JP4995473B2 - Oil-in-water sunscreen - Google Patents

Description

The present invention relates to an oil-in-water sunscreen comprising an oil-in-water sunscreen using a higher fatty acid salt as an emulsifier and a titanium oxide having an average particle size of 0.5 to 2 μm and an ultraviolet absorber. More specifically, underwater with no bluish white at the time of application, excellent transparency, good spread, UV-A to UV-B, a wide range of UV rays, and excellent stability over time. It relates to oil-type sunscreen.

  In recent years, the harmful effects of ultraviolet rays have attracted attention due to the destruction of the ozone hole, and various sunscreens have been developed and put on the market. Such sunscreens include oil-in-water, water-in-oil, and solvent types. In the water-in-oil type and the solvent type, the continuous phase becomes an oil agent or solvent, so that the cosmetic film formed on the skin becomes hydrophobic and a sunscreen with excellent water resistance can be obtained. In some cases, it may feel poor in size and spread, and it is not a preferable dosage form particularly for use in midsummer.

  For this reason, in these water-in-oil types and solvent types, studies have been made such as selecting an oil agent to be blended that has as little oiliness as possible, or blending a porous spherical powder that absorbs excess oil agent. Yes. On the other hand, an oil-in-water sunscreen is a dosage form that has a fresh feel and a good spread when applied to the skin because the continuous phase is water. As sunscreens, UV absorbers such as 2-ethylhexyl paramethoxycinnamate and UV screening agents such as titanium oxide and zinc oxide having fine particles of less than 0.1 μm are widely used.

  However, when a large amount of the ultraviolet absorber is blended, some people may feel irritation, and the blending amount is limited. Further, sunscreens (for example, see Patent Document 1) containing fine particle titanium oxide which is an ultraviolet shielding agent are excellent in transparency and can well shield ultraviolet rays in the UV-B region. And the ultraviolet rays in the UV-A region cannot be sufficiently shielded. Furthermore, the sunscreen containing fine zinc oxide (see, for example, Patent Document 2) eliminates the bluishness at the time of coating as fine titanium oxide, and shields a wide range of UV-A to UV-B ultraviolet rays. However, since zinc oxide is partially ionized in water, an anionic surfactant typified by higher fatty acids and water-insoluble metal soaps are formed, which causes gelation and crystal precipitation over time. It was difficult to blend into the stopper.

Japanese Patent Laid-Open No. 10-212224 JP 2002-60329 A

For this reason, in oil-in-water sunscreens using higher fatty acid salts as emulsifiers, there is no bluish white at the time of application, excellent transparency, good spread, and shielding a wide range of UV-A to UV-B ultraviolet rays. It has been desired to develop an oil-in-water sunscreen that can be used and that has excellent stability over time.

  As a result of studying the relationship between the average particle size of titanium oxide, which is an ultraviolet shielding agent, and the ultraviolet shielding effect, transparency, and elongation spread at the time of application, the present inventors have conducted earnest studies in the above-described actual situation. By using titanium oxide of 0.5-2 μm, it effectively shields a wide range of UV rays from UV-A to UV-B, and is used in combination with higher fatty acids that are oil-in-water emulsifiers without any bluish white when applied. However, the present inventors have found that no water-insoluble metal soap is produced and there is no gelation or crystal precipitation over time, and the present invention has been completed.

That is, the present invention includes the following components (a) to (c);
(A) An oil-in-water sunscreen comprising titanium oxide (b) having an average particle size of 0.5 to 2 μm, (b) an ultraviolet absorber, and (c) a higher fatty acid salt is provided.

  Furthermore, the present invention provides the oil-in-water sunscreen, wherein component (d) titanium oxide having an average particle size of 0.01 to 0.14 μm is blended.

  And the crystal form of the titanium oxide of the said component (a) is a rutile type, The said oil-in-water type sunscreen is provided.

The oil-in-water sunscreen of the present invention has excellent temporal stability even when used in combination with higher fatty acids, has no bluish white at the time of application, has excellent transparency, and has good spread, UV-A to UV-B An oil-in-water sunscreen that can shield a wide range of ultraviolet rays can be obtained.

Hereinafter, the configuration of the present invention will be described in detail.
Component (a) used in the present invention is titanium oxide having an average particle size of 0.5 to 2 μm. Titanium oxide having an average particle size of less than 0.5 μm (conventional pigment-grade titanium oxide) is not preferable because the elongation and spread at the time of application deteriorates and the bluish white at the time of application occurs. Further, titanium oxide having an average particle size exceeding 2 μm is not preferable because it is inferior in the ultraviolet shielding effect. In the present invention, the average particle diameter is a volume average diameter obtained by image analysis (LUZEX AP) of an electron micrograph (TEM).

  The crystal form of the component (a) titanium oxide may be any of anatase, rutile, brookite, etc., but if the crystal form is the rutile type, it effectively shields a wide range of UV-A to UV-B ultraviolet rays. This is preferable because it is possible. And the manufacturing method of such a titanium oxide may be obtained by any manufacturing methods, such as a chlorine method and a sulfuric acid method.

  As such component (a) titanium oxide, commercially available products such as MP-70 having an average particle diameter of 0.7 μm, MP-100 having an average particle diameter of 1 μm (both manufactured by Teika), etc. can be used. .

  Furthermore, the titanium oxide of the component (a) is an inorganic compound such as alumina, silica, iron oxide, etc., which are usually known surface treatment agents, fluorine compounds, silicone compounds, phospholipids, phospholipid derivatives, metals, if necessary. It may be used after being surface-treated with soap, wax, surfactant, oil or fat, hydrocarbon or the like.

  The blending amount of the component (a) in the oil-in-water sunscreen of the present invention is not particularly limited, but is preferably 0.1 to 30% by mass (hereinafter simply referred to as “%”). When component (a) is used within this range, an oil-in-water sunscreen with better spreading and stability over time can be obtained.

  The ultraviolet absorber of the component (b) used for this invention will not be restrict | limited especially if normally used for cosmetics and a skin external preparation, For example, paramethoxycinnamic acid benzyl, paramethoxycinnamic acid 2 -Cinnamic acid UV absorbers such as ethylhexyl, 2-ethoxyethyl paramethoxycinnamate, glyceryl mono-2-ethylhexanoate diparamethoxycinnamate, isopropyl dimethoxycinnamate and diisopropyl cinnamate ester mixture Benzo such as hydroxymethoxybenzophenone, hydroxymethoxybenzophenone sulfonic acid, sodium hydroxymethoxybenzophenone sulfonate, dihydroxymethoxybenzophenone, dihydroxymethoxybenzophenone sodium disulfonate, dihydroxybenzophenone, tetrahydroxybenzophenone Phenone ultraviolet absorber, paraaminobenzoic acid, ethyl paraaminobenzoate, glyceryl paraaminobenzoate, amyl paradimethylaminobenzoate, octyl paradimethylaminobenzoate, 4- [N, N-di (2-hydroxypropyl) amino] Benzoic acid ester ultraviolet absorbers such as ethyl benzoate, salicylic acid ultraviolet absorbers such as ethylene glycol salicylate, phenyl salicylate, octyl salicylate, benzyl salicylate, para-tert-butylphenyl salicylate, homomenthyl salicylate, 2,4,6- Triazine-based ultraviolet absorbers such as trianilino-para- (carbo-2′-ethylhexyl-1′-oxy) -1,3,5-triazine, 4-tert-butyl-4′-methoxydibenzoylmethane, oxybenzone, Menthyl tranylate, 2- (2-hydroxy-5-methylphenyl) benzotriazole, dimethoxybenzylidenedioxoimidazolidinepropionate 2-ethylhexyl, 2-phenylbenzimidazole-5-sulfonic acid, etc. Two or more kinds can be used. Among these, as component (b), 2-methoxyhexyl paramethoxycinnamate, 2-ethoxyethyl paramethoxycinnamate, glyceryl mono-2-ethylhexanoate diparamethoxycinnamate, paramethoxycinnamate It is preferable to select a cinnamic acid-based ultraviolet absorber such as an isopropyl / diisopropyl cinnamate ester mixture, since the spreading at the time of application becomes better.

  Although the compounding quantity of a component (b) in the oil-in-water type sunscreen of this invention is not specifically limited, 0.1 to 10% is preferable. When component (b) is used within this range, an oil-in-water sunscreen with better spreading and stability over time can be obtained.

  The higher fatty acid salt of component (c) used in the present invention is used as an emulsifier in the present invention. Such higher fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, undecylenic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid, isostearic acid, 12-hydroxystearic acid, etc. One or more of these can be used. Of these, one or two or more selected from lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, undecylenic acid, oleic acid, and isostearic acid are preferred in view of the function as an emulsifier.

  In addition, component (c) may be used as a higher fatty acid salt neutralized with a base in advance, or may be added as a higher fatty acid salt by neutralization by adding a basic substance during the cosmetic production process. Examples of such basic substances include sodium hydroxide, potassium hydroxide, triethanolamine and the like. The neutralization amount is determined by the equivalent amount of higher fatty acid.

  Although the compounding quantity of a component (c) in the oil-in-water type sunscreen of this invention is not specifically limited, 0.1 to 5% is preferable. When component (c) is used within this range, an oil-in-water sunscreen with good emulsification and better stability over time can be obtained.

  In the oil-in-water sunscreen of the present invention, in addition to the above components, a higher ultraviolet shielding effect is obtained by blending titanium oxide having an average particle size of 0.01 to 0.14 μm as component (d). Can do.

  Titanium oxide of such component (d) is an inorganic compound such as alumina, silica, iron oxide, etc., which are usually known surface treatment agents, fluorine compounds, silicone compounds, phospholipids, phospholipid derivatives, if necessary. It may be used after being surface-treated with metal soap, wax, surfactant, oil or fat, hydrocarbon or the like.

  Although the compounding quantity of a component (d) in the oil-in-water type sunscreen of this invention is not specifically limited, 0.1 to 10% is preferable. When component (d) is used within this range, the spread of elongation at the time of application is not deteriorated, the bluishness at the time of application is not noticeable, and an oil-in-water sunscreen with a higher UV shielding effect can be obtained in a wider range. it can.

  In the oil-in-water sunscreen of the present invention, water constituting the oil-in-water outer layer (continuous phase) is essentially blended. In the oil-in-water sunscreen of the present invention, the amount of water is preferably 40 to 95%.

  In addition to the above components, the oil-in-water sunscreen of the present invention is a component other than the components (a) and (d), which is a component blended in ordinary cosmetics as long as the effects of the present invention are not hindered. , Oil agent, oily gelling agent, water-soluble polymer, film forming agent, surfactant other than component (c), alcohol, organically modified clay mineral, resin, moisturizer, antiseptic, antibacterial agent, fragrance, salt, Antioxidants, pH adjusters, chelating agents, refreshing agents, anti-inflammatory agents, skin beautifying ingredients, vitamins, amino acids, nucleic acids, hormones, inclusion compounds, and the like can be blended.

  The powders other than the components (a) and (d) that can be blended in the present invention are blended for the purpose of adjusting the feel and imparting a makeup effect, and may be blended in ordinary cosmetics. For example, it is not particularly limited by the shape of a plate, spindle, needle, etc., particle size, particle structure such as porous, nonporous, etc., inorganic powders, glitter powders, organic powders, Examples thereof include pigments and composite powders. Specifically, zinc oxide, zirconium oxide, cerium oxide, iron oxide, conger, ultramarine, anhydrous silicic acid, magnesium carbonate, calcium carbonate, aluminum hydroxide, chromium hydroxide, carbon black, aluminum silicate, magnesium silicate, Inorganic powders such as magnesium aluminum silicate, mica, smectite, bentonite, kaolin, synthetic mica, synthetic sericite, sericite, talc, silicon carbide, barium sulfate, boron nitride, bismuth oxychloride, titanium mica, iron oxide coating Bright powders such as mica, iron oxide coated mica titanium, organic pigment coated mica titanium, aluminum powder, magnesium stearate, zinc stearate, N-acyl lysine, polystyrene, nylon, polymethyl methacrylate, polymethylsilsesquioxane Powder Organic powders such as organopolysiloxane elastomer powder and the like, can be used in combination thereof to one or more kinds. In addition, these powders may be used singly or in combination of two or more, and if necessary, usually known surface treatment agents, inorganic compounds such as alumina, silica, iron oxide, fluorine compounds, It may be used after being surface-treated with a silicone compound, phospholipid, phospholipid derivative, metal soap, wax, surfactant, oil or fat, hydrocarbon or the like. 0.1-40% of the compounding quantity in the case of mix | blending powder other than a component (d) with the oil-in-water type sunscreen of this invention is preferable.

  The oil agent that can be blended in the present invention is not particularly limited as long as it is an oil agent blended in ordinary cosmetics, and the origin of animal oil, vegetable oil, synthetic oil, etc., and solid oil, semi-solid oil, liquid oil, volatile oil Oils such as hydrocarbons, fats and oils, waxes, hardened oils, ester oils, higher alcohols, silicone oils, fluorine-based oils, lanolin derivatives, and the like. Specifically, hydrocarbons such as liquid paraffin, α-olefin oligomer, squalane and petrolatum, oils and fats such as olive oil, castor oil, mink oil, macadamian nut oil, beeswax, carnauba wax, candelilla wax, gay wax Wax, jojoba oil, diisobutyl adipate, 2-hexyldecyl adipate, di-2-heptylundecyl adipate, alkyl glycol monoisostearate, isocetyl isostearate, trimethylolpropane triisostearate, di-2- Ethylene glycol ethylhexanoate, cetyl 2-ethylhexanoate, neopentyl glycol di-2-ethylhexanoate, trimethylolpropane tri-2-ethylhexanoate, pentaerythritol tetra-2-ethylhexanoate, octa Cetyl acid, octyldodecyl gum ester, oleyl oleate, octyldodecyl oleate, decyl oleate, neopentyl glycol dicaprate, triethyl citrate, 2-ethylhexyl succinate, amyl acetate, ethyl acetate, butyl acetate, isocetyl stearate, Butyl stearate, diisopropyl sebacate, di-2-ethylhexyl sebacate, cetyl lactate, myristyl lactate, isopropyl palmitate, 2-ethylhexyl palmitate, 2-hexyldecyl palmitate, 2-heptyl undecyl palmitate, 12-hydroxy Cholesteryl stearyl, dipentaerythritol fatty acid ester, isopropyl myristate, 2-octyldodecyl myristate, 2-hexyldecyl myristate, myristine Myristyl acid, hexyldecyl dimethyloctanoate, ethyl laurate, hexyl laurate, N-lauroyl-L-glutamic acid-2-octyldodecyl ester, malic acid diisostearyl, rosin acid pentaerythritol ester, acetoglyceryl, triisooctanoic acid Esters such as glyceryl, glyceryl triisostearate, glyceryl triisopalmitate, glyceryl tri-2-ethylhexanoate, glyceryl monostearate, glyceryl di-2-heptylundecanoate, glyceryl trimyristate, diglyceryl myristate N-lauroyl-L-glutamate di (phytostearyl 2-octyldodecyl), N-lauroyl-L-glutamate di (cholesteryl behenyl octyldodecyl) ), Amino acid oils such as N-lauroyl-L-glutamic acid di (cholesteryl / octyldodecyl), higher alcohols such as stearyl alcohol, cetyl alcohol, behenyl alcohol, lauryl alcohol, oleyl alcohol, isostearyl alcohol, and low polymerization dimethylpoly Siloxane, methylphenylpolysiloxane, decamethylcyclopentasiloxane, octamethylcyclotetrasiloxane, alkoxy-modified polysiloxane, silicones such as fluorine-modified silicone, fluorine oils such as perfluoropolyether, lanolin, lanolin acetate, lanolin fatty acid Lanolin derivatives such as isopropyl and lanolin alcohol, dextrin fatty acid ester, sucrose fatty acid ester, starch fatty acid ester, calcium stearate Oily gelling agents and the like, and these can be used singly or in combination. As for the compounding quantity in the case of mix | blending an oil agent with the oil-in-water type sunscreen of this invention, 1 to 30% is preferable.

  The water-soluble polymer that can be blended in the present invention is used to impart viscosity to an oil-in-water sunscreen, improve usability, stabilize an emulsion, etc. It is not particularly limited as long as it is a water-soluble polymer blended in, for example, gum arabic, gum tragacanth, galactan, carob gum, guar gum, caraya gum, carrageenan, pectin, agar Plant polymers such as quince seed (malmello), starch (rice, corn, potato, wheat), alge colloid, locust bean gum, microbial polymers such as xanthan gum, dextran, succinoglucan, pullulan, collagen, casein , Animal polymers such as albumin and gelatin, carboxymethyl starch, methyl hydride Modified starch polymers such as xylpropyl starch, cellulose polymers such as methylcellulose, methylhydroxypropylcellulose, carboxymethylcellulose, hydroxymethylcellulose, hydroxypropylcellulose, sodium cellulose sulfate, sodium carboxymethylcellulose, crystalline cellulose, cellulose powder, sodium alginate , Alginate polymers such as propylene glycol alginate, vinyl polymers such as polyvinyl methyl ether and carboxyvinyl polymer, polyoxyethylene polymers, polyoxyethylene / polyoxypropylene copolymer polymers, sodium polyacrylate , Acrylic polymers such as polyethyl acrylate and polyacrylamide, polyethyleneimine, cationic poly Chromatography, and the like. Moreover, in this, polyvinyl alcohol, polyvinylpyrrolidone, etc. are mentioned, These can be used 1 type, or 2 or more types. The blending amount in the case of blending a water-soluble polymer with the oil-in-water sunscreen of the present invention is preferably 0.001 to 5%.

  As surfactants other than the component (c) that can be blended in the present invention, there are anionic, cationic, nonionic and amphoteric surfactants. Anionic surfactants include alkyl ether carboxylic acids and their surfactants. Carboxylates such as salts, condensates of amino acids and fatty acids, alkyl sulfonic acids, alkene sulfonates, sulfonates of fatty acid esters, sulfonates of fatty acid amides, sulfonates of alkyl sulfonates and their formalin condensates , Alkyl sulfates, secondary higher alcohol sulfates, alkyl and allyl ether sulfates, fatty acid ester sulfates, fatty acid alkylolamide sulfates, sulfate oils such as funnel oil, alkyl phosphoric acid Salt, ether phosphate, alkyl allyl ether phosphate, amide phosphorus Salts, N-acylamino acid based surfactants, etc .; cationic surfactants include alkylamine salts, amine salts such as polyamines and aminoalcohol fatty acid derivatives, alkyl quaternary ammonium salts, aromatic quaternary ammonium salts, pyridium salts, Imidazolium salts, etc .; nonionic surfactants include sorbitan fatty acid ester, glycerin fatty acid ester, polyglycerin fatty acid ester, propylene glycol fatty acid ester, polyethylene glycol fatty acid ester, sucrose fatty acid ester, polyoxyethylene alkyl ether, polyoxy Propylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fat Ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene propylene glycol fatty acid ester, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene phytostanol ether, polyoxyethylene phytosterol ether, polyoxyethylene cholestanol ether, Polyoxyethylene cholesteryl ether, polyoxyalkylene-modified organopolysiloxane, polyoxyalkylene / alkyl co-modified organopolysiloxane, alkanolamide, sugar ether, sugar amide, etc .; amphoteric surfactants include betaine, aminocarboxylate, imidazoline A derivative etc. are mentioned, These can be used 1 type, or 2 or more types.

  Moisturizers that can be blended in the present invention include sorbitol, xylitol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, glycerin, diglycerin, polyethylene glycol, hyaluronic acid, chondroitin sulfate, pyrrolidone carboxylate, and the like. 1 type, or 2 or more types can be used. Further, as preservatives, paraoxybenzoic acid alkyl ester, benzoic acid, sodium benzoate, sorbic acid, potassium sorbate, phenoxyethanol, etc., as antibacterial agents, benzoic acid, salicylic acid, carboxylic acid, sorbic acid, paraoxybenzoic acid ester, Parachlorometacresol, hexachlorophene, benzalkonium chloride, chlorhexidine chloride, trichlorocarbanilide, photosensitizer, phenoxyethanol, etc., antioxidants such as tocopherol, butylhydroxyanisole, dibutylhydroxytoluene, etc. Lactic acid, citric acid, glycolic acid, succinic acid, tartaric acid, dl-malic acid, potassium carbonate, sodium hydrogen carbonate, ammonium hydrogen carbonate, etc. Chelating agents include alanine, sodium edetate, Sodium phosphate, sodium metaphosphate, phosphoric acid, etc., L-menthol, camphor, etc. as refreshing agents, allantoin, glycyrrhetic acid, tranexamic acid, azulene, etc. as anti-inflammatory agents, placenta extract , Whitening agents such as arbutin, glutathione, yukinoshita extract, royal jelly, photosensitizer, cholesterol derivatives, cell activators such as calf blood extract, rough skin improver, nonyl acid wallenylamide, nicotinic acid benzyl ester, nicotinic acid β- Butoxyethyl ester, capsaicin, gingerone, cantalis tincture, ictamol, caffeine, tannic acid, alpha-borneol, tocopherol nicotinate, inositol hexanicotinate, cyclandrate, cinnarizine, trazoline, acetylcholine, verapamil Examples include blood circulation promoters such as cephalanthin and γ-oryzanol, skin astringents such as tannic acid, antiseborrheic agents such as sulfur and thianthol, and vitamins include vitamin A oil, retinol, retinol acetate, and palmitic acid. Vitamin A such as retinol, vitamin B2 such as riboflavin, riboflavin acetate and flavin adenine nucleotide, vitamin B6 such as pyridoxine hydrochloride and pyridoxine dioctanoate, L-ascorbic acid, L-ascorbic acid dipalmitate, Vitamin C such as L-ascorbic acid-2-sodium sulfate, dl-α-tocopherol-L-ascorbic acid phosphate diester dipotassium, calcium pantothenate, D-pantothenyl alcohol, pantothenyl ethyl ether, acetyl pantothenyl ethyl Pantothenic acids such as ether, vitamin D such as ergocalciferol and cholecalciferol, nicotinic acids such as nicotinic acid, benzyl nicotinate and nicotinamide, dl-α-tocopherol, dl-α-tocopherol acetate, nicotinic acid dl -Vitamin E such as α-tocopherol and dl-α-tocopherol succinate, vitamin P, biotin and the like. Amino acids include arginine, aspartic acid, cystine, cysteine, methionine, serine, leucine, tryptophan, etc., nucleic acids include deoxyribonucleic acid, etc., hormones include estradiol, etenyl estradiol, etc. The above can be used.

  The oil-in-water sunscreen of the present invention provides not only a sunscreen, but also a makeup cosmetic such as a foundation and a foundation, a skin care cosmetic such as a milky lotion, a cream and a cosmetic liquid, and a hair cosmetic, etc. It can also be applied to finished cosmetics. The form of the oil-in-water sunscreen of the present invention may be any of cream, gel, emulsion, liquid, and solid.

  Although the manufacturing method of the oil-in-water type sunscreen of this invention is not specifically limited, A component (b) and a component (c) are mixed with another oil agent, a component (a) is disperse | distributed to this, and is disperse | distributed in water. Examples thereof include a method, a method in which the component (b) and the component (c) are mixed with other oil agent, and this is dispersed in water, and then the component (a) is added and uniformly dispersed.

EXAMPLES Next, although an Example is given and this invention is further demonstrated, this invention is not limited at all by this.

Examples 1 to 4 and Comparative Examples 1 to 3: Sunscreen Creams Sunscreen creams having the compositions shown in Tables 1 and 2 below were prepared by the following production method. Each item of “None” and “Stability over time” was evaluated by the following evaluation methods, and the results are shown in Tables 1 and 2.

(Manufacturing method) A: The components 1-8 are heated and mixed at 70 degreeC. B: Add components 9 to 13 to A, disperse uniformly, and keep at 70 ° C. C: Components 14 to 18 are heated to 70 ° C. and mixed. D: B is added to C and emulsified. E: D was cooled to room temperature and filled into a tube to obtain a sunscreen cream.

[Evaluation methods: “Elongation and spread during application”, “No bluishness during application”]
Twenty cosmetic evaluation panels used the sunscreen creams of the above-mentioned examples and comparative examples. For each item of “Elongation at application” and “No whiteness at application” Was evaluated according to the following evaluation criteria, given a score for each sunscreen, and the average score of all panels was determined according to the following criteria.
Evaluation criteria:
[Evaluation Result]: [Score]
Very good: 5 points Good: 4 points Normal: 3 points Somewhat bad: 2 points Bad: 1 point Criteria:
[Average score]: [Judgment]
4.5 or more: ◎
3.5 or more and less than 4.5: ○
1.5 or more and less than 3.5: △
Less than 1.5: ×

[Evaluation method: Stability over time]
The sunscreen creams of the examples and comparative examples were stored in a constant temperature bath at 40 ° C. for 1 month, and the changes in the emulsified state and the aggregated state were determined using the following four-stage criteria based on the state immediately after preparation. .
Judgment criteria:
[Average score]: [Judgment]
No change: ◎
Slightly rough texture: ○
Powder aggregation and gelation occur: △
Significant change: ×

  As is clear from the results of Tables 1 and 2, the sunscreen creams of Examples 1 to 4 which are the products of the present invention are “elongation and spread at the time of application”, “no whiteness at the time of application”, It was an excellent sunscreen for all items of “time stability”. Moreover, as a result of measuring the ultraviolet shielding effect with the spectrophotometer, the sunscreen creams of Examples 1 to 4 were excellent in a wide ultraviolet shielding effect of UV-A to UV-B. On the other hand, the comparative example 1 which mix | blended the titanium oxide with an average particle diameter of 0.28 micrometer instead of a component (a) is inferior to "no blueness at the time of application | coating", and "elongation spread at the time of application | coating" is also It was not good. Further, Comparative Example 2 in which zinc oxide having an average particle size of 0.025 μm was blended in place of the component (a) was inferior in “aging stability” and “elongation spread during application” was not good. Furthermore, Comparative Example 3 in which only the titanium oxide of component (d) was blended instead of component (a) was inferior to “elongation at the time of application” and “no whiteness at the time of application”. Was not good either.

Example 5: Sunscreen base emulsion (component) (%)
1. Stearic acid 1.5
2. Cetanol 0.8
3. Glycerol monostearate 0.6
4). Sorbitan sesquioleate 0.3
5. Polyoxyethylene sorbitan monooleate 0.5
6). 2-Ethylhexyl paramethoxycinnamate 5
7). Glyceryl tri-2-ethylhexanoate 5
8). Titanium oxide with an average particle size of 0.7 μm (Note 1) 7
9. Fine particle titanium oxide with an average particle size of 0.035 μm (Note 4) 5
10. Mica titanium (Note 6) 3
11. Purified water remaining amount 12.1, 3-butylene glycol 12
13. Alkyl acrylate copolymer emulsion 0.5
14 Triethanolamine 1
15. Methyl paraoxybenzoate 0.2
16. Carboxyvinyl polymer 0.2
Note 4: MT-500SA (manufactured by Teika)
Note 6: FLAMENCO RED 420C (manufactured by Engelhard)

(Production method)
A: Components 11 to 16 are heated to 70 ° C. and mixed.
B: Add components 8 to 10 to A, disperse uniformly, and keep at 70 ° C.
C: Components 1 to 7 are heated to 70 ° C. and mixed.
D: C is added to B and emulsified.
E: D was cooled to room temperature and filled into a container to obtain a sunscreen base emulsion.
The sunscreen base emulsion of Example 5 was a sunscreen excellent in all the items of “elongation and spread during application”, “no whiteness during application”, and “stability over time”. Moreover, as a result of measuring the ultraviolet shielding effect with a spectrophotometer, it was excellent in a wide ultraviolet shielding effect of UV-A to UV-B.

Example 6: Sunscreen foundation (cream)
(Ingredient) (%)
1. Stearic acid 2
2. Cetanol 2.5
3. Glycerol monostearate 2
4). Squalane 15
5. Methyl polysiloxane 7
6). 2-Ethylhexyl paramethoxycinnamate 5
7). Methyl paraoxybenzoate 0.2
8). Titanium oxide having an average particle size of 0.7 μm (Note 1) 15
9. Fine particle titanium oxide with an average particle size of 0.035 μm (Note 4) 3
10. Bengala 0.1
11. Yellow iron oxide 0.6
12 Black iron oxide 0.2
13. Purified water remaining amount 14. Sorbitan sesquioleate 0.3
15. Polyoxyethylene sorbitan monooleate 0.4
16. Hydrogenated soybean phospholipid 0.5
17.1,3-Butylene glycol 11
18. Triethanolamine 1.3
19. Carboxyvinyl polymer 0.2

(Production method)
A: Components 13 to 19 are heated to 70 ° C. and mixed.
B: Components 8 to 12 are added to A, dispersed uniformly, and kept at 70 ° C.
C: Components 1 to 7 are heated to 70 ° C. and mixed.
D: B is added to C and emulsified.
E: D was cooled to room temperature and filled into a jar container to obtain a sunscreen foundation.
The sunscreen foundation of Example 6 was a sunscreen excellent in all of the items of “Elongation at the time of application”, “No whiteness at the time of application”, and “Stability with time”. Moreover, as a result of measuring the ultraviolet shielding effect with a spectrophotometer, it was excellent in a wide ultraviolet shielding effect of UV-A to UV-B.
that's all

Claims (2)

The following components (a) to (c);
(A) 0.1-30 mass% of titanium oxide whose average particle diameter is 0.5-2 micrometers
(B) 0.1 to 10% by mass of an ultraviolet absorber
(C) Higher fatty acid salt 0.1 to 5% by mass
( D) 0.1 to 10% by mass of titanium oxide having an average particle size of 0.01 to 0.035 μm
An oil-in-water sunscreen that contains   2. The oil-in-water sunscreen according to claim 1, wherein the crystal form of the component (a) titanium oxide is a rutile type.