JPH0825864B2 - Shiba outside absorbent - Google Patents

Description

TECHNICAL FIELD The present invention relates to an ultraviolet absorber containing a furanone derivative.

More specifically, the present invention provides the following formula (1) In the formula, R represents a hydrogen atom, a group selected from the group consisting of OR ¹ , NH ₂ , and N (R ¹ ) ₂ , and R ¹ represents an alkyl group having 1 to 4 carbon atoms. For example, a UV absorber that can effectively block UV rays by blending the derivative with sunscreen cosmetics or various plastic materials
-A UV absorber in the A wavelength range.

(Prior Art) It has also been reported that for humans, excessive ultraviolet rays may cause acute skin dermatitis or contribute to premature aging of skin and skin cancer due to long-term exposure.

In general, this ultraviolet light is divided into three bands. In other words, 320-400 nm long-wavelength ultraviolet rays (UV-A) that promote melanin production of the skin called the suntan wavelength and cause browning, erythema of the skin called sunburn wavelength, cause inflammation such as blisters 280- It is an ultraviolet ray of 320 nm (UV-B) and an ultraviolet ray of a low wavelength of 240 to 280 nm (UV-C) which is absorbed in the atmosphere, hardly reaches the surface of the earth, and does not pose a problem to the human body.

Usually, sunscreen cosmetics and sunscreen cosmetics are used for the purpose of protecting the skin from the ultraviolet rays that are harmful to the human body. The sunburn cosmetics are used in cases where ultraviolet rays of sunburn wavelength are blocked, inflammations such as erythema and blisters are prevented, and a healthy sunburn is required. On the other hand, sunscreen cosmetics also block ultraviolet rays of sunburn and suntan wavelengths and protect the skin from ultraviolet rays over a wide area.

As mentioned above, to protect the skin from UV rays, UV
It is important to protect the skin from UV-A as well as -B. However, an ultraviolet absorber in the UV-A wavelength range is, for example, N- (p-dialkylaminocinnamic acid) -p.
-Ethyl aminobenzoate (JP-B-52-35738), UV A
4- (1,1-dimethylethyl) -4 as a line filter
A cosmetic shielding agent containing methoxydibenzoylmethane and having excellent skin acceptability and stability (JP-A-55-66535),
UV absorbers containing chalcone derivatives such as 4-methoxy-4-methyl branched isostearoyloxy chalcone (JP-A-60-109544), para-dialkylaminocinnamic acid cinnamic ester and the like (JP-B-52-31021) However, the number is extremely small compared with the UV-B absorber.

(Problems to be Solved by the Invention) As described above, there are few ultraviolet absorbers in the UV-A region, and most of them are benzophenone-based, benzoic acid-based, and cinnamic acid-based.

Accordingly, the inventors of the present invention have conducted extensive studies on compounds having an ultraviolet absorbing ability for compounds other than the above-mentioned compounds, and as a result, the furanone derivative of the above formula (1) of the present invention that has never been used as an ultraviolet absorber at all. However, it shows excellent ultraviolet absorption ability, has a large absorbance coefficient especially in the UV-A wavelength range, is excellent in solubility, miscibility and compatibility with various base materials for cosmetics and organic solvents, and is toxic and irritating to the skin. Of the present invention, it has high stability to heat and light, and also has good stability to various cosmetic base materials and additives, and also has excellent ultraviolet absorbing ability when compounded in various plastic base materials. Completed.

Therefore, an object of the present invention is to provide a UV absorber capable of effectively absorbing UV rays in the UV-A wavelength range,
Effective UV-A for cosmetics and plastic materials
It is to provide a wavelength range ultraviolet absorber.

(Means for Solving the Problems) The ultraviolet absorbent of the present invention has the following formula (1): In the formula, R represents a group selected from the group consisting of hydrogen atom, OR ¹ , NH ₂ , and N (R ¹ ) ₂ , and R ¹ has 1 to 4 carbon atoms, preferably 1 to 4 carbon atoms.
The present invention is characterized in that the phenone derivative represented by, which represents the alkyl group of, is contained as an active ingredient.

2,2-Dimethyl-5-phenyl-2- (H-3-furanone (when R is a hydrogen atom, hereinafter referred to as bratenone) included in the compound of the general formula (1) is Lophomyrtu.
s bullata is contained as a component of essential oil, and can be easily synthesized, for example, by the method proposed in Japanese Patent Application No. 62-23995 filed by the present applicant.

Further, in the above formula (1), 2,2-dimethyl-5- (p-methoxyphenyl) -2 (H) -furanone in which R is OMe is, for example, p-halogenated anisole and 3-methyl- From 1-butyn-3-ol, Japanese Patent Application No. 62-23395
It is easily synthesized by carrying out the same method as that described in No. In addition, 2,2-dimethyl-5- (p in which R is NH ₂
-Aminophenyl) -2 (H) -furanone is, for example,
p-Halogenated aniline and 3-methyl-1-butyne-3
-It can be easily produced from oar by the same method as described in Japanese Patent Application No. 62-23395. Also, R
2,2-dimethyl-5- (p-dimethylaminophenyl) -2 (H) -furanone wherein N is N (Me) ₂ is, for example, p-
Halogenated-N, N-dimethylaniline and 3-methyl-1
-Butin-3-ol can be easily synthesized by the method described in Japanese Patent Application No. 62-23995.

Other furanone derivatives belonging to the present invention include 2,2
-Dimethyl-5- (p-diethylaminophenyl) -2
(H) -furanone, 2,2-dimethyl-5- (p-dipropylaminophenyl) -2 (H) -furanone, 2,2-dimethyl-5- (p-dibutylaminophenyl) -2
(H) -furanone, 2,2-dimethyl-5- (p-ethoxyphenyl) -2 (H) -furanone, 2,2-dimethyl-
5- (p-dipropoxyphenyl) -2 (H) -furanone, 2,2-dimethyl-5- (p-butoxyphenyl)-
Examples include 2 (H) -furanone.

The furanone derivative of the above formula (1) of the present invention is shown in FIG.
As shown in FIG. 4, it has a remarkable characteristic that it has a maximum absorption value around 305 to 390 nm, a large molar absorption coefficient, and a small absorption in the visible region (400 nm or more). ing. Further, the compounds included in the furanone derivative of the above formula (1) of the present invention can be appropriately mixed and used, and these effectively absorb a wide range of ultraviolet rays.

In addition, the compound of the formula (1) is soluble in various base materials and various organic solvents used in cosmetics,
It has the characteristics of excellent miscibility and compatibility.
In particular, organic solvents often used in cosmetics, for example, ethanol, isopropyl alcohol, lauryl alcohol, cetanol, stearyl alcohol, oleyl alcohol, propylene glycol, isopropyl myristate, isopropyl palmitate, various other animal oils and various Excellent solubility in vegetable oils.

The ultraviolet absorber of the above formula (1) of the present invention is, for example,
Various makeup bases such as creams, milky lotions, lotions, packs, and face washes, various makeup agents such as foundations, blushers, lipsticks, and white powders, various hair cosmetics such as hair styling agents, hair nourishing agents, soaps, shampoos, rinses, and beauty products. It can be blended with various known base materials for cosmetics such as nails, perfumes, colognes, and other cosmetics. Further, various cosmetics such as solutions, emulsions, ointments, oils, waxes, gels, sols, powders and sprays can be applied. These ultraviolet absorbers are various cosmetics for sun protection and alteration of the cosmetics themselves by ultraviolet rays,
It can be used for preventing changes. Further, the ultraviolet absorber has no toxicity and irritation to the skin,
It has excellent heat and light stability, and also has the outstanding property of not changing various cosmetic base materials and cosmetic additives.

The amount of the ultraviolet absorber of the formula (1) of the present invention to be blended may be appropriately selected depending on the use form of the composition to be blended,
Although not particularly limited, it is usually 0.01
It is desirable that the amount is blended in the range of about 30% by weight, preferably about 0.1-10% by weight.

Further, the ultraviolet absorbent of the present invention may be prepared by blending only the compound of the formula (1) alone into various cosmetic base materials, or may be blended in plural, and further, various known UV-A
It can also be used in combination with an absorber and a UV-B absorber. Even when used in combination with such another ultraviolet absorber, an excellent synergistic effect can be exhibited. Furthermore, the ultraviolet absorber according to the present invention can be used in combination with various other additives such as various surfactants, solvents, pigments, fragrances, preservatives, antioxidants, humectants, vitamins, animal and plant extracts. . The ultraviolet absorber of the present invention is based on the characteristics of the compound (1) such as excellent compatibility with various organic solvents and the like, and is not limited to the above-mentioned cosmetics, and other applications such as various paints, inks and Its excellent UV absorption effect and UV light can be applied to various other technical fields such as plastic materials, plastic films and other organic polymer materials, and organic polymer films (particularly remarkable in the technical field of packaging materials and containers). It can exert outstanding effects such as the effect of preventing aging.

(Examples and Reference Examples) Reference Example 1 Brathenone synthesis (when R is a hydrogen atom).

Iodobenzene 61.2 g (0.3 mol), 3-methyl-1-
25.2 g (0.3 mol) of butyn-3-ol, 3.9 g of bistriphenylphosphinocobalt dichloride and 262 ml of triethylamine were charged into an autoclave and heated and stirred under a pressure of 20 kg / cm ² of carbon dioxide and carbon monoxide, respectively. , 10.2 g of bratenone was obtained.

NMR (60 MHz, CDCl ₃ ) δ1.42 (6H, S), δ5.90 (1H, S), δ7.18 to 7.84 (5H,
m).

Incidentally, FIG. 1 shows the ultraviolet absorption spectrum of brathenone.

Reference Example 2 2,2-Dimethyl-5- (p-methoxyphenyl) -2
(H) - Synthesis of furanone (when R is OCH _3).

46.8 g (0.2 mol) of p-iodoanisole, 16.8 g (0.2 mol) of 3-methyl-1-buten-3-ol, 2.6 g of bistriphenylphosphinocobalt dichloride and 175 ml of triethylamine were charged in an autoclave and mixed with carbon dioxide. By heating and stirring under a pressure of 20 kg / cm ² of carbon oxide, respectively, 8.9 g of the title compound was obtained.

NMR (90MHz, CDCl ₃ ) δ1.48 (6H, S), δ3.87 (3H, S), δ5.84 (1H, S), δ
6.97 (2H, d, J = 9Hz), δ7.78 (2H, d, J = 9Hz). Incidentally, FIG. 2 shows an ultraviolet absorption spectrum of 2,2-dimethyl-5- (p-methoxyphenyl) -2 (H) -furanone.

Reference Example 3 2,2-Dimethyl-5- (p-aminophenyl) -2
(H) - Synthesis of furanone (when R is NH _2).

P-iodoaniline 43.8 g (0.2 mol), 3-methyl-
16.8 g (0.2 mol) of 1-butyn-3-ol, 2.6 g of bistriphenylphosphinocobalt dichloride and 175 ml of triethylamine were charged into an autoclave, and heated and stirred under a pressure of 20 kg / cm ² of carbon dioxide and carbon monoxide, respectively. Responded. 11.3 g of the title compound was obtained.

NMR (90MHz, CDCl ₃ ) δ1.46 (6H, S), δ4.31 (2H, broad singlets), 5.76
(1H, S), 6.69 (2H, d, J = 9Hz), 7.63 (2H, d, J = 9H)
z).

Incidentally, FIG. 3 shows an ultraviolet absorption spectrum of 2,2-dimethyl-5- (p-aminophenyl) -2 (H) -furanone.

Reference Example 4 Synthesis of 2,2-dimethyl-5- (p-dimethylaminophenyl) -2 (H) -furanone [when R is N (Me) ₂ ].

0.2 mol of p-iodo-N, N-dimethylaniline, 0.2 mol of 3-methyl-1-butyn-3-ol, 2.6 g of bistriphenylphosphinocobalt dichloride and 175 ml of triethylamine were charged into an autoclave, and carbon dioxide and carbon monoxide were added. Each of them was heated and stirred under a pressure of 20 g / cm ² and reacted. NMR (90 MHz, CDCl ₃ ) δ1.46 (6H, S), 3.00 (2H, S), 5.80 (1H, S), 6.88 that gave the title compound 13.5 g.
(2H, d, J = 9Hz), 7.82 (2H, d, J = 9Hz). Incidentally, FIG. 4 shows an ultraviolet spectrum of 2,2-dimethyl-5- (p-dimethylaminophenyl) -2 (H) -furanone.

Example 1 Sunscreen Cosmetic (Prescription) A Component Weight% Brettanone 4.0 Stearic Acid 3.5 Cetanol 2.0 Beeswax 3.5 Liquid Paraffin Oil 12.0 Methylphenyl Silicone 4.0 Olive Oil 14.0 Polyoxyethylenesorbitan Mono 0.5 Starate Butylparaben 0.05 Perfume 0.2 B Component Propylene Glycol 10.0 Triethanolamine 1.0 Borax 0.5 Methylparaben 0.05 Titanium oxide 2.0 Non-ionic water balance 100.00 (Production method) 1. A components other than the fragrance were mixed, heated, dissolved and uniformly dispersed.

2. B component was mixed and dissolved by heating.

3. The B component was added to the A component, and the mixture was emulsified with stirring and cooled.

4. During the cooling, flavor was added and mixed well.

5. The product was filled in a container.

Example 2 Sunscreen Cake Foundation (Formulation) A Component Weight% 2,2-Dimethyl-5- (p-methoxyphenyl) -2
(H) -Furanone 3.0 UV-B absorber 2.0 Talc 50.0 Sericite 17.0 Titanium oxide 1.0 Kaolin 11.0 Coloring pigment Amount B component isostearic acid 3.5 Ester gum 1.5 Sorbitan sesquioleate 0.8 Fluid paraffin 2.6 Octyldodecanol 3.3 Octyldodecyl myristate 1.5 Methylparaben 0.1 Butylparaben 0.1 C component fragrance 0.2 100.0 (Production method) 1. After mixing the A component with a Henschel mixer, the B component was added and mixed again with the Henschel mixer.

2. The component C was added to the above, mixed and toned, and then pulverized with an atomizer.

3. This powder was placed on a metal dish and pressure-molded with a press.

Example 3 Sunscreen Cream (Formulation) A Component Weight% 2,2-Dimethyl-5- (p-aminophenyl) -2
(H) -Furanone 2.0 UV-B absorber 2.0 Ceresin 7.0 Liquid paraffin 33.0 Octyldodecanyl myristate 20.0 Oleyl alcohol 12.0 Sesame oil 10.0 Antioxidant Amount B component Titanium oxide 6.0 Talc 9.0 Amount C component Perfume Amount (production method) A component Are melted by heating and mixed uniformly. After cooling, (B)
After adding the component (C) and treating with a roll mill, the mixture was filled in a container to prepare a sunscreen cream.

Example 4 Sunscreen Cream (Formulation) A Component Weight% 2,2-Dimethyl-5- (dimethylaminophenyl) -2
(H) -Furanone 2.0 UV-B absorber 4.0 Liquid paraffin 38.0 Cetanol 1.5 Beeswax 6.0 Polyoxyethylene cetyl stearate 1.5 Ether Sorbitan monostearate 2.5 Preservative proper amount Antioxidant proper amount B component 10% caustic soda 1.0 Purified water 31.5 C component Glycerin 6.0 Titanium oxide 5.0 D component fragrance Suitable amount (manufacturing method) A component is melted by heating and heated to 80 degrees. On the other hand, the component B was heated and melted and heated to 75 ° C., the component B was added to the component A and emulsified, the component D was added at 60 ° C., the component C was finally added at 50 ° C., and the mixture was cooled to 30 ° C.

(Effects of the Invention) The furanone derivative of the formula (1) of the present invention is a novel ultraviolet absorber that has never been used in the past, and exhibits excellent ultraviolet absorbing ability, particularly in the UV-A wavelength region. It has a large absorption coefficient, excellent solubility, miscibility, and compatibility with various base materials for cosmetics and organic solvents, has no toxicity and irritation to skin, and has high heat and light stability. It has the outstanding property of being highly stable against materials and additives, and can be applied as a sunscreen cosmetic and also to various plastic materials.
It can exert excellent effects such as its excellent effect of absorbing ultraviolet rays and the effect of preventing aging due to ultraviolet rays.

[Brief description of drawings]

Fig. 1 shows the ultraviolet absorption spectrum of bratenone (when R is a hydrogen atom), and Fig. 2 shows 2,2-dimethyl-5- (p
-Methoxyphenyl) -2 (H) -furanone (R is OMe
3) is the ultraviolet absorption spectrum of 2,2-dimethyl-5- (p-aminophenyl) -2 (H) -furanone (when R is NH ₂ ).
The figure shows the ultraviolet spectrum of 2,2-dimethyl-5- (p-dimethylaminophenyl) -2 (H) -furanone [when R is N (Me) ₂ ].

Claims (1)

[Claims] 1. The following formula (1) In the formula, R represents a hydrogen atom, a group selected from the group consisting of OR ¹ , NH ₂ , and N (R ¹ ) ₂ , and R ¹ represents an alkyl group having 1 to 4 carbon atoms. UV absorbers containing derivatives.