WO2017057675A1 - Sunscreen cosmetic - Google Patents
Sunscreen cosmetic Download PDFInfo
- Publication number
- WO2017057675A1 WO2017057675A1 PCT/JP2016/079010 JP2016079010W WO2017057675A1 WO 2017057675 A1 WO2017057675 A1 WO 2017057675A1 JP 2016079010 W JP2016079010 W JP 2016079010W WO 2017057675 A1 WO2017057675 A1 WO 2017057675A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- powder
- fatty acid
- alkaline earth
- earth metal
- higher fatty
- Prior art date
Links
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/35—Ketones, e.g. benzophenone
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/36—Carboxylic acids; Salts or anhydrides thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
- A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
Definitions
- the present invention relates to a sunscreen cosmetic. More specifically, it includes a dibenzoylmethane derivative that is an ultraviolet absorber and an ultraviolet scattering agent that has been subjected to a specific surface treatment, and exhibits high UV protection ability in a wide wavelength range from UVA to UVB, and is also stable. Also related to excellent sunscreen cosmetics.
- Sunscreen cosmetics a type of UV care cosmetics, reach the skin by absorbing or scattering UVA and UVB by covering the skin with a coating film containing UV absorbers and UV scattering agents. It is a cosmetic intended to suppress the amount of ultraviolet rays to be protected and protect the skin from the harm of ultraviolet rays (Non-patent Document 1).
- Dibenzoylmethane derivatives are widely used in sunscreen cosmetics as organic UV absorbers that have an absorption peak in the UVA region. However, they reduce the photoprotective ability due to photolysis and interact with other coexisting components, especially metal ions. There are problems such as crystal precipitation and discoloration (yellowing) due to action.
- Patent Document 1 the discoloration (yellowing) and the reduction of light protection in a composition containing a dibenzoylmethane derivative and titanium oxide are suppressed by coating the surface of titanium oxide with silicone (siloxane or silane derivative).
- silicone silicone or silane derivative
- Patent Document 2 discloses that zinc oxide particles are surface-treated in order to prevent deterioration due to the reaction between dibenzoylmethane and zinc oxide.
- silicone fatty acid, protein, peptide, amino acid, N-acylamino acids, monoglycerides, diglycerides, triglycerides, mineral oil, silica, phospholipids, sterols, hydrocarbons, polyacrylates, alumina and mixtures thereof are mentioned (page 13).
- Metal oxide powders such as titanium oxide and zinc oxide are blended in sunscreen cosmetics as UV scattering agents, but they may also be subjected to surface hydrophobization for the purpose of improving dispersibility in oil and transparency. is there.
- Patent Document 3 describes that when fine particles of titanium oxide surface-treated with metal soap are used, the transparency is improved, but the ultraviolet shielding effect is lowered (page 3).
- the general surface treatment substances for example, alumina listed in Patent Documents 1 and 2 contain metals, the powder surface-treated with these substances is dibenzoyl. When coexisting with methane derivatives, the possibility of discoloration and crystal precipitation cannot be denied.
- silica-coated titanium oxide is blended, the white color when applied to the skin tends to be unnaturally conspicuous.
- the problem in the present invention is that the instability of the dibenzoylmethane derivative, which is a UVA absorber, can be eliminated, and an excellent UV protection ability can be exhibited in a wide wavelength range from UVA to UVB. Is to provide a sunscreen cosmetic that is stable, does not cause discoloration or crystal precipitation, and does not become unnaturally whitened.
- the present inventors have conducted a treatment with a metal soap composed of a higher fatty acid and an alkaline earth metal on the surface of a metal oxide to be blended as an ultraviolet scattering agent, or a higher fatty acid.
- the present invention has found that a stable sunscreen cosmetic can be obtained without causing crystal precipitation or discoloration even when co-existing with a dibenzoylmethane derivative by performing a composite treatment with alkenyl and an alkaline earth metal hydroxide. It came to complete.
- the present invention (A) a dibenzoylmethane derivative, and (b) a powder that has been surface-hydrophobized by a metal soap treatment comprising a higher fatty acid and an alkaline earth metal or a composite treatment of a higher fatty acid and an alkaline earth metal hydroxide.
- a sunscreen cosmetic characterized by containing.
- a dibenzoylmethane derivative known to have a property of being altered or decomposed is co-blended with a powder (ultraviolet scattering agent) that has been subjected to a specific surface treatment, so that it has an ultraviolet shielding ability during storage. It is possible to provide a sunscreen cosmetic that does not decrease and does not cause problems in use or appearance such as crystal precipitation and discoloration.
- the sunscreen cosmetic of the present invention has a surface treated by (a) a dibenzoylmethane derivative and (b) a metal soap treatment comprising a higher fatty acid and an alkaline earth metal or a composite treatment of a higher fatty acid and an alkaline earth metal hydroxide. Hydrophobized powder is contained as an essential component.
- Dibenzoylmethane derivative The dibenzoylmethane derivative (component a) is widely used in cosmetics and the like as an ultraviolet absorber having a maximum absorption wavelength in the UVA region.
- Examples of the dibenzoylmethane derivative used in the present invention include 2-methyldibenzoylmethane, 4-methyldibenzoylmethane, 4-isopropyldibenzoylmethane, 4-tert-butyldibenzoylmethane, and 2,4-dimethyldibenzene.
- Benzoylmethane 2,5-dimethyldibenzoylmethane, 4,4'-diisopropyldibenzoylmethane, 4-methoxy-4'-tert-butyldibenzoylmethane, 2-methyl-5-isopropyl-4'-methoxydibenzoyl Methane, 2-methyl-5-tert-butyl-4'-methoxydibenzoylmethane, 2,4-dimethyl-4'-methoxydibenzoylmethane, 2,6-dimethyl-4-tert-butyl-4'-methoxy And dibenzoylmethane.
- 4-methoxy-4′-tert-butyldibenzoylmethane (designated name: t-butylmethoxybenzoylmethane) is particularly preferably used.
- the dibenzoylmethane derivative a commercially available product may be used.
- 4-methoxy-4′-tert-butyldibenzoylmethane commercially available from DSM Nutrition Japan Co., Ltd. under the name “Pulsol 1789” may be used. it can.
- the blending amount of the dibenzoylmethane derivative in the sunscreen cosmetic of the present invention is preferably 0.5 to 4.0% by mass, and more preferably 1.0 to 3.0% by mass. If the blending amount is less than 0.5% by mass, sufficient UV protection effect cannot be obtained, and even if it exceeds 4.0% by mass, further improvement in UV protection effect cannot be obtained, and the use property such as stickiness is not improved. May cause problems.
- the powder blended in the sunscreen cosmetic of the present invention is a powder that physically blocks ultraviolet rays by reflection or scattering (also referred to as “ultraviolet scattering agent”), and has been subjected to a specific surface hydrophobization treatment. Is the body.
- the specific hydrophobizing treatment in the present invention means (1) treatment with a metal soap composed of higher fatty acid and alkaline earth metal, or (2) combined treatment with higher fatty acid and alkaline earth metal hydroxide.
- the higher fatty acid used here is preferably a linear or branched carboxylic acid having 8 to 24 carbon atoms (preferably 12 to 18 carbon atoms). Specific examples include stearic acid, isostearic acid, myristic acid, lauric acid and the like, and isostearic acid is particularly preferable.
- the alkaline earth metal calcium and magnesium are preferable, and magnesium is particularly preferable.
- hydrophobizing method a wet method using a solvent, a gas phase method, a mechanochemical method, or the like can be used, and it is not particularly limited.
- the specific hydrophobized powder (mother core) is not particularly limited as long as it is a powder used as an ultraviolet scattering agent in the cosmetic field.
- Specific examples include one selected from titanium oxide, zinc oxide, barium sulfate, iron oxide, talc, mica, sericite, kaolin, titanium mica, bitumen, chromium oxide, chromium hydroxide, silica, cerium oxide, and the like. Two or more types can be mentioned. In particular, it is preferable from the viewpoint of optical properties to use a powder having a refractive index of 1.5 or more.
- the powder (mother core) is not particularly limited as long as it is conventionally blended in cosmetics and the like.
- the average primary particle diameter is 100 nm or less, preferably 50 nm or less, more preferably 30 nm or less. Are preferably used.
- the lower limit value of the average primary particle size is not particularly limited, but it becomes more expensive as the particle size becomes smaller.
- the average primary particle diameter in the present specification means the diameter of the primary particle of the powder measured by a generally used method. Specifically, from the transmission electron micrograph, It is a value obtained as an arithmetic average of the length of the major axis and the length of the minor axis.
- the particle form of the powder is not particularly limited, and includes a spherical shape, an elliptical shape, a crushed shape, and the like, and may be a primary particle state or an aggregated secondary aggregate.
- the powder (component b) subjected to the specific treatment is simply referred to as “ultraviolet scattering agent”.
- the blending amount of the ultraviolet light scattering agent (component b) in the sunscreen cosmetic of the present invention is preferably 1 to 15% by mass, and more preferably 2 to 8% by mass.
- the blending amount is less than 1% by mass, a sufficient UV protection effect cannot be obtained, and when the blending amount exceeds 15% by mass, the usability tends to decrease.
- Dibenzoylmethane derivatives especially 4-methoxy-4'-tert-butyldibenzoylmethane
- powders such as titanium oxide are also used as UV scattering agents.
- Various types of surface hydrophobized powders are known.
- the most widely used metal soap used for the surface treatment of powder is a metal soap containing aluminum, which is a trivalent metal, and is a powder treated with a metal soap containing an alkaline earth metal such as magnesium.
- a metal soap is selected from the known surface treatment agents, and a metal soap containing an alkaline earth metal, preferably calcium or magnesium, is selected from the metal soap. It has been found for the first time that even if it is blended, stability can be maintained without causing crystal precipitation.
- the composition containing the dibenzoylmethane derivative was subjected to surface hydrophobization treatment by a metal soap treatment comprising a higher fatty acid and an alkaline earth metal or a composite treatment of a higher fatty acid and an alkaline earth metal hydroxide.
- the present invention provides a method for stabilizing the composition, comprising blending powder.
- the sunscreen cosmetic of the present invention is a range that does not inhibit the effects of the present invention, in addition to (a) a dibenzoylmethane derivative and (b) an ultraviolet scattering agent, and other optional components that can be usually added to the sunscreen cosmetic. May be included.
- the other optional components are not particularly limited, but for example, by further adding an ultraviolet absorber other than the dibenzoylmethane derivative, the ultraviolet protection ability in the UVA and / or UVB region can be further improved.
- the ultraviolet absorber other than the dibenzoylmethane derivative can be selected from those usually used in cosmetics and is not particularly limited.
- para-aminobenzoic acid derivatives for example, para-aminobenzoic acid derivatives, salicylic acid derivatives, cinnamic acid derivatives, ⁇ , ⁇ -diphenyl acrylate derivatives, benzophenone derivatives, benzylidene camphor derivatives, phenylbenzimidazole derivatives, triazine derivatives, phenylbenzotriazole derivatives, anthranyl derivatives, imidazolines
- examples thereof include one or more selected from derivatives, benzalmalonate derivatives, 4,4-diarylbutadiene derivatives and the like.
- Other optional components include water-soluble polymers, oil-soluble polymers, waxes, alcohols, hydrocarbon oils, fatty acids, higher alcohols, fatty acid esters, silicone oils, surfactants, powder components other than UV scattering agents, Although a medicine etc. are mentioned, it is not limited to these illustrations.
- water-soluble polymer examples include homopolymers or copolymers of 2-acrylamido-2-methylpropanesulfonic acid (hereinafter abbreviated as “AMPS”).
- the copolymer is a copolymer composed of a comonomer such as vinyl pyrrolidone, acrylic acid amide, sodium acrylate, or hydroxyethyl acrylate. That is, an AMPS homopolymer, a vinylpyrrolidone / AMPS copolymer, a dimethylacrylamide / AMPS copolymer, an acrylic amide / AMPS copolymer, a sodium acrylate / AMPS copolymer, and the like are exemplified.
- carboxyvinyl polymer ammonium polyacrylate, sodium polyacrylate, sodium acrylate / alkyl acrylate / sodium methacrylate / alkyl methacrylate copolymer, carrageenan, pectin, mannan, curdlan, chondroitin sulfate, starch, Glycogen, gum arabic, sodium hyaluronate, tragacanth gum, xanthan gum, mucoitin sulfate, hydroxyethyl guar gum, carboxymethyl guar gum, guar gum, dextran, kerato sulfate, locust bean gum, succinoglucan, chitin, chitosan, carboxymethyl chitin, agar etc. Illustrated.
- oil-soluble polymer examples include trimethylsiloxysilicic acid, alkyl-modified silicone, polyamide-modified silicone, dimethicone crosspolymer, (dimethicone / vinyl dimethicone) crosspolymer, polymethylsilsesquioxane, and the like.
- waxes examples include beeswax, candelilla wax, carnauba wax, lanolin, liquid lanolin, jojoballow and the like.
- alcohols examples include lower alcohols such as ethanol and isopropanol, higher alcohols such as isostearyl alcohol, octyldodecanol and hexyldecanol, ethylene glycol, propylene glycol, 1,3-butylene glycol, dipropylene glycol and polybutylene glycol. Examples thereof include monohydric alcohols.
- hydrocarbon oil examples include liquid paraffin, ozokerite, squalane, pristane, paraffin, ceresin, squalene, petrolatum, microcrystalline wax, polyethylene wax, and Fischer-Tropsch wax.
- fatty acids examples include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, arachidonic acid and the like.
- Higher alcohols include lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, aralkyl alcohol, batyl alcohol, chimyl alcohol, carnervir alcohol, ceryl alcohol, coryranyl alcohol, myricyl alcohol, lacteryl alcohol, elayl
- Illustrative examples include zircyl alcohol, isostearyl glyceryl ether, octyl alcohol, triacontyl alcohol, ceralkyl alcohol, cetostearyl alcohol, oleyl alcohol, lanolin alcohol, hydrogenated lanolin alcohol, hexyl decanol, and octyl decanol.
- fatty acid esters examples include myristyl myristate, cetyl palmitate, cholesteryl stearate, beeswax fatty acid 2-octyldodecyl, and the like.
- silicone oils examples include methylpolysiloxane, octamethylsiloxane, decamethyltetrasiloxane, methylhydrogenpolysiloxane, methylphenylpolysiloxane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and the like. be able to.
- Preferred examples include octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane.
- the surfactant examples include anionic, cationic, nonionic, and amphoteric surfactants, and include silicone-based or hydrocarbon-based surfactants.
- the powder component other than the ultraviolet scattering agent (component b) examples include nylon and acrylic polymer spherical powder, silica powder, silicone powder, metal oxide powder surface-treated with a surface treatment agent containing no metal, and the like. . However, it is preferable not to add a metal oxide powder that has not been surface-treated, such as zinc oxide powder, because it may inhibit the stability of the dibenzoylmethane derivative.
- Examples of the drug include salts of L-ascorbic acid and its derivatives, glycyrrhizic acid and its derivatives such as dipotassium glycyrrhizinate and monoammonium glycyrrhizinate, glycyrrhetinic acid and its derivatives such as stearyl glycyrrhetinate, allantoin, tranexamic acid and its derivatives And salts of alkoxysalicylic acid and its derivatives, glutathione and its derivatives, allantoin, azulene and the like.
- the sunscreen cosmetic of the present invention can be provided in the form of an oil-in-water emulsified cosmetic, a water-in-oil emulsified cosmetic, or an oily cosmetic.
- an oil-in-water emulsified cosmetic emulsified cosmetic
- a water-in-oil emulsified cosmetic emulsified cosmetic
- an oily cosmetic emulsified cosmetic
- dosage forms such as sunscreen milky lotion and sunscreen cream, which can be produced using a conventional method suitable for each dosage form.
- the blending amount is expressed in mass% with respect to the system in which the component is blended.
- a sample of a water-in-oil emulsified sunscreen cosmetic was prepared according to the formulation listed in Table 1 below. Next, the prepared samples of each example were evaluated as follows: (1) crystal precipitation, (2) whiteness during coating, and (3) dispersibility in oil. The evaluation results are also shown in Table 1.
- the surface is hydrophobized with a metal soap containing an alkaline earth metal (magnesium).
- a metal soap containing an alkaline earth metal magnesium
- crystal precipitation did not occur even when a dibenzoylmethane derivative was present, unnatural whiteness was not felt, and the dispersibility in oil of the powder (ultraviolet scattering agent) was also good. It was.
- the effect of the present invention that can suppress crystal precipitation with the dibenzoylmethane derivative by surface treatment with a metal soap containing an alkaline earth metal depends on the type of powder base material (host nucleus).
- the effect of the present invention cannot be obtained when the metal of the surface treatment agent is replaced with a metal soap, metal oxide or silicone containing a trivalent metal (aluminum).
- a water-in-oil emulsion composition (sample) was prepared according to the formulation described in Table 2 below. The compounding amount of the metal chloride was determined so that the number of moles of metal ions contained in each sample was equal.
- oil phase parts (light isoparaffin, decamethylcyclopentasiloxane, glyceryl tri-2-ethylhexanoate, PEG-9 polydimethylsiloxyethyl dimethicone, 2-methoxyhexyl paramethoxycinnamate and 4-tert-butyl-4 '-Methoxydibenzoylmethane) was added, stirred and mixed, and each metal chloride was added and dissolved in ion-exchanged water in a separate container to obtain an aqueous phase part. Subsequently, the water phase part was added to the oil phase part, and it emulsified with the homogenizer.
- oil phase parts light isoparaffin, decamethylcyclopentasiloxane, glyceryl tri-2-ethylhexanoate, PEG-9 polydimethylsiloxyethyl dimethicone, 2-methoxyhexyl paramethoxycinnamate and
- Formulation example 1 W / O sunscreen Compounding component Compounding amount (mass%) Ion exchange water Residual ethanol 5 Glycerin 3 PEG-9 polydimethylsiloxyethyl dimethicone 2 Light isoparaffin 20 Glyceryl tri-2-ethylhexanoate 15 Cetyl 2-ethylhexanoate 10 Decamethylcyclopentasiloxane 15 4-tert-butyl-4′-methoxydibenzoylmethane 3 Diethylaminohydroxybenzoyl hexyl benzoate 1 Psycho extract 0.05 Hydrolyzed conchiolin 0.03 Theanine 0.01 Magnesium isostearate treated fine particle titanium oxide 10 Magnesium myristate-coated barium sulfate 3
- Formulation example 2 P / O / W sunscreen Compounding component Compounding amount (mass%) Ion exchange water Residual ethanol 5 Glycerin 3 1,3-butylene glycol 5 Polyoxyethylene hydrogenated castor oil 1.5 Octocrylene 5 2-methoxyhexyl paramethoxycinnamate 5 Glyceryl tri-2-ethylhexanoate 10 Light isoparaffin 10 4-tert-butyl-4′-methoxydibenzoylmethane 2 2,4,6-tris [4- (2-ethylhexyloxycarbonyl) anilino] -1,3,5-triazine 2 2,4-bis-[ ⁇ 4- (2-ethylhexyloxy) -2- Hydroxy ⁇ -phenyl] -6- (4-methoxyphenyl)- 1,3,5-triazine 0.5 Magnesium isostearate treated fine particle titanium oxide 5 Isostearic acid 0.5 Dimethylacrylamide / acryl
- Formulation Example 3 Makeup base Blending ingredients Blending amount (% by mass) Ion exchange water Residue Dipropylene glycol 9 Polyoxyethylene hydrogenated castor oil 1 Carboxymethylcellulose 0.1 Xanthan gum 0.6 Sorbitan sesquiisostearate 0.35 Isostearic acid 0.5 Isopropyl myristate 2 Isododecane 12 4-tert-Butyl-4′-methoxydibenzoylmethane 1.5 Octocrylene 5 Oxybenzone 1.5 Pigment grade titanium oxide treated with magnesium isostearate 1 Magnesium isostearate treated fine particle titanium oxide 5 Spherical cellulose powder 2 Porous silica 1 Potassium 4-methoxysalicylate 1 Toki Root Extract 0.001 PEG / PPG-14 / 7 dimethyl ether 1 PEG-12 Dimethicone 0.01 Polyquaternium-51 0.04
- Formulation example 4 W / O sunscreen Compounding component Compounding amount (mass%) Ion exchange water Residual ethanol 2 Glycerin 3 Dipropyl glycol 5 PEG-9 polydimethylsiloxyethyl dimethicone 2 Light isoparaffin 20 Glyceryl tri-2-ethylhexanoate 15 Dimethicone 5 Di-2-ethylhexyl succinate 5 Decamethylcyclopentasiloxane 15 4-tert-butyl-4′-methoxydibenzoylmethane 3 Phenylbenzimidazolesulfonic acid 0.5 Triethanolamine 0.2 Calcium myristate-coated talc 5 Dipotassium glycyrrhizinate 0.001 Ethyl vitamin C 0.01 Trehalose 0.5
Abstract
The purpose of the present invention is to provide a sunscreen cosmetic which eliminates instability of a dibenzoylmethane derivative that is a UVA absorbing-agent, which can exhibit excellent ultraviolet radiation protection performance across a wide wavelength region from UVA to UVB, which exhibits excellent light resistance, is stable over time, does not suffer from discoloration or crystal precipitation, and with which unnatural whiteness does not occur. The present invention provides a sunscreen cosmetic that is characterized by containing (a) a dibenzoylmethane derivative and (b) a powder that is surface-hydrophobized by means of treatment with a metal soap comprising a higher fatty acid and an alkaline earth metal or a combined treatment involving the use of a higher fatty acid and an alkaline earth metal hydroxide. The alkaline earth metal is preferably calcium or magnesium, and the higher fatty acid is preferably isostearic acid.
Description
本発明は日焼け止め化粧料に関する。より詳細には、紫外線吸収剤であるジベンゾイルメタン誘導体と特定の表面処理をされた紫外線散乱剤とを含み、ＵＶＡからＵＶＢに渡る広い波長領域で高い紫外線防御能を発揮し、なおかつ安定性にも優れた日焼け止め化粧料に関する。
The present invention relates to a sunscreen cosmetic. More specifically, it includes a dibenzoylmethane derivative that is an ultraviolet absorber and an ultraviolet scattering agent that has been subjected to a specific surface treatment, and exhibits high UV protection ability in a wide wavelength range from UVA to UVB, and is also stable. Also related to excellent sunscreen cosmetics.
紫外線の害から皮膚を守ることはスキンケア、ボディケアにおける重要な課題の一つであり、紫外線が皮膚に与える悪影響を最小限に抑えるために種々のＵＶケア化粧料が開発されている。ＵＶケア化粧料の一種である日焼け止め化粧料（サンスクリーン化粧料）は、紫外線吸収剤や紫外線散乱剤を配合した塗膜で皮膚を覆うことによりＵＶＡ及びＵＶＢを吸収又は散乱させて皮膚に到達する紫外線量を抑制し、紫外線の害から皮膚を守ることを意図した化粧料である（非特許文献１）。
Protecting the skin from the damage of ultraviolet rays is one of the important issues in skin care and body care, and various UV care cosmetics have been developed to minimize the adverse effects of ultraviolet rays on the skin. Sunscreen cosmetics (sunscreen cosmetics), a type of UV care cosmetics, reach the skin by absorbing or scattering UVA and UVB by covering the skin with a coating film containing UV absorbers and UV scattering agents. It is a cosmetic intended to suppress the amount of ultraviolet rays to be protected and protect the skin from the harm of ultraviolet rays (Non-patent Document 1).
ジベンゾイルメタン誘導体はＵＶＡ領域に吸収ピークを持つ有機紫外線吸収剤として日焼け止め化粧料に汎用されているが、光分解による光防御能の低下や、共存する他の成分、特に金属イオンとの相互作用による結晶析出や変色（黄変）といった問題を有している。
Dibenzoylmethane derivatives are widely used in sunscreen cosmetics as organic UV absorbers that have an absorption peak in the UVA region. However, they reduce the photoprotective ability due to photolysis and interact with other coexisting components, especially metal ions. There are problems such as crystal precipitation and discoloration (yellowing) due to action.
特許文献１では、ジベンゾイルメタン誘導体と酸化チタンとを配合した組成物において生ずる変色（黄変）や光保護力の減少を、酸化チタン表面をシリコーン（シロキサンもしくはシラン誘導体）で被覆することにより抑制している（段落０００９～００１２）。
特許文献２には、ジベンゾイルメタンと酸化亜鉛との反応による劣化を防止するために酸化亜鉛粒子を表面処理することが開示され、当該表面処理物質として、シリコーン、脂肪酸、タンパク質、ペプチド、アミノ酸、Ｎ－アシルアミノ酸、モノグリセリド、ジグリセリド、トリグリセリド、鉱油、シリカ、リン脂質、ステロール、炭化水素、ポリアクリレート、アルミナ及びその混合物が挙げられている（第１３頁）。 In Patent Document 1, the discoloration (yellowing) and the reduction of light protection in a composition containing a dibenzoylmethane derivative and titanium oxide are suppressed by coating the surface of titanium oxide with silicone (siloxane or silane derivative). (Paragraphs 0009 to 0012).
Patent Document 2 discloses that zinc oxide particles are surface-treated in order to prevent deterioration due to the reaction between dibenzoylmethane and zinc oxide. As the surface treatment substance, silicone, fatty acid, protein, peptide, amino acid, N-acylamino acids, monoglycerides, diglycerides, triglycerides, mineral oil, silica, phospholipids, sterols, hydrocarbons, polyacrylates, alumina and mixtures thereof are mentioned (page 13).
特許文献２には、ジベンゾイルメタンと酸化亜鉛との反応による劣化を防止するために酸化亜鉛粒子を表面処理することが開示され、当該表面処理物質として、シリコーン、脂肪酸、タンパク質、ペプチド、アミノ酸、Ｎ－アシルアミノ酸、モノグリセリド、ジグリセリド、トリグリセリド、鉱油、シリカ、リン脂質、ステロール、炭化水素、ポリアクリレート、アルミナ及びその混合物が挙げられている（第１３頁）。 In Patent Document 1, the discoloration (yellowing) and the reduction of light protection in a composition containing a dibenzoylmethane derivative and titanium oxide are suppressed by coating the surface of titanium oxide with silicone (siloxane or silane derivative). (Paragraphs 0009 to 0012).
Patent Document 2 discloses that zinc oxide particles are surface-treated in order to prevent deterioration due to the reaction between dibenzoylmethane and zinc oxide. As the surface treatment substance, silicone, fatty acid, protein, peptide, amino acid, N-acylamino acids, monoglycerides, diglycerides, triglycerides, mineral oil, silica, phospholipids, sterols, hydrocarbons, polyacrylates, alumina and mixtures thereof are mentioned (page 13).
酸化チタンや酸化亜鉛等の金属酸化物粉体は紫外線散乱剤として日焼け止め化粧料に配合されているが、油中での分散性や透明性の向上を目的として表面疎水化処理される場合もある。例えば特許文献３では、金属石鹸で表面処理した酸化チタンの微粒子を用いると透明性が向上するが、紫外線遮蔽効果は低下することが記載されている（第３頁）。
しかし、前記特許文献１や２に挙げられているような一般的な表面処理物質の一部（例えばアルミナ）には金属が含まれているので、これらの物質で表面処理した粉体をジベンゾイルメタン誘導体と共存させると変色や結晶析出を生じる可能性は否定できない。一方、シリカ被覆した酸化チタンを配合すると皮膚に塗布した際の白さが不自然に目立ってしまう傾向があった。 Metal oxide powders such as titanium oxide and zinc oxide are blended in sunscreen cosmetics as UV scattering agents, but they may also be subjected to surface hydrophobization for the purpose of improving dispersibility in oil and transparency. is there. For example, Patent Document 3 describes that when fine particles of titanium oxide surface-treated with metal soap are used, the transparency is improved, but the ultraviolet shielding effect is lowered (page 3).
However, since some of the general surface treatment substances (for example, alumina) listed in Patent Documents 1 and 2 contain metals, the powder surface-treated with these substances is dibenzoyl. When coexisting with methane derivatives, the possibility of discoloration and crystal precipitation cannot be denied. On the other hand, when silica-coated titanium oxide is blended, the white color when applied to the skin tends to be unnaturally conspicuous.
しかし、前記特許文献１や２に挙げられているような一般的な表面処理物質の一部（例えばアルミナ）には金属が含まれているので、これらの物質で表面処理した粉体をジベンゾイルメタン誘導体と共存させると変色や結晶析出を生じる可能性は否定できない。一方、シリカ被覆した酸化チタンを配合すると皮膚に塗布した際の白さが不自然に目立ってしまう傾向があった。 Metal oxide powders such as titanium oxide and zinc oxide are blended in sunscreen cosmetics as UV scattering agents, but they may also be subjected to surface hydrophobization for the purpose of improving dispersibility in oil and transparency. is there. For example, Patent Document 3 describes that when fine particles of titanium oxide surface-treated with metal soap are used, the transparency is improved, but the ultraviolet shielding effect is lowered (page 3).
However, since some of the general surface treatment substances (for example, alumina) listed in Patent Documents 1 and 2 contain metals, the powder surface-treated with these substances is dibenzoyl. When coexisting with methane derivatives, the possibility of discoloration and crystal precipitation cannot be denied. On the other hand, when silica-coated titanium oxide is blended, the white color when applied to the skin tends to be unnaturally conspicuous.
よって本発明における課題は、ＵＶＡ吸収剤であるジベンゾイルメタン誘導体の不安定性を解消し、ＵＶＡからＵＶＢに渡る広い波長領域で優れた紫外線防御能を発揮できるとともに、耐光性に優れ、経時的にも安定で、変色や結晶析出を生じず、なおかつ不自然に白くならない日焼け止め化粧料を提供することにある。
Therefore, the problem in the present invention is that the instability of the dibenzoylmethane derivative, which is a UVA absorber, can be eliminated, and an excellent UV protection ability can be exhibited in a wide wavelength range from UVA to UVB. Is to provide a sunscreen cosmetic that is stable, does not cause discoloration or crystal precipitation, and does not become unnaturally whitened.
本発明者等は上記の課題を解決すべく鋭意研究を行った結果、紫外線散乱剤として配合する金属酸化物の表面に、高級脂肪酸とアルカリ土類金属からなる金属石鹸による処理、あるいは、高級脂肪酸とアルカリ土類金属水酸化物とによる複合処理を施すことにより、ジベンゾイルメタン誘導体と共存させても結晶の析出や変色を起こさず、安定な日焼け止め化粧料が得られることを見出し、本発明を完成するに至った。
As a result of diligent research to solve the above-mentioned problems, the present inventors have conducted a treatment with a metal soap composed of a higher fatty acid and an alkaline earth metal on the surface of a metal oxide to be blended as an ultraviolet scattering agent, or a higher fatty acid. The present invention has found that a stable sunscreen cosmetic can be obtained without causing crystal precipitation or discoloration even when co-existing with a dibenzoylmethane derivative by performing a composite treatment with alkenyl and an alkaline earth metal hydroxide. It came to complete.
すなわち、本発明は、
（ａ）ジベンゾイルメタン誘導体、及び
（ｂ）高級脂肪酸とアルカリ土類金属からなる金属石鹸処理又は高級脂肪酸とアルカリ土類金属水酸化物との複合処理によって表面疎水化処理された粉体、を含むことを特徴とする日焼け止め化粧料を提供する。 That is, the present invention
(A) a dibenzoylmethane derivative, and (b) a powder that has been surface-hydrophobized by a metal soap treatment comprising a higher fatty acid and an alkaline earth metal or a composite treatment of a higher fatty acid and an alkaline earth metal hydroxide. Provided is a sunscreen cosmetic characterized by containing.
（ａ）ジベンゾイルメタン誘導体、及び
（ｂ）高級脂肪酸とアルカリ土類金属からなる金属石鹸処理又は高級脂肪酸とアルカリ土類金属水酸化物との複合処理によって表面疎水化処理された粉体、を含むことを特徴とする日焼け止め化粧料を提供する。 That is, the present invention
(A) a dibenzoylmethane derivative, and (b) a powder that has been surface-hydrophobized by a metal soap treatment comprising a higher fatty acid and an alkaline earth metal or a composite treatment of a higher fatty acid and an alkaline earth metal hydroxide. Provided is a sunscreen cosmetic characterized by containing.
本発明は、変質、分解する性質を持つことが知られたジベンゾイルメタン誘導体に、特定の表面処理を施した粉体（紫外線散乱剤）を共配合することによって、保存中に紫外線遮蔽能が低下することがなく、結晶の析出や変色といった使用上又は外観上の問題も生じない日焼け止め化粧料を提供することができる。
In the present invention, a dibenzoylmethane derivative known to have a property of being altered or decomposed is co-blended with a powder (ultraviolet scattering agent) that has been subjected to a specific surface treatment, so that it has an ultraviolet shielding ability during storage. It is possible to provide a sunscreen cosmetic that does not decrease and does not cause problems in use or appearance such as crystal precipitation and discoloration.
本発明の日焼け止め化粧料は、（ａ）ジベンゾイルメタン誘導体、及び（ｂ）高級脂肪酸とアルカリ土類金属からなる金属石鹸処理又は高級脂肪酸とアルカリ土類金属水酸化物との複合処理によって表面疎水化処理された粉体を必須成分として含有している。
The sunscreen cosmetic of the present invention has a surface treated by (a) a dibenzoylmethane derivative and (b) a metal soap treatment comprising a higher fatty acid and an alkaline earth metal or a composite treatment of a higher fatty acid and an alkaline earth metal hydroxide. Hydrophobized powder is contained as an essential component.
（ａ）ジベンゾイルメタン誘導体
ジベンゾイルメタン誘導体（成分ａ）は、ＵＶＡ領域に最大吸収波長を持つ紫外線吸収剤として化粧料等に広く用いられている。
本発明で用いられるジベンゾイルメタン誘導体としては、例えば、２－メチルジベンゾイルメタン、４－メチルジベンゾイルメタン、４－イソプロピルジベンゾイルメタン、４－ｔｅｒｔ－ブチルジベンゾイルメタン、２，４－ジメチルジベンゾイルメタン、２，５－ジメチルジベンゾイルメタン、４，４’－ジイソプロピルジベンゾイルメタン、４－メトキシ－４’－ｔｅｒｔ－ブチルジベンゾイルメタン、２－メチル－５－イソプロピル－４’－メトキシジベンゾイルメタン、２－メチル－５－ｔｅｒｔ－ブチル－４’－メトキシジベンゾイルメタン、２，４－ジメチル－４’－メトキシジベンゾイルメタン、２，６－ジメチル－４－ｔｅｒｔ－ブチル－４’－メトキシジベンゾイルメタン等が挙げられる。 (A) Dibenzoylmethane derivative The dibenzoylmethane derivative (component a) is widely used in cosmetics and the like as an ultraviolet absorber having a maximum absorption wavelength in the UVA region.
Examples of the dibenzoylmethane derivative used in the present invention include 2-methyldibenzoylmethane, 4-methyldibenzoylmethane, 4-isopropyldibenzoylmethane, 4-tert-butyldibenzoylmethane, and 2,4-dimethyldibenzene. Benzoylmethane, 2,5-dimethyldibenzoylmethane, 4,4'-diisopropyldibenzoylmethane, 4-methoxy-4'-tert-butyldibenzoylmethane, 2-methyl-5-isopropyl-4'-methoxydibenzoyl Methane, 2-methyl-5-tert-butyl-4'-methoxydibenzoylmethane, 2,4-dimethyl-4'-methoxydibenzoylmethane, 2,6-dimethyl-4-tert-butyl-4'-methoxy And dibenzoylmethane.
ジベンゾイルメタン誘導体（成分ａ）は、ＵＶＡ領域に最大吸収波長を持つ紫外線吸収剤として化粧料等に広く用いられている。
本発明で用いられるジベンゾイルメタン誘導体としては、例えば、２－メチルジベンゾイルメタン、４－メチルジベンゾイルメタン、４－イソプロピルジベンゾイルメタン、４－ｔｅｒｔ－ブチルジベンゾイルメタン、２，４－ジメチルジベンゾイルメタン、２，５－ジメチルジベンゾイルメタン、４，４’－ジイソプロピルジベンゾイルメタン、４－メトキシ－４’－ｔｅｒｔ－ブチルジベンゾイルメタン、２－メチル－５－イソプロピル－４’－メトキシジベンゾイルメタン、２－メチル－５－ｔｅｒｔ－ブチル－４’－メトキシジベンゾイルメタン、２，４－ジメチル－４’－メトキシジベンゾイルメタン、２，６－ジメチル－４－ｔｅｒｔ－ブチル－４’－メトキシジベンゾイルメタン等が挙げられる。 (A) Dibenzoylmethane derivative The dibenzoylmethane derivative (component a) is widely used in cosmetics and the like as an ultraviolet absorber having a maximum absorption wavelength in the UVA region.
Examples of the dibenzoylmethane derivative used in the present invention include 2-methyldibenzoylmethane, 4-methyldibenzoylmethane, 4-isopropyldibenzoylmethane, 4-tert-butyldibenzoylmethane, and 2,4-dimethyldibenzene. Benzoylmethane, 2,5-dimethyldibenzoylmethane, 4,4'-diisopropyldibenzoylmethane, 4-methoxy-4'-tert-butyldibenzoylmethane, 2-methyl-5-isopropyl-4'-methoxydibenzoyl Methane, 2-methyl-5-tert-butyl-4'-methoxydibenzoylmethane, 2,4-dimethyl-4'-methoxydibenzoylmethane, 2,6-dimethyl-4-tert-butyl-4'-methoxy And dibenzoylmethane.
前記のジベンゾイルメタン誘導体の中でも、４－メトキシ－４’－ｔｅｒｔ－ブチルジベンゾイルメタン（表示名称：ｔ－ブチルメトキシベンゾイルメタン）が特に好ましく用いられる。
ジベンゾイルメタン誘導体は市販品を用いてもよく、例えば、「パルソール１７８９」の名称でＤＳＭニュートリションジャパン株式会社から市販されている４－メトキシ－４’－ｔｅｒｔ－ブチルジベンゾイルメタンを例示することができる。 Among the above-mentioned dibenzoylmethane derivatives, 4-methoxy-4′-tert-butyldibenzoylmethane (designated name: t-butylmethoxybenzoylmethane) is particularly preferably used.
As the dibenzoylmethane derivative, a commercially available product may be used. For example, 4-methoxy-4′-tert-butyldibenzoylmethane commercially available from DSM Nutrition Japan Co., Ltd. under the name “Pulsol 1789” may be used. it can.
ジベンゾイルメタン誘導体は市販品を用いてもよく、例えば、「パルソール１７８９」の名称でＤＳＭニュートリションジャパン株式会社から市販されている４－メトキシ－４’－ｔｅｒｔ－ブチルジベンゾイルメタンを例示することができる。 Among the above-mentioned dibenzoylmethane derivatives, 4-methoxy-4′-tert-butyldibenzoylmethane (designated name: t-butylmethoxybenzoylmethane) is particularly preferably used.
As the dibenzoylmethane derivative, a commercially available product may be used. For example, 4-methoxy-4′-tert-butyldibenzoylmethane commercially available from DSM Nutrition Japan Co., Ltd. under the name “Pulsol 1789” may be used. it can.
本発明の日焼け止め化粧料におけるジベンゾイルメタン誘導体の配合量は、０．５～４．０質量％とするのが好ましく、１．０～３．０質量％とするのが更に好ましい。配合量が０．５質量％未満では十分な紫外線防御効果が得られず、４．０質量％を超えて配合しても紫外線防御効果の更なる向上は得られず、べたつき等の使用性の問題を生ずることがある。
The blending amount of the dibenzoylmethane derivative in the sunscreen cosmetic of the present invention is preferably 0.5 to 4.0% by mass, and more preferably 1.0 to 3.0% by mass. If the blending amount is less than 0.5% by mass, sufficient UV protection effect cannot be obtained, and even if it exceeds 4.0% by mass, further improvement in UV protection effect cannot be obtained, and the use property such as stickiness is not improved. May cause problems.
（ｂ）粉体（紫外線散乱剤）
本発明の日焼け止め化粧料に配合される粉体は、反射もしくは散乱により紫外線を物理的に遮断する粉体（「紫外線散乱剤」とも呼ばれる）であり、特定の表面疎水化処理をされた粉体である。 (B) Powder (UV scattering agent)
The powder blended in the sunscreen cosmetic of the present invention is a powder that physically blocks ultraviolet rays by reflection or scattering (also referred to as “ultraviolet scattering agent”), and has been subjected to a specific surface hydrophobization treatment. Is the body.
本発明の日焼け止め化粧料に配合される粉体は、反射もしくは散乱により紫外線を物理的に遮断する粉体（「紫外線散乱剤」とも呼ばれる）であり、特定の表面疎水化処理をされた粉体である。 (B) Powder (UV scattering agent)
The powder blended in the sunscreen cosmetic of the present invention is a powder that physically blocks ultraviolet rays by reflection or scattering (also referred to as “ultraviolet scattering agent”), and has been subjected to a specific surface hydrophobization treatment. Is the body.
本発明における特定の疎水化処理とは、（１）高級脂肪酸とアルカリ土類金属からなる金属石鹸による処理、又は（２）高級脂肪酸とアルカリ土類金属水酸化物とによる複合処理を意味する。ここで用いられる高級脂肪酸は、炭素数８～２４（好ましくは炭素数１２～１８）の直鎖状もしくは分岐鎖状のカルボン酸とするのが好ましい。具体例としては、ステアリン酸、イソステアリン酸、ミリスチン酸、ラウリン酸等が挙げられ、イソステアリン酸が特に好ましい。
また、アルカリ土類金属としてはカルシウム、マグネシウムが好ましく、マグネシウムが特に好ましい。
なお、粉体表面に高級脂肪酸とアルカリ土類金属水酸化物とによる複合処理を施すと、当該粉体表面には高級脂肪酸とアルカリ土類金属との塩からなる金属石鹸の層が形成されると考えられる。即ち、前記（１）又は（２）の処理によって粉体表面に形成される表面被覆層は同等の組成を有すると推測される。 The specific hydrophobizing treatment in the present invention means (1) treatment with a metal soap composed of higher fatty acid and alkaline earth metal, or (2) combined treatment with higher fatty acid and alkaline earth metal hydroxide. The higher fatty acid used here is preferably a linear or branched carboxylic acid having 8 to 24 carbon atoms (preferably 12 to 18 carbon atoms). Specific examples include stearic acid, isostearic acid, myristic acid, lauric acid and the like, and isostearic acid is particularly preferable.
Further, as the alkaline earth metal, calcium and magnesium are preferable, and magnesium is particularly preferable.
When the powder surface is subjected to a composite treatment with a higher fatty acid and an alkaline earth metal hydroxide, a metal soap layer made of a salt of the higher fatty acid and the alkaline earth metal is formed on the powder surface. it is conceivable that. That is, it is presumed that the surface coating layer formed on the powder surface by the treatment (1) or (2) has an equivalent composition.
また、アルカリ土類金属としてはカルシウム、マグネシウムが好ましく、マグネシウムが特に好ましい。
なお、粉体表面に高級脂肪酸とアルカリ土類金属水酸化物とによる複合処理を施すと、当該粉体表面には高級脂肪酸とアルカリ土類金属との塩からなる金属石鹸の層が形成されると考えられる。即ち、前記（１）又は（２）の処理によって粉体表面に形成される表面被覆層は同等の組成を有すると推測される。 The specific hydrophobizing treatment in the present invention means (1) treatment with a metal soap composed of higher fatty acid and alkaline earth metal, or (2) combined treatment with higher fatty acid and alkaline earth metal hydroxide. The higher fatty acid used here is preferably a linear or branched carboxylic acid having 8 to 24 carbon atoms (preferably 12 to 18 carbon atoms). Specific examples include stearic acid, isostearic acid, myristic acid, lauric acid and the like, and isostearic acid is particularly preferable.
Further, as the alkaline earth metal, calcium and magnesium are preferable, and magnesium is particularly preferable.
When the powder surface is subjected to a composite treatment with a higher fatty acid and an alkaline earth metal hydroxide, a metal soap layer made of a salt of the higher fatty acid and the alkaline earth metal is formed on the powder surface. it is conceivable that. That is, it is presumed that the surface coating layer formed on the powder surface by the treatment (1) or (2) has an equivalent composition.
疎水化処理方法としては、溶媒を使用する湿式法、気相法、メカノケミカル法等を用いることができ、特に限定されない。
As the hydrophobizing method, a wet method using a solvent, a gas phase method, a mechanochemical method, or the like can be used, and it is not particularly limited.
前記特定の疎水化処理される粉体（母核）は、化粧料の分野で紫外線散乱剤として用いられる粉体であれば特に限定されない。具体例としては、酸化チタン、酸化亜鉛、硫酸バリウム、酸化鉄、タルク、マイカ、セリサイト、カオリン、雲母チタン、紺青、酸化クロム、水酸化クロム、シリカ、酸化セリウム等から選択される１種又は２種以上が挙げられる。特に、１．５以上の屈折率を有する粉体を用いるのが光学的特性から好ましい。
The specific hydrophobized powder (mother core) is not particularly limited as long as it is a powder used as an ultraviolet scattering agent in the cosmetic field. Specific examples include one selected from titanium oxide, zinc oxide, barium sulfate, iron oxide, talc, mica, sericite, kaolin, titanium mica, bitumen, chromium oxide, chromium hydroxide, silica, cerium oxide, and the like. Two or more types can be mentioned. In particular, it is preferable from the viewpoint of optical properties to use a powder having a refractive index of 1.5 or more.
前記粉体（母核）は、従来から化粧料等に配合されているものであればよく、特に限定されないが、例えば、平均一次粒子径が１００ｎｍ以下、好ましくは５０ｎｍ以下、より好ましくは３０ｎｍ以下のものが好適に用いられる。平均一次粒子径の下限値は特に限定されるものでないが、粒径が小さくなるほど高価になるので、経済性を考慮すれば５ｎｍ以上でよく、好ましくは１０ｎｍ以上である。ここで、本明細書における平均一次粒子径とは、一般的に用いられる方法で測定される粉体の一次粒子の径を意味するものであり、具体的には透過電子顕微鏡写真から、粒子の長軸の長さと短軸の長さの相加平均として求められる値である。
また、粉体の粒子形態も特に限定されるものでなく、球状、楕円形状、破砕状等が含まれ、一次粒子の状態であっても、凝集した二次集合体を形成したものでもよい。
なお、以下では、前記特定の処理を施された粉体（成分ｂ）を単に「紫外線散乱剤」と呼称する。 The powder (mother core) is not particularly limited as long as it is conventionally blended in cosmetics and the like. For example, the average primary particle diameter is 100 nm or less, preferably 50 nm or less, more preferably 30 nm or less. Are preferably used. The lower limit value of the average primary particle size is not particularly limited, but it becomes more expensive as the particle size becomes smaller. Here, the average primary particle diameter in the present specification means the diameter of the primary particle of the powder measured by a generally used method. Specifically, from the transmission electron micrograph, It is a value obtained as an arithmetic average of the length of the major axis and the length of the minor axis.
Further, the particle form of the powder is not particularly limited, and includes a spherical shape, an elliptical shape, a crushed shape, and the like, and may be a primary particle state or an aggregated secondary aggregate.
Hereinafter, the powder (component b) subjected to the specific treatment is simply referred to as “ultraviolet scattering agent”.
また、粉体の粒子形態も特に限定されるものでなく、球状、楕円形状、破砕状等が含まれ、一次粒子の状態であっても、凝集した二次集合体を形成したものでもよい。
なお、以下では、前記特定の処理を施された粉体（成分ｂ）を単に「紫外線散乱剤」と呼称する。 The powder (mother core) is not particularly limited as long as it is conventionally blended in cosmetics and the like. For example, the average primary particle diameter is 100 nm or less, preferably 50 nm or less, more preferably 30 nm or less. Are preferably used. The lower limit value of the average primary particle size is not particularly limited, but it becomes more expensive as the particle size becomes smaller. Here, the average primary particle diameter in the present specification means the diameter of the primary particle of the powder measured by a generally used method. Specifically, from the transmission electron micrograph, It is a value obtained as an arithmetic average of the length of the major axis and the length of the minor axis.
Further, the particle form of the powder is not particularly limited, and includes a spherical shape, an elliptical shape, a crushed shape, and the like, and may be a primary particle state or an aggregated secondary aggregate.
Hereinafter, the powder (component b) subjected to the specific treatment is simply referred to as “ultraviolet scattering agent”.
本発明の日焼け止め化粧料における紫外線散乱剤（成分ｂ）の配合量は、１～１５質量％とするのが好ましく、２～８質量％とするのが更に好ましい。配合量が１質量％未満では十分な紫外線防御効果が得られず、１５質量％を超えて配合すると使用性が低下する傾向がある。
The blending amount of the ultraviolet light scattering agent (component b) in the sunscreen cosmetic of the present invention is preferably 1 to 15% by mass, and more preferably 2 to 8% by mass. When the blending amount is less than 1% by mass, a sufficient UV protection effect cannot be obtained, and when the blending amount exceeds 15% by mass, the usability tends to decrease.
本発明の日焼け止め化粧料にあっては、（ａ）ジベンゾイルメタン誘導体と（ｂ）紫外線散乱剤との配合量比率を、（ａ）：（ｂ）＝１：２４～３：１、より好ましくは、１：１０～２：１、さらに好ましくは１：５～１：１の範囲に調整するのが好ましい。配合量比率を前記範囲内とすることにより、ＵＶＡからＵＶＢの波長範囲に渡って効果的に紫外線防御効果が得られる。
In the sunscreen cosmetic of the present invention, the blending ratio of (a) the dibenzoylmethane derivative and (b) the ultraviolet scattering agent is such that (a) :( b) = 1: 24 to 3: 1 It is preferable to adjust to a range of 1:10 to 2: 1, more preferably 1: 5 to 1: 1. By setting the blending ratio within the above range, an ultraviolet protection effect can be effectively obtained over the wavelength range from UVA to UVB.
ジベンゾイルメタン誘導体、中でも４－メトキシ－４’－ｔｅｒｔ－ブチルジベンゾイルメタンは、ＵＶＡ領域の有機紫外線吸収剤として従来から化粧料に汎用されており、酸化チタン等の粉体も紫外線散乱剤として知られ、各種の表面疎水化処理された粉末が用いられている。しかしながら、粉体の表面処理に用いられる金属石鹸として最も汎用されているのは３価金属であるアルミニウムを含む金属石鹸であり、マグネシウム等のアルカリ土類金属を含む金属石鹸で表面処理された粉体とジベンゾイルメタン誘導体とを組み合わせた例は知られていない。
Dibenzoylmethane derivatives, especially 4-methoxy-4'-tert-butyldibenzoylmethane, has been widely used in cosmetics as an organic UV absorber in the UVA region, and powders such as titanium oxide are also used as UV scattering agents. Various types of surface hydrophobized powders are known. However, the most widely used metal soap used for the surface treatment of powder is a metal soap containing aluminum, which is a trivalent metal, and is a powder treated with a metal soap containing an alkaline earth metal such as magnesium. There is no known example of a combination of a body with a dibenzoylmethane derivative.
本発明は、公知の表面処理剤の中から金属石鹸を選択し、さらに金属石鹸の中からアルカリ土類金属、好ましくはカルシウム又はマグネシウムを含む金属石鹸を特に選択することにより、ジベンゾイルメタン誘導体とともに配合しても結晶析出を起こさず安定性を維持できることを初めて見出したものである。
According to the present invention, a metal soap is selected from the known surface treatment agents, and a metal soap containing an alkaline earth metal, preferably calcium or magnesium, is selected from the metal soap. It has been found for the first time that even if it is blended, stability can be maintained without causing crystal precipitation.
従って本発明は、ジベンゾイルメタン誘導体を含有する組成物に、高級脂肪酸とアルカリ土類金属からなる金属石鹸処理又は高級脂肪酸とアルカリ土類金属水酸化物との複合処理によって表面疎水化処理された粉体を配合することを含む、前記組成物の安定化方法を提供するものである。
Therefore, in the present invention, the composition containing the dibenzoylmethane derivative was subjected to surface hydrophobization treatment by a metal soap treatment comprising a higher fatty acid and an alkaline earth metal or a composite treatment of a higher fatty acid and an alkaline earth metal hydroxide. The present invention provides a method for stabilizing the composition, comprising blending powder.
本発明の日焼け止め化粧料は、（ａ）ジベンゾイルメタン誘導体及び（ｂ）紫外線散乱剤に加えて、日焼け止め化粧料に通常配合し得る他の任意成分を、本発明の効果を阻害しない範囲で含んでいてもよい。
The sunscreen cosmetic of the present invention is a range that does not inhibit the effects of the present invention, in addition to (a) a dibenzoylmethane derivative and (b) an ultraviolet scattering agent, and other optional components that can be usually added to the sunscreen cosmetic. May be included.
他の任意成分は特に限定されないが、例えば、ジベンゾイルメタン誘導体以外の紫外線吸収剤を更に配合することにより、ＵＶＡ及び／又はＵＶＢ領域の紫外線防御能を更に向上させることができる。
ジベンゾイルメタン誘導体以外の紫外線吸収剤としては、化粧料に通常用いられるものから選択でき、特に限定されるものでない。例えば、パラ－アミノ安息香酸誘導体、サリチル酸誘導体、ケイ皮酸誘導体、β，β－ジフェニルアクリラート誘導体、ベンゾフェノン誘導体、ベンジリデンショウノウ誘導体、フェニルベンゾイミダゾール誘導体、トリアジン誘導体、フェニルベンゾトリアゾール誘導体、アントラニル誘導体、イミダゾリン誘導体、ベンザルマロナート誘導体、４，４－ジアリールブタジエン誘導体等から選択される１種又は２種以上が例示される。 The other optional components are not particularly limited, but for example, by further adding an ultraviolet absorber other than the dibenzoylmethane derivative, the ultraviolet protection ability in the UVA and / or UVB region can be further improved.
The ultraviolet absorber other than the dibenzoylmethane derivative can be selected from those usually used in cosmetics and is not particularly limited. For example, para-aminobenzoic acid derivatives, salicylic acid derivatives, cinnamic acid derivatives, β, β-diphenyl acrylate derivatives, benzophenone derivatives, benzylidene camphor derivatives, phenylbenzimidazole derivatives, triazine derivatives, phenylbenzotriazole derivatives, anthranyl derivatives, imidazolines Examples thereof include one or more selected from derivatives, benzalmalonate derivatives, 4,4-diarylbutadiene derivatives and the like.
ジベンゾイルメタン誘導体以外の紫外線吸収剤としては、化粧料に通常用いられるものから選択でき、特に限定されるものでない。例えば、パラ－アミノ安息香酸誘導体、サリチル酸誘導体、ケイ皮酸誘導体、β，β－ジフェニルアクリラート誘導体、ベンゾフェノン誘導体、ベンジリデンショウノウ誘導体、フェニルベンゾイミダゾール誘導体、トリアジン誘導体、フェニルベンゾトリアゾール誘導体、アントラニル誘導体、イミダゾリン誘導体、ベンザルマロナート誘導体、４，４－ジアリールブタジエン誘導体等から選択される１種又は２種以上が例示される。 The other optional components are not particularly limited, but for example, by further adding an ultraviolet absorber other than the dibenzoylmethane derivative, the ultraviolet protection ability in the UVA and / or UVB region can be further improved.
The ultraviolet absorber other than the dibenzoylmethane derivative can be selected from those usually used in cosmetics and is not particularly limited. For example, para-aminobenzoic acid derivatives, salicylic acid derivatives, cinnamic acid derivatives, β, β-diphenyl acrylate derivatives, benzophenone derivatives, benzylidene camphor derivatives, phenylbenzimidazole derivatives, triazine derivatives, phenylbenzotriazole derivatives, anthranyl derivatives, imidazolines Examples thereof include one or more selected from derivatives, benzalmalonate derivatives, 4,4-diarylbutadiene derivatives and the like.
他の任意成分としては、水溶性高分子、油溶性高分子、ロウ類、アルコール類、炭化水素油、脂肪酸、高級アルコール、脂肪酸エステル、シリコーン油、界面活性剤、紫外線散乱剤以外の粉末成分、薬剤等が挙げられるが、これらの例示に限定されるものではない。
Other optional components include water-soluble polymers, oil-soluble polymers, waxes, alcohols, hydrocarbon oils, fatty acids, higher alcohols, fatty acid esters, silicone oils, surfactants, powder components other than UV scattering agents, Although a medicine etc. are mentioned, it is not limited to these illustrations.
水溶性高分子としては、２－アクリルアミド－２－メチルプロパンスルホン酸（以下、「ＡＭＰＳ」と略記する）のホモポリマー、あるいはコポリマーが挙げられる。コポリマーは、ビニルピロリドン、アクリル酸アミド、アクリル酸ナトリウム、アクリル酸ヒドロキシエチル等のコモノマーとからなるコポリマーである。すなわち、ＡＭＰＳホモポリマー、ビニルピロリドン／ＡＭＰＳ共重合体、ジメチルアクリルアミド／ＡＭＰＳ共重合体、アクリル酸アミド／ＡＭＰＳ共重合体、アクリル酸ナトリウム／ＡＭＰＳ共重合体等が例示される。
Examples of the water-soluble polymer include homopolymers or copolymers of 2-acrylamido-2-methylpropanesulfonic acid (hereinafter abbreviated as “AMPS”). The copolymer is a copolymer composed of a comonomer such as vinyl pyrrolidone, acrylic acid amide, sodium acrylate, or hydroxyethyl acrylate. That is, an AMPS homopolymer, a vinylpyrrolidone / AMPS copolymer, a dimethylacrylamide / AMPS copolymer, an acrylic amide / AMPS copolymer, a sodium acrylate / AMPS copolymer, and the like are exemplified.
さらには、カルボキシビニルポリマー、ポリアクリル酸アンモニウム、ポリアクリル酸ナトリウム、アクリル酸ナトリウム／アクリル酸アルキル／メタクリル酸ナトリウム／メタクリル酸アルキル共重合体、カラギーナン、ペクチン、マンナン、カードラン、コンドロイチン硫酸、デンプン、グリコーゲン、アラビアガム、ヒアルロン酸ナトリウム、トラガントガム、キサンタンガム、ムコイチン硫酸、ヒドロキシエチルグアガム、カルボキシメチルグアガム、グアガム、デキストラン、ケラト硫酸、ローカストビーンガム、サクシノグルカン、キチン、キトサン、カルボキシメチルキチン、寒天等が例示される。
Furthermore, carboxyvinyl polymer, ammonium polyacrylate, sodium polyacrylate, sodium acrylate / alkyl acrylate / sodium methacrylate / alkyl methacrylate copolymer, carrageenan, pectin, mannan, curdlan, chondroitin sulfate, starch, Glycogen, gum arabic, sodium hyaluronate, tragacanth gum, xanthan gum, mucoitin sulfate, hydroxyethyl guar gum, carboxymethyl guar gum, guar gum, dextran, kerato sulfate, locust bean gum, succinoglucan, chitin, chitosan, carboxymethyl chitin, agar etc. Illustrated.
油溶性高分子としては、トリメチルシロキシケイ酸、アルキル変性シリコーン、ポリアミド変性シリコーン、ジメチコンクロスポリマー、（ジメチコン／ビニルジメチコン）クロスポリマー、ポリメチルシルセスキオキサン等が例示される。
Examples of the oil-soluble polymer include trimethylsiloxysilicic acid, alkyl-modified silicone, polyamide-modified silicone, dimethicone crosspolymer, (dimethicone / vinyl dimethicone) crosspolymer, polymethylsilsesquioxane, and the like.
ロウ類としては、例えば、ミツロウ、カンデリラロウ、カルナウバロウ、ラノリン、液状ラノリン、ジョジョバロウ等が例示される。
Examples of waxes include beeswax, candelilla wax, carnauba wax, lanolin, liquid lanolin, jojoballow and the like.
アルコール類としては、エタノール、イソプロパノールなどの低級アルコール、イソステアリルアルコール、オクチルドデカノール、ヘキシルデカノール等の高級アルコール、エチレングリコール、プロピレングリコール、１，３－ブチレングリコール、ジプロピレングリコール、ポリブチレングリコールなどの多価アルコール等が例示される。
Examples of alcohols include lower alcohols such as ethanol and isopropanol, higher alcohols such as isostearyl alcohol, octyldodecanol and hexyldecanol, ethylene glycol, propylene glycol, 1,3-butylene glycol, dipropylene glycol and polybutylene glycol. Examples thereof include monohydric alcohols.
炭化水素油としては、流動パラフィン、オゾケライト、スクワラン、プリスタン、パラフィン、セレシン、スクワレン、ワセリン、マイクロクリスタリンワックス、ポリエチレンワックス、フィッシャートロプッシュワックス等が例示される。
Examples of the hydrocarbon oil include liquid paraffin, ozokerite, squalane, pristane, paraffin, ceresin, squalene, petrolatum, microcrystalline wax, polyethylene wax, and Fischer-Tropsch wax.
脂肪酸としては、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、ベヘニン酸、アラキドン酸等が例示される。
Examples of fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, arachidonic acid and the like.
高級アルコールとしては、ラウリルアルコール、ミリスチルアルコール、セチルアルコール、ステアリルアルコール、ベヘニルアルコール、アラキルアルコール、バチルアルコール、キミルアルコール、カルナービルアルコール、セリルアルコール、コリヤニルアルコール、ミリシルアルコール、ラクセリルアルコール、エライジルアルコール、イソステアリルグリセリルエーテル、オクチルアルコール、トリアコンチルアルコール、セラキルアルコール、セトステアリルアルコール、オレイルアルコール、ラノリンアルコール、水添ラノリンアルコール、ヘキシルデカノール、オクチルデカノール等が例示される。
Higher alcohols include lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, aralkyl alcohol, batyl alcohol, chimyl alcohol, carnervir alcohol, ceryl alcohol, coryranyl alcohol, myricyl alcohol, lacteryl alcohol, elayl Illustrative examples include zircyl alcohol, isostearyl glyceryl ether, octyl alcohol, triacontyl alcohol, ceralkyl alcohol, cetostearyl alcohol, oleyl alcohol, lanolin alcohol, hydrogenated lanolin alcohol, hexyl decanol, and octyl decanol.
脂肪酸エステルとしては、ミリスチン酸ミリスチル、パルミチン酸セチル、ステアリン酸コレステリル、ミツロウ脂肪酸２－オクチルドデシル等が例示される。
Examples of fatty acid esters include myristyl myristate, cetyl palmitate, cholesteryl stearate, beeswax fatty acid 2-octyldodecyl, and the like.
シリコーン油としては、メチルポリシロキサン、オクタメチルシロキサン、デカメチルテトラシロキサン、メチルハイドロジェンポリシロキサン、メチルフェニルポリシロキサン、ヘキサメチルシクロトリシロキサン、オクタメチルシクロテトラシロキサン、デカメチルシクロペンタシロキサン等を例示することができる。好ましくは、オクタメチルシクロテトラシロキサンおよびデカメチルシクロペンタシロキサン等が例示される。
Examples of silicone oils include methylpolysiloxane, octamethylsiloxane, decamethyltetrasiloxane, methylhydrogenpolysiloxane, methylphenylpolysiloxane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and the like. be able to. Preferred examples include octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane.
界面活性剤は、アニオン性、カチオン性、ノニオン性、又は両性の界面活性剤が挙げられ、シリコーン系又は炭化水素系の界面活性剤が含まれる。
紫外線散乱剤（成分ｂ）以外の粉末成分としては、ナイロンやアクリル系のポリマー球状粉末、シリカ粉末、シリコーン粉末、金属を含まない表面処理剤で表面処理された金属酸化物粉末等が例示される。ただし、表面処理されていない金属酸化物粉末、例えば酸化亜鉛粉末等はジベンゾイルメタン誘導体の安定性を阻害する可能性があるため配合しないのが好ましい。 Examples of the surfactant include anionic, cationic, nonionic, and amphoteric surfactants, and include silicone-based or hydrocarbon-based surfactants.
Examples of the powder component other than the ultraviolet scattering agent (component b) include nylon and acrylic polymer spherical powder, silica powder, silicone powder, metal oxide powder surface-treated with a surface treatment agent containing no metal, and the like. . However, it is preferable not to add a metal oxide powder that has not been surface-treated, such as zinc oxide powder, because it may inhibit the stability of the dibenzoylmethane derivative.
紫外線散乱剤（成分ｂ）以外の粉末成分としては、ナイロンやアクリル系のポリマー球状粉末、シリカ粉末、シリコーン粉末、金属を含まない表面処理剤で表面処理された金属酸化物粉末等が例示される。ただし、表面処理されていない金属酸化物粉末、例えば酸化亜鉛粉末等はジベンゾイルメタン誘導体の安定性を阻害する可能性があるため配合しないのが好ましい。 Examples of the surfactant include anionic, cationic, nonionic, and amphoteric surfactants, and include silicone-based or hydrocarbon-based surfactants.
Examples of the powder component other than the ultraviolet scattering agent (component b) include nylon and acrylic polymer spherical powder, silica powder, silicone powder, metal oxide powder surface-treated with a surface treatment agent containing no metal, and the like. . However, it is preferable not to add a metal oxide powder that has not been surface-treated, such as zinc oxide powder, because it may inhibit the stability of the dibenzoylmethane derivative.
薬剤としては、Ｌ－アスコルビン酸およびその誘導体の塩、グリチルリチン酸ジカリウム、グリチルリチン酸モノアンモニウム等のグリチルリチン酸およびその誘導体、グリチルレチン酸ステアリルなどのグリチルレチン酸およびその誘導体、アラントイン、トラネキサム酸およびその誘導体の塩、アルコキシサリチル酸およびその誘導体の塩、グルタチオンおよびその誘導体の塩、アラントイン、アズレンなどが例示される。
Examples of the drug include salts of L-ascorbic acid and its derivatives, glycyrrhizic acid and its derivatives such as dipotassium glycyrrhizinate and monoammonium glycyrrhizinate, glycyrrhetinic acid and its derivatives such as stearyl glycyrrhetinate, allantoin, tranexamic acid and its derivatives And salts of alkoxysalicylic acid and its derivatives, glutathione and its derivatives, allantoin, azulene and the like.
本発明の日焼け止め化粧料は、水中油型乳化化粧料、油中水型乳化化粧料、あるいは油性化粧料の形態で提供することが可能である。具体的な剤型としては、日焼け止め乳液、日焼け止めクリームといった剤型であり、各剤型に適した常法を用いて製造することができる。
The sunscreen cosmetic of the present invention can be provided in the form of an oil-in-water emulsified cosmetic, a water-in-oil emulsified cosmetic, or an oily cosmetic. As a specific dosage form, there are dosage forms such as sunscreen milky lotion and sunscreen cream, which can be produced using a conventional method suitable for each dosage form.
以下に実施例を挙げて本発明をさらに詳述するが、本発明はこれらにより何ら限定されるものではない。配合量は特記しない限り、その成分が配合される系に対する質量％で示す。
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. Unless otherwise specified, the blending amount is expressed in mass% with respect to the system in which the component is blended.
下記表１に掲げる処方で油中水型乳化日焼け止め化粧料の試料を調製した。次いで、調製した各例の試料について、（１）結晶析出、（２）塗布時の白さ、及び（３）油分への分散性を以下のように評価した。評価結果も表１に併せて示す。
A sample of a water-in-oil emulsified sunscreen cosmetic was prepared according to the formulation listed in Table 1 below. Next, the prepared samples of each example were evaluated as follows: (1) crystal precipitation, (2) whiteness during coating, and (3) dispersibility in oil. The evaluation results are also shown in Table 1.
（１）結晶析出
－１０℃～２０℃の温度サイクルで１か月間保管した後、偏光顕微鏡で結晶析出の有無を確認した。
Ａ：結晶析出が認められない。
Ｂ：結晶析出が認められた。 (1) Crystal Precipitation—After storage for 1 month at a temperature cycle of 10 ° C. to 20 ° C., the presence or absence of crystal precipitation was confirmed with a polarizing microscope.
A: Crystal precipitation is not recognized.
B: Crystal precipitation was observed.
－１０℃～２０℃の温度サイクルで１か月間保管した後、偏光顕微鏡で結晶析出の有無を確認した。
Ａ：結晶析出が認められない。
Ｂ：結晶析出が認められた。 (1) Crystal Precipitation—After storage for 1 month at a temperature cycle of 10 ° C. to 20 ° C., the presence or absence of crystal precipitation was confirmed with a polarizing microscope.
A: Crystal precipitation is not recognized.
B: Crystal precipitation was observed.
（２）塗布時の白さ
女性パネル（１０名）が各実施例、比較例の試料を塗布した後の白さについて、下記の評価基準に基づいて評価した。
（評価）
Ａ：塗布後の白さが許容しがたいと回答した人数が４名以下。
Ｂ：塗布後の白さが許容しがたいと回答した人数が５名以上。 (2) Whiteness at the time of application The female panel (10 persons) evaluated the whiteness after apply | coating the sample of each Example and a comparative example based on the following evaluation criteria.
(Evaluation)
A: The number of people who answered that the white color after application was unacceptable was 4 or less.
B: The number of people who answered that the white color after application was unacceptable was 5 or more.
女性パネル（１０名）が各実施例、比較例の試料を塗布した後の白さについて、下記の評価基準に基づいて評価した。
（評価）
Ａ：塗布後の白さが許容しがたいと回答した人数が４名以下。
Ｂ：塗布後の白さが許容しがたいと回答した人数が５名以上。 (2) Whiteness at the time of application The female panel (10 persons) evaluated the whiteness after apply | coating the sample of each Example and a comparative example based on the following evaluation criteria.
(Evaluation)
A: The number of people who answered that the white color after application was unacceptable was 4 or less.
B: The number of people who answered that the white color after application was unacceptable was 5 or more.
（３）油分への分散性（粉末凝集等の有無）
各例の試料を黒色プレート上に塗布した際に生じる粉末の細かな凝集塊（粉末ブツ）や粉末凝集から生ずる色むらの有無を目視観察した。
（評価）
Ａ：プレートに塗布した際に粉末の細かな凝集塊や凝集から生ずる粉末色むらが全く見られない。
Ｂ：プレートに塗布した際に極く小さな粉末の凝集塊や凝集から生ずる粉末色むらが僅かに見られた。
Ｃ：プレートに塗布した際に小さな粉末の凝集塊や凝集から生ずる粉末色むらが見られた。 (3) Dispersibility in oil (presence or absence of powder aggregation)
The presence or absence of fine agglomerates (powder) of the powder generated when the sample of each example was applied on the black plate and color unevenness resulting from the powder agglomeration were visually observed.
(Evaluation)
A: When coated on a plate, fine powder agglomerates and powder color unevenness resulting from aggregation are not seen at all.
B: When coated on a plate, a slight powder agglomeration and powder color unevenness resulting from the aggregation were slightly observed.
C: When coated on a plate, small powder aggregates and powder color unevenness resulting from the aggregation were observed.
各例の試料を黒色プレート上に塗布した際に生じる粉末の細かな凝集塊（粉末ブツ）や粉末凝集から生ずる色むらの有無を目視観察した。
（評価）
Ａ：プレートに塗布した際に粉末の細かな凝集塊や凝集から生ずる粉末色むらが全く見られない。
Ｂ：プレートに塗布した際に極く小さな粉末の凝集塊や凝集から生ずる粉末色むらが僅かに見られた。
Ｃ：プレートに塗布した際に小さな粉末の凝集塊や凝集から生ずる粉末色むらが見られた。 (3) Dispersibility in oil (presence or absence of powder aggregation)
The presence or absence of fine agglomerates (powder) of the powder generated when the sample of each example was applied on the black plate and color unevenness resulting from the powder agglomeration were visually observed.
(Evaluation)
A: When coated on a plate, fine powder agglomerates and powder color unevenness resulting from aggregation are not seen at all.
B: When coated on a plate, a slight powder agglomeration and powder color unevenness resulting from the aggregation were slightly observed.
C: When coated on a plate, small powder aggregates and powder color unevenness resulting from the aggregation were observed.
表１に示した結果から明らかなように、基材（母核）が酸化チタンであっても硫酸バリウムであっても、その表面をアルカリ土類金属（マグネシウム）を含む金属石鹸で疎水化処理（被覆）した実施例１及び２は、ジベンゾイルメタン誘導体が共存しても結晶析出が起こらず、不自然な白さも感じず、粉体（紫外線散乱剤）の油中分散性も良好であった。
As is clear from the results shown in Table 1, whether the base material (matrix) is titanium oxide or barium sulfate, the surface is hydrophobized with a metal soap containing an alkaline earth metal (magnesium). In the coated Examples 1 and 2, crystal precipitation did not occur even when a dibenzoylmethane derivative was present, unnatural whiteness was not felt, and the dispersibility in oil of the powder (ultraviolet scattering agent) was also good. It was.
基材（母核）が実施例１と同じ酸化チタンであっても、含水シリカで表面処理した比較例１は、結晶析出は起こらないものの、塗布時の白さが不自然で許容しがたく、粉体の油中分散性も劣っていた。酸化チタンをステアリン酸アルミニウムで表面処理した比較例２では、塗布時の白さや油中分散性は許容できるが、結晶析出が生じた。表面が酸化亜鉛である比較例３及び５は、基材（母核）がシリコーン樹脂であってもマグネシウム含有化合物（タルク）であっても結晶析出が起こり、酸化亜鉛をシリコーン表面処理した比較例４でも同様に結晶析出が観察された。
Even if the base material (mother core) is the same titanium oxide as in Example 1, in Comparative Example 1 that was surface-treated with hydrous silica, crystal precipitation did not occur, but whiteness during coating was unnatural and unacceptable. The dispersibility of the powder in oil was also poor. In Comparative Example 2 in which titanium oxide was surface-treated with aluminum stearate, whiteness during coating and dispersibility in oil were acceptable, but crystal precipitation occurred. Comparative Examples 3 and 5 whose surfaces are zinc oxide are comparative examples in which crystal precipitation occurs regardless of whether the base material (host nucleus) is a silicone resin or a magnesium-containing compound (talc), and zinc oxide is surface-treated with silicone. 4 also showed crystal precipitation.
以上より、アルカリ土類金属を含む金属石鹸で表面処理することによりジベンゾイルメタン誘導体との間での結晶析出を抑制できる本発明の効果は、粉体の基材（母核）の種類によらず達成できるが、表面処理剤の金属を３価金属（アルミニウム）を含む金属石鹸、金属酸化物あるいはシリコーンに置換した場合には本発明の効果が得られないことが明らかになった。
From the above, the effect of the present invention that can suppress crystal precipitation with the dibenzoylmethane derivative by surface treatment with a metal soap containing an alkaline earth metal depends on the type of powder base material (host nucleus). However, it has been clarified that the effect of the present invention cannot be obtained when the metal of the surface treatment agent is replaced with a metal soap, metal oxide or silicone containing a trivalent metal (aluminum).
ジベンゾイルメタン誘導体に対する各種金属イオンの直接的な影響を確認するため、以下の試験を実施した。
下記表２に記載した処方で油中水型乳化組成物（試料）を調製した。なお、各試料に含まれる金属イオンのモル数が等しくなるように金属塩化物の配合量を決定した。
まず、ビーカーに油相パーツ（軽質イソパラフィン、デカメチルシクロペンタシロキサン、トリ２－エチルヘキサン酸グリセリル、ＰＥＧ－９ポリジメチルシロキシエチルジメチコン、パラメトキシケイ皮酸２－エチルヘキシル及び４－ｔｅｒｔ－ブチル－４’－メトキシジベンゾイルメタン）を添加して撹拌・混合し、前記と別容器で、イオン交換水の中に各金属塩化物を添加・溶解して水相パーツとした。次いで、油相パーツに水相パーツを添加し、ホモジェナイザーで乳化した。 In order to confirm the direct influence of various metal ions on the dibenzoylmethane derivative, the following tests were conducted.
A water-in-oil emulsion composition (sample) was prepared according to the formulation described in Table 2 below. The compounding amount of the metal chloride was determined so that the number of moles of metal ions contained in each sample was equal.
First, oil phase parts (light isoparaffin, decamethylcyclopentasiloxane, glyceryl tri-2-ethylhexanoate, PEG-9 polydimethylsiloxyethyl dimethicone, 2-methoxyhexyl paramethoxycinnamate and 4-tert-butyl-4 '-Methoxydibenzoylmethane) was added, stirred and mixed, and each metal chloride was added and dissolved in ion-exchanged water in a separate container to obtain an aqueous phase part. Subsequently, the water phase part was added to the oil phase part, and it emulsified with the homogenizer.
下記表２に記載した処方で油中水型乳化組成物（試料）を調製した。なお、各試料に含まれる金属イオンのモル数が等しくなるように金属塩化物の配合量を決定した。
まず、ビーカーに油相パーツ（軽質イソパラフィン、デカメチルシクロペンタシロキサン、トリ２－エチルヘキサン酸グリセリル、ＰＥＧ－９ポリジメチルシロキシエチルジメチコン、パラメトキシケイ皮酸２－エチルヘキシル及び４－ｔｅｒｔ－ブチル－４’－メトキシジベンゾイルメタン）を添加して撹拌・混合し、前記と別容器で、イオン交換水の中に各金属塩化物を添加・溶解して水相パーツとした。次いで、油相パーツに水相パーツを添加し、ホモジェナイザーで乳化した。 In order to confirm the direct influence of various metal ions on the dibenzoylmethane derivative, the following tests were conducted.
A water-in-oil emulsion composition (sample) was prepared according to the formulation described in Table 2 below. The compounding amount of the metal chloride was determined so that the number of moles of metal ions contained in each sample was equal.
First, oil phase parts (light isoparaffin, decamethylcyclopentasiloxane, glyceryl tri-2-ethylhexanoate, PEG-9 polydimethylsiloxyethyl dimethicone, 2-methoxyhexyl paramethoxycinnamate and 4-tert-butyl-4 '-Methoxydibenzoylmethane) was added, stirred and mixed, and each metal chloride was added and dissolved in ion-exchanged water in a separate container to obtain an aqueous phase part. Subsequently, the water phase part was added to the oil phase part, and it emulsified with the homogenizer.
得られた各試料について、以下の要領で色調変化（変色）の有無を測定した。
＜測定方法＞
各試料を１か月間、５０℃で保管した後、目視で変色の有無を確認した。
＜測定結果＞
Ａ：変色が認められない。
Ｂ：変色が認められた。 About each obtained sample, the presence or absence of a color tone change (discoloration) was measured in the following ways.
<Measurement method>
Each sample was stored at 50 ° C. for one month and then visually checked for discoloration.
<Measurement results>
A: No discoloration is observed.
B: Discoloration was recognized.
＜測定方法＞
各試料を１か月間、５０℃で保管した後、目視で変色の有無を確認した。
＜測定結果＞
Ａ：変色が認められない。
Ｂ：変色が認められた。 About each obtained sample, the presence or absence of a color tone change (discoloration) was measured in the following ways.
<Measurement method>
Each sample was stored at 50 ° C. for one month and then visually checked for discoloration.
<Measurement results>
A: No discoloration is observed.
B: Discoloration was recognized.
表２に示した結果により、アルカリ土類金属であるマグネシウム及びカルシウムのイオンが共存していてもジベンゾイルメタン誘導体（４－ｔｅｒｔ－ブチル－４’－メトキシジベンゾイルメタン）の変色は起こらないが、他の金属であるアルミニウムや遷移金属である亜鉛が共存すると変色が生じることが確認された。
According to the results shown in Table 2, discoloration of the dibenzoylmethane derivative (4-tert-butyl-4′-methoxydibenzoylmethane) does not occur even in the presence of ions of magnesium and calcium, which are alkaline earth metals. Further, it was confirmed that discoloration occurs when aluminum as another metal and zinc as a transition metal coexist.
以下に本発明にかかる日焼け止め化粧料の処方例を示すが、本発明の範囲はこれらに限定されるものではない。
処方例１：Ｗ／Ｏサンスクリーン
配合成分 配合量（質量％）
イオン交換水 残余
エタノール ５
グリセリン ３
ＰＥＧ－９ポリジメチルシロキシエチルジメチコン ２
軽質イソパラフィン ２０
トリ２－エチルヘキサン酸グリセリル １５
２－エチルヘキサン酸セチル １０
デカメチルシクロペンタシロキサン １５
４－ｔｅｒｔ－ブチル－４’－メトキシジベンゾイルメタン ３
ジエチルアミノヒドロキシベンゾイル安息香酸ヘキシル １
サイコエキス ０．０５
加水分解コンキオリン ０．０３
テアニン ０．０１
イソステアリン酸マグネシウム処理微粒子酸化チタン １０
ミリスチン酸マグネシウム被覆硫酸バリウム ３ Although the example of formulation of the sunscreen cosmetics concerning this invention is shown below, the scope of the present invention is not limited to these.
Formulation example 1: W / O sunscreen Compounding component Compounding amount (mass%)
Ion exchange water Residual ethanol 5
Glycerin 3
PEG-9 polydimethylsiloxyethyl dimethicone 2
Light isoparaffin 20
Glyceryl tri-2-ethylhexanoate 15
Cetyl 2-ethylhexanoate 10
Decamethylcyclopentasiloxane 15
4-tert-butyl-4′-methoxydibenzoylmethane 3
Diethylaminohydroxybenzoyl hexyl benzoate 1
Psycho extract 0.05
Hydrolyzed conchiolin 0.03
Theanine 0.01
Magnesium isostearate treated fine particle titanium oxide 10
Magnesium myristate-coated barium sulfate 3
処方例１：Ｗ／Ｏサンスクリーン
配合成分 配合量（質量％）
イオン交換水 残余
エタノール ５
グリセリン ３
ＰＥＧ－９ポリジメチルシロキシエチルジメチコン ２
軽質イソパラフィン ２０
トリ２－エチルヘキサン酸グリセリル １５
２－エチルヘキサン酸セチル １０
デカメチルシクロペンタシロキサン １５
４－ｔｅｒｔ－ブチル－４’－メトキシジベンゾイルメタン ３
ジエチルアミノヒドロキシベンゾイル安息香酸ヘキシル １
サイコエキス ０．０５
加水分解コンキオリン ０．０３
テアニン ０．０１
イソステアリン酸マグネシウム処理微粒子酸化チタン １０
ミリスチン酸マグネシウム被覆硫酸バリウム ３ Although the example of formulation of the sunscreen cosmetics concerning this invention is shown below, the scope of the present invention is not limited to these.
Formulation example 1: W / O sunscreen Compounding component Compounding amount (mass%)
Ion exchange water Residual ethanol 5
Glycerin 3
PEG-9 polydimethylsiloxyethyl dimethicone 2
Light isoparaffin 20
Glyceryl tri-2-ethylhexanoate 15
Cetyl 2-ethylhexanoate 10
Decamethylcyclopentasiloxane 15
4-tert-butyl-4′-methoxydibenzoylmethane 3
Diethylaminohydroxybenzoyl hexyl benzoate 1
Psycho extract 0.05
Hydrolyzed conchiolin 0.03
Theanine 0.01
Magnesium isostearate treated fine particle titanium oxide 10
Magnesium myristate-coated barium sulfate 3
処方例２：Ｐ／Ｏ／Ｗサンスクリーン
配合成分 配合量（質量％）
イオン交換水 残余
エタノール ５
グリセリン ３
１，３ーブチレングリコール ５
ポリオキシエチレン水添ヒマシ油 １．５
オクトクリレン ５
パラメトキシケイ皮酸２－エチルヘキシル ５
トリ２－エチルヘキサン酸グリセリル １０
軽質イソパラフィン １０
４－ｔｅｒｔ－ブチル－４’－メトキシジベンゾイルメタン ２
２，４，６－トリス［４－（２－エチルヘキシル
オキシカルボニル）アニリノ］－１，３，５－トリアジン ２
２，４－ビス－[{４－(２－エチルヘキシルオキシ)－２－
ヒドロキシ}－フェニル]－６－(４－メトキシフェニル)－
１，３，５－トリアジン ０．５
イソステアリン酸マグネシウム処理微粒子酸化チタン ５
イソステアリン酸 ０．５
ジメチルアクリルアミド／アクリロイルジメチルタウリンＮａ
クロスポリマー ０．３
サクシノグルカン ０．２
球状セルロース粉末 ３
トラネキサム酸 ２
加水分解シルク ０．０１
ハイビスカス花エキス ０．１
アセチルヒアルロン酸Ｎａ ０．０００１
タイムエキス ０．０１
ウコンエキス ０．０３
ＥＤＴＡ－３Ｎａ・２Ｈ２Ｏ ０．００１ Formulation example 2: P / O / W sunscreen Compounding component Compounding amount (mass%)
Ion exchange water Residual ethanol 5
Glycerin 3
1,3-butylene glycol 5
Polyoxyethylene hydrogenated castor oil 1.5
Octocrylene 5
2-methoxyhexyl paramethoxycinnamate 5
Glyceryl tri-2-ethylhexanoate 10
Light isoparaffin 10
4-tert-butyl-4′-methoxydibenzoylmethane 2
2,4,6-tris [4- (2-ethylhexyloxycarbonyl) anilino] -1,3,5-triazine 2
2,4-bis-[{4- (2-ethylhexyloxy) -2-
Hydroxy} -phenyl] -6- (4-methoxyphenyl)-
1,3,5-triazine 0.5
Magnesium isostearate treated fine particle titanium oxide 5
Isostearic acid 0.5
Dimethylacrylamide / acryloyldimethyltaurine Na
Cross polymer 0.3
Succinoglucan 0.2
Spherical cellulose powder 3
Tranexamic acid 2
Hydrolyzed silk 0.01
Hibiscus flower extract 0.1
Acetyl hyaluronic acid Na 0.0001
Time extract 0.01
Turmeric extract 0.03
EDTA-3Na · 2H 2 O 0.001
配合成分 配合量（質量％）
イオン交換水 残余
エタノール ５
グリセリン ３
１，３ーブチレングリコール ５
ポリオキシエチレン水添ヒマシ油 １．５
オクトクリレン ５
パラメトキシケイ皮酸２－エチルヘキシル ５
トリ２－エチルヘキサン酸グリセリル １０
軽質イソパラフィン １０
４－ｔｅｒｔ－ブチル－４’－メトキシジベンゾイルメタン ２
２，４，６－トリス［４－（２－エチルヘキシル
オキシカルボニル）アニリノ］－１，３，５－トリアジン ２
２，４－ビス－[{４－(２－エチルヘキシルオキシ)－２－
ヒドロキシ}－フェニル]－６－(４－メトキシフェニル)－
１，３，５－トリアジン ０．５
イソステアリン酸マグネシウム処理微粒子酸化チタン ５
イソステアリン酸 ０．５
ジメチルアクリルアミド／アクリロイルジメチルタウリンＮａ
クロスポリマー ０．３
サクシノグルカン ０．２
球状セルロース粉末 ３
トラネキサム酸 ２
加水分解シルク ０．０１
ハイビスカス花エキス ０．１
アセチルヒアルロン酸Ｎａ ０．０００１
タイムエキス ０．０１
ウコンエキス ０．０３
ＥＤＴＡ－３Ｎａ・２Ｈ２Ｏ ０．００１ Formulation example 2: P / O / W sunscreen Compounding component Compounding amount (mass%)
Ion exchange water Residual ethanol 5
Glycerin 3
1,3-butylene glycol 5
Polyoxyethylene hydrogenated castor oil 1.5
Octocrylene 5
2-methoxyhexyl paramethoxycinnamate 5
Glyceryl tri-2-ethylhexanoate 10
Light isoparaffin 10
4-tert-butyl-4′-methoxydibenzoylmethane 2
2,4,6-tris [4- (2-ethylhexyloxycarbonyl) anilino] -1,3,5-triazine 2
2,4-bis-[{4- (2-ethylhexyloxy) -2-
Hydroxy} -phenyl] -6- (4-methoxyphenyl)-
1,3,5-triazine 0.5
Magnesium isostearate treated fine particle titanium oxide 5
Isostearic acid 0.5
Dimethylacrylamide / acryloyldimethyltaurine Na
Cross polymer 0.3
Succinoglucan 0.2
Spherical cellulose powder 3
Tranexamic acid 2
Hydrolyzed silk 0.01
Hibiscus flower extract 0.1
Acetyl hyaluronic acid Na 0.0001
Time extract 0.01
Turmeric extract 0.03
EDTA-3Na · 2H 2 O 0.001
処方例３：化粧下地
配合成分 配合量（質量％）
イオン交換水 残余
ジプロピレングリコール ９
ポリオキシエチレン水添ヒマシ油 １
カルボキシメチルセルロース ０．１
キサンタンガム ０．６
ソルビタンセスキイソステアレート ０．３５
イソステアリン酸 ０．５
ミリスチン酸イソプロピル ２
イソドデカン １２
４－ｔｅｒｔ－ブチル－４’－メトキシジベンゾイルメタン １．５
オクトクリレン ５
オキシベンゾン １．５
イソステアリン酸マグネシウム処理顔料級酸化チタン １
イソステアリン酸マグネシウム処理微粒子酸化チタン ５
球状セルロース粉末 ２
多孔質シリカ １
４－メトキシサリチル酸カリウム １
トウキ根エキス ０．００１
ＰＥＧ／ＰＰＧ－１４／７ジメチルエーテル １
ＰＥＧ－１２ジメチコン ０．０１
ポリクオタニウム－５１ ０．０４ Formulation Example 3: Makeup base Blending ingredients Blending amount (% by mass)
Ion exchange water Residue Dipropylene glycol 9
Polyoxyethylene hydrogenated castor oil 1
Carboxymethylcellulose 0.1
Xanthan gum 0.6
Sorbitan sesquiisostearate 0.35
Isostearic acid 0.5
Isopropyl myristate 2
Isododecane 12
4-tert-Butyl-4′-methoxydibenzoylmethane 1.5
Octocrylene 5
Oxybenzone 1.5
Pigment grade titanium oxide treated with magnesium isostearate 1
Magnesium isostearate treated fine particle titanium oxide 5
Spherical cellulose powder 2
Porous silica 1
Potassium 4-methoxysalicylate 1
Toki Root Extract 0.001
PEG / PPG-14 / 7 dimethyl ether 1
PEG-12 Dimethicone 0.01
Polyquaternium-51 0.04
配合成分 配合量（質量％）
イオン交換水 残余
ジプロピレングリコール ９
ポリオキシエチレン水添ヒマシ油 １
カルボキシメチルセルロース ０．１
キサンタンガム ０．６
ソルビタンセスキイソステアレート ０．３５
イソステアリン酸 ０．５
ミリスチン酸イソプロピル ２
イソドデカン １２
４－ｔｅｒｔ－ブチル－４’－メトキシジベンゾイルメタン １．５
オクトクリレン ５
オキシベンゾン １．５
イソステアリン酸マグネシウム処理顔料級酸化チタン １
イソステアリン酸マグネシウム処理微粒子酸化チタン ５
球状セルロース粉末 ２
多孔質シリカ １
４－メトキシサリチル酸カリウム １
トウキ根エキス ０．００１
ＰＥＧ／ＰＰＧ－１４／７ジメチルエーテル １
ＰＥＧ－１２ジメチコン ０．０１
ポリクオタニウム－５１ ０．０４ Formulation Example 3: Makeup base Blending ingredients Blending amount (% by mass)
Ion exchange water Residue Dipropylene glycol 9
Polyoxyethylene hydrogenated castor oil 1
Carboxymethylcellulose 0.1
Xanthan gum 0.6
Sorbitan sesquiisostearate 0.35
Isostearic acid 0.5
Isopropyl myristate 2
Isododecane 12
4-tert-Butyl-4′-methoxydibenzoylmethane 1.5
Octocrylene 5
Oxybenzone 1.5
Pigment grade titanium oxide treated with magnesium isostearate 1
Magnesium isostearate treated fine particle titanium oxide 5
Spherical cellulose powder 2
Porous silica 1
Potassium 4-methoxysalicylate 1
Toki Root Extract 0.001
PEG / PPG-14 / 7 dimethyl ether 1
PEG-12 Dimethicone 0.01
Polyquaternium-51 0.04
処方例４：Ｗ／Ｏサンスクリーン
配合成分 配合量（質量％）
イオン交換水 残余
エタノール ２
グリセリン ３
ジプロピルグリコール ５
ＰＥＧ－９ポリジメチルシロキシエチルジメチコン ２
軽質イソパラフィン ２０
トリ２－エチルヘキサン酸グリセリル １５
ジメチコン ５
コハク酸ジ２－エキルヘキシル ５
デカメチルシクロペンタシロキサン １５
４－ｔｅｒｔ－ブチル－４’－メトキシジベンゾイルメタン ３
フェニルベンズイミダゾールスルホン酸 ０．５
トリエタノールアミン ０．２
ミリスチン酸カルシウム被覆タルク ５
グチチルリチン酸ジカリウム ０．００１
エチルビタミンＣ ０．０１
トレハロース ０．５ Formulation example 4: W / O sunscreen Compounding component Compounding amount (mass%)
Ion exchange water Residual ethanol 2
Glycerin 3
Dipropyl glycol 5
PEG-9 polydimethylsiloxyethyl dimethicone 2
Light isoparaffin 20
Glyceryl tri-2-ethylhexanoate 15
Dimethicone 5
Di-2-ethylhexyl succinate 5
Decamethylcyclopentasiloxane 15
4-tert-butyl-4′-methoxydibenzoylmethane 3
Phenylbenzimidazolesulfonic acid 0.5
Triethanolamine 0.2
Calcium myristate-coated talc 5
Dipotassium glycyrrhizinate 0.001
Ethyl vitamin C 0.01
Trehalose 0.5
配合成分 配合量（質量％）
イオン交換水 残余
エタノール ２
グリセリン ３
ジプロピルグリコール ５
ＰＥＧ－９ポリジメチルシロキシエチルジメチコン ２
軽質イソパラフィン ２０
トリ２－エチルヘキサン酸グリセリル １５
ジメチコン ５
コハク酸ジ２－エキルヘキシル ５
デカメチルシクロペンタシロキサン １５
４－ｔｅｒｔ－ブチル－４’－メトキシジベンゾイルメタン ３
フェニルベンズイミダゾールスルホン酸 ０．５
トリエタノールアミン ０．２
ミリスチン酸カルシウム被覆タルク ５
グチチルリチン酸ジカリウム ０．００１
エチルビタミンＣ ０．０１
トレハロース ０．５ Formulation example 4: W / O sunscreen Compounding component Compounding amount (mass%)
Ion exchange water Residual ethanol 2
Glycerin 3
Dipropyl glycol 5
PEG-9 polydimethylsiloxyethyl dimethicone 2
Light isoparaffin 20
Glyceryl tri-2-ethylhexanoate 15
Dimethicone 5
Di-2-ethylhexyl succinate 5
Decamethylcyclopentasiloxane 15
4-tert-butyl-4′-methoxydibenzoylmethane 3
Phenylbenzimidazolesulfonic acid 0.5
Triethanolamine 0.2
Calcium myristate-coated talc 5
Dipotassium glycyrrhizinate 0.001
Ethyl vitamin C 0.01
Trehalose 0.5
Claims (6)
- （ａ）ジベンゾイルメタン誘導体、及び
（ｂ）高級脂肪酸とアルカリ土類金属からなる金属石鹸処理又は高級脂肪酸とアルカリ土類金属水酸化物との複合処理によって表面疎水化処理された粉体、を含むことを特徴とする日焼け止め化粧料。 (A) a dibenzoylmethane derivative, and (b) a powder that has been surface-hydrophobized by a metal soap treatment comprising a higher fatty acid and an alkaline earth metal or a composite treatment of a higher fatty acid and an alkaline earth metal hydroxide. Sunscreen cosmetics characterized by containing. - 前記アルカリ土類金属がカルシウムまたはマグネシウムである、請求項１に記載の化粧料。 The cosmetic according to claim 1, wherein the alkaline earth metal is calcium or magnesium.
- 前記高級脂肪酸が炭素数１２～１８の脂肪酸である、請求項１又は２に記載の化粧料。 The cosmetic according to claim 1, wherein the higher fatty acid is a fatty acid having 12 to 18 carbon atoms.
- 前記（ａ）ジベンゾイルメタン誘導体の配合量が０．５～４．０質量％であり、前記（ｂ）表面疎水化処理された粉体の配合量が１．０～１５．０質量％である、請求項１から３のいずれか一項に記載の化粧料。 The blending amount of the (a) dibenzoylmethane derivative is 0.5 to 4.0% by mass, and the blending amount of the powder (b) hydrophobized is 1.0 to 15.0% by mass. The cosmetic according to any one of claims 1 to 3, wherein:
- 前記（ａ）ジベンゾイルメタン誘導体の配合量と、前記（ｂ）表面疎水化処理された粉体の配合量との配合量比率が、（ａ）：（ｂ）＝１：２４～３：１の範囲内である、請求項１から４のいずれか一項に記載の化粧料。 The blending ratio between the blending amount of the (a) dibenzoylmethane derivative and the blending amount of the (b) powder subjected to the surface hydrophobization treatment is (a) :( b) = 1: 24 to 3: 1. The cosmetic according to any one of claims 1 to 4, wherein the cosmetic is within the range.
- ジベンゾイルメタン誘導体を含有する組成物に、高級脂肪酸とアルカリ土類金属からなる金属石鹸処理又は高級脂肪酸とアルカリ土類金属水酸化物との複合処理によって表面疎水化処理された粉体を配合することを含む、前記組成物を安定化する方法。 A composition containing a dibenzoylmethane derivative is blended with a powder that has been surface-hydrophobized by a metal soap treatment comprising a higher fatty acid and an alkaline earth metal or a composite treatment of a higher fatty acid and an alkaline earth metal hydroxide. Comprising stabilizing the composition.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020187011864A KR101944787B1 (en) | 2015-09-30 | 2016-09-30 | UV-blocking cosmetics |
| EP16851844.7A EP3357483B1 (en) | 2015-09-30 | 2016-09-30 | Sunscreen cosmetic |
| US15/764,089 US20180271757A1 (en) | 2015-09-30 | 2016-09-30 | Sunscreen cosmetic |
| CN201680069247.6A CN108289811A (en) | 2015-09-30 | 2016-09-30 | Sun care preparations |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015-194610 | 2015-09-30 | ||
| JP2015194610 | 2015-09-30 | ||
| JP2016188954A JP6113899B2 (en) | 2015-09-30 | 2016-09-28 | Sunscreen cosmetics |
| JP2016-188954 | 2016-09-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2017057675A1 true WO2017057675A1 (en) | 2017-04-06 |
Family
ID=58423722
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2016/079010 WO2017057675A1 (en) | 2015-09-30 | 2016-09-30 | Sunscreen cosmetic |
Country Status (1)
| Country | Link |
|---|---|
| WO (1) | WO2017057675A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018225768A1 (en) * | 2017-06-08 | 2018-12-13 | 株式会社 資生堂 | Water-in-oil emulsified cosmetic preparation |
| WO2018225765A1 (en) * | 2017-06-08 | 2018-12-13 | 株式会社 資生堂 | Water-in-oil emulsified cosmetic preparation |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5849307A (en) * | 1981-09-16 | 1983-03-23 | Pola Chem Ind Inc | Cosmetic |
| JP2000503677A (en) * | 1996-09-27 | 2000-03-28 | ザ、プロクター、エンド、ギャンブル、カンパニー | Stable light protection composition |
| JP2001058934A (en) * | 1999-08-19 | 2001-03-06 | Shiseido Co Ltd | Antisuntan cosmetic |
| JP2007106714A (en) * | 2005-10-14 | 2007-04-26 | Shiseido Co Ltd | Oil-in-water type external preparation for skin |
| JP2010195773A (en) * | 2009-01-27 | 2010-09-09 | Shiseido Co Ltd | Water-in-oil type emulsified sunburn care cosmetic |
-
2016
- 2016-09-30 WO PCT/JP2016/079010 patent/WO2017057675A1/en active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5849307A (en) * | 1981-09-16 | 1983-03-23 | Pola Chem Ind Inc | Cosmetic |
| JP2000503677A (en) * | 1996-09-27 | 2000-03-28 | ザ、プロクター、エンド、ギャンブル、カンパニー | Stable light protection composition |
| JP2001058934A (en) * | 1999-08-19 | 2001-03-06 | Shiseido Co Ltd | Antisuntan cosmetic |
| JP2007106714A (en) * | 2005-10-14 | 2007-04-26 | Shiseido Co Ltd | Oil-in-water type external preparation for skin |
| JP2010195773A (en) * | 2009-01-27 | 2010-09-09 | Shiseido Co Ltd | Water-in-oil type emulsified sunburn care cosmetic |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018225768A1 (en) * | 2017-06-08 | 2018-12-13 | 株式会社 資生堂 | Water-in-oil emulsified cosmetic preparation |
| WO2018225765A1 (en) * | 2017-06-08 | 2018-12-13 | 株式会社 資生堂 | Water-in-oil emulsified cosmetic preparation |
| CN110709055A (en) * | 2017-06-08 | 2020-01-17 | 株式会社资生堂 | Water-in-oil type emulsion cosmetic |
| KR20200013664A (en) * | 2017-06-08 | 2020-02-07 | 가부시키가이샤 시세이도 | Water-in-oil type cosmetic |
| JPWO2018225765A1 (en) * | 2017-06-08 | 2020-04-09 | 株式会社 資生堂 | Water-in-oil emulsion cosmetics |
| JPWO2018225768A1 (en) * | 2017-06-08 | 2020-04-09 | 株式会社 資生堂 | Water-in-oil emulsion cosmetics |
| US11166887B2 (en) | 2017-06-08 | 2021-11-09 | Shiseido Company, Ltd. | Water-in-oil emulsion cosmetic |
| JP7295797B2 (en) | 2017-06-08 | 2023-06-21 | 株式会社 資生堂 | Water-in-oil emulsified cosmetic |
| KR102627144B1 (en) | 2017-06-08 | 2024-01-19 | 가부시키가이샤 시세이도 | Water-in-oil type emulsified cosmetics |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4560122B2 (en) | Titanium oxide dispersion and cosmetics containing the same | |
| JP6867293B2 (en) | Sunscreen cosmetics | |
| JP2010222349A (en) | Sunscreen cosmetic | |
| JP6815310B2 (en) | Underwater oil type UV protection cosmetics | |
| CN108135817B (en) | Sunscreen cosmetic | |
| JP2007145722A (en) | Sun-screen cosmetic | |
| JP5260060B2 (en) | Fine particle titanium oxide dispersion and cosmetics containing the same | |
| WO2014069173A1 (en) | Sunscreen cosmetic | |
| JP2007204459A (en) | Water-in-oil type emulsion sunscreen cosmetic material | |
| JP7043803B2 (en) | Underwater oil type emulsified cosmetic | |
| JP6113899B2 (en) | Sunscreen cosmetics | |
| KR102606444B1 (en) | UV protection cosmetics | |
| WO2017057675A1 (en) | Sunscreen cosmetic | |
| JP2019043920A (en) | Water-in-oil type emulsion cosmetic preparation | |
| WO2021100676A1 (en) | External preparation for skin | |
| WO2022210145A1 (en) | Cosmetic | |
| WO2021125211A1 (en) | Sunscreen cosmetic |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 16851844 Country of ref document: EP Kind code of ref document: A1 |
|
| WWE | Wipo information: entry into national phase |
Ref document number: 15764089 Country of ref document: US |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| ENP | Entry into the national phase |
Ref document number: 20187011864 Country of ref document: KR Kind code of ref document: A |
|
| WWE | Wipo information: entry into national phase |
Ref document number: 2016851844 Country of ref document: EP |