30% by mass or less with respect to the amount of cosmetics. Further, in the case of an emulsified cosmetic, it is preferable to add an ester oil having an IOB value of 0.3 or more to the oil phase. Product forms include not only sunscreen cosmetics, but also makeup cosmetics such as foundations with sunscreen effects, makeup bases, and hair cosmetics (hair sprays and hair treatments to protect hair and scalp from ultraviolet rays, etc.) (Including various hair products), spray-type cosmetics, etc. can be provided.

Further, by blending the spherical powder with the cosmetic, stickiness is suppressed, the usability is improved, and a smooth and good feel can be obtained. The spherical powder can be arbitrarily used without particular limitation as long as it is generally used in cosmetics and the like. For example, (meth) acrylic acid ester resin powder, polyamide resin powder (nylon powder), polyethylene powder, polystyrene powder, styrene and (meth) acrylic acid copolymer resin powder, benzoguanamine resin powder, polytetrafluorinated ethylene powder, Examples thereof include cellulose powder, trimethylsilsesquioxane powder and the like, and organopolysiloxane elastomer spherical powder or a composite spherical powder using the same as a mother powder. The average particle size of the spherical powder is preferably 3 to 20 μm. If it is smaller than 3 μm, the effect of suppressing stickiness is not seen, and if it is larger than 20 μm, roughness may occur on the contrary. The blending amount of the spherical powder is not particularly limited, but is preferably 1 to 30% by mass, more preferably 3 to 20% by mass.

The effect obtained by the additive of the present invention (the effect of improving the ultraviolet protection ability by heating) is confirmed, for example, by an evaluation method including the following steps (i) to (iv).
(I) Step of forming a coating film of the sample composition on the substrate,
(Ii) A step of heat-treating the coating film of the sample composition,
(Iii) A step of measuring the ultraviolet protection effect of the coating film of the sample composition which has not been heat-treated and the coating film of the sample composition which has been heat-treated, and (iv) a step of comparing the measured ultraviolet protection effect.

The case where the above evaluation method is carried out in vitro will be described below with reference to FIG.
In the step (i), a predetermined amount of the cosmetic sample 1 is applied to the substrate 2 and optionally dried to form a coating film of the sample 1 on the substrate 2. As the substrate, a resin substrate such as PMMA, nylon, or an acrylic plate, or an inorganic substrate such as glass or quartz can be used. Preferably, a skin substitute membrane (also referred to as "S plate": see Patent No. 4453995) made of a PMMA plate having a V-shaped groove on the surface is used. Next, the UV protection effect (absorbance, etc.) of the formed sample coating film before heating is measured (step (i')).

In the next step (ii), heat is applied to the sample coating film formed in the step (i).
The heating temperature in the step (ii) is preferably in the range of 30 ° C. to 70 ° C. If the heating temperature exceeds 70 ° C., problems such as melting of the resin substrate may occur. The temperature is not particularly limited as long as it is within the above range, and can be, for example, 32 ° C or higher, 35 ° C or higher, 37 ° C or higher, or 40 ° C or higher, and is 65 ° C or lower, 60 ° C or lower, 55 ° C or lower, or 50 ° C. Heat treatment may be performed at a temperature of ° C. or lower.
The heating time is preferably 1 minute or longer, more preferably 10 minutes or longer, in order to accurately evaluate the effect of heat. The upper limit of the heating time is not particularly limited, but is usually 60 minutes or less, preferably 30 minutes or less.

After the completion of the step (ii), the substrate is preferably left to stand until the temperature of the substrate returns to room temperature, and the absorbance of the sample coating film of each substrate at a predetermined wavelength (UVA or UVB region) is measured (step (iii)).

Finally, in the step (iv), the UV protection effect of the heated sample coating film and the UV protection effect of the sample coating film before heating (step i') are compared (not shown).

The ultraviolet protection effect is typically measured by measuring the absorbance of the coating film over 280 to 400 nm with a spectrophotometer or the like, and using the integrated absorbance value of the sample coating film as an index. That is, from the integrated absorbance value of the coating film (heated sample) after the heat treatment and the integrated absorbance value of the coating film (non-heated sample) before the heat treatment, the following formula:
Thermal reaction rate (%) = (integrated absorbance after heat treatment) / (integrated absorbance before heat treatment) x 100
When the thermal reaction rate required in (1) exceeds 100%, it is defined that the ultraviolet protection effect is improved by heating.
Instead of the above-mentioned integrated absorbance value, SPF or UVAPF (or PFA) calculated based on the absorbance at a single wavelength (ultraviolet region), the critical wavelength, or the measured absorbance may be used as an index.

In the above evaluation method, from the viewpoint of eliminating the influence of factors other than heat, it is preferable to carry out the heat treatment (step (ii)) in an environment in which ultraviolet rays are blocked.

The present invention will be described in more detail with reference to Examples below, but the present invention is not limited thereto. Unless otherwise specified, the blending amount is shown in mass% with respect to the system in which the component is blended.

Sunscreen cosmetics (samples) having the formulations shown in each of the examples in Tables 1 to 5 below were prepared.
The obtained sample was applied to a PMMA plate at room temperature (25 ° C.) at ^{a coating amount of 2} mg / cm 2, and then the absorbance at 280 to 400 nm was measured using an absorptiometer.
A sample of each example was added dropwise to a pseudo-skin PMMA plate (SPFMASTER-PA01) at ^{an amount of 2} mg / cm 2, applied with a finger for 60 seconds, and dried for 15 minutes to form a coating film. Using the uncoated plate as a control, the absorbance (280-400 nm) of the coating film was measured with a U-3500 self-recording spectrophotometer manufactured by Hitachi, Ltd., and the absorbance was integrated before heat treatment from the obtained measurement data. The value was calculated.

Next, the measured plate was heated at 37 ° C. for 30 minutes in a constant temperature bath, returned to room temperature, and then the absorbance was measured under the same conditions as above, and the integrated absorbance value after heat treatment was obtained from the obtained measurement data.
The thermal reaction rate was calculated from the integrated absorbance values before and after heating according to the above formula. The values of the thermal reaction rate (%) of each example are also shown.

(1) Water-in-oil emulsified cosmetics In the samples of each example shown in Tables 1 to 3, the powder was dispersed in the oily components mixed using a homomixer, and then the well-mixed aqueous components were added to the oil. A medium-water emulsified sunscreen cosmetic was used.

(2) Oil-in-water emulsified cosmetics In the sample of the example shown in Table 4, the powder is dispersed in the oily components mixed using a homomixer, and then the oily components are added to the separately mixed aqueous components to make the oil in water. Emulsified sunscreen cosmetics.

(3) Oil-based cosmetics For each example shown in Table 5 below, all the ingredients were mixed using a homomixer to obtain an oil-based sunscreen cosmetic. In the example containing an oil-based solidifying agent, an oil-based solidifying agent was added to the oil-based component to heat and melt it, a moisturizer was added, mixed and homogenized, and then cooled to obtain an oil-based solid sunscreen cosmetic.

As shown in Tables 1 to 5, it was confirmed that the addition of the additive of the present invention to various forms of sunscreen cosmetics exerts a unique effect of improving the ultraviolet protection effect by heating. ..

The formulation of the cosmetic of the present invention is illustrated below. It goes without saying that the present invention is not limited to these prescription examples, and is specified by the scope of claims. In addition, all the compounding amounts are expressed by mass% with respect to the total amount of cosmetics.

Formulation example 1: Two-layer makeup base (ingredient name) Blending amount (mass%)
Purified water Residual ethanol 5
PEG / PPG-9 / 2 dimethyl ether 5
Glycerin 1
Xylitol 1
Tormentilla extract 0.3
Sodium hyaluronate 0.1
2-O-ethyl-L-ascorbic acid 0.1
Dipotassium glycyrrhizinate 0.05
Isododecane 3
Diisopropyl sebacate 10
PBG / PPG-9 / 1 copolymer 1
Dimethicone 13
Caprilyl methicone 3
Highly Polymerized Aminopropyl Dimethicone 20% Dimethicone Solution
1
Trifluoroalkyldimethyltrimethylsiloxysilicic acid 50% dimethicone solution
3
Dextrin palmitate 0.5
Ethylhexyl methoxycinnamate 7
Octocrylene 5
Diethylaminohydroxybenzoyl hexyl benzoate 1
Bisethylhexyloxyphenol methoxyphenyl triazine
0.5
Hydrophobicized fine particle titanium oxide 2
Hydrophobicized fine particle zinc oxide 5
Hydrophobicized pigment grade titanium oxide 1
Hydrophobicized iron oxide 0.07
Methyl methacrylate crosspolymer 2
(Vinyl dimethicone / methicone silsesquioxane) Cross polymer
2
Hydrophobicized talc 2
PEG-9 Polydimethylpolysiloxyethyl dimethicone 1.5
PEG / PPG-19 / 19 Dimethicone 0.3
Dimethyl distearyl ammonium hectorite 0.4
Isostearic acid 0.3
EDTA ・ 3Na Appropriate amount Salt Appropriate amount Sodium pyrosulfite Appropriate amount Tocopherol Appropriate amount Fragrance Appropriate amount Total 100

Prescription example 2: Creamy foundation (ingredient name) Blending amount (mass%)
Purified water Residual ethanol 5
Phenoxyethanol 1
PEG / PPG-9 / 2 dimethyl ether 5
Glycerin 3
Erythritol 1
Xylitol 1
Tormentilla extract 1
Glycylglycine 0.1
Tranexamic acid 1
Dipotassium glycyrrhizinate 0.05
Tripropylene glycol pivalate 2
Diisopropyl sebacate 5
Dimethicone 10
Cyclomethicone 5
Cyclopentasiloxane solution of 50% trisiloxysilicic acid
2
Dextrin palmitate 1
Ethylhexyl methoxycinnamate 7
Hydrophobicized fine particles Titanium oxide 3
Hydrophobicized fine particle zinc oxide 3
Hydrophobicized pigment grade titanium oxide 6
Hydrophobicized iron oxide 3.2
Hydrophobized barium sulfate coated mica titanium 0.01
Hydrophobicized mica titanium 0.01
Dimethicone crosspolymer 13% cyclopentasiloxane mixture
2
Polymethylsilsesquioxane 2
Methyl methacrylate crosspolymer 2
Hydrophobicized fine particle silica 0.5
Lauryl PEG-9 polydimethylpolysiloxyethyl dimethicone
2
(Dimethicone / (PEG-10 / 15)) Crosspolymer
1
Dimethyl distearyl ammonium hectorite 1
Isostearic acid 0.2
Tocopherol Appropriate amount EDTA ・ 3Na Appropriate amount Salt Appropriate amount Sodium metabisulfite Appropriate amount Fragrance Appropriate amount Total 100

Prescription example 3: Aerosol spray type sunscreen (ingredient name) Blending amount (mass%)
Purified water Residual ethanol 5
Polyethylene glycol 300 2
Silica 0.5
Glycerin 1
PEG / PPG-14 / 7 dimethyl ether 6
DL-α-tocopherol acetate 0.5
D-glutamic acid 0.1
Stearyl glycyrrhizinate 0.1
Isododecane 10
Glyceryl tri2-ethylhexanoate 5
Isopropyl myrstate 3
Diisopropyl sebacate 5
PBG / PPG-9 / 1 copolymer 1
Dimethicone 13
Cyclopentasiloxane solution of 50% trisiloxysilicic acid
0.5
Sucrose tetrastearate triacetate 0.5
Dextrin palmitate 1
Ethylhexyl methoxycinnamate 5
Diethylaminohydroxybenzoyl hexyl benzoate 2
Bisethylhexyloxyphenol methoxyphenyl triazine
1
Polysilicone-15 2
Octocrylene 5
Methyl methacrylate crosspolymer 5
(Vinyl dimethicone / methicone silsesquioxane) Cross polymer
3
Hydrophobicized talc 1
Cetyl PEG / PPG-10 / 1 Dimethicone 1
Lauryl PEG-9 polydimethylpolysiloxyethyl dimethicone
1
Dimethyl distearyl ammonium hectorite 0.5
Isostearic acid 0.3
Sorbitan sesquiisostearate 0.3
EDTA ・ 3Na Appropriate amount Tocopherol Appropriate amount Fragrance Appropriate amount Total 100
The above components were mixed to prepare a stock solution, and the stock solution and LPG were filled in a spray can at a ratio of 50:50 to obtain an aerosol spray type sunscreen.

Prescription example 4: Gel-like BB cream (ingredient name) Blending amount (mass%)
Purified water Residual ethanol 8
PEG / PPG-9 / 2 dimethyl ether 5
Izayoi Rose Extract 0.1
Stearoxy hydroxypropyl methylcellulose 0.2
(Dimethylacrylamide / Acryloyldimethyltaurine Na) Copolymer
0.2
Succino glucan 0.1
Glycerin 3
Polyethylene glycol 300 1
Bis PEG-18 Methyl Ether Dimethyl Silane 3
PEG / PPG-14 / 7 dimethyl ether 1
Ethylhexyl methoxycinnamate 10
Diisopropyl sebacate 5
Diethylaminohydroxybenzoyl hexyl benzoate 1
Bisethylhexyloxyphenol methoxyphenyl triazine
3
Hydrophobicized fine particles Titanium oxide 3
Hydrophobicized fine particle zinc oxide 5
Hydrophobicized pigment grade titanium 4
Hydrophobicized iron oxide 0.4
Isopropyl myrstate 2
Polypropylene glycol (17) 2
N-lauroyl-L-glutamic acid di (cholesteryl phytosteryl)
0.5
(Palmitate / Ethyl Caproic Acid) Dextrin 0.5
Fragrance Appropriate amount silica 1
100 in total

Prescription example 5: Emulsion to creamy BB cream (ingredient name) Blending amount (mass%)
Purified water Residual ethanol 6
L-Ascorbic Magnesium Phosphate 0.5
Acetylated sodium hyaluronate 0.1
Water-soluble collagen 0.1
Izayoi Rose Extract 0.1
(Dimethylacrylamide / Acryloyldimethyltaurine Na) Copolymer
0.3
Succino glucan 0.2
Cellulose gum 0.2
Glycerin 2
Butylene glycol 4
PEG / PPG-14 / 7 dimethyl ether 3
PEG / PPG-9 / 2 dimethyl ether 2
Polyethylene glycol 300 1
Polyoxyethylene hydrogenated castor oil (100 mol) 1
Polyoxyethylene (8 mol) behenyl ether 1
Stearoyl methyl taurine sodium 0.1
Stearyl alcohol 0.5
Behenyl alcohol 0.5
Ethylhexyl methoxycinnamate 8
Octocrylene 2
Ethylhexyltriazine 1
Diethylaminohydroxybenzoyl hexyl benzoate 1
Bisethylhexyloxyphenol methoxyphenyl triazine
1
Isododecane 10
Diisopropyl sebacate 5
Dimethicone 2
Macadamia nut oil fatty acid phytosteryl 1
N-lauroyl-L-glutamic acid di (phytosteryl octyldodecyl)
0.5
(Palmitate / Ethyl Caproic Acid) Dextrin 0.5
Hydrophobicized fine particles zinc oxide 8
Pigment-grade hydrophobized titanium oxide 4
Hydrophobicized iron oxide 0.2
Isostearic acid 0.5
Sorbitan sesquiisostearate 0.5
EDTA-2Na / H2O Appropriate amount Sodium hexametaphosphate Appropriate amount Citric acid Appropriate amount Sodium citrate Appropriate amount Fragrance Appropriate amount Tarku 3
Silica 3
100 in total

1: Sample, 2: Base

Claims (4)

Addition for enhancing the UV protection effect of sunscreen cosmetics by heating, which comprises at least one selected from the group consisting of amphipathic substances or moisturizers having an IOB value of 5.0 or less. Agent. The amphipathic substance or moisturizer has the following formula (I):
R ₁ O-[(AO) _m (EO) _n ] -R ₂ (I)
(In the formula (I), AO represents an oxyalkylene group having 3 to 4 carbon atoms, EO represents an oxyethylene group, and R ₁ and R ₂ are independently hydrocarbons having 1 to 4 carbon atoms. Indicates a group or hydrogen atom, 1 ≦ m ≦ 70, 1 ≦ n ≦ 70)
Polyoxyalkylene polyoxyethylene copolymer dialkyl ether represented by; and
The following formula (II):
HO (RO) _p H (II)
(In the formula, RO represents an oxyalkylene group having 2 to 4 carbon atoms, and p is 3 to 500.)
Polyalkylene glycol represented by, and polyhydric alcohol selected from the group consisting of butylene glycol, dipropylene glycol, diglycerin, propanediol, erythritol, xylitol, methylgluces-10, and sorbitol;
The additive according to claim 1, which is selected from. At least one of the polyoxyalkylene / polyoxyethylene copolymer dialkyl ethers represented by the above formula (I), and
The additive according to claim 2, which comprises at least one of the polyalkylene glycols represented by the above formula (II). The polyoxyalkylene polyoxyethylene copolymer dialkyl ether represented by the above formula (I) is PEG / PPG-9 / 2 dimethyl ether, and the polyalkylene glycol represented by the above formula (II) is polyethylene glycol 300. The additive according to claim 2 or 3.

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