JPH0726247A - Ultraviolet absorber and external dermatologic preparation containing the same - Google Patents

Abstract

PURPOSE:To obtain an ultraviolet absorber which is highly safe, has an excellent ultraviolet absorbing effect and is desirable as e.g. a starting material for an external dermatologic preparation by using a specified diphenyl unsaturated compound which is a natural analogue. CONSTITUTION:This absorber is produced by using a diphenyl unsaturated compound represented by formula I (wherein R1, R2 and R3 are each H, OH or alkoxyl; provided at least one of them is OH or alkoxyl). A compound of formula I (wherein R1 is OH, and R2 and R3 are each H) is produced by reacting o-hydroxyacetophenone with cinnamaldehyde. The absorber can also be produced by using a compound represented by formula II (wherein R is H or OH), formula III (wherein R1, R2, R3 and R4 are each H or alkoxyl) or formula IV. An external dermatologic preparation obtained by mixing the obtained ultraviolet absorber with necessary additives such as a surfactant and a humectant is safe and has a high ultraviolet absorbing effect.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ultraviolet absorber and a skin external preparation containing the same, and more particularly to improvement of its ultraviolet absorbing ability.

[0002]

2. Description of the Related Art Most of the ultraviolet rays that affect real life are derived from sun rays. The ultraviolet rays contained in the sun rays are dermatologically long-wavelength ultraviolet rays (UV-A) of 400 to 320 nm, and medium wavelength ultraviolet rays (UV of 320 to 280 nm).
-B) It is classified into short wavelength ultraviolet rays (UV-C) of 280 nm or less. Among these, short-wavelength ultraviolet rays of 290 nm or shorter are absorbed by the ozone layer and do not reach the surface of the earth. However, ultraviolet rays reaching the surface of the earth have various effects on human skin. Of the ultraviolet rays that reach the ground, UV-
B forms erythema and blisters on the skin, and further promotes melanin pigment formation.

On the other hand, UV-A causes browning of the skin,
It promotes the loss of elasticity of the skin and the development of wrinkles, resulting in rapid aging. It may also accelerate the onset of the erythema reaction or, in some patients, enhance this erythema reaction and even cause phototoxicity or even a photoallergic reaction. Various UV absorbers have been developed to protect the skin from such harmful effects of UV-A and UV-B. That is, as an ultraviolet absorber by chemical synthesis,
Dibenzoylmethane derivatives, benzophenone derivatives, urocanine derivatives, P-aminobenzoic acid derivatives, cinnamic acid derivatives such as 2-ethylhexyl P-dimethylaminobenzoate, salicylic acid derivatives, heterocyclic derivatives, etc. have been proposed and used for the prevention of ultraviolet rays. Has been.

[0004]

However, the above-mentioned conventional UV absorbers do not always have sufficient UV absorption ability, and also have UV absorption characteristics that do not match the UV absorption wavelength actually required. There were also many. The present invention has been made in view of the above problems of the prior art, and an object thereof is to provide an ultraviolet absorbent having excellent ultraviolet absorption properties and a skin external preparation containing the ultraviolet absorbent.

[0005]

Means for Solving the Problems As a result of intensive studies by the present inventors in order to achieve the above object, the number of carbon atoms in a carbon chain connecting both phenyl groups of a diphenyl compound was increased,
It has been found that the absorption wavelength region and the absorption intensity are improved by extending the resonance system, and the present invention has been completed. That is, the ultraviolet absorber according to claim 1 of the present application is characterized by containing a diphenyl unsaturated compound represented by the following general formula 5.

[Chemical 5] In the above chemical formula 5, R ₁ , R ₂ and R ₃ represent H, OH or an alkoxyl group, and at least one is OH or an alkoxyl group. The ultraviolet absorber according to claim 2 of the present application is characterized by containing a diphenyl unsaturated compound represented by the following general formula (6).

[Chemical 6] In the above chemical formula 6, R is H or OH. The ultraviolet absorber according to claim 3 of the present application is
And a diphenyl unsaturated compound represented by

[Chemical 7] In the above chemical formula 7, R ₁ , R ₂ , R ₃ and R ₄ represent H or an alkoxyl group. The ultraviolet absorber according to claim 4 is characterized by containing a diphenyl unsaturated compound represented by the following general formula 8.

[Chemical 8] In the above chemical formula 8, R ₁ , R ₂ , R ₃ and R ₄ represent H or an alkoxyl group. The external preparation for skin according to claim 5 is characterized in that it contains the ultraviolet absorber shown in Chemical formulas 5 to 8 above.

The structure of the present invention will be described in more detail below. All of the diphenyl unsaturated compounds according to the present invention are obtained by modifying a substance derived from a natural product and have high safety. Then, by adding a C = C unit to the carbon chain connecting both phenyl groups, the ultraviolet absorption wavelength region and absorption intensity are improved. When an alkoxyl group is used as R _{n in the} general formula, a methoxyl group is preferable from the viewpoint of ease of production. When the ultraviolet absorbent according to the present invention is used by being blended in the external preparation for skin, the total amount of the external preparation for skin is preferably 0.005 to 30% by weight, particularly preferably 0.1 to 10% by weight. If it is less than 0.005% by weight, the effect of absorbing ultraviolet rays is not sufficiently exerted, and 30
The effect is not enhanced even if it is blended in an amount of not less than wt%.

The external preparation for skin according to the present invention contains, in addition to the above-mentioned essential components, various components generally used in cosmetics, quasi-drugs, pharmaceuticals, etc. within the range where the effect of the present invention is not impaired, if necessary. For example, water-soluble components, moisturizers, thickeners, surfactants, preservatives, antioxidants, fragrances, coloring agents and the like can be added. That is, as these components, hydrocarbons such as solid or liquid paraffin, crystal oil, ceresin, ozokerite, and montan wax, silicone oils, olive oil, ground wax, carnauba wax, lanolin and other vegetable or animal oils and waxes. , Stearic acid, palmitic acid, oleic acid, glycerin monostearate ester, glycerin monooleate ester, isopropyl myristate ester, isopropyl stearic acid ester, and their esters, branched fatty acid monohydric alcohol or polyhydric alcohol Esters, alcohols such as ethyl alcohol, isopropyl alcohol, cetyl alcohol, stearyl alcohol, palmityl alcohol, etc., and polyhydric alcohols such as glycol, glycerin, sorbitol, etc. Lumpur, nonionic surfactants as emulsifiers or solubilizers, anionic surfactants, cationic surfactants and the like. Further, the external preparation for skin of the present invention may have any dosage form, and may be in the form of liquid, emulsion, cream or stick.

[0008]

The preferred embodiments of the present invention will be described below. The present invention is not limited to these examples. In addition, the compounding amount is shown by weight% unless otherwise specified. Chalcone Derivative (Chemical Formula 5) Examples of the chalcone derivative shown in the chemical formula 5 are as follows. (1) Chalcone derivative 1 (R ₁ = 0H, R ₂ = R ₃ = H)

<Production Method> O-Hydroxyacetophenone 1.4
g (10 mmol) and Cinnamaldehyde 1.3 g (10
mmol) in 30 ml of ethanol and stirred to 50%
10 ml of KOH was added. The reaction solution was allowed to stand overnight at room temperature and poured into 200 ml of 1N-HCl to deposit deep red crystals (2.1 g). A part thereof was recrystallized from methanol and purified.

<Identification data> Chemical formula: C ₁₇ H ₁₄ O ₂ Molecular weight: 250 Melting point: 131-133 ° C. (MeOH) Property: Orange, needle crystal EIMS m / z (rel.int.): 250 (100, 100, M ⁺ ), 2
32 (7), 221 (6), 207 (6), 173 (2
4), 147 (16), 128 (34), 121 (5
9) ¹ H-NMR (CDCl ₃ , 270 MHz) δ: 6.90-
7.86 (13H, m), 12.90 (1H, s, O
H) (2) Chalcone derivative 2 (R ₁ = H, R ₂ = OMe, R ₃ =
H)

<Production Method> According to chalcone derivative 1. <Identification data> Chemical formula: C ₁₈ H ₁₆ O ₂ Molecular weight: 264 Property: Red, oily EIMS m / z (rel.int.): 264 (89, M ⁺ ), 24
9 (6), 235 (11), 187 (21), 135
(100), 128 (27) ¹ H-NMR (CDCl ₃ ) δ: 3.85 (3H, s, O
Me), 6.90-8.02 (13H, m) (3) Chalcone derivative 3 (R ₁ = OH, R ₂ = OMe, R ₃ =
H)

<Production Method> According to chalcone derivative 1. <Identification data> Chemical formula: C ₁₈ H ₁₆ O ₂ Molecular weight: 280 Melting point: 89 to 91 ° C. Property: Orange, powder EIMS m / z (rel.int.): 280 (100, M ⁺ ), 2
51 (11), 237 (7), 203 (20), 177
(24), 161 (20), 151 (78), 128
(18), 124 (22)

Flavone Derivatives (Chemical Formula 6) Examples of the flavone derivatives shown in the chemical formula 6 are as follows. (1) Flavone derivative 1 (R = OH) <Production method> 1.5 g of the chalcone derivative 1 was suspended in 40 ml of methanol, and 10 ml of 10% H ₂ O ₂ and 50 ml of 2N NaOH were added under ice cooling. After stirring for 20 minutes at room temperature, the reaction solution was poured into 100 ml of 1N-HCl to precipitate yellow crystals. This was collected by filtration, and a part thereof was recrystallized with methanol for purification. <Identification data> Chemical formula: C ₁₇ H ₁₂ O ₃ Molecular weight: 264 Melting point: 162-163 ° C. (MeOH) Property: Dark orange, needle crystal EIMS m / z (rel.int.): 264 (absent, M ⁺ ), 2
38 (100), 237 (82), 210 (7), 18
1 (18), 152 (6), 105 (16) ¹ H-NMR (CDCl ₃ ) δ: 7.01 (1H, s, O
H), 7.36-7.61 (11H, m)

(2) Flavone derivative 2 (R = H) <Production method> 0.7 g of β-diketone described below was added to 1 g of glacial acetic acid.
Dissolve in 0 ml and add glacial acetic acid-sulfuric acid mixture (10: 1)
10 ml was added and left on the water bath for 10 minutes. When the reaction solution was poured into 150 ml of water, 0.45 g of colorless crystals were precipitated. A part thereof was recrystallized from methanol and purified. <Identification data> Chemical formula: C ₁₇ H ₁₂ O ₂ Molecular weight: 248 Melting point: 132-133 ° C. (MeOH) Property: colorless, needle crystal EIMS m / z (rel.int.): 248 (70, M ⁺ ), 24
7 (100), 231 (44), 219 (9), 191
(9), 155 (16), 128 (60), 121 (1
7) ¹ H-NMR (CDCl ₃ ) δ: 6.33 (1H, s, H
-3), 6.80 (1H, d , J = 16Hz, C H = CH
-Φ), 7.57 (1H, d , J = 16Hz, CH = C H
-Φ), 7.35-8.21 (9H, m)

Ester Derivatives (Chemical Formula 7) Examples of the ester derivative shown in the chemical formula 7 are as follows. (1) Ester derivative 1 (R ₁ = R ₂ = R ₃ = R ₄ = H) <Production method> O-Hydroxyacetophenone 1.4 g (10 mmo
l) is dissolved in 10 ml of pyridine and cinnamoylchlo is added to the solution.
1.7 g (10 mmol) of ride was added. The reaction solution is kept at 110 ° C. for 5 hours while stirring. After cooling, the reaction liquid is 1N-H
Pouring into 200 ml of Cl precipitated colorless crystals (2.6 g). A part thereof was recrystallized from methanol and purified.

<Identification data> Chemical formula: C ₁₇ H ₁₄ O ₃ Molecular weight: 266 Melting point: 68 to 69 ° C. (MeOH) Property: Colorless, rectangular EIMS m / z (rel.int.): 266 (0.7, M ⁺ ), 1
31 (100), 106 (25) ¹ H-NMR (CDCl ₃ ) δ: 2.57 (3H, s, A
c), 6.67 (1H, d, J = 16Hz, H-α),
7.18-7.85 (9H, m), 7.90 (1H,
d, J = 16Hz, H- β) (2) ester derivative _{2 (R 1 = OMe, R} 2 = R 3 = R 4 =
H) <Production method> According to ester derivative 1. <Identification data> Chemical formula: C ₁₈ H ₁₆ O ₄ Molecular weight: 296 Melting point: 95 to 96 ° C. (MeOH) Property: colorless, needle crystal EIMS m / z (rel.int.): 296 (3.8, M ⁺ ), 1
51 (9), 148 (7), 131 (100), 103
(31) ¹ H-NMR (CDCl ₃ ) δ: 2.53 (3H, s, A
c), 3.86 (3H, s, OMe), 6.85 (1
H, dd, J = 8.8, 2.5 Hz, H-5 '), 6.6
9 (1H, d, J = 2.5Hz, H-3 '), 6.70
(1H, d, J = 16Hz, H-α), 7.26-7.6
2 (5H, m, H-2, 3, 4, 5, 6), 7.87
(1H, d, J = 8.8Hz, H-6 '), 7.90 (1
H, d, J = 16Hz, H-β)

(3) Ester derivative 3 (R ₄ = OMe, R ₁
= R ₂ = R ₃ = H) <Production method> p-Methoxycinnamic acid 1.8 g (10 mmo
l) was suspended in 10 ml of benzene, and 1 ml of trifluoroacetic anhydride was added thereto, and the solution became transparent. Then, 1.4 g (10 mmol) of O-Hydroxyacetophenone was added and the mixture was reacted at room temperature for 6 hours with stirring. The reaction solution was poured into 100 ml of water and extracted with ethyl acetate to obtain 2.8 g of ester derivative 3. <Identification data> Chemical formula: C ₁₈ H ₁₆ O ₄ Molecular weight: 296 Melting point: 102 to 104 ° C. (MeOH) Property: colorless, rectangular EIMS m / z (rel.int.): 296 (1.4, M ⁺ ). , 1
61 (100), 133 (16) ¹ H-NMR (CDCl ₃ ) δ: 2.57 (3H, s, A
c), 3.86 (3H, s, OMe), 6.54 (1
H, d, J = 16 Hz, H-α), 6.94 (2H, d,
J = 8.8 Hz, H-3, 5), 7.17-7.84 (4
H, m, H-3 ', 4', 5 ', 6') 7.55 (2
H, d, J = 8.8 Hz, H-2, 6), 7.85 (1
H, d, J = 16Hz, H-β)

(4) Ester derivative 4 (R ₁ = R ₄ = OM
e, R ₂ = R ₃ = H) <Production method> According to the ester derivative 3. <Identification data> Chemical formula: C ₁₉ H ₁₈ O ₅ Molecular weight: 326 Melting point: 168-169 ° C. (MeOH) Property: Brown, needle crystal EIMS m / z (rel.int.): 326 (1.3, M ⁺ ), 1
92 (9), 178 (13), 166 (18), 161
(100), 151 (52), 133 (17)

(5) Ester derivative 5 (R ₁ = R ₂ = OM
e, R ₃ = R ₄ = H) <Production method> According to ester derivative 1. <Identification data> Chemical formula: C ₁₉ H ₁₈ O ₅ Molecular weight: 326 Melting point: 104 to 105 ° C. (MeOH) Property: colorless, needle crystal EIMS m / z (rel.int.): 326 (4.9, M ⁺ ), 1
96 (9), 181 (3), 131 (100), 103
(22) ¹ H-NMR (CDCl ₃ ) δ: 2.54 (3H, s, A
c), 3.93, 3.94 (3H each, s, OM
e), 6.66 (1H, s, H-3 '), 6.68 (1
H, d, J = 16 Hz, H-α), 7.43 (1 H, s,
H = 6 ′), 7.44 (3H, m, H = 3,4,5),
7.61 (2H, m, H-2, 6), 7.93 (1H,
d, J = 16Hz, H-β)

(6) Ester derivative 6 (R ₃ = R ₄ = OM
e, R ₁ = R ₂ = H) <Production method> According to the ester derivative 3. <Identification data> Chemical formula: C ₁₉ H ₁₈ O ₅ Molecular weight: 326 Melting point: 101 to 103 ° C. (MeOH) Property: colorless, rectangular EIMS m / z (rel.int.): 326 (5.1, M ⁺ ). , 1
91 (100), 163 (9) ¹ H-NMR (CDCl ₃ ) δ: 2.58 (3H, s, A
c), 3.93 (6H, s, OMe x 2), 6.54
(1H, d, J = 16Hz, H-α), 6.90 (1H,
d, J = 8 Hz, H-5), 7.13-7.84 (6H,
m, H-2, 6, 3 ', 4', 5 ', 6'), 7.84
(1H, d, J = 16Hz, H-β)

Β-Diketone Derivative (Chemical Formula 8) Examples of the β-diketone derivative shown in the Chemical Formula 7 include the following. (1) β-diketone derivative 1 (R ₁ ═R ₂ ═R ₃ ═R ₄ ═H) <Production Method> 1.5 g of the ester derivative 1 was added to pyridine 1
Dissolve in 0 ml, add 3 g of powdered KOH to this, and keep at 110 ° C. for 10 minutes while stirring. Reaction liquid is 1N-HC
l poured into 100 ml and extracted with EtOAc. EtOAc
After washing the layer with water, EtOAc was distilled off under reduced pressure, and the residue was recrystallized from MeOH for purification. <Identification data> Chemical formula: C ₁₇ H ₁₄ O ₃ Molecular weight: 266 Melting point: 122 to 123 ° C. (MeOH) Property: Yellow, needle crystal EIMS m / z (rel.int.): 266 (16, M ⁺ ), 24
7 (4), 231 (3), 145 (13), 131 (1
00), 121 (48), 103 (31) ¹ H-NMR (CDCl ₃ ) δ: <β-diketone> (76
%) 12.22 (1H, s, OH), <enol> (24
%), 6.31 (2H, s, COCH ₂ CO), 6.6
1 (1H, d, J = 16 Hz, H-α), 6.86-7.
70 (9H, m), 7.62 (1H, d, J = 16Hz,
H-β)

(2) β-diketone derivative 2 (R ₁ = OMe,
R ₂ = R ₃ = R ₄ = H) <Production method> According to the β-diketone derivative 1. <Identification data> Chemical formula: C ₁₈ H ₁₆ O ₄ Molecular weight: 296 Melting point: 114 to 116 ° C. (MeOH) Property: Yellow, powder EIMS m / z (rel.int.): 296 (27, M ⁺ ), 27
7 (4), 151 (78), 131 (100), 124
(13), 103 (33) ¹ H-NMR (CDCl ₃ ) δ: <β-diketone> (74
%) 3.84 (3H, s, OMe), 12.69 (1
H, s, OH), <enol> (26%), 3.85 (3
H, s, OMe), 12.86, 14.51 (1H eac
h, s, OH), 6.19-7.83 (12H, m)

(3) β-diketone derivative 3 (R ₄ = OMe,
R ₁ = R ₂ = R ₃ = H) <Production Method> According to the β-diketone derivative 1. <Identification data> Chemical formula: C ₁₈ H ₁₆ O ₄ Molecular weight: 296 Melting point: 123 to 124 ° C. (MeOH) Property: Yellow, acicular EIMS m / z (rel.int.): 296 (15, M ⁺ ), 27
9 (7), 261 (3), 175 (29), 161 (1
00), 133 (18), 121 (35) ¹ H-NMR (CDCl ₃ ) δ: <β-diketone> (79
%) 3.84 (3H, s, OMe), 12.27 (1
H, s, OH), <enol> (21%) 3.84 (3H,
s, OMe), 12.27, 14.74 (1H each,
s, OH), 6.27 (2H, s, COCH ₂ CO),
6.45 (1H, d, J = 16Hz, H-α) 6.86-
7.69 (4H, m, H-3,4,5,6), 6.92
(2H, d, J = 9Hz, H-3 ', 5'), 7.51
(2H, d, J = 9Hz, H-2 ', 6'), 7.61
(1H, d, J = 16Hz, H-β)

(4) β-diketone derivative 4 (R ₁ ═R ₄ ═O
Me, R ₂ = R ₃ = H) <Production Method> According to the β-diketone derivative 1. <Identification data> Chemical formula: C ₁₉ H ₁₈ O ₅ Molecular weight: 326 Melting point: 134 to 136 ° C. (MeOH) Property: yellow, powder EIMS m / z (rel.int.): 326 (11, M ⁺ ), 30
8 (4), 175 (25), 161 (100), 151
(62), 133 (18), 121 (11) ¹ H-NMR (CDCl ₃ ) δ: <β-diketone> (66
%) 12.73 (1H, s, OH), <enol> (34
%) 12.73, 14.60 (1H each, s, O
H), 3.84, 3.85 (3H each, s, OM
e), 6.16 (2H, s, COCH ₂ CO), 6.4
2-7.62 (3H, m, H-3, 5, 6), 6.45
(1H, d, J = 16Hz, H-α), 6.93 (2H,
d, J = 9 Hz, H-3 ', 5'), 7.50 (2H,
d, J = 9 Hz, H-2 ′, 6 ′), 7.51 (1H,
d, J = 16Hz, H-β)

(5) β-diketone derivative 5 (R ₁ ═R ₂ ═O
Me, R ₃ = R ₄ = H) <Production method> According to the β-diketone derivative 1. <Identification data> Chemical formula: C ₁₉ H ₁₈ O ₅ Molecular weight: 326 Melting point: 118 to 120 ° C. (MeOH) Property: Orange, needle-shaped EIMS m / z (rel.int.): 326 (20, M ⁺ ), Thirty
8 (4), 196 (4), 181 (26), 165
(4), 131 (100), 103 (24) ¹ H-NMR (CDCl ₃ ) δ: <β-diketone> (77
%) 12.56 (1H, s, OH), <enol> (23
%) 12.56, 14.60 (1H each, s, O
H), 3.89, 3.91 (3H each, s, OM
e), 6.13 (2H, s, COCH ₂ CO), 6.4
6 (1H, s, H-3), 6.60 (1H, d, J = 1
5 Hz, H-α), 7.02 (1H, s, H-6), 7.
36-7.57 (5H, m, H-2 ', 3', 4 ',
5 ', 6'), 7.61 (1H, d, J = 15Hz, H-
β)

(6) β-diketone derivative 6 (R ₃ ═R ₄ ═O
Me, pursuant to _{R 1 = R 2 = OMe)} <Preparation> The β- diketone derivative 1. <Identification data> Chemical formula: C ₁₉ H ₁₈ O ₅ Molecular weight: 326 Melting point: 141-142 ° C. (MeOH) Property: Orange, needle-shaped EIMS m / z (rel.int.): 326 (16, M ⁺ ), Thirty
8 (20), 291 (5), 205 (48), 191
(100), 163 (15), 151 (7), 121
(31) ¹ H-NMR (CDCl ₃ ) δ: <β-diketone> (72
%) 12.26 (1H, s, OH), <enol> (28
%) 12.26, 14.73 (1H each, s, O
H), 3.93, 3.94 (3H each, s, OM
e), 6.30 (2H, s, COCH ₂ CO), 6.4
6 (1H, d, J = 16 Hz, H-α), 6.86-7.
70 (4H, m, H-3, 4,5, 6), 6.89 (1
H, d, J = 8 Hz, H-5 '), 7.08 (1H, d,
J = 2 Hz, H-2 ′), 7.15 (1H, dd, J =
8.2Hz, H-6 '), 7.61 (1H, d, J = 16)
Hz, H-β)

The ultraviolet absorbing effect of the ultraviolet absorbent according to each of the above-mentioned examples was examined by dissolving each substance in ethanol so as to have a concentration of 30 ppm and measuring the absorbance at 310 nm and 360 nm. The results are shown in FIGS. 1 and 2. As is clear from the figure, particularly the ester derivative showed an excellent ultraviolet ray absorbing effect in the UV-A region, and the β-diketone derivative showed an excellent ultraviolet ray absorbing effect in the UV-B region.

Next, preferable compounding examples of the external preparation for skin according to the present invention will be shown. Formulation Example 1 Cream A. Oil phase Stearic acid 10.0% Stearyl alcohol 4.0 Glycerin monostearate 8.0 Vitamin E acetate 0.5 Perfume 0.4 Ethylparaben 0.1 Butylparaben 0.1 Propylparaben 0.1 Chalcone derivative 1 1 .0 B. Aqueous phase 1,3-butylene glycol 10.0 Propylene glycol 8.0 Glycerin 2.0 Potassium hydroxide 0.4 Purified water Residue <Preparation method> Aqueous phase Each component is dissolved to produce an aqueous phase B.
Then, the oil phase A and the water phase B are heated to 70 ° C. and completely dissolved by a conventional method. Phase A is added to phase B and emulsified with an emulsifier. The emulsion was cooled using a heat exchanger to obtain a cream.

Formulation Example 2 Cream A. Oil phase Cetanol 4.0 Vaseline 7.0 Isopropyl myristate 8.0 Squalane 12.0 Dimethyl polysiloxane 3.0 Glycerine monostearate 2.2 POE (20) sorbitan monostearate 2.8 Glycyrrhetinic acid stearate 0 .02 ethylparaben 0.1 butylparaben 0.1 ester derivative 1 3.0 B.I. Aqueous phase 1,3 Butylene glycol 7.0 Phenoxyethanol 0.2 L-Ascorbic acid phosphoric acid ester magnesium salt 3.0 Ascorbic acid phosphoric acid ester magnesium salt 1.0 Purified water Residue <Preparation method> According to Formulation Example 1 Got the cream.

Formulation Example 3 Emulsion A. Oil phase Squalane 5.0 Oleyl oleate 3.0 Vaseline 2.0 Sorbitan sesquioleate 0.8 Polyoxyethylene (20) oleyl ether 1.2 2-Ethylhexyl-p-methoxycinnamate 3.0 Perfume 0.12 Ester derivative 2 0.1 B. Aqueous phase Dipropylene glycol 5.0 Ethanol 3.0 Carboxyvinyl polymer 0.17 Sodium hyaluronate 0.1 Potassium hydroxide 0.08 Methylparaben 0.15 Sodium hexametaphosphate 0.05 Purified water Residual <Preparation method> Compounding example An emulsion was obtained according to 1.

Formulation Example 4 Cream A. Oil phase Behenyl alcohol 0.5 12-Hydroxystearic acid cholestanol ester 2.0 Squalane 7.0 Jojoba oil 5.0 Self-emulsifying glyceryl monostearate 2.5 Polyoxyethylene (20) sorbitan monostearate 1.5 2-hydroxy-4-methoxybenzophenone 3.0 ethylparaben 0.2 butylparaben 0.1 fragrance 0.1 β-diketone derivative 2 0.5 B. Aqueous phase 1,3-butylene glycol 6.0 Glycerin 3.5 Zinc oxide 1.5 Kaolin 0.5 Bentonite 0.3 Sodium hexamethanoate 0.03 Purified water Residual <Preparation method> By a manufacturing method according to Formulation Example 1. A powdered cream was obtained.

Formulation Example 5 Essence A. Oil phase Stearic acid 3.0% Cetanol 1.0 Lanolin derivative 3.0 Liquid paraffin 5.0 2-Ethylhexyl stearate 3.0 POE Cetyl alcohol ether 2.0 Glycerin monostearate 2.0 Diketone derivative 3 5.0 Preservative Appropriate amount Perfume Appropriate amount B. Aqueous phase 1,3-butylene glycol 6.0 Triethanolamine 10.0 Purified water balance <Production method> Triethanolamine and 1,3-butylene glycol are dissolved in purified water to prepare an aqueous phase B. Stearic acid, cetanol, lanolin derivative, liquid paraffin,
2-Ethylhexyl stearate, glyceryl monostearate and β-diketone derivative 3 were heated and dissolved at 70 to 80 ° C, and then POE cetyl alcohol ether, preservative and perfume were sequentially dissolved, and the temperature was raised to 70 ° C to obtain oil phase A. To manufacture. Add the oil phase A to the above-mentioned water phase B with stirring,
Emulsify. After uniformly adjusting the emulsified particles with a homomixer,
After degassing and cooling, the essence was obtained.

Formulation 6 Essence A. Ethanol phase Sorbitan monooleate 1.0% Oleyl alcohol 0.5 Vitamin E acetate 0.2 Perfume proper amount ethanol 10.0 POE Sorbitan dilaurate monostearate 1.0 chalcone derivative 3 0.1 Preservative proper amount fading Proper amount B. Aqueous phase Dipropylene glycol 5.0 Polyethylene glycol 400 5.0 Carboxyvinyl polymer 0.3 Sodium alginate 0.3 Potassium hydroxide 0.15 POE Sorbitan dilaurate monostearate 1.0 Placenta extract 0.2 Purified water balance <Manufacturing Method> After dissolving the carboxyvinyl polymer in purified water, dipropylene glycol, polyethylene glycol 400 and anti-fading agent are sequentially dissolved to obtain an aqueous phase B. POE sorbitan dilaurate monostearate ester, sorbitan monooleate ester, oleyl alcohol, vitamin E acetate, perfume, preservative, chalcone derivative 3 are sequentially dissolved in ethanol to obtain ethanol phase A, and the ethanol phase A is converted to aqueous phase B And emulsify. Potassium hydroxide is dissolved in a part of purified water, which is added, stirred, degassed, and filtered.

Formulation Example 7 Oil-in-water foundation A. Powder talc 3.0% Titanium dioxide 5.0 Red iron oxide 0.5 Yellow iron oxide 1.4 Black iron oxide 0.1 B. Water phase Bentonite 0.5 Polyoxyethylene sorbitan monostearate 0.9 Triethanolamine 1.0 Propylene glycol 10.0 Purified water 56.4 C.I. Oil phase Stearic acid 2.2 Isohexadecyl alcohol 7.0 Glycerin monostearate 2.0 Liquid lanolin 2.0 Liquid paraffin 8.0 Diketone derivative 4 2.0 Preservatives Suitable amount Perfume Suitable amount <Manufacturing method> Propylene glycol, in which bentonite as a thickening agent is dispersed, is added to purified water, and a homomixer treatment is performed at 70 ° C, and then the remaining aqueous phase components are added and sufficiently stirred. The powder portion that has been thoroughly mixed and pulverized is added to this while stirring and subjected to homomixer treatment at 70 ° C. Next 70 ℃ ～ 8
The oil phase heated and dissolved at 0 ° C. is gradually added, and the mixture is homomixed at 70 ° C. This is cooled with stirring, 45 ° C
Add flavor and cool to room temperature. Finally, degas and fill the container.

Formulation Example 8 W / O emulsion type foundation (cream type) A. Powder sericite 5.36% Kaolin 4.0 Titanium dioxide 9.32 Red iron oxide 0.36 Yellow iron oxide 0.8 Black iron oxide 0.16 B. Oil phase Liquid paraffin 5.0 Decamethylcyclopentanesiloxane 12.0 Polyoxyethylene-modified dimethylpolysiloxane 4.0 β-diketone derivative 5 7.0 C.I. Water phase dispersant 0.1 1,3 butylene glycol 5.0 purified water 51.9 preservative proper amount D. Others Stabilizer 2.0 Perfume Proper amount <Production method> After heating and stirring the aqueous phase at 70 ° C, a powder portion that has been sufficiently mixed and pulverized is added, and a homomixer treatment is performed at 70 ° C. A stabilizer dissolved in a part of purified water is added to this and stirred. Further, the oil phase heated to 70 ° C. is added, and the mixture is homomixed at 70 ° C. This is cooled with stirring, the amount of light is added at 45 ° C., and the mixture is cooled to room temperature. Finally, degas and fill the container.

Formulation Example 9 O / W type cream type A. Water phase Purified water 54.95% 1,3 Butylene glycol 7.0 Titanium dioxide 5.0 Disodium edetate 0.05 Lauryl dimethylamine oxide 1.0 Triethanolamine 99% 1.0 Diketone derivative 6 0.5 B ． Oil phase Oxybenzone 2.0 Octyl paramethoxycinnamate 5.0 Squalane 10.0 Vaseline 5.0 Stearyl alcohol 3.0 Stearic acid 3.0 Glyceryl monostearate 3.0 Polyethyl acrylate 1.0 Antioxidant Appropriate amount Preservative Appropriate amount Perfume Appropriate amount <Manufacturing method> The oil phase part and the water phase part are heated to 70 ° C to dissolve them. In the water phase part, titanium dioxide is sufficiently dispersed, the oil phase part is added, and the mixture is emulsified using a homogenizer. The emulsion is cooled using a heat exchanger.

Formulation Example 10 O / W type emulsion type A. Aqueous phase Purified water 68.2 Dipropylene glycol 6.0 Ethanol 3.0 Hydroxyethyl cellulose 0.3 Lauryl dihydroxyethylamine oxide 0.1 B. Oil phase Octyl paramethoxycinnamate 6.0 Glyceryloctyl diparamethoxycinnamate 2.0 4-tert-Butyl-4′-methoxydibenzoylmethane 2.0 Oxybenzone 3.0 Oleyyloleate 5.0 Dimethylpolysiloxane 3.0 Vaseline 0.5 Cetyl alcohol 1.0 Sorbitan sesquioleate 0.8 POE (20) oleyl alcohol ether 1.2 Ester derivative 1 0.005 Antioxidant proper amount Preservative proper amount Perfume proper amount <Production method>> Heat and dissolve the water phase components at 70 ° C. to prepare the water phase. Then, the oil phase portion is heated to 70 ° C. to be dissolved. Add to the water phase, add the oil phase, and emulsify using a homogenizer. The emulsion is cooled using a heat exchanger.

Formulation Example 11 W / O type cream type A. Aqueous phase Purified water 36.5% 1,3 Butylene glycol 5.0 Triethanolamine 1.0 B. Oil phase Octyl paramethoxycinnamate 5.0 Oxybenzone 3.0 4-tert-Butyl-4'-methoxydibenzoylmethane 1.0 Hydrophobized titanium dioxide 3.0 Squalane 40.0 Glycerin diisostearate 3.0 Organic Modified montmorillonite 1.5 Diketone derivative 6 0.6 Preservative Appropriate amount Perfume Appropriate amount <Production method> The oil phase part and the water phase part are heated to 70 ° C. to be dissolved. In the oil phase part, titanium dioxide is sufficiently dispersed, and the water phase part is added while performing a homogenizer treatment.

Formulation 12 Lotion Purified water 40.0% Dipropylene glycol 5.0 1,3 Butylene glycol 10.0 Polyethylene glycol 400 10.0 Ethyl alcohol 20.0 Polyoxyethylene (60) hydrogenated castor oil 3.0 Paramethoxycinnamic acid octyl 1.0 Ester derivative 6 0.5 Triethanolamine 5.0 Perfume Appropriate amount <Manufacturing method> Polyoxyethylene (6
0) Dissolve hydrogenated castor oil, octyl paramethoxycinnamate, fragrance and ester derivative 6 (alcohol phase). On the other hand, a polyhydric alcohol is added to purified water to be sufficiently dissolved (aqueous phase). Add the alcohol phase to the aqueous phase and stir well.

Formulation Example 13 O / W type emulsion type A. Oil phase Liquid paraffin 3.0% Isopropyl myristate 2.0 Oleyl oleate 4.0 Vaseline 2.0 Stearyl alcohol 1.0 Stearic acid 2.0 Glyceryl monostearate 2.0 β-diketone derivative 3 2.0 Vitamin E Acetate Proper amount Preservative Proper amount Perfume Proper amount B. Aqueous phase Purified water 77.8 1,3 Butylene glycol 5.0 Carboxyvinyl polymer 0.2 Triethanolamine 1.0 <Production method> The oil phase part and the water phase part are heated to 70 ° C. to be dissolved. The oil phase is added to the aqueous phase, and the mixture is emulsified using a homogenizer. The emulsion is cooled using a heat exchanger.

[0041]

As described above, according to the ultraviolet absorbent of the present invention and the external preparation for skin containing the ultraviolet absorbent, since the diphenyl unsaturated compound which is a natural substance-related substance is added, the safety is improved. A high and excellent ultraviolet absorption effect can be obtained.

[Brief description of drawings]

FIG. 1 is an explanatory diagram showing the results of measuring the absorbance of an ultraviolet absorbent according to the present invention at 310 nm.

FIG. 2 is an explanatory diagram showing the results of measuring the absorbance of the ultraviolet absorbent according to the present invention at 360 nm.

Claims (5)

[Claims] 1. An ultraviolet absorber comprising a diphenyl unsaturated compound represented by the following general formula 1. [Chemical 1] In the above chemical formula 1, R ₁ , R ₂ and R ₃ represent H, OH or an alkoxyl group, and at least one is OH or an alkoxyl group. 2. An ultraviolet absorber comprising a diphenyl unsaturated compound represented by the following general formula 2. [Chemical 2] In the above chemical formula 2, R is H or OH. 3. An ultraviolet absorber comprising a diphenyl unsaturated compound represented by the following general formula 3. [Chemical 3] In the above chemical formula 3, R ₁ , R ₂ , R ₃ and R ₄ represent H or an alkoxyl group. 4. An ultraviolet absorber comprising a diphenyl unsaturated compound represented by the following general formula 4. [Chemical 4] In the above chemical formula 4, R ₁ , R ₂ , R ₃ and R ₄ represent H or an alkoxyl group. 5. An external preparation for skin, comprising the ultraviolet absorbent according to any one of claims 1 to 4.