JPH11228373A - Ultraviolet protecting composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition having high ultraviolet protecting effect, excellent in persistency of the effect and having good water resistance and sebum resistance. SOLUTION: This ultraviolet protecting composition contains (A) fluorine compound-treated ultraviolet scattering powder and (B) a fluorinated organic compound which is liquid at ordinary temperature in a 1/>=10 weight ratio of component B to the component A. Although the fluorine-treated ultraviolet scattering powder is not especially limited if the powder comprises a substance substantially insoluble in water or oil, etc., and reflecting ultraviolet light, especially having 250-400 nm wavelength, it is preferable to use titanium oxide, zinc oxide, titanium oxide-zinc oxide complex powder, fine particle titanium oxide, fine particle zinc oxide, laminar zinc oxide as the component A.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an ultraviolet ray protective composition which has a high ultraviolet ray protective effect, is excellent in the persistence of the effect, and has good resistance to water and sebum.

[0002]

2. Description of the Related Art Components having an ultraviolet protection effect are broadly classified into two types, based on their mechanism, an ultraviolet absorber that absorbs ultraviolet light and an ultraviolet scattering agent that scatters and blocks ultraviolet light.
In order to improve the UV protection effect, the effects of the structure, form, dispersibility, etc. of these UV protection agents on the UV protection effect have been studied, and materials having higher effects have been searched for.

[0003] Decreasing the particle size of the UV protection powder increases transparency and enhances UV protection, but reducing the particle size decreases the dispersibility of the powder and tends to aggregate. growing. In other words, even if the powder has a small particle size and a high UV protection ability at the time of dispersion,
If it exists as a higher-order aggregate, it actually has the same characteristics as a large powder, and cannot exhibit the expected ultraviolet protection ability. Therefore, in order to improve the dispersion stability of the powder, use of a dispersant or a dispersing agent or surface treatment of the powder has been performed.

On the other hand, cosmetics for the purpose of protecting against ultraviolet rays are required to have water resistance and sebum resistance. By treating the surface of the ultraviolet protective powder with a fluorine compound, it is possible to prevent sweat and sebum. Attempts have been made to develop highly durable UV protection cosmetics, especially oil-in-water emulsion cosmetics.

[0005] However, the dispersibility of the powder treated with the fluorine compound in the emulsion is low, and when the emulsion is applied on the solid surface, the dispersion medium permeates, diffuses or evaporates. Since the powder in the emulsion was agglomerated, a sufficient UV protection effect was not obtained, and it was difficult to mix the fluorine compound-treated powder into the UV protection cosmetic.

[0006]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an ultraviolet ray protective composition which has a high ultraviolet ray protective effect, is excellent in the persistence of the effect, and has good water and sebum resistance. is there.

[0007]

Means for Solving the Problems In view of this situation, the present inventors have conducted intensive studies and as a result, if a fluorine compound-treated ultraviolet scattering powder and a fluorinated organic compound which is liquid at room temperature are blended in a specific ratio, The dispersibility of the UV protection powder in the composition is enhanced, it can be applied uniformly without agglomeration on the solid surface, and because it is treated with a fluorine compound, it has high resistance to water and sebum and protects against UV rays. The present inventors have found that the sustainability of the effect is improved, and completed the present invention.

That is, the present invention provides the following components (A) and (B): (A) a fluorine compound-treated ultraviolet scattering powder, (B) a fluorinated organic compound which is liquid at ordinary temperature, and the component (B) is It is intended to provide an ultraviolet protection composition characterized by having a weight ratio of 1/10 or more to the component (A).

[0009]

DETAILED DESCRIPTION OF THE INVENTION In the component (A), the ultraviolet scattering powder to be treated with a fluorine compound is a substance substantially insoluble in water or oil, etc.
There is no particular limitation as long as it reflects ultraviolet light of 00 nm. For example, talc, mica, sericite, kaolin,
Bentonite, vermiculite, hectorite, zeolite, silica, alumina, heidilite, aluminum silicate, magnesium silicate, calcium silicate, aluminum magnesium silicate, magnesium carbonate, calcium carbonate, barium sulfate, hydroxyapatite,
Inorganic pigments such as boron nitride and barium sulfate-treated mica; organic-inorganic composite powders such as zirconium oxide-coated nylon powder and titanium oxide-coated nylon powder; spherical polymethyl methacrylate-mica composite powder; spherical polymethyl methacrylate-sericite Spherical-plate-like powder composite pigments such as composite powder, spherical polymethyl methacrylate-talc composite powder, spherical silica-mica composite powder; titanium oxide;
Inorganic white pigments such as zinc oxide and zirconium oxide, or composite powders of two or more of these; inorganic red pigments such as iron oxide (iron oxide), iron titanate, and calamine; inorganic brown pigments such as γ-iron oxide; Inorganic yellow pigments such as yellow iron oxide and loess; inorganic black pigments such as black iron oxide, carbon black and lower titanium oxide; inorganic purple pigments such as mango violet and cobalt violet; chromium oxide, chromium hydroxide, and titanium Inorganic green pigments such as cobalt oxide; inorganic blue pigments such as ultramarine and navy blue; titanium oxide coated mica, bismuth oxychloride, titanium oxide coated bismuth oxychloride, titanium oxide coated talc, colored titanium oxide coated mica, fish scale foil, etc. Pearl pigments; metal powder pigments such as aluminum powder and copper powder; fine particles of titanium oxide and fine particles Examples include fine metal oxides such as zinc oxide, flaky zinc oxide, fine zirconium oxide, and fine cerium oxide, and composite powders of two or more of these. Among these, titanium oxide, zinc oxide, and titanium oxide-oxide It is preferable to use zinc composite powder, fine particle titanium oxide, fine particle zinc oxide, and flaky zinc oxide.

On the other hand, the fluorine compound used for treating the above-mentioned ultraviolet scattering powder is not particularly limited as long as it is a solid at room temperature. For example, the following general formula (1)

[0011]

Embedded image [C _m F _{2m + 1} C _{m ′} H _{2m ′} O] _L PO (OH) _3-L (1)

(Wherein m represents an integer of 1 to 20, and m ′
Represents an integer of 1 to 5, and L represents 1 or 2. ) (US Patent No. 363)
2744) and fluoroalkyldi (oxyethyl) amine phosphoric acid esters (JP-A-62-275074).
No.), a polymer having a fluoroalkyl group (JP-A-55
-167209, 61-55481, 61-4
8803), fluorine-based resins such as ethylene tetrafluoride resin (JP-A-57-38707), fluoroalcohols (JP-A-63-2251 and JP-A-63-2252), perfluoroepoxy compounds, sulfamide fluor Phosphoric acid, perfluorosulfate, perfluorocarboxylate, perfluoroalkylsilane (Japanese Unexamined Patent Publication No. 1-3180)
No. 70, No. 2-218603, No. 1-160907
No. 2-127777, Shin-Etsu Silicone, LP
Silane coupling agents such as -1T, LP-4T and LP-8T), and fluorinated halogenated hydrocarbons (fluorocarbons) such as trichlorotrifluoroethane (JP-A-1-318070)
No.), a fluoroalkyl-containing polyhydric alcohol, and a fluoroalkyl-containing polyoxyethylene compound (Japanese Patent Laid-Open No. 1-1)
Nos. 80810 and 1-180811), fluoroalkyl-containing sulfamidocarboxylic acids, fluoroalkyl-containing acrylate-based copolymers and the like (U.S. Pat.
No. 32744) and other fluorine compounds containing a fluorine atom in the molecule.

The method of treating the ultraviolet scattering powder with the fluorine compound is not particularly limited, and the treatment can be carried out according to a usual method. From the viewpoint of obtaining excellent water resistance and sebum resistance, the amount is preferably 0.01 to 50 parts by weight, particularly preferably 0.5 to 20 parts by weight based on 100 parts by weight of the ultraviolet scattering powder.

The component (A) is preferably used in an amount of 0.1 to 50% by weight, particularly 1.0 to 25% by weight of the total composition, since a sufficient ultraviolet ray protective effect and water and sebum resistance can be obtained. .

The fluorinated organic compound of the component (B) of the present invention is not particularly limited as long as it is a liquid fluorinated compound at ordinary temperature, but the fluorine modification ratio [the number of fluorine atoms in the molecule /
(Number of hydrogen atoms in molecule + number of fluorine atoms in molecule) x
100] is preferably 10 to 100%, particularly 30
~ 100% is preferred.

The component (B) in the present invention is represented by the following general formula (2)

[0017]

## STR2 ## RX- (CH ₂ ) _n Rf (2)

(Wherein, R represents a hydrocarbon group, X represents a group connecting R and CH ₂ , n represents an integer, and Rf represents a fluorocarbon group or a fluorocarbon having only a terminal hydrogen atom. Perfluoropolyether is more preferable in addition to the fluorinated organic compound represented by the formula:

The fluorinated organic compound represented by the general formula (2) (hereinafter referred to as “fluorine compound (2)”) can be easily emulsified and has strong water repellency and oil repellency. In the general formula (2), the hydrocarbon group represented by R is preferably a straight-chain or branched chain having 2 to 30 carbon atoms, particularly preferably a straight-chain or branched chain having 2 to 20 carbon atoms. Chain alkyl groups are more preferred, with ethyl, butyl, hexyl, octyl, decyl and dodecyl being particularly preferred. The group represented by Rf is a fluorocarbon group or a fluorocarbon group in which a hydrogen atom is bonded only to a terminal carbon, and such a fluorocarbon group is a straight-chain carbon having 3 to 20, particularly 3 to 18 carbon atoms. Or a branched-chain perfluoroalkyl group or an ω-hydroperfluoroalkyl group, for example,
Perfluoropropyl, perfluorobutyl, perfluoropentyl, perfluorohexyl, perfluoroheptyl, perfluorooctyl, perfluorononyl, perfluorodecyl, perfluoroundecyl, perfluorostearyl And the like. X is a group linking R and CH ₂ , and an ester,
Ether, amide, urethane or urea linkage or group-
CH (OH) CH ₂ O— is preferable, and an ester or ether bond is particularly preferable. The integer n is preferably 1 or 2. The total carbon number of the fluorine compound (2) is 6 to 50, particularly 10 to 50 to prevent skin irritation.
Preferably it is 50.

Among the fluorine compounds (2), a compound in which X is represented by an ester bond is, for example, Rf (CH ₂ ) _n O
It is produced by reacting a reactive derivative of R-COOH with an alcohol represented by H. Compounds in which X is an ether bond include, for example, Rf (CH ₂ ) _n
The following formula is used for the alcohol represented by OH

[0021]

Embedded image

Is produced by reacting the carbonyl compound represented by the formula in a hydrogen atmosphere in the presence of a hydrogenation catalyst.

Preferred examples of the fluorine compound (2) include perfluorooctylethyl octanoate, perfluorooctylethyl stearate, perfluorooctylethyl caprylate, perfluorooctylethyl decyl ether, perfluorohexylethyl-1,2
3-dimethylbutyl ether, perfluorooctylethyl ethyl ether, perfluorostearyl methyl ethyl ether, perfluoropropyl ethyl octyl ether, perfluorooctyl ethyl octyl ether, perfluorobutyl ethyl hexyl ether, and the like. These fluorine compounds (2) can be used alone or in combination of two or more. The compounding amount is 0.0001 to 20% by weight, particularly 0.001 to 10% by weight in the whole composition.
% Is preferable.

Further, as the perfluoropolyether, a compound represented by the following general formula (3) is preferable.

[0025]

Embedded image

(Wherein R ³ , R ⁵ , R ⁶ and R ⁷ may be the same or different and each represents a fluorine atom, a perfluoroalkyl group or a perfluoroalkyloxy group, and R ⁴ represents a fluorine atom or a perfluoroalkyloxy group) A ₁ , b ₁ and c ₁ have a molecular weight of 500 to 100,0
Indicates a number equal to or greater than 0 that is 00. Where a ₁ = b ₁ = c
₁ = 0 never occurs. Here, the perfluoro groups shown in parentheses need not be arranged in this order, and may be random polymerization or block polymerization. Such a perfluoropolyether has a viscosity of especially 5 to 5,000 cs (centistokes).
Is preferable, for example, the following general formula (4)

[0027]

Embedded image

(Wherein d ₁ and e ₁ have a molecular weight of 500 to
The number is 10,000, and d ₁ / e ₁ is 0.2 to 2
It is. ) FOMBLIN HC-04
(Average molecular weight 1,500), HC-25 (3,20)
0) and HC-R (6,600) (both manufactured by Montefros) and the following general formula (5)

[0029]

Embedded image

(Where f ₁ represents a number of 4 to 500)
Demnum S-20 (weight average molecular weight 25,
000), S-65 (4,500), S-100
(5,600) and S-200 (8,400)
Commercially available products (such as those manufactured by Daikin Industries, Ltd.) can be used.

The compounding amount of the fluorinated organic compound of the component (B) is 1 / weight ratio to the component (A) from the viewpoint of improving the dispersibility of the component (A) -treated ultraviolet scattering powder. 10 or more, but 3/10 or more, especially 3/10
It is preferably set to -10/1.

When the component (A) and the component (B) are mixed and used in another component, it is not necessary to mix the component (A) and the component (B) in advance. As long as the above components are uniformly mixed, it is preferable to disperse the component (A) uniformly in the component (B) in advance and to add this to other components.

It is preferable that the ultraviolet ray protective composition of the present invention contains (C) an ultraviolet ray absorbent. The component (C) used in the present invention is not particularly limited, and any of an oil-soluble ultraviolet absorber and a water-soluble ultraviolet absorber can be suitably used.

As the oil-soluble ultraviolet absorber, benzoic acid-based ones such as para-aminobenzoic acid (hereinafter abbreviated as PABA), glyceryl PABA, ethyldihydroxypropyl PABA, N-ethoxylate PABA ethyl ester, and N-dimethyl PABA ethyl Esters, N-dimethyl PABA butyl ester, N-dimethyl PABA amyl ester, octyl dimethyl PABA, etc .; anthranilic acid-based ones; homomenthyl-N-acetylanthranilate, etc .; salicylic acid-based ones; Octylsine such as citrate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, p-isopropanol phenyl salicylate; Mate, ethyl-4-isopropylcinnamate, ethyl-2,4-diisopropylcinnamate, methyl-2,4-diisopropylcinnamate, propyl-p-methoxycinnamate, isopropyl-p-methoxycinnamate, isoamyl-p- Methoxycinnamate, 2-ethylhexyl-p-methoxycinnamate, 2-ethoxyethyl-p-methoxycinnamate, cyclohexyl-p-methoxycinnamate, ethyl-α-cyano-β-phenylcinnamate,
2-ethylhexyl-α-cyano-β-phenylcinnamate, glycerylmono-2-ethylhexanoyldiparamethoxycinnamate and the like; 2,4-dihydroxybenzophenone,
2'-dihydroxy-4-methoxybenzophenone,
2,2'-dihydroxy-4,4'-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2-hydroxy-4-methoxybenzophenone, 4-phenyl Benzophenone, 2-ethylhexyl-4'-phenylbenzophenone-2-carboxylate, 2-hydroxy-4-n-octoxybenzophenone, 4-hydroxy-3-carboxybenzophenone, and the like; 3- (4 ' -Methylbenzylidene) -dl-camphor, 3-benzylidene-d
l-camphor, urocanic acid ethyl ester, 2-phenyl-5-methylbenzoxazole, 2,2'-hydroxy-5-methylphenylbenzotriazole, 2-
(2'-Hydroxy-5-t-octylphenyl) benzotriazole, dibenzarazin, dianisoylmethane, 4-methoxy-4'-t-butyldibenzoylmethane, 5- (3,3-dimethyl-2-norbonylidene)-
Examples thereof include 3-pentan-2-one, a benzene bis-1,3-diketone derivative described in JP-A-2-221579, and a benzoylpinacolone derivative described in JP-A-3-220153.

Examples of the water-soluble ultraviolet absorber include diethanolamine p-methoxycinnamate, sodium 2-hydroxy-4-methoxybenzophenone-5-sulfonate, tetrahydroxybenzophenone, methylherperidine, and 3-hydroxy-4-methoxycinnamate. Sodium acid, sodium ferulate, urocanic acid and the like, and extracts of animals and plants such as yarrow, aloe, below mallow, burdock, salvia and the like, which have an ultraviolet absorbing effect, are exemplified.

From the viewpoint of synergistically enhancing the ultraviolet protection effect, the amount of the ultraviolet absorber of the component (C) is from 1 to 1 in the total composition.
It is preferably 20% by weight, particularly preferably 3 to 10% by weight.

Further, the ultraviolet protection composition of the present invention includes:
It is preferable to blend (D) a fluorine-modified silicone.
The fluorine-modified silicone of the component (D) has, for example, one or more selected from structural units represented by the following general formulas (6) to (9) and a structural unit represented by the following general formula (10) Things.

[0038]

Embedded image

Wherein Rf and Rf 'are the same or different
And may be a linear or branched chain having 1 to 20 carbon atoms.
-Fluoroalkyl group or the following formula: H (CF_Two)_g1− (G
₁Represents an integer of 1 to 20).
R represents a fluoroalkyl group; ⁸, R¹¹And R¹²Is the same
May be one or different, and may have 1-20 carbon atoms
Or a branched chain aliphatic hydrocarbon group or a C5-C10 fat
A cyclic or aromatic hydrocarbon group;⁹Is a hydrogen source
, Linear or branched aliphatic carbonization having 1 to 20 carbon atoms
Hydrogen group, alicyclic or aromatic hydrocarbon having 5 to 10 carbon atoms
Element group, perfluoroalkyl group having 1 to 20 carbon atoms or
Formula: H (CF_Two)_g1− (G₁Represents an integer of 1 to 20)
An ω-H-perfluoroalkyl group represented by the formula:
R^TenRepresents a divalent hydrocarbon group having 2 to 6 carbon atoms; X¹
And Y¹Is a single bond, -CO- or divalent having 1 to 6 carbon atoms
A hydrocarbon group; i₁Represents a number from 2 to 16, and j₁
And k₁Represents the number of 1 to 16, respectively, h₁Is 1-2
Indicates the number 00, w₁Represents a number from 0 to 20;₁Is 0
~ 200 number is shown)

In the structural units represented by the general formulas (6) to (10), as the perfluoroalkyl group represented by Rf and Rf ', any of a linear or branched chain can be used. _{CF 3 -, C 2 F 5} -, C 4 F
_{9 -, C 6 F 13 -} , C 8 F 17 -, C 10 F 21 -, H (CF 2)
_{2 -, H (CF 2)} 4 -, H (CF 2) 6 -, H (CF 2) 8
—, (C ₃ F ₇ ) C (CF ₃ ) ₂ — and the like. Further, _{g in} H (CF ₂ ) _g − is 6 to 2
An integer of 0 is preferred. Examples of the hydrocarbon group represented by R ⁸ , R ¹¹ and R ¹² include straight-chain groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl. Branched alkyl group such as isopropyl group, s-butyl group, t-butyl group, neopentyl group, 1-ethylpropyl group, and 2-ethylhexyl group; cyclic alkyl group such as cyclopentyl group and cyclohexyl group; phenylnaphthyl And an aromatic hydrocarbon group such as a group. As the divalent hydrocarbon group represented by R ^10, preferably is a linear or branched alkylene group having 2 to 4 carbon atoms, particularly an ethylene group, a propylene group are preferable.

As the fluorine-modified silicone having such a structural unit, for example, the following general formula (11)

[0042]

Embedded image

[In the formula, at least one of Z ¹ and Z ² represents a structural unit selected from the general formulas (6) to (9), the remainder represents a single bond, and v ₁ , R ¹¹ and R ¹² represent the same as above. Having the same meaning as in the formula) or the following general formula (12)

[0044]

Embedded image

[Wherein, Z ³ represents a structural unit selected from the general formulas (6) to (9), and R ¹³ represents a linear or branched aliphatic hydrocarbon group having 1 to 20 carbon atoms or a carbon atom. Number 5-1
0 represents an alicyclic or aromatic hydrocarbon group, p ₁ represents a number of 0 to 200, and v ₁ , R ¹¹ and R ¹² have the same meanings as described above] it can.

In the structural units represented by the general formulas (6) to (10) and the fluorine-modified silicone represented by the general formulas (11) and (12), the groups in each formula are: Considering the properties, the following are preferred. Rf and Rf 'each represent a linear or branched perfluoroalkyl group having 6 to 20 carbon atoms or the following formula;
_{H (CF 2) q1 - (} q 1 is an integer of 6-20) preferably omega-H- perfluoroalkyl group represented by.
R ⁸ , R ¹¹ and R ¹² may be the same or different, and are preferably a linear or branched aliphatic hydrocarbon group having 1 to 4 carbon atoms. R ⁹ is a hydrogen atom, a carbon number of 6 to 2;
A perfluoroalkyl group of 0 or the following formula: H (CF ₂ ) _q1
Ω-H represented by-(q ₁ represents an integer of 6 to 20)
-Perfluoroalkyl groups are preferred. The R ^10,
A divalent hydrocarbon group having 2 to 4 carbon atoms is preferred. X ¹ and Y ¹ are preferably a single bond, —CO— or a divalent hydrocarbon group having 1 to 4 carbon atoms, i ₁ is preferably a number of 2 to 10, especially 2 to 5, and j ₁ and k ₁ respectively 2 to 10, preferably in particular the number of 1 to 6, h ₁ is from 1 to 100, particularly 1 to 1
Preferably the number of 0, w ₁ is 0 to 20, particularly preferably the number of 0 to 5, v ₁ is 0 to 100, in particular the number of 0 preferred. The arrangement of the structural units of the fluorine-modified silicone represented by the general formula (12) may be alternate, block, or random.

Further, preferred examples of the fluorine-modified silicone include those having structural units represented by the general formulas (7) and (10) and having a polymerization degree of 2 to 200 described in JP-A-5-247214. Fluorine-modified silicone,
Japanese Unexamined Patent Application Publication No.
No. 184312, a fluorine-modified silicone having a polymerization degree of 2 to 200, a commercially available FSL manufactured by Asahi Glass Co., Ltd.
-300, Shin-Etsu Chemical's X-22-819, X-
22-820, X-22-821, X-22-822 and FL-100, FS-1265 manufactured by Dow Corning Toray Silicone Co., Ltd., and the like.

The ultraviolet protection composition of the present invention contains, in addition to the above-mentioned components, components to be added to ordinary cosmetics, for example, liquid oil, solid fat (wax), semi-solid oil, inorganic powder, humectant, Water-soluble polymer, oil-soluble polymer, polymer latex,
Various surfactants, fragrances, antioxidants, preservatives, drugs, thickeners, plant extracts, ceramides and ceramide-like structural substances, blood circulation promoters, cooling agents, antiperspirants, bactericides, skin activators , A pH adjuster, alcohols, water and the like can be appropriately compounded as long as the effects of the present invention are not impaired.

The ultraviolet protection composition of the present invention includes, for example, cosmetics such as lotion, emulsion, cream, cosmetic oil, gel, foundation, powder, lipstick, blusher, eyeshadow, nail enamel, car wax, car wax Washing soap,
It can be a paint or the like.

[0050]

The ultraviolet protection composition of the present invention has a high ultraviolet protection effect, is excellent in the persistence of the effect, and has good water and sebum resistance.

[0051]

Next, the present invention will be further described with reference to examples, but the present invention is not limited to these examples.

Example 1 An oil-in-water emulsified cosmetic having the composition shown in Table 1 was prepared by a conventional method, and evaluated for the ultraviolet ray protective effect and water resistance by the following methods.

(Evaluation method) (1) Ultraviolet ray protection effect The SPF value was measured using an SPF analyzer (manufactured by Optometrics) and indicated by the following criteria. Evaluation criteria: A; SPF value 20 or more. ；: SPF value 15 or more and less than 20. Δ: SPF value less than 15.

(2) Water resistance Each composition is applied to a leather to give 2 μl / cm ² ,
Let stand for 10 minutes. This was affixed to a square stirring blade, placed in a water bath at a water temperature of 30 ° C., and stirred at 250 rpm for 80 minutes. Then, the amount of the ultraviolet absorber (ethyl para-aminobenzoate) remaining in the leather was measured by a spectrophotometer. The residual ratio of the ultraviolet absorbent was calculated from the measured values and evaluated according to the following criteria. Evaluation criteria: ；; the residual ratio of ethyl paraaminobenzoate is 90% or more. ；: Residual rate of ethyl paraaminobenzoate is 80% or more 9
Less than 0%. Δ: The residual ratio of ethyl paraaminobenzoate is less than 80%.

[0055]

[Table 1]

[0056]

Embedded image

As is clear from the results shown in Table 1, the product of the present invention containing the fluorinated organic compound (perfluoropolyether) and the ultraviolet scattering powder treated with the fluorine compound has a higher ultraviolet protection effect than the comparative product. It was excellent in water resistance.

Example 2 Sunscreen emulsion An emulsion having the following composition was produced by a conventional method.

[0059]

(Table 2) (Composition) (% by weight) Polyoxyethylene / methylpolysiloxane copolymer (Silicone SH3775C: manufactured by Dow Corning Toray Silicone Co., Ltd.) 1.5 Ceramide-like structural substance ^{* 1} 1.5 Dimethylpolysiloxane ( Silicone KF96-A (6cs): Shin-Etsu Chemical Co., Ltd. 5.0 Methylcyclopolysiloxane (Equivalent mixture of SH244 / SH245: Shin-Etsu Chemical Co., Ltd.) 15.0 Squalane 1.0 2-Ethylhexyl paramethoxycinnamate 3 0.0 Fluorine compound-treated zinc oxide ^{* 2} 9.0 Fluorine compound-treated titanium oxide ^{* 2} 3.0 Perfluoropolyether ^{* 3} 6.0 Ethanol (55 v / v%) 10.0 Glycerin 2.0 Fragrance 0.01 Water balance

Example 3 Sunscreen cream A cream having the following composition was produced by a conventional method.

[0061]

(Composition) (% by weight) Poly (N-propionylethyleneimine) -modified silicone (produced according to Synthesis Example 3 of JP-A-7-133352) 0.5 Polyoxyethylene methylpolysiloxane Copolymer (Silicone SH3775C: Dow Corning Toray Silicone Co., Ltd.) 3.0 Ceramide-like structural substance ^{* 1} 2.5 Dimethylpolysiloxane (Silicone KF96-A (6cs): Shin-Etsu Chemical Co., Ltd.) 3.5 Methyl Cyclopolysiloxane (Equivalent mixture of SH244 / SH245: manufactured by Shin-Etsu Chemical Co., Ltd.) 5.0 Squalane 2.0 2-ethylhexyl paramethoxycinnamate 3.0 Fluorine compound-treated zinc oxide ^{* 2} 9.0 Fluorine compound-treated titanium oxide ^{* 2} 3.0 Perfluoropolyether ^{* 3} 6.0 Ethanol (55 v / v%) 5.0 Glycerin 5.0 Fragrance 0.01 Water Balance

Example 4 Gel Cosmetic A cosmetic having the following composition was produced by a conventional method.

[0063]

(Composition) (% by weight) Water-soluble alkyl-substituted polysaccharide derivative ^{* 6} 1.0 Neosambale (PW-1010: manufactured by Catalyst Chemicals, Inc.) 5.0 Poly (N-propionylethyleneimine) -modified silicone 0 Ceramide-like structural substance ^{* 1} 3.0 Polyoxyethylene (60) hydrogenated castor oil 1.0 2-Ethylhexyl paramethoxycinnamate 3.0 Fluorine compound-treated zinc oxide ^{* 2} 9.0 Fluorine compound-treated titanium oxide ^{* 2} 0 Perfluoropolyether ^{* 3} 6.0 Ethanol 10.0 Glycerin 2.0 Sodium citrate 1.0 L-arginine 0.1 Fragrance 0.1 Water Balance

For the compositions obtained in Examples 2 to 4,
When the UV protection effect and the water resistance were evaluated in the same manner as in Example 1, the SPF value was 20 or more, the residual ratio of the UV absorber was 90% or more, the UV protection effect was high, and the water resistance was excellent. Was something.

Claims (3)

[Claims] 1. The following components (A) and (B): (A) a fluorine compound-treated ultraviolet scattering powder, (B) a fluorinated organic compound which is liquid at room temperature, and component (B) is component (A). A UV protection composition, wherein the composition has a weight ratio of 1/10 or more of the composition. 2. The composition according to claim 1, which contains an ultraviolet absorbent (C).
The ultraviolet protection composition according to the above. 3. The ultraviolet protection composition according to claim 1, comprising a fluorine-modified silicone (D).