JP3133506B2 - UV absorber - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to paints, plastics,
The present invention relates to an ultraviolet absorbent which is extremely useful as a compound imparted to a synthetic fiber or the like to impart ultraviolet absorbing ability and as a sunscreen in an external preparation for skin.

[0002]

2. Description of the Related Art Ultraviolet absorbers are added to paints, plastics, synthetic fibers and the like to prevent deterioration and discoloration due to ultraviolet rays contained in sunlight and protect the added material itself. are doing. Also, in external preparations for skin such as cosmetics, ultraviolet absorbers are used for the purpose of protecting the skin from ultraviolet rays which have various effects on the skin. The ultraviolet light has a short wavelength ultraviolet region (UV-C) of less than 280 nm depending on the size of the wavelength,
Medium wavelength ultraviolet region (UV-
B), a long wavelength ultraviolet region (UV-A) of 320 nm or more and less than 400 nm.

Conventional UV absorbers mainly absorb UV-B, which causes erythema and blister formation, as benzophenones, paraaminobenzoic acids, cinnamic acids, and the like.
Salicylic acid, etc.
UV- which is considered to be a cause of buckwheat and skin aging
Dibenzoylmethane, cinnamic acid, chalcone and hydantoin compounds are known to absorb A. (Cosmetics and toiletries
21, page 102, 1987, Journal of the Society of Color Materials, 298 pages,
65, 1992, West German Patent Publication Nos. 2728241 and 2728243, JP-A-51-6164.
No. 1, No. 52-46056, No. 57-598
Nos. 40, 57-197209 and 60-1
JP-A-09544, JP-A-63-101371, and JP-A-6-101371
However, none of these ultraviolet absorbers has sufficient ultraviolet absorbing ability, safety, stability, and solubility in solvents and the like.

On the other hand, as compounds having a biphenyl structure, dehydrodieugenol, dehydrodiguaiacol, dehydrodidihydroeugenol and the like are known to be highly safe (have no sensitization). (Japanese Patent Application No. 3-38089) There is also a report on its UV absorbing ability, but its absorption wavelength range is from 280 nm to 2 nm.
It is 90 nm, which is not enough for use as an ultraviolet absorber. Further, as biphenyl ketone derivatives, dehydrodivanillin, dehydrodiacetvanilone, and dehydro-diaguayl ethyl ketone (4,4'-dipropionyl-6,6'-bigiacol) have been reported. There is no report on ultraviolet absorbing ability. (Journal of Organic Chemistry 28
Volume 1048, 1963, Vol. 34, 585
P. 1969)

[0005] An object of the present invention, UV-B及beauty U V
An object of the present invention is to provide an ultraviolet absorber capable of effectively absorbing ultraviolet light in the A region.

[0006]

The present inventors have conducted intensive studies on biphenyl compounds, and as a result, a specific biphenyl ketone derivative described below was converted to UV-B and / or UV-B.
The present inventors have found that the ultraviolet light in the region B is effectively absorbed, and completed the present invention.

Namely, the present invention relates to an ultraviolet absorber characterized by containing a biphenyl ketone derivative represented by the following general formula can effectively absorb UV rays in the UV-B及beauty U V-A region.

Embedded image (Although hydrocarbon straight or side chain of R is from carbon number 1 12
Base . )

[0008] biphenyl ketone derivative der Lud <br/> hydro diacetoxy vanillin of the invention J. than vanillin and acetoacetic vanillin C. It can be easily obtained by dimerization according to the method of Pew et al. (Journal of Organic Chemistry Vol. 28 1048
P. 1963) Further, other biphenyl ketone derivatives are obtained by using guaiacol as a starting material to obtain an alkyl ester compound by a known method, and then reacting it with aluminum chloride in nitrobenzene to obtain a guaiacyl alkyl ketone as a monomer. Get the body. (Organic Reaction Vol. 1, p. 342, 1942,
Journal of Organic Chemistry 5
Vol. 645, 1940) The obtained guaiacylalkyl ketone can be easily obtained according to the above method.

The biphenyl ketone derivative used in the present invention not only has a high ultraviolet absorbing ability, is safe without skin irritation and sensitization, and is easily soluble in a base used in a usual external preparation for skin. Therefore, the range of application is wide, and the compounding amount can be appropriately selected according to the application.

[0010]

Embodiments will be described below. In addition,% shown in an Example means weight%. The biphenyl ketone derivatives shown in the examples are as follows. When R of the phenyl ketone derivative is C ₂ H ₅ , BP-C 2, C ₅ H ₁₁
In the case of BP-C5 and BP-C8 a case of C ₈ H ₁₇
Abbreviated below. The test method of the ultraviolet protection ability is as follows.

(1) Test method of ultraviolet protection ability Multiport solar UV simulator 6 as a light source
The minimum erythema value (MED value) and the UV protection index value (SPF value) of each sample were obtained using Model 00 (manufactured by Solar Light) according to the following methods. (I) MED Measurement The back of a Hartley-type guinea pig (female) weighing 450 g to 500 g was treated with a depilatory cream. Twenty-four hours later, the hair was lightly shaved with a shaver, and then, using the above-mentioned ultraviolet irradiation device, 2.20, 1.76, 1.41, 1.1.
UVA at 3,0.90,0.72 MED / min intensity
And UVB. 24 hours later, the minimum irradiation dose at which erythema appeared was 1 MED.

(Ii) SPF Measurement After the back of a Hartley-type guinea pig (female) weighing 450 g to 500 g was treated by the above-described method, each test sample was uniformly applied to ² μl / cm ² . UVA and UVB with the same intensity as the MED measurement using an ultraviolet irradiation device
For 2 minutes. The MED after 24 hours was determined, and the SPF value was calculated from the following equation.

Sample SPF value = (M at the time of sample application)
(ED value / MED value when not applied)

Example 1 (Synthesis of BP-C2) 3 g of guaiacyl ethyl ketone obtained by a conventional method was added to 30 m
After dissolving in 1 l of ethanol, about 15 ml of water was added with stirring. To this aqueous solution was added a peroxidase (origin; horseradish) aqueous solution (25 mg / 50 ml). 3% more
12 ml of an aqueous hydrogen peroxide solution was gradually dropped over about 30 minutes. After the completion of the dropwise addition, the mixture was stirred for about 30 minutes. After removing the ethanol under reduced pressure, the organic layer was extracted with 50 ml of ethyl acetate. 1. The ethyl acetate layer was dried using sodium sulfate, and then concentrated under reduced pressure.
9 g of a pale yellow oil was obtained. The oily substance is subjected to silica gel chromatography (developing solvent: benzene / acetone = 1).
0/1), a fraction containing a spot having an Rf value of about 0.3 in thin layer chromatography (developing solvent: benzene / acetone = 6/1) was obtained. After the developing solvent was removed by concentration under reduced pressure, 1.3 g of white crystals were obtained by using acetone as a crystallization solvent.

According to ¹³ C-NMR (internal standard substance: TMS, measuring solvent: deuterated chloroform) of the obtained white crystal, carbonyl carbon was added to 197.7 ppm at 147.7,14.
7.2, 129.5, 125.3, 122.6, 10
An aromatic carbon was detected at 9.4 ppm, a methyl ether carbon at 56.4 ppm, and an ethyl group carbon signal at 30.8 and 8.6 ppm. Also, m / z 35 in MS measurement.
The peaks at 8,344, 329 and 223 confirmed that the white crystals obtained were BP-C2 of the present invention. Examples of the IR spectrum and ultraviolet absorption spectrum of BP-C2 are shown in FIGS. Table 1 shows the results of measuring the ultraviolet absorption spectrum.

Example 2 (Synthesis of BP-C5) 3 g of guaiacyl ethyl ketone used in Example 1 was changed to 3.5 g of guaiacyl amyl ketone, and an Rf value of about 0.33 was obtained using the same method. 1.5g from spot
Was obtained as white crystals. ¹³ C-NMR measurement (internal standard:
199. TMS, measurement solvent: deuterated chloroform).
Carbonyl carbon, 147.6, 147.1, 1 ppm
129.7, 125.4, 122.5, 109.4 pp
m, aromatic carbon; 56.4 ppm, methyl ether carbon; 38.2,31.6,24.4,22.6,13.
An amyl group carbon signal was confirmed at 9 ppm. Also, M
M / z 442, 386, 371, 330 in S measurement
It was confirmed that the white crystal obtained from the confirmation of the peak was BP-C5 of the present invention. BP-C5
FIG. 3 shows the ¹³ C-NMR spectrum. Table 1 shows the results of measuring the ultraviolet absorption spectrum.

Example 3 (Synthesis of BP-C8) 3 g of guaiacyl ethyl ketone used in Example 1 was changed to 4.0 g of guaiacyl octyl ketone, and an Rf value of about 0.33 was obtained using the same method. 1.2 from the spot
g of white crystals were obtained. M / z 526 in MS measurement
It was confirmed that the white crystal obtained by confirming the peak at 418 was BP-C8 of the present invention. Also,
Table 1 shows the results of measurement of the ultraviolet absorption spectrum.

Example 4 (Measurement of UV Absorbing Ability) Table 1 shows the results of measuring the ultraviolet absorption spectrum of the biphenyl ketone derivative of the present invention.

[0019]

[Table 1]

As apparent from Table 1, the biphenyl ketone derivative of the present invention has an excellent ultraviolet absorbing ability in the UV-B and / or UV-A region.

Example 5 (Measurement of UV protection ability) According to the formulation in Table 2, the UV absorber solutions of Example 5 and Comparative Examples 1 and 2 were prepared, and the SPF value was measured according to the UV protection ability. Table 3 shows the results. In addition, parasol M
CX and ASL-24 are typical ones conventionally used as ultraviolet absorbers.

[0022]

[Table 2]

As is clear from Table 3, the biphenyl ketone derivative BP-C2 of the present invention has excellent ultraviolet protection ability as in the comparative example.

[0024]

[Table 3]

[0025]

According to the present invention can provide a UV-B及beauty ultraviolet absorber can effectively absorb the region of U V-A.

[Brief description of the drawings]

FIG. 1 is a novel biphenyl compound BP described in Example 1.
3 shows an IR spectrum of C2.

FIG. 2 shows the novel biphenyl compound BP described in Example 1.
3 shows the ultraviolet absorption spectrum of C2.

FIG. 3 shows a novel biphenyl compound BP described in Example 2.
3 shows the ¹³ C-NMR spectrum of —C5. CDCl
₃ indicates deuterated trichloroform as a measurement solvent, and TMS indicates tetramethylsilane as an internal standard substance.

────────────────────────────────────────────────── ─── Continuation of front page (56) References Patent No. 2968067 (JP, B2) Japanese Patent Publication No. 6-65136 (JP, B2) Chemical Abstracts, Vol. 90: 192461 (1979) (58) Fields investigated (Int. Cl. ⁷ , DB name) A61K ^7/ 00-7/50 C09K 3/00 104 CA (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. An ultraviolet absorber comprising a biphenyl ketone derivative represented by the following general formula. Embedded image (Although hydrocarbon straight or side chain of R is from carbon number 1 12
Base . ) 2. R is a straight or side chain carbon having 2 to 8 carbon atoms.
The ultraviolet absorbent according to claim 1, which is a hydrogen group.