JPH0532532A - Anti-sunburn cosmetic - Google Patents

Abstract

PURPOSE:To obtain an excellent anti-sunburn cream by combining a specific amine-modified or ammonium modified polymer silicone with a volatile silicone, a volatile hydrocarbon oil and an ultraviolet absorber or an ultraviolet ray scattering agent. CONSTITUTION:One or more of amine-modified and ammonium modified polymer silicones shown by the formula {R<1> is methyl or partially phenyl; R<2> and R<3> are the same and are methyl or OH; R<3> is R<4>Z (R<4> is alkylene; Z is amino or ammonium shown by NR<5>2, N<+>R<5>3A, etc., (R<5> is alkyl; A is Cl)]; (m) and (n) are positive number, (m+n) are 3,000-20,000 integer and (n/m) is 1/500 to 1/10,000} [e.g. compound wherein R<1> and R<2> are methyl, R<3> is (CH2)3N(CH3)2, (m)=5,000 and (n)=5] are blended with a volatile silicone (e.g. dimethylpolysiloxane having 0.65-5 cst/25 deg.C viscosity) and/or a volatile hydrocarbon oil (e.g. Isoper A), an ulraviolet absorber (e.g. p-amine or benzoic acid) and/or an ultraviolet ray scattering agent (e.g. titanium oxide) to give the objective antisunburn cream.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to sunscreen cosmetics. More specifically, it relates to an improved sunscreen cosmetic which is effective in preventing erythema and blackening of the skin due to the ultraviolet rays of the sun rays and has excellent usability without skin irritation.

[0002]

[Prior Art and its Problems] Many people who want to tan their skin actively by tanning their skin to brown or light brown are mainly for young people who are conscious of fashion or fashion. , They apply cosmetics to their entire body and expose their skin to intense sunlight. However, in recent years, the awareness of protecting the skin from ultraviolet rays has increased, and even in cosmetics, ultraviolet rays (wavelength 290 that cause blisters, erythema, etc.)
UV absorbers that absorb (nm to 320 nm) have been added. However, not to mention people who are hypersensitive to UV rays or who have not exposed their skin to the sun's rays for a long time, healthy people can enjoy moderate sunburn with intense sunlight in the midsummer in order to use UV rays in cosmetics. Absorbent must be incorporated in large amounts. However, since most UV absorbers have skin irritating properties, the UV absorbing effect may cause skin irritation or pigmentation when a product containing a large amount is repeatedly applied. Therefore, the addition of a large amount of an ultraviolet absorber is effective for preventing blisters and erythema due to ultraviolet rays, but it is not preferable. In addition, conventional sunscreen cosmetics do not have sufficient water resistance, and when they enter the water such as in a sea bath or swimming, or when they sweat a lot, they easily run off and cause unexpected inflammation when reapplication is forgotten. Cause of. Further, when it is used in a pool, there is a drawback that the oil content as a base material is eluted to cause water pollution.

[0003]

Means for Solving the Problems As a result of intensive studies conducted by the present inventors to solve these drawbacks of conventional sunscreen cosmetics, the result was that a sunscreen containing a specific amino-modified or ammonium-modified polymer silicone was blended. It has been found that the anti-static cosmetics have a remarkably increased ultraviolet absorption effect and further improved water resistance. That is, the present invention has the general formula 1:

[Chemical 2] [In the formula, R ¹ represents a methyl group or a part thereof represents a phenyl group, and R ² represents the same as R ³ or represents a methyl group or a hydroxyl group. R ³ is wherein R ⁴ Z {R ⁴ represents a divalent alkylene group having carbon atoms of 3 to 6, Z is _{^{-NR 5 2, -N + R 5}} 3
_{^{A -, -NR 5 (CH 2}} ) a NR 5 2, -NR 5 (CH 2) a N +
R ⁵ ₃ A ⁻ and —NR ⁵ (CH ₂ ) _a N (R ⁵ ) C═O
(R ⁶ ) (R ⁵ represents hydrogen or an alkyl group having 1 to 4 carbon atoms, R ⁶ represents an alkyl group having 1 to 4 carbon atoms, A represents Cl, Br or I, a
Is an integer from 2 to 6. 1) selected from the group consisting of
Represents a valence group. } And represents a substituent having an amino group or an ammonium group, m and n are positive integers, m + n is an integer of 3,000 to 20,000, and n / m is 1/500 to 1 / It is 10,000. ]
Characterized by containing one or more of amino-modified or ammonium-modified polymer silicones represented by, a volatile silicone and / or volatile hydrocarbon oil, and an ultraviolet absorber and / or an ultraviolet scatterer. Sunscreen cosmetics. According to the present invention, it is possible to obtain a desired ultraviolet ray absorbing effect with a small amount of ultraviolet ray absorbent, so that it is possible to obtain a sunscreen cosmetic having high skin safety and excellent water resistance, which can be used even in a pool. I can.

The high molecular silicone represented by the above general formula 1 of the present invention has m + n of 3,000 to 20,000,
It is preferably 4,000 to 10,000. 3,0
If it is less than 00, it is oily and the water resistance is insufficient.
When it exceeds 00, it is not dissolved in other cosmetic raw materials such as silicone oil and cannot be blended in cosmetics. Also, n / m
Is 1/500 to 1 / 10,000, and preferably,
It is 1/500 to 1/2000. When it exceeds 1/500, the content of amino groups or ammonium groups in the silicone becomes high, a crosslinking reaction or the like occurs during the production, and it is not preferable from the viewpoint of raw material odor. If it is less than 1 / 10,000, the interaction with the skin becomes weak and the water resistance becomes poor. The amino-modified or ammonium-modified polymer silicone of the present invention can be produced by the same production method as that of general amino-modified or ammonium-modified silicone. For example, it can be produced by polycondensation reaction of γ-aminopropylmethyldiethoxysilane, cyclic dimethylpolysiloxane and hexamethyldisiloxane under an alkali catalyst. The amino-modified or ammonium-modified polymer silicone used in the present invention is in the form of a soft rubber, and even if used in a large amount, it is possible to obtain an extremely excellent sunscreen cosmetic without stickiness. The amount of the amino-modified or ammonium-modified polymer silicone used in the present invention is 1 to 50% by weight, preferably 1 to 30% by weight, based on the total amount of the cosmetic. If it is less than 1% by weight, a sufficient effect cannot be obtained, and 5
If it exceeds 0% by weight, it becomes difficult to dissolve in other cosmetic raw materials.

The volatile silicone used in the present invention is volatile at room temperature and has a viscosity of, for example, 0.
65-5 cSt / 25 ° C. dimethyl polysiloxane,
Cyclic silicones such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane can be used. The volatile hydrocarbon oil used in the present invention has a boiling point of 260 ° C. at normal pressure.
The following are, for example, Isopar (registered trademark) A, same C, same D, same E, same G, same H, same K, same L, same M (Exxon), Shersol (registered trademark) 71 (shell Company), Softroll (registered trademark) 100, the same 130, the same 220 (Philipp Corporation) and the like. The blending amount of the volatile silicone and the volatile hydrocarbon oil in the present invention is 1 to 95% by weight in the total amount of the cosmetic, preferably,
It is 5 to 60% by weight.

As the ultraviolet absorber used in the present invention, all known ultraviolet absorbers can be effectively used. Typical ultraviolet absorbers are listed below. Benzoic acid-based compounds include para-aminobenzoic acid (hereinafter abbreviated as PABA), glyceryl PABA, ethyldihydroxypropyl PABA, N-ethoxylate PABA ethyl ester, N-dimethyl PABA ethyl ester, N-dimethyl PABA butyl ester, N-dimethyl PABA amyl ester, octyl dimethyl PABA, anthranilic acid-based ones such as homomenthyl-N-acetylanthranilate, salicylic acid-based ones such as amyl salicylate, menthyl salicylate, homomenthyl salicylate, Octyl salicylate, phenyl salicylate, benzyl salicylate, p-isopropanol phenyl salicylate, cinnamic acid type octyl cinnamate, ethyl-4-isopropyl cinnamate
, 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-phenyl cinnamate, 2-ethylhexyl-α-cyano-β-phenyl cinnamate, glyceryl mono-2-ethylhexanoyl diparamethoxy cinnamate, and benzophenone-based compounds of 2 , 4-
Dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dihydroxybenzophenone, 2,2
′, 4,4′-Tetrahydroxybenzophenone, 2-
Hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2
-Hydroxy-4-methoxybenzophenone, 4-phenylbenzophenone, 2-ethylhexyl-4'-phenylbenzophenone-2-carboxylate, 2-hydroxy-4-n-octoxybenzophenone, 4-hydroxy-3-carboxybenzophenone , And others, 3- (4'-methylbenzylidene) -d, l-
Camphor, 3-benzylidene-d, l-camphor,
Urocanic acid, urocanic acid ethyl ester, 2-phenyl-5-methylbenzoxazol, 2,2'-hydroxy-5-methylphenyl-benzotriazole, 2-
(2'-hydroxy-5-t-octylphenyl) benzotriazole, dibenzalazine, dianisoylmethane, 4-methoxy-4'-t-butyldibenzoylmethane, 5- (3,3-dimethyl-2-norbornylidene) −
3-pentan-2-one and the like can be mentioned.

Further, typical ultraviolet scattering agents include titanium oxide, fine particle titanium oxide, zinc oxide, fine particle zinc oxide, iron oxide, fine particle iron oxide and the like. The blending amount and combination of the ultraviolet absorber or the ultraviolet scatterer are determined according to the desired ultraviolet absorbing effect, but in consideration of the ultraviolet preventing effect, it is necessary to be 0.05% by weight or more. Although the upper limit differs from the viewpoint of skin safety, for example, for homomenthyl salicylate 15% by weight, octyl dimethyl PAB
A is 8% by weight, and 2,2-dihydroxy-4-methoxybenzophenone is 3% by weight. In addition to the above essential constituents, the sunscreen cosmetic of the present invention contains an aqueous component and a suitable surfactant, and by using emulsification technology, water-in-oil type or water It is also possible to use an oil-based emulsion composition.

In addition to the above-mentioned essential constituents, the sunscreen cosmetic of the present invention contains olive oil, coconut oil, safflower oil, castor oil within a quantitative and qualitative range depending on the purpose, without impairing the effects of the present invention. , Fats and oils such as cottonseed oil, waxes such as lanolin, jojoba oil and carnauba wax, hydrocarbon oils such as liquid paraffin, squalane and vaseline, fatty acids, alcohols, ester oils such as cetyl octanoate and isopropyl myristate, dimethyl poly Moisturizing agents such as silicone oils such as siloxane and methylphenylpolysiloxane, silicone resins, propylene glycol, dipropylene glycol, 1,3-butylene glycol, glycerin, isoprene glycol, polyethylene glycol, hyaluronic acid, chondroitin sulfate, and pyrrolidone carboxylate. , Tocofenault , Antioxidants such as butylhydroxyanisole, dibutylhydroxytoluene, preservatives such as methylparaben, ethylparaben, propylparaben, butylparaben, powders of mica, bentonite, kaolin, talc, mica titanium, bismuth oxychloride, silicic acid anhydride, etc. , Guanine, laminating resin pearl,
Mica-Pearls such as titanium-based pearls, Gunjou,
Inorganic pigments such as chromium oxide and cobalt blue, Sudan II
Dyes such as I, quinizanin green SS, quinoline yellow SS, span type, tween type, POE alkyl ether type, POE-POP type, glycerin fatty acid ester type,
It is possible to mix surfactants such as POE glycerin fatty acid ester-based, thickeners such as carboxyvinyl polymer, anti-inflammatory agents, drugs such as vitamins and hormones, and other ingredients commonly used in cosmetics such as fragrances. ..

[0009]

EXAMPLES Next, examples of the present invention will be described. The present invention is not limited to these. All compounding amounts are% by weight. Example 1 (Sunscreen oil) (1) Dimethylpolysiloxane (1 cSt / 25 ° C.) 35.0% (2) Dimethyl polysiloxane (2 cSt / 25 ° C.) 23.0 (3) Amino-modified polymer silicone 30 .0 (in the general formula 1, R ¹ and R ² are methyl groups, R ³ is — (CH ₂ ) ₃ N (CH ₃ ) ₂ , m = 5,000, n = 5) (4) Glyceryl triisostearea To 10.0 (5) Octyl dimethyl PABA 2.0 (6) Perfume Suitable amount To (5) dissolved in (4) and cooled at 80 ° C,
(1)-(3), (6) is stirred and mixed with a solution mixed,
The container was filled to obtain sunscreen oil. Comparative Example 1 (Sunscreen oil) (3) of Example 1 was treated with dimethylpolysiloxane (5 cSt).
/ 25 ° C.), but sunscreen oil was obtained in the same manner as in Example 1.

Example 2 (oil foundation) (1) Kaolin 25.0% (2) Fine particle titanium oxide 15.0 (3) Iron oxide 3.0 (4) Microcrystalline wax 4.0 (5) Fluid Paraffin 5.0 (6) Sorbitan sesquioleate 1.0 (7) Amino-modified polymer silicone 2.0 (In the general formula 1, R ¹ and R ² are methyl groups, and R ³ is-(CH ₂ ). ₃ N (CH ₃ ) (CH ₂ ) ₂ N (CH ₃ ) ₂ , m = 10,000, n = 5) (8) Isopar (registered trademark) G 45.0 (9) Perfume proper amount (10) Oxidation Inhibitor A suitable amount of (4) to (8) and (10) is dissolved by stirring at 70 to 80 ° C, and then (1) to (3) are added and dispersed. After deaeration, (9) was added and filled in a predetermined container to obtain an oily foundation. Comparative Example 2 (oil-based foundation) An oil-based foundation was obtained in the same manner as in Example 2 except that (7) and (8) of Example 2 were replaced with liquid paraffin.

Example 3 (Sunscreen milky lotion) (1) Decamethylcyclopentasiloxane 10.0 (2) Ammonium modified polymer silicone 20.0 (10% of R ^{1 in} the general formula 1 remains as phenyl group) Is a methyl group, R ² is a methyl group, R ³ is — (CH ₂ ) ₃ N ⁺ (CH ₃ ) ₃ Cl ⁻ , m = 10,000, n = 2) (3) Liquid paraffin 4.0 (4) Sorbitan diisostearate 3.0 (5) Polyoxyethylene-modified dimethylpolysiloxane (EO 70 wt%, viscosity 150 cSt / 25 ° C) 3.0 (6) Ion-exchanged water 47.0 (7) Glycerin 3.0 ( 8) Fine particle iron oxide 5.0 (9) Octyldimethyl PABA 2.0 (10) 4-methoxy-4'-t-butyldibenzoylmethane 2.0 (11) Preservative proper amount (12) Antioxidant proper amount ( 3) Perfume q.s. (1) to (5) and (9), (10), (12),
(13) is dissolved by stirring at 70 ° C., and (8) is dispersed therein. Pre-dissolved in this at 70 ℃ (6),
(7) and (11) were added, emulsified and dispersed, and then cooled to obtain a target emulsion. Comparative Example 3 (Sunscreen emulsion) (2) of Example 3 was treated with high molecular weight dimethylpolysiloxane (degree of polymerization n =
A sunscreen emulsion was obtained in the same manner as in Example 3 except that the emulsion was replaced with 7,000).

Experimental Example 1 The samples obtained in Examples 1 to 3 and Comparative Examples 1 to 3 were evaluated for their sunburn preventive effect by an SPF measuring method using animals. That is, a guinea pig whose back hair has been removed by a depilation cream is coated with the sample at 2 μl / cm ² . After 15 minutes, ultraviolet rays were emitted from 12 Toshiba FL-SE lamps. At 24 hours after the irradiation, the erythema of the sample-applied part and the sample-unapplied part was observed, and the minimum amount of ultraviolet ray required to cause faint erythema was determined. SPF (Sun Protection Factor) according to the following formula from the calculated minimum UV amount
To calculate.

[Equation 1] The results are shown in Table 1.

[Table 1] From the results of this experiment, the examples in which the amino-modified or ammonium-modified polymer silicone and the volatile silicone or / and the volatile hydrocarbon oil were blended together with the ultraviolet absorber or / and the ultraviolet scatterer were compared with the comparative examples. By comparison, it can be seen that the ultraviolet protection effect is greatly increased.

Experimental Example 2 As an evaluation of the water resistance of the samples of Examples 1 and 3 and Comparative Examples 1 and 3, the amount of the ultraviolet absorber immediately after the sample was applied to the arm and after washing with constant running water was adjusted with ethanol. It was quantified by extraction with a filter, and the residual ratio (%) of the ultraviolet absorber was expressed as (amount of ultraviolet absorber on skin after washing with water) / (amount of ultraviolet absorber on skin before washing with water) × 100. The results are shown in Table 2.

[Table 2] It can be seen that the example has excellent water resistance as compared with the comparative example.

Example 4 (Cosmetic base) (1) Dimethylpolysiloxane (2 cSt / 25 ° C.) 14.0% (2) Amino-modified polymer silicone 5.0 (R ^{1 in the} general formula ¹ is a methyl group, R ² is a hydroxyl group, R ³ is — (CH ₂ ) ₃ N (CH ₃ ) ₂ , m = 3,000, n = 6) (3) ISOPAR® G 5.0 (4) glyceryl triisostea Alate 10.0 (5) Sorbitan sesquioleate 1.0 (6) Polyoxyethylene-modified dimethylpolysiloxane (EO 50 wt%, viscosity 100 cSt / 25 ° C.) 3.0 (7) Ion-exchanged water 45.0 (8) 1,3-butylene glycol 5.0 (9) Fine particle titanium oxide 10.0 (10) Octyldimethyl PABA 2.0 (11) Preservative proper amount (12) Antioxidant proper amount (13) Perfume proper amount (1) to (6 And (10), (12), and (13) were dissolved by stirring at 70 ° C., (7), (8), and (12) previously dissolved at 70 ° C. were added, and the mixture was emulsified and dispersed, and then cooled. I got a makeup base.

Example 5 (Liquid blusher) (1) Methylphenylpolysiloxane (20 cSt / 25 ° C.) 10.0% (2) Decamethylcyclopentasiloxane 49.0 (3) Solid paraffin 4.0 (4) Micro Crystalline wax 3.0 (5) Sorbitan sesquioleate 1.0 (6) Ammonium-modified polymer silicone 30.0 (In the general formula 1, R ¹ is a methyl group, R ² is a hydroxyl group, and R ³ is-( CH ₂ ) ₃ N ⁺ (CH ₃ ) ₃ Cl ⁻ , m = 18,000, n = 2) (7) Mica 15.0 (8) Titanium dioxide 2.0 (9) Iron oxide 2.0 (10) Red No. 226 1.0 (11) Isopropyl-p-methoxycinnamate 1.0 (12) 4-methoxy-4′-t-butyldibenzoylmethane 1.0 (13) Antioxidant Proper amount (14) Perfume Suitable amount (1 To (6) and (11) - (13) 70 to 80
Mix and dissolve at ℃. Separately, (7) to (10) are mixed and pulverized. Both were mixed with stirring, and after degassing, (14) was added to obtain a liquid blusher.

Example 6 (Sunscreen Azol) (1) Isopropyl-p-methoxycinnamate 3.0% (2) Amino-modified polymer silicone 30.0 (R ¹ and R in general formula 1) R ² is a methyl group, R ³ is — (CH ₂ ) ₃ N (CH ₃ ) ₂ , m = 8,000, n = 10) (3) Isopropyl myristate 10.0 (4) Volatile isoparaffin 5.0 (5) Perfume proper amount (6) Trichlorofluoromethane (CFC 11) 12.0 (7) Dichlorotetrafluoroethane (CFC 114) 40.0 (1) to (5) are dissolved with stirring at 70 ° C. After filling the can, the valve was crimped and filled with (6) and (7).

Example 7 (Sunscreen Azol) (1) Octyldimethyl PABA 3.0% (2) 2-Hydroxy-4-methoxybenzophenone 3.0 (3) Glyceryl mono-2-ethylhexanoyl dipara Methoxycinnamate 4.0 (4) Squalane 5.0 (5) Octamethylcyclotetrasiloxane 10.0 (6) Amino-modified polymer silicone 10.0 (In the general formula 1, R ¹ and R ² are methyl, R ³ is _{- (CH 2) 3 n (} CH 3) (CH 2) 2 n (CH 3) C = O (C 2 H 5), m = 15,000, n = 4) (7) LPG 10.0 (8) Dichlorodifluoromethane (CFC 12) 10.0 (9) Dichlorotetrafluoroethane (CFC 114) 45.0 (1) to (6) are dissolved by stirring at 70 ° C. Fill the can After clamping mounting a valve, the propellant (7),
(8) and (9) were filled.

[0018]

EFFECT OF THE INVENTION The sunscreen cosmetic of the present invention has an enhanced UV protection effect, and when the same protection effect is to be obtained,
Small amounts of UV absorbers or UV scatterers have the desired effect and can reduce the skin irritation caused by these agents. Moreover, since the water resistance is improved by the effect of the high-molecular silicone, it becomes possible to avoid the blistering and erythema due to the unexpected sunburn.

Claims (1)

What is claimed is: 1. A general formula: [In the formula, R ¹ represents a methyl group or a part thereof represents a phenyl group, and R ² represents the same as R ³ or represents a methyl group or a hydroxyl group. R ³ is wherein R ⁴ Z {R ⁴ represents a divalent alkylene group having carbon atoms of 3 to 6, Z is _{^{-NR 5 2, -N + R 5}} 3
_{^{A -, -NR 5 (CH 2}} ) a NR 5 2, -NR 5 (CH 2) a N +
R ⁵ ₃ A ⁻ and —NR ⁵ (CH ₂ ) _a N (R ⁵ ) C═O
(R ⁶ ) (R ⁵ represents hydrogen or an alkyl group having 1 to 4 carbon atoms, R ⁶ represents an alkyl group having 1 to 4 carbon atoms, A represents Cl, Br or I, a
Is an integer from 2 to 6. 1) selected from the group consisting of
Represents a valence group. } And represents a substituent having an amino group or an ammonium group, m and n are positive integers, m + n is an integer of 3,000 to 20,000, and n / m is 1/500 to 1 / It is 10,000. ]
Characterized by containing one or more of amino-modified or ammonium-modified polymer silicone represented by, volatile silicone and / or volatile hydrocarbon oil, and an ultraviolet absorber and / or an ultraviolet scattering agent. Sunscreen cosmetics.