JPH02164817A - Ultraviolet ray absorber - Google Patents

Abstract

PURPOSE:To obtain an ultraviolet ray absorber, containing a furanone derivative as an active ingredient, having high stability to heat and light without toxicity and irritancy to the skin, capable of exhibiting excellent ultraviolet ray absorptivity and good in solubility and miscibility with organic solvents, etc. CONSTITUTION:An ultraviolet ray absorber containing a furanone derivative expressed by the formula [R is H, OR<1>, NH2 or N(R<1>)2; R<1> is 1-4C alkyl] as an active ingredient. In use, the amount of the blended above-mentioned absorber is about 0.01-30wt.%, preferably about 0.1-10wt.% in the composition. Furthermore, 2,2-dimethyl-5(p-methoxyphenyl)-(2H)-furanone that is a compound wherein R is OMe in the aforementioned compound expressed by the formula which is the active ingredient can be readily synthesized from a p-halogenated anisole and 3-methyl-1-buten-3-ol.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to an ultraviolet absorber containing a furanone derivative.

More specifically, in the following formula (1), R represents a hydrogen atom, a group selected from the group consisting of OR', NH2, N(R?)2, and R1 has 1 to 4 carbon atoms. A furanone derivative represented by the following, which represents an alkyl group of
This invention relates to an ultraviolet absorber in the VA wavelength range.

(Prior Art) For humans, it has been reported that excessive ultraviolet rays can cause acute dermatitis of the skin, and long-term exposure can cause premature aging of the skin and skin cancer, leading to scaling.

Generally, this ultraviolet light is divided into three bands.

In other words, long wavelength ultraviolet rays (UV-A) of 320 to 400 nm, called the suntan wavelength, which promotes melanin production in the skin and causes browning; and UV-A, which has a long wavelength of 320 to 400 nm, which is called the sunburn wavelength, which causes inflammation such as erythema and blisters on the skin. 32
0nm ultraviolet rays (UV-B), and 240-280nm ultraviolet rays (UV-B) that are absorbed in the atmosphere, rarely reach the earth's surface, and pose no problem to the human body.
C).

Normally, sunburn cosmetics and sunscreen cosmetics are used to protect the skin from ultraviolet rays that are harmful to the human body. Sunburn cosmetics block ultraviolet rays in the sunburn wavelength, prevent inflammation such as erythema and blisters, and are used when a healthy tan is required.

On the other hand, sunscreen cosmetics block sunburn and ultraviolet rays of suntan wavelengths, and protect the skin from ultraviolet rays over a wide range.

As mentioned above, in order to protect the skin from ultraviolet rays,
It becomes important to protect the skin not only from UV-B but also from UV-A. However, ultraviolet absorbers in the UV-human wavelength range, for example, N-(p-dialkylaminocinnamic acid)-
A cosmetic with excellent skin tolerance and stability, containing ethyl p-aminobenzoate (Japanese Patent Publication No. 52-35738) and 4-(1,1-dimethylethyl)-4-methoxydibenzoylmethane as an ultraviolet A filter. UV absorbers containing chalcone derivatives such as 4-methoxy-4-methyl branched isostearoyloxychalcone (Japanese Patent Application Laid-open No. 60-109544)
), para-dialkylaminocinnamic acid cinnamic ester, etc. (Special Publication No. 52-31021), but the number of UV-
The amount is extremely small compared to B absorbent.

(Problems to be Solved by the Invention) As mentioned above, there are only a few ultraviolet absorbers in the UV-A region, and most of these are benzophenone-based, benzoic acid-based,
It is a cinnamic acid type.

Therefore, the present inventors conducted extensive research on compounds other than the above-mentioned compounds that have ultraviolet absorbing ability, and as a result, the furanone derivative of the present invention of formula (1), which has never been used as an ultraviolet absorber, was found. It exhibits excellent ultraviolet absorption ability, especially a large absorbance coefficient in the UV-A wavelength region, and has excellent solubility, miscibility, and compatibility with various base materials for cosmetics and organic solvents, and has no toxicity or irritation to the skin. The present invention was based on the discovery that the present invention has excellent ultraviolet absorbing ability when blended with various plastic base materials, and has good stability against various cosmetic base materials and additives. completed.

Therefore, an object of the present invention is to provide an ultraviolet absorber that can effectively absorb ultraviolet rays particularly in the UV-A wavelength range,
UV-effective for cosmetics, plastic materials, etc.
The purpose of the present invention is to provide an ultraviolet absorber in the A wavelength region.

(Means for Solving the Problems) The ultraviolet absorber of the present invention has the following formula (1), in which R represents a hydrogen atom, a group selected from the group consisting of OR1, NH2, and N (R')2. , R1 represents an alkyl group having 1 to 4 carbon atoms, preferably 1 to 4 carbon atoms, as an active ingredient.

2,2-dimethyl-5-phenyl-2(H)-3-furanone (hereinafter referred to as bratenone when R is a hydrogen atom) included in the compound of general formula (1) is Lopho
It is contained as a component of the essential oil of myrtus bullata, for example, as disclosed in Japanese Patent Application No. 62-23 filed by the applicant of the present application.
It can be easily synthesized by the method proposed in No. 995.

Further, in the above formula (1), 2, 2 where R is OMe
-dimethyl-5(p-methoxyphenyl) -2(H)
- Furanones can be used, for example, with p-halogenated anisole and 3
-Methyl-1-butyn-3-ol, patent application 1982
It can be easily synthesized by performing the same method as described in No.-23395. Also, 2,2- where R is NH2
Dimethyl-5-(p-aminophenyl)-2(H)-
Furanone can be obtained, for example, from p-halogenated aniline and 3=methyl-1-butyn-3-ol, as disclosed in Japanese Patent Application No. 1982-2.
It is easily produced by performing the same method as described in Japanese Patent No. 3395. In addition, 2,2-dimethyl-5-(p-dimethylaminophenyl)-2(i()-furanone in which R is N(Me)2) can be, for example, p-halogenated-N,N-dimethylaniline. It is easily synthesized from 3-methyl-1-butyn-3-ol by the method described in Japanese Patent Application No. 62-23995.

Furanone derivatives belonging to the thin ice 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)-
Examples include furanone and 2,2-dimethyl-5-(p-butoxyphenyl)-2(H)-furanone.

As illustrated in FIGS. 1 to 4, the furanone derivative of the formula (1) of the present invention has a maximum absorption value in the vicinity of 305 to 390 nm, has a large molar absorption coefficient, and has a visible region ( It has a remarkable characteristic of having low absorption in the wavelength region (400 nm or more). Furthermore, the above formula (
It is also possible to use an appropriate mixture of compounds included in the furanone derivatives in 1), which effectively absorb a wide range of ultraviolet rays.

Furthermore, the compound of formula (1) has excellent solubility, miscibility, and compatibility with various base materials and various organic solvents used in cosmetics. In particular, organic solvents commonly used in cosmetics, e.g.
It has excellent solubility in ethanol, isopropyl alcohol, lauryl alcohol, cetanol, stearyl alcohol, oleyl alcohol, propylene glycol, isopropyl myristate, isopropyl valmitate, and other various animal oils and various vegetable oils.

The ultraviolet absorber of the formula (1) of the present invention can be used, for example, in various cosmetic base materials such as creams, milky lotions, lotions, bags, and facial cleansers, various makeup products such as foundations, rouges, lipsticks, and white powders, and hair styling products. It can be incorporated into various known cosmetic base materials such as hair cosmetics, hair tonics, soaps, hair conditioners, nail polishes, perfumes, colognes, and other cosmetics. In addition, the various cosmetics mentioned above include solutions,
emulsion, ointment, oil, wax, gel, sol,
It can be applied in various forms such as powder and spray. These ultraviolet absorbers can be used in various cosmetics for preventing sunburn and for preventing the cosmetics themselves from deteriorating or changing due to ultraviolet rays. In addition, the ultraviolet absorber has outstanding properties such as being non-toxic and non-irritating to the skin, highly stable against heat and light, and does not change various cosmetic base materials or cosmetic additives. have.

The amount of the ultraviolet absorber of the formula (1) of the present invention may be appropriately selected depending on the usage form of the composition to be blended, and is not particularly limited, but usually 0. O
It is desirable that the amount is about 1 to 30% by weight, preferably 0.1 to 10% by weight.

Furthermore, the ultraviolet absorber of the present invention may be blended with only the compound of the formula (1) alone or in combination with various cosmetic base materials, etc. Furthermore, various known UV-A
It can also be used in combination with absorbers, UV-B absorbers and the like. Even when used in combination with such other ultraviolet absorbers, excellent synergistic effects 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, and animal and plant extracts. The ultraviolet absorber of the present invention can be used not only in cosmetics but also in other applications such as various paints, inks, etc., based on the properties of the compound (1), such as its excellent compatibility with various organic solvents. It can be applied to various other technical fields such as plastic materials, plastic films and other organic polymer materials, and organic polymer films (particularly noticeable in the technical fields of packaging materials and containers) due to its excellent ultraviolet absorption effect and ultraviolet ray protection. It can exhibit outstanding effects such as anti-aging effects.

(Examples and reference examples) Reference example 1 Synthesis of bratenone (when R is a hydrogen atom).

Iodobenzene 61.2 g (0.3 mol), 3-methyl-1-butyn-3-ol 25.2 g (0.3 mol), bistriphenylphosphinocobalt dichloride 3
．． 9 g and 282 ml of triethylamine were charged into an autoclave, and 20 ml of each of carbon dioxide and -carbon oxide were charged.
By heating and stirring under a pressure of "Kg/cm", 10.2 g of bratenone was obtained.

NMR (60MHz, CDC13) 61.42 (6H,S), 65.90 (IH,S
), 87.18-7.84 (5H, m).

Note that FIG. 1 shows the ultraviolet absorption spectrum of bratenone.

Reference example 2 2.2-dimethyl-5-(p-methoxyphenyl) -
Synthesis of 2(H)-furanone (when R is OCH3).

p-iodoanisole 46.8g (0.2 mol), 3
-Methyl-1-buten-3-ol 16°8g (0,
2 moles), 2.6 g of bistriphenylphosphinocobalt dichloride and 175 ml of triethylamine were placed in an autoclave, and heated and stirred under pressure of 20 kg/cm2 of carbon dioxide and carbon monoxide each.
8.9 g of the title compound was obtained.

NMR (90MHz, CDC13) 81.48 (8H,S), δ3.87 (3H,S)
, 85.84 (IH,S), δ6.97 (2H+
cL J=9Hz), 87.78 (2H, d, J
Note that FIG. 2 shows the ultraviolet absorption spectrum of 2,2-dimethyl-5-(p-methoxyphenyl)-2(H)-furanone.

Reference example 3 2.2-dimethyl-5-(p-aminophenyl)-2(
Synthesis of H)-furanones (when R is NH2).

P-iodoaniline 43.8g (0.2 mol), 3-
16.8 g (0.2 mol) of methyl-1-butyn-3-ol, 2.6 g of bistriphenylphosphinocobalt dichloride and 175 ml of triethylamine were charged into an autoclave, and 20 ml each of carbon dioxide and carbon monoxide were charged.
The reaction was carried out under heating and stirring under a pressure of Kg/cm2. 11.3 g of the title compound was obtained.

NMR (90MHz, CDC13) 81.46 (6H,S), δ4.31 (2H,b
road singlets), 5.78 (IH, S
), 6.69 (2H, d, J=9Hz), 7.6
3 (2H, d, J=9Hz).

Note that FIG. 3 shows the 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 [R is N(Me)2
in the case of].

p-iodo-N,N-dimethylaniline 0.2 mol, 3
- 0.2 mol of methyl-1-butyn-3-ol, 2.6 g of bistriphenylphosphinocobalt dichloride and 175 ml of triethylamine were placed in an autoclave, and the mixture was heated and stirred under pressure of 20 g/cm2 each of carbon dioxide and carbon monoxide. and reacted. Title compound 13.5g
Obtained NMR (90MHz, CDC13) 81.46 (6H,S), 3.00 (2H,S)
, 5.80 (IH, S') , 6.88 (2H, d
.

J=9Hz), 7.82 (2H, d, J=9Hz)
.

In addition, FIG. 4 shows the ultraviolet absorption spectrum of 2,2-dimethyl-5-(p-dimethylaminophenyl)-2(H)-furanone.

Example 1 Sun smoldering cosmetics (prescription) A component Brettanon stearic acid Setanol Beeswax liquid paraffin oil methylphenyl silicone olive oil polyoxyethylene sorbitan mono stearate butyl paraben fragrance B component Propylene glycol triethanolamine borax weight% 4,0 3, 5 2,0 3, 5 12,0 4,0 14,0 0, 5 0.05 0, 2 10, 0 1.0 0, 5 Methylparaben titanium oxide non-ionized water 0,05 2,0 Remaining amount ioo, o.

(!!Method) 1. Component A other than fragrance was mixed and heated to dissolve and disperse uniformly.

2.8 components were mixed and dissolved by heating.

3. Component B was added to component A, emulsified with stirring, and cooled.

4. Add flavoring while cooling and stir well.

5. Filled into a container to prepare a product.

Example 2 Sunscreen cake foundation (formulation) m-bean 2.2-dimethyl-5-(p-methoxyphenyl)-2(H)-furanone weight % 3.0 UV-B absorber 2.0 Talc
50.0 Serizite
17.0 titanium oxide
2.0 kaolin
11.0 colored pigments
Appropriate amount of B component isostearic acid 3.5 Ester gum 1.5 Sorbitan sesquioleate 0.8 Liquid paraffin
2.6 octyltodecanol
3.3 Octyldodecyl myristate 1.
5 Methylparahen 0. 1 Butylparaben 0. IC ingredient fragrance 0.2ioo,
.

(Production method) 1. After mixing ingredients A with a Henschel mixer,
The ingredients were added and mixed again using the Henschel mixer.

2. Add component C to the above, and after mixing and toning,
A pulverization process was performed using an atomizer.

3. This powder was placed on a metal plate and molded under pressure using a press.

Example 3 Sunscreen cream (prescription) Including 1''2 Weight% 2.2
-dimethyl-5-(p-amino 1.0 phenyl)
-2(H)-furanone UV-B absorber 2.0 Ceresin 7.0 Liquid paraffin 33.0 Octyldodecanyl myristate 20.0 Oleyl alcohol
12.0 sesame oil
1O10 antioxidant
Appropriate amount Component B Titanium oxide 6.0 Talc pigment C component Perfume 9.0 Appropriate amount Appropriate amount (i!!! method) Component A is dissolved by heating and mixed uniformly. After cooling, components (B) and (C) were added, treated with a roll mill, and filled into containers to prepare a sunscreen cream.

Example 4 Sunscreen cream (formulation) Ingredient A Weight% 2.2
-dimethyl-6-(dimethylamino 2.0 phenyl)
-2(H)-furanone UV-B absorber 4.0 Liquid paraffin 38.0 Cetanol
1. δ beeswax
6.0 Polyoxyethylene heptyl stearate 1.5 Ether monostearate sorbitan 2.5 Preservative Appropriate amount of antioxidant
Appropriate amount Ingredient B 10% caustic soda 1.0 Purified water 31.5 Anti-bloating glycerin 6.0 Titanium oxide 5. OD acid component material Appropriate amount (manufacturing method) Heat and dissolve component A and heat to 80°C. On the other hand, component B was dissolved by heating, heated to 75°C, added to component A and emulsified, added component D at 60°C, and finally heated to 50°C to
The ingredients were added and 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 before, and exhibits excellent ultraviolet absorption ability, particularly in the UV-wavelength region. It has a large absorbance coefficient, has excellent solubility, miscibility, and compatibility with various base materials for cosmetics and organic solvents, has no toxicity or irritation to the skin, has high stability against heat and light, and is suitable for various cosmetic base materials. It has the outstanding property of being highly stable against materials and additives, and can be used as a sunscreen cosmetic and for various plastic materials.
It can exhibit excellent effects such as excellent ultraviolet absorption effect and anti-aging effect due to ultraviolet rays.

[Brief explanation of the drawing]

Figure 1 shows the ultraviolet absorption spectrum of bradenone (when R is a hydrogen atom), and Figure 2 shows 2,2-dimethyl-5-(
The ultraviolet absorption spectrum of p-methoxyphenyl)-2(H)-furanone (when R is OM e), FIG.
2,2-dimethyl-5-(p-aminophenyl)-2
The ultraviolet absorption spectrum of (H)-furanone (R is NH2), Figure 4 shows the ultraviolet absorption spectrum of 2,2-dimethyl-5-(p-dimethylaminophenyl)-2(H)-furanone [R is N(Me ) In the case of 2, the ultraviolet spectrum of ko is shown. Patent applicant Hasegawa Perfume Co., Ltd. Agent Patent attorney Masaaki Kobayashi Procedural amendment (method) % formula % 1. Indication of the case 1988 Patent Application No. 318264 2. Name of the invention Ultraviolet absorber 3. Person making the amendment Relationship with the incident

Claims (1)

[Claims] The following formula (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (1) In the formula, R is a hydrogen atom, OR^1, NH_2, N(R^1
)2, and R^1 represents an alkyl group having 1 to 4 carbon atoms. An ultraviolet absorber containing a furanone derivative represented by: