WO2008041525A1

WO2008041525A1 - Furylmethylene malonamide compound and salt thereof, ultraviolet ray absorbent, and external preparation for skin

Info

Publication number: WO2008041525A1
Application number: PCT/JP2007/068434
Authority: WO
Inventors: Takuya Hiruma; Masaru Suetsugu
Original assignee: Shiseido Company Ltd.
Priority date: 2006-10-04
Filing date: 2007-09-21
Publication date: 2008-04-10
Also published as: JP2008088126A; JP5022659B2

Abstract

Disclosed is a furylmethylene malonamide compound which is highly water-soluble, shows an excellent absorption in the ultraviolet ray wavelength region but no absorption in the visible region, and has excellent stability. Specifically disclosed is a furylmethylene malonamide compound represented by the general formula (1) or a salt thereof. (1) wherein R1, R2 and R3 independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms; R4 and R5 independently represent a group [(CH2)m-O]n-R6 where R6 represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms; m represents an integer of 2 to 4; and n represents an integer of 1 to 5, provided that R4 and R5 may be the same as or different from each other.

Description

Specification

Furylmethylenemalonamide compound and salts thereof, UV absorber, topical skin preparation

Related applications

[0001] This application claims the priority of Japanese Patent Application No. 2006-272614 filed on Oct. 04, 2006, and is incorporated herein.

Technical field

The present invention relates to a furylmethylenemalonamide compound and a salt thereof, in particular, an ultraviolet absorber comprising the compound, an ultraviolet absorbing composition containing this as an active ingredient, and a skin external preparation containing the same.

Background art

[0003] Among ultraviolet rays contained in sunlight, ultraviolet rays having a wavelength of 290 nm or less are absorbed by the ozone layer and do not reach the ground surface, but ultraviolet rays of 290 nm to 400 nm reach the ground surface and have various effects. Dermatologically, it is known that medium-wavelength ultraviolet rays of 290 nm to 320 nm cause erythema and blister formation, increased melanogenesis, and pigmentation. In addition, 320-400 nm long-wavelength ultraviolet rays have an immediate blackening effect that darkens the skin immediately after irradiation, and because the energy reaches the dermis, it also affects elastic fibers in the blood vessel wall and connective tissue. It is said to have an effect. These medium to long wavelength ultraviolet rays promote skin aging and are thought to contribute to the formation of spots, freckles, wrinkles and the like.

[0004] In order to protect the skin from such ultraviolet rays, ultraviolet absorbers such as benzotriazole derivatives, benzophenone derivatives, salicylic acid derivatives, paraaminobenzoic acid derivatives, cinnamic acid derivatives, urocanic acid derivatives and the like have been conventionally used. .

[0005] However, these UV absorbers are generally oil-soluble and could not be incorporated into aqueous-based products. Recently, UV protection is considered important not only in summer bathing and winter ski resorts, but also in everyday life, and even ordinary skin care cosmetics are desired to have UV protection effects. Therefore, it is desired to develop a water-soluble ultraviolet absorber that can be added to a sufficient amount of water-based skin care cosmetics such as lotion. [0006] So far, few water-soluble UV absorbers are currently used, and 2-hydroxy-4-methoxy-5-sulfononium benzophenone sodium is known. However, since the substance is a sulfonate, it has an effect on the pH of the blending system, and the ultraviolet absorption region varies depending on the pH of the blending system. In addition, although the substance is water-soluble, its solubility is only about 6% at 25 ° C, and there is a problem that it precipitates at a low temperature when blended in a high concentration in the product. Furthermore, since the substance has absorption even in the visible light region, it has a disadvantage that it is colored pale yellow and affects the color tone of the product.

[0007] Further, as a water-soluble ultraviolet absorber, Patent Document 1 discloses a p-aminobenzoic acid amide derivative having a 2-deoxyhexose residue. Patent Document 2 discloses a cinnamic acid amide having a 2-deoxyhexose residue. However, the solubility of these substances in water is low and not fully satisfactory.

On the other hand, ultraviolet absorbers are also used in fields other than pharmaceuticals and cosmetics. For example, they are added to various materials such as paints, dyes, pigments, various resins, synthetic rubbers, latexes, films and fibers. Used to maintain the quality by imparting UV-absorbing ability, protecting the product itself, or the product covered with its coating film or film from UV rays, preventing deterioration and alteration due to UV rays, etc. Yes. However, conventional UV absorbers have the problem that they sublimate and volatilize by heating during baking of the coating film or resin molding, or gradually evaporate over time without heating. It was.

In addition, when a UV absorber is added to an external preparation for skin, the compound itself is not decomposed by sun exposure! / And stability is also important.

Patent Document 1: JP-A-10-120698

Patent Document 2: JP 2002-363195 A

Disclosure of the invention

Problems to be solved by the invention

[0009] The present invention has been made in view of the above-mentioned circumstances, and its problem is that it has a high water-solubility, a wide range, and an excellent ultraviolet-absorbing ability over the ultraviolet wavelength region, and its absorption in the visible region. A compound having excellent yield and stability, an ultraviolet absorber comprising the compound, and having the compound An object of the present invention is to provide an ultraviolet-absorbing composition containing as an active ingredient and a skin external preparation containing the compound.

Means for solving the problem

[0010] As a result of intensive studies by the present inventors in order to achieve the above-mentioned problems, a furylmethylenemalonamide compound represented by the following general formula (1) and a salt thereof were synthesized, and the properties thereof were! / As a result of an investigation, it was found that the compound has an excellent ability to absorb ultraviolet rays over a wide range and in the ultraviolet wavelength range, and has excellent water solubility and stability without absorption in the visible range. The present invention has been completed.

[0011] That is, the first subject of the present invention is to provide a furylmethylenemalonamide compound represented by the following general formula (1) and a salt thereof.

[Chemical 1

(Wherein R, R and R are each independently a hydrogen atom or carbon number;! To 4 linear or branched

one two Three

Represents an alkyl group, R and R each represent {(CH 2) -〇} -R, and R represents a hydrogen atom or

4 5 2 m n 6 6

A linear or branched alkyl group having 1 to 4 carbon atoms represents an alkyl group. m is an integer from 2 to 4, n is from! to 5. R and R may be the same or different. )

4 5

[0012] The second subject of the present invention is to provide an ultraviolet absorber comprising the furylmethylenemalonamide compound of the general formula (1) and / or a salt thereof.

Furthermore, the third subject of the present invention is to provide an ultraviolet absorbing composition containing the furylmethylenemalonamide compound of the above general formula (1) and / or a salt thereof as an active ingredient.

[0013] The fourth subject of the present invention is to provide a skin external preparation having the furylmethylenemalonamide compound of the above general formula (1) and / or a salt thereof.

It is preferable that the skin external preparation further contains an inorganic powder. The invention's effect

[0014] Since the furylmethylenemalonamide compound and its salt of the present invention have high UV absorption ability over a wide ultraviolet wavelength region, and the structure of the compound itself has excellent stability, It can be effectively used as an ultraviolet absorber having excellent stability. Further, since the compound is excellent in water solubility, it can be blended into an aqueous base product. Therefore, by blending the compound, it is possible to obtain an ultraviolet ray absorbing composition and an external preparation for skin which are excellent in ultraviolet ray preventing effect and stability.

In addition, since the furylmethylenemalonamide compound and salts thereof of the present invention do not absorb in the visible region, there is a change in appearance over time that is not colored when the compound is added to a product. I can't.

BEST MODE FOR CARRYING OUT THE INVENTION

[0015] The furylmethylenemalonamide compound and the salt thereof of the present invention are represented by the following general formula (1).

one two Three

4 5 2 m n 6 6

Carbon number; represents a linear or branched alkyl group having from 4 to 4 carbon atoms. m is an integer from 2 to 4, and n is an integer from 1 to 5. R and R may be the same or different. )

4 5

In the furylmethylenemalonamide compound represented by the general formula (1) and a salt thereof, R, R, and R are each independently a hydrogen atom or a carbon number;!

one two Three

Represents an alkyl group. Specific examples include methyl, ethyl, propyl, n-butyl, and isopropyl groups. Of these, R, R, and R are each independently a hydrogen atom, a methyl group,

one two Three

It is preferred to select from any power of the ethyl group. [0017] Further, in the furylmethylenemalonamide compound represented by the above general formula (1) and a salt thereof according to the present invention, R and R each represent {(CH) —〇} — R, and R represents a hydrogen atom Also

4 5 2 m n 6 6

Represents a linear or branched alkyl group having 1 to 4 carbon atoms. Examples of the straight chain or branched alkyl group having carbon atoms of! To 4 include methyl, ethyl, propyl, n-butyl, isopropyl group and the like. In the present invention, R is preferably a hydrogen atom. Also,

6

R and R may be the same or different.

4 5

m is an integer of 2 to 4, and n is an integer of 1 to 5. In the present invention, it is preferable that m force is 3 and n is 2.

In the present invention, it is particularly preferable that R and R are each {(CH 2) 10} 1 H.

4 5 2 2 2

That is, it is represented by the following general formula (2).

[Chemical 3

In the compound represented by the general formula (2), R, R, and R in the formula are the same as described above.

one two Three

It is a thing with a sign, and within this range!

The chemical names of the furylmethylenemalonamide compound represented by the above general formula (1) and the salt thereof according to the present invention are different forces depending on R, R, R, and R. For example, 2- (2-furylmethyle)

1 2 3 4

¹ ) N ¹ , N ³ bis [2- (2-hydroxyethoxy) ethinole] malonamide, N ¹ , N ³ bis [2- (2 hydroxyethoxy) ethyl] -2-[[(5 methyl-2-furyl) methylene] Malonamide, 2— [(5 ethyl 2 furyl) methylene] — N ¹ , N ³ bis [2— (2 hydroxyethoxy) ethynole] malonamide, 2— [(4,5 dimethyl-2-furyl) methylene] N ¹ , N ³ -bis [2- (2-hydroxyethoxy) ethyl] malonamide and the like. The structures of these compounds correspond to the following compounds (3) to (6) in order. Examples of the compound represented by the general formula (2) include the following compounds (3) to (6).

[Chemical 4]

[0020] The furylmethylenemalonamide compound represented by the general formula (1), which is suitable for the present invention, can be produced using a known synthetic reaction.

The following is a representative force S for illustrating the production method S, and the present invention is not limited to this.

. Unless otherwise specified in the following production methods, R, R, R, R, R, and R are the same as above.

1 2 3 4 5 6 As defined in general formula (1).

[0021] <Production method 1>

[Chemical 5]

First, the said manufacturing method 1 is demonstrated. As a first step, it has a substituent represented by the above general formula (7)! /, May! /, 2-furaldehyde (furfural), and represented by the above general formula (8). Known with malonic acid esters (eg, jetyl malonate when R is an ethyl group) Through the condensation reaction, the compound represented by the above formula (9) can be synthesized. It is preferred to use about 1 equivalent of the compound of formula (8) in molar ratio to the compound of formula (7)! /.

As the reaction solvent used in this condensation reaction, for example, toluene, benzene, pyridine and the like can be used alone or a mixed solvent thereof can be appropriately selected and used. As the reaction catalyst, for example, piperidine, acetic acid, ammonium acetate and the like can be used alone or in combination. The reaction solvent is preferably used in such an amount as to give a concentration in a usual synthesis reaction. For example, the mass ratio of the compound (7) is; Further, the amount of the reaction catalyst to be used may be in accordance with the amount of the catalyst for the normal reaction, for example, an amount of 0.01 to 0.9 in terms of molar ratio with respect to the compound of formula (7). The compounds of the formulas (7) and (8) and the reaction catalyst are mixed in a reaction solvent and then refluxed to obtain the compound of the formula (9).

[0023] Subsequently, as the second step, the amine NH—R and / or the compound of the formula (9) is used.

twenty four

By reacting NH—R under heating conditions, the desired furylmethylenemalo of the formula (1)

twenty five

Namide compounds can be synthesized. The reaction temperature at this time is preferably 50 to 200 ° C. When R and R are the same for the compound of formula (9),

As for 4 5 2 4, it is preferable to use about 2 equivalents of either NH 2 -R in molar ratio. R and R are different

In the case of 2 5 4 5, it is preferable to first react one of them in a molar ratio of about 1 equivalent and then react the other in a molar ratio of about 1 equivalent.

[0024] Further, the compound of formula (9) is hydrolyzed to obtain a dicarboxylic acid of formula (10), and then amine NH.

R and / or NH-R can be easily synthesized by a known amide bond formation method.

2 4 2 5

You can also. That is, by activating the carboxyl group as an activated form and reacting the activated form with amine NH 2 -R and / or NH 2 -R, the free radical of formula (1) is obtained.

2 4 2 5

A noremethylenemalonamide compound can be synthesized.

As a method for activating the carboxyl group, the following methods (i) to (iii) can be used.

(i) An active ester method using p-nitrophenyl ester, N-hydroxysuccinimide ester or the like.

(ii) A mixed acid anhydride method using a mixed acid anhydride with a monoalkyl ester carbonate using isobutyloxycarbonyl chloride, ethyloxycarbonyl chloride or the like. (iii) Acid chloride method using an acid chloride obtained by reacting with phosphorus trichloride, phosphorus pentachloride, thionyl chloride or the like.

[0025] Furthermore, a mixture of a dicarboxylic acid of formula (10) and an amine NH 2 -R and / or NH 2 -R

A furylmethylenmalonamide compound of the formula (1) can also be synthesized by adding a coupling reagent to the 2 4 2 5 solution for coupling. As the coupling reagent, N, N′-dicyclohexylcarpositimide (DCC), N-hydroxysuccinimide and DCC, 1-hydroxybenzotriazole and DCC, etc. can be used.

[0026] Further, it can be produced by the production method 2 shown below.

[Chemical 6]

[0027] That is, as the first 'stage, the malonic acid ester represented by the formula (8) and the amine NH 2 -R

2 4 and / or NH—R is reacted to synthesize a diamide compound represented by the formula (11). Ma

twenty five

In addition, malonic acid and amine NH 2 -R and / or NH 2 -R can be formed by known amide bond formation methods

2 4 2 5

It is also possible to synthesize a diamide compound of the formula (11) by The specific method of the amide bond generation method is as described above. When R and R are the same for the compound of formula (8)

4 5

Use about 2 equivalents of either amine NH-R or NH-R in molar ratio.

2 4 2 5

Is preferred. If R and R are different, first, react one of them in a molar ratio of about 1 equivalent.

4 5

It is preferable to react the other with a molar ratio of about 1 equivalent.

Further, as the 2 ′ stage, the diamide compound of formula (11) and a 2-phenyl which may have a substituent may be used. Lualdehyde (furfural) can be subjected to a known condensation reaction to synthesize a furylmethylenemalonamide compound of formula (1). As the reaction solvent used in this condensation reaction, for example, toluene, benzene, pyridine and the like can be used alone or a mixed solvent thereof can be appropriately selected and used. As the reaction catalyst, for example, piperidine, acetic acid, ammonium acetate and the like can be used alone or in combination. It is preferable to use the reaction solvent in an amount that provides a concentration in a normal synthesis reaction, for example, a mass ratio of 1 to 50 with respect to the compound (7). Further, the amount of the reaction catalyst to be used may be in accordance with the amount of the catalyst for the normal reaction, for example, an amount of 0.01 · 0.9 to 9 in molar ratio with respect to the compound of the formula (7). The compounds of the formula (7) and (11) and the reaction catalyst are mixed in a reaction solvent and then refluxed to obtain the compound of the formula (1).

[0028] The compounds necessary for the above production method are furfural (manufactured by Tokyo Chemical Industry Co., Ltd.), 5-methyl-2-furaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), and jetyl malonate (manufactured by Wako Pure Chemical Industries Ltd.) ), 2- (2-aminoethoxy) ethanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and the like can be used.

[0029] The furylmethylenemalonamide compound of the present invention can be converted into an inorganic salt or an organic salt according to a conventional method. The salt is not particularly limited, but examples of the inorganic salt include hydrochloride, sulfate, phosphate, hydrobromide, sodium salt, potassium salt, magnesium salt, calcium salt, ammonium salt, and the like. It is done. Organic salts include acetate, lactate, maleate, fumarate, tartrate, kenate, methanesulfonate, P-toluenesulfonate, triethanolamine salt, diethanolamine salt, amino acid salt, etc. Can be mentioned.

The furyl methylene malonamide compound and / or salt thereof of the present invention is useful as an ultraviolet absorber. In addition, a UV-absorbing composition can be prepared by blending a furylmethylenemalonamide compound and / or a salt thereof as an effective component and mixing with other various substances.

In addition, the ultraviolet absorber and the ultraviolet absorbing composition can be blended in various products that exhibit an ultraviolet absorbing effect. In particular, it is preferable to blend in an external preparation for skin. The external preparation for skin containing the furylmethylenemalonamide compound and / or salt thereof of the present invention exhibits an excellent ultraviolet ray preventing effect and absorbs ultraviolet rays even under sun exposure. Since the agent does not decompose, the effect is stably exhibited over a long period of time. In addition, since it does not absorb the visible region, there is no change in appearance over time, which does not cause coloring of the product. Such a feature can be said to be an advantageous effect because changes in appearance over time tend to lead to a negative image of the effect that users sometimes expect. Furthermore, skin troubles occur, and it is extremely useful as an external preparation for skin especially for sunscreens.

[0031] In a skin external preparation for sunscreen, in order to enhance the ultraviolet shielding effect, it is desirable to use an inorganic powder ultraviolet shielding agent together with an organic compound ultraviolet absorber. Also, makeup powders often contain inorganic powders. However, when an organic UV absorber is used in combination with inorganic powder, discoloration may occur. The furylmethylenemalonamide compound and / or salt thereof of the present invention does not cause discoloration even when blended with an external skin preparation together with the inorganic powder, and can be used in combination with the inorganic powder.

[0032] The inorganic powder used in the present invention is not particularly limited as long as it is usually blended in cosmetics and pharmaceuticals. For example, talc, kaolin, boron nitride, mica, sericite (sericite), muscovite, biotite, phlogopite, synthetic mica, synthetic myth, permequilite, magnesium carbonate, calcium carbonate, anhydrous calcium, key Aluminum oxide, aluminum oxide, sodium silicate, calcium silicate, magnesium silicate, metal tungstate, magnesium, silica, zeolite, barium sulfate, calcined calcium sulfate, calcined calcium, calcium phosphate, fluorapatite, In addition to inorganic powders such as hydroxyapatite, ceramic powder, metal sarcophagus (zinc myristate, calcium palmitate, aluminum stearate, etc.), titanium dioxide, zinc oxide, iron oxide, iron titanate, carbon, low-order titanium oxide, Mango violet, cobalt violet, acid Inorganic pigments such as chromium, chromium hydroxide, cobalt titanate, ultramarine blue, bitumen, titanium oxide coated my strength, titanium oxide coated bismuth oxychloride, titanium oxide coated talc, colored titanium oxide coated my strength, bismuth oxychloride, fish scale foil Is mentioned.

In particular, fine particle titanium oxide and fine particle zinc oxide are preferably added to sunscreen skin preparations such as sunscreen cosmetics.

[0033] When the furylmethylenemalonamide compound and / or salt thereof of the present invention is combined with an external preparation for skin, the blending amount may be appropriately determined according to the desired ultraviolet absorbing ability. It is not limited to. Usually, it is preferably 0.00 to 20% by mass, more preferably 0.01 to 10% by mass with respect to the total amount of the external preparation for skin.

Further, the blending amount of the inorganic powder is not limited. Appropriately determined according to the product for external preparation for skin, and usually about 0.;! To 99.5% by mass based on the total amount of external preparation for skin. For example, when preparing a skin external preparation for sunscreen, it is preferable that the inorganic powder is blended in an amount of about 0.1 to 30% by mass based on the total amount! /.

[0034] The product form of the external preparation for skin of the present invention is not particularly limited. For example, skin care cosmetics such as lotion, milky lotion, cream, beauty liquid, self-tanning agent, base cosmetics, makeup, lipstick, face color, eyeliner makeup cosmetics, hair spray, hair tonic, Examples include hair liquids and other cosmetics for hair and scalp.

[0035] In addition to the above-mentioned essential components, the external preparation for skin of the present invention, in addition to components that can be usually added to cosmetics and pharmaceuticals, for example, liquid oils, solid oils, waxes, hydrocarbons, higher fatty acids, higher alcohols. , Esters, silicones, anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, humectants, water-soluble polymer compounds, thickeners, coating agents, sequestering agents, Lower alcohol, polyhydric alcohol, sugars, amino acids, organic amines, pH adjusters, skin nutrients, vitamins, antioxidants, fragrances, powders, coloring materials, water, etc. should be added as necessary. Can do. In addition, it is also possible to mix | blend ultraviolet absorbers other than a furyl methylene malonamide compound and its salt with the skin external preparation of this invention.

[0036] Further, the furylmethylenemalonamide compound and / or salt thereof of the present invention is incorporated into products other than skin external preparations, for example, paints, dyes, pigments, various resins, synthetic rubbers, latexes, finalenes, fibers and the like. Thus, it is possible to protect against ultraviolet rays. When the furylmethylene malonamide compound of the present invention and its salt or UV absorber are blended in various products,

It is also possible to prepare an ultraviolet-absorbing composition by mixing with other raw material compounds or preparing an aqueous solution and blending it.

Since the furylmethylenemalonamide compound and the salt thereof of the present invention are excellent in thermal stability and do not volatilize, the efficacy can be maintained for a long time. The amount of furylmethylenemalonamide compound and / or its salt in various products and UV-absorbing compositions is generally Normally 0 - 00;! ~ 20 mass ^_0/0, preferably 0. 01; 10 mass ^_0/0.

Example 1

Hereinafter, the present invention will be specifically described with reference to examples. The present invention is not limited to these.

Example 1-1: 2- (2-Furylmethylene) Ν ^1. ^{≤ ≤} — Bis “2- (2-hydroxyethoxy) ethyl Ί Synthesis of malonamide

[Chemical 7]

(Ι) Ν ¹ , Ν ^{ύ —Synthesis of} bis [2- (2-hydroxyethoxy) ethinole] malonamide

Jetyl malonate (3 · 59 mL, 23.78 mmol) and 2- (2 aminoethoxy) ethanol (5.00 g, 4.56 mmol) were stirred at 130 ° C. for 6 hours. The mixture was allowed to cool and then concentrated, and the residue was purified by silica gel chromatography (chromium form / methanol = 20/1) to give N ¹ , N ³ bis [2- (2 hydroxyethoxy) ethyl] malonamide ( 6. 58 g, 99% yield). The obtained compound was identified by ¹ H-NMR (ECP400, manufactured by JEOL). Tetramethylsilane (TMS) was used as an internal standard. Chemical analysis values are as follows.

('H-NMR CDMSO-d, TMS, ppm)

δ: 7.98 (t, J = 4.8Hz, 2H), 4.49 (t, J = 5.3Hz, 2H), 3.52—3.48 (m, 4H), 3.44-3 41 (m, 8H), 3.25— 3.17 (m, 4H), 3.05 (s, 2H).

(2) Synthesis of 2- (2-furylmethylene) N ¹ , N ³ —bis [2- (2-hydroxyethoxy) ethinole] malonamide

N ¹ , N ³ bis [2- (2 hydroxyethoxy) ethinole] malonamide (0.50 g, 1.80 mm ο1) ί 卜ノレユン (6 mL), funolefuranore (0.15 mL, 1.80 mmol), piperidine ( (0.09 mL, 0.90 mmol) was added. The reaction was refluxed for 7 hours, then allowed to cool and concentrated. The obtained residue was purified by silica gel column chromatography (chloroform / methanol = 25/1) to give 2- (2-furylmethylene) N ¹ , N ³ bis [2- (2-hydroxyethoxy) ethynole. ] Ronamide was obtained (0.51 g, yield 80%).

The obtained compound was identified by ¹ H-NMR (ECP400, manufactured by JEOL). Tetramethylsilane (TMS) was used as an internal standard. Chemical analysis values are as follows.

('H-NMR CDMSO-d, TMS, ppm)

6

δ: 8.42 (t, J = 5.8Hz, 1H), 7.77 (d, J = l.9Hz, 1H), 7.53 (t, J = 5.8Hz, 1H), 7.18 (s, 1H), 6.86 (d, J = 3.4 Hz, 1H), 6.58 (dd, J = l .9 Hz, J = 3.4 Hz, 1H), 4. 50-4. 47 (m, 2H), 3.55—3.31 (m, 16H).

Example 1 2: Synthesis of N N--bis “2- (2 hydroxyethoxy) ethyl Ί 2-” (5 methyl —2-furyl) methylene Ίmalonamide

[Chemical 8]

N ¹ , N ³ bis [2- (2 hydroxyethoxy) ethinole] malonamide (0.70 g, 2.52 mm ο1) ί 卜 (6 mL), funolefuranol (0.25 mL, 2.52 mmol), piperidine ( 0.04 mL, 0.50 mmol) and acetic acid (0.09 mL, 1.51 mmol) were added. The reaction was refluxed for 3 hours, then allowed to cool and concentrated. The obtained residue was purified by silica gel column chromatography (black form / methanol = 25/1), and N ¹ , N ³ bis [2- (2 hydroxyethoxy) ethyl] -2- [(5 methyl 2 Furyl) methylene] malonamide was obtained (0.18 g, yield 19%). The obtained compound was identified by ¹ H-NMR (ECP400, manufactured by JEOL). Tetramethylsilane (TMS) was used as an internal standard. Chemical analysis values are as follows.

('H-NMR CDMSO-d, TMS, ppm)

6

δ: 8.37 (t, J = 5.8Hz, 1H), 7.49 (t, J = 5.8Hz, 1H), 7.13 (s, 1H), 6.77 (d, J = 2 9Hz, 1H), 6.22 (d, J = 2.9Hz, 1H), 4.50—4.48 (m, 2H), 3.5 6-3.41 (m, 12H), 3. 39—3.30 (m, 4H), 2.29 (s, 3H).

[0042] Evaluation 1: Measurement of absorbance in the ultraviolet wavelength region The ultraviolet absorption spectrum (solvent: water, concentration lOppm, optical path length lcm) of the furylmethylenemalonamide compound of the present invention was measured with a spectrophotometer (V-560 manufactured by JASCO Corporation). The results are shown in Table 1 below. As is clear from Table 1, it was confirmed that the furylmethylenemalonamide compound of the present invention has an excellent absorption ability in the ultraviolet wavelength region (290 to 400 nm).

[Table 1] Compound Maximum absorption wavelength (nm) Absorbance

(Example 1-1)

2-(2-Frinolemethylene) 1 N ¹ , N ³

One screw [2— (2-hydroxyethoxy)

Ethyl] Maronamide 3 1 0 0. 5 1

(Example 1 1 2)

N ¹ , N ³ —Bis [2— (2-Hydroxy

Etoxy) Etinore] _ 2 _ [(5-Metinore

— 2—furyl) methylene] malonamide 3 27 0. 55

[0043] mi: Visible, light absorption extinction I constant

The absorbance (solvent: water, optical path length 1 cm) of visible light at 405 nm of the furylmethylenemalonamide compound of the present invention was measured with a spectrophotometer (V-560 manufactured by JASCO Corporation). Further, as a comparative example, a conventional water-soluble ultraviolet absorber, 2-hydroxy-4-methoxy-5-sulfoxonium benzophenone sodium, was also measured in the same manner. The results are shown in Table 2 below.

[0044] [Table 2] Compound concentration (mass%) Absorbance

(Example 1-1)

2-(2-Frinolemethylene) N ¹ , N ³

—Bis [2— (2-Hydroxyethoxy)

Echinore] Maron Amid

(Example 1 2)

N ¹ , N ³ —Bis [2— (2-Hydroxy

Ethoxy) ethyl] _2 _ [(5-methinole

2-Furyl) methylene] malonamide

(Comparative example)

2 Hydroxy 4-Metoxy 5— 1. 99

Snorefoxonium benzophenone sodium 0.32

0. 0. 06

As is apparent from Table 2 above, the furylmethylenemalonamide compound of the present invention does not absorb in the visible region longer than 400 ηm. Therefore, the crystals were white and the aqueous solution was colorless and transparent.

On the other hand, since the comparative compound has absorption in the visible region, the crystals are colored light yellow and the aqueous solution is colored yellow. I can't expect.

[0046] Evaluation 3: Solubility in water

Original f: The solubility of the compound in water was measured. In addition, as a comparative example, 2-hydroxy-1,4-methoxy-1,5-sulfoxonium

It measured similarly about. The results are shown in Table 3.

[0047] [Table 3] Compound solubility (room temperature) [mass%]

Example 1-D

2- (2-Furylmethylene) N ¹ , N ³

—Bis [2— (2-Hydroxyethoxy)

Ethyl] Maronamide 35 or more

(Example 1 2)

N ', Ν' _ ^_bis [2— (2- ^hydroxyl

Xy) chill] ー 2 — [(5-methyl)

2 Furyl) methylene] malonamide over 17

(Comparative example)

2—Hydroxy 4-Methoxy 5— 6

Sulfononium benzophenone sodium

[0048] As apparent from Table 3 above, the furylmethylenemalonamide compound of the present invention is excellent in solubility in water and can be blended at a high concentration. On the other hand, it is difficult to blend the comparative compound at a high concentration with low water solubility. If blended at a high concentration, it tends to precipitate when stored at low temperature. If the blending amount is limited to avoid this, a sufficient UV absorption effect cannot be expected as a result.

[0049] ii-. M ^^

Using the furylmethylenemalonamide compound of the present invention, a sample was prepared as follows, and an actual test was conducted. The results of the samples are shown in Table 4 and Table 5 below.

The following formula ω lotion and (b) cream were prepared. Examples of the ultraviolet absorber include Example 1-1 of the present invention; 2- (2-furylmethylene) N ¹ , N ³ —bis [2- (2-hydroxyethoxy) ethyl] malonamide, and Example l— ZiN ¹ , N ³ —Bis [2— (2-hydroxyethoxy) ethyl] 2 — [(5 Methyl-2-furyl) methylene] malonamide) and _2- hydroxy- _4- methoxysulfoxoni, a water-soluble UV absorber as a comparative example Umbenzo Sodium phenone was used.

[0050] (a) Lotion

(Alcohol phase)

95% ethanol 25 · 0% by mass

POE (25) hydrogenated castor oil 2.0 Preservatives appropriate amount Fragrance appropriate amount (aqueous phase)

UV absorber;! ~ 10 Glycerin 5. 0

Sodium hexametaphosphate Appropriate amount Ion exchange water Residue (Production method)

An aqueous phase and an alcohol phase were prepared and mixed.

[0051] (b) Cream

Stearyl alcoholone 7.0 Weight ⁰ / o Stearic acid 2. 0 Hydrogenated lanolin 2. 0

2-Otachidodecyl alcohol 6.0

POE (25) Cetinoleetenole 3 · 0 Glycerol monostearate esterol 2. 0 Propylene glycol 5. 0 UV absorber;! ~ 10 Fragrance Appropriate amount Sodium hydrogen sulfite Appropriate amount Ethylparaben 0.3 Residue (Manufacturing method)

Propylene glycol and an ultraviolet absorber were added to ion-exchanged water and dissolved, and heated to 70 ° C (water phase). The other ingredients were mixed, heated and melted and kept at 70 ° C (oil phase). The oil phase was added to the water phase, pre-emulsified, and uniformly emulsified with a homomixer, and then cooled to 30 ° C while stirring well.

[0052] <Test method>

An actual use test was conducted at the beach in summer. An equal amount of each sample was applied to the back of the panel. The degree of sunburn after exposure to direct sunlight was evaluated according to the following criteria. In addition, 10 people per group were fi.

(Criteria)

Remarkable: There was no power at all, and almost no sunburn symptoms were observed.

Effective: Mild sunburn was observed.

Invalid: Severe sunburn was observed.

(Judgment)

A: More than 80% of subjects are effective or effective.

B: 50% or more and less than 80% of subjects who are effective or effective.

C: 30% or more and less than 50% of subjects who are effective or effective.

D: Less than 30% of subjects are effective or effective.

[0053] [Table 4]

(a) Lotion compound amount UV protection effect Appearance

(Example 1-1)

2— (2-Frinolemethylene) N ¹ , N ³ Colorless and transparent — Bis [2— (2-Hydroxyethoxy) Colorless and transparent Ethyl] Malonamide Colorless and transparent

(Example 1 2)

N ¹ , N ³ —Bis [2— (2-Hydroxy, colorless, transparent ethoxy) Eth / Le] —2 — [(5-Methinole, colorless, transparent — 2-furyl) methylene] malonamide, colorless, transparent

(Comparative example)

2 Hydroxy 4-Metoxy 5— Not dissolved Susolefoxonium benzophenone Yellow transparent * Sodium Yellow transparent No compound D Colorless transparent

*: Not measured because the UV absorber did not dissolve.

**: Crystal precipitates at low temperature storage.

(b) Cream compound content UV protection effect Appearance

(Example 1-1)

2-(2-Furylmethylene) N ¹ , N ³ 10 A white

Bis [2— (2-Hydroxyethoxy) 5 A White

Echinore] Maronamide 1 A white

(Example 1 2)

N ¹ , N ³ bis [2— (2-hydroxy 10 A white

Ethoxy) ethyl] _2 _ [(5 methyl 5 A white

_ 2—furyl) methylene] malonamide 1 A white

(Comparative example)

2—Hydroxy _4—Methoxy _5_ 10 — * Undissolved Sulfoxonium benzophenone 5 C Yellow

Sodium 1 C Yellow No compound D White

*: Not measured because the UV absorber did not dissolve.

**: Crystal precipitates at low temperature storage.

[0055] As is apparent from Tables 4 and 5 above, the external preparation for skin containing the furylmethylenemalonamide compound of the present invention has an excellent anti-ultraviolet effect compared to the case where a conventional water-soluble ultraviolet absorber is added. Had. Moreover, no precipitation of the UV absorber was observed even at low temperature storage.

[0056] As described above, the furylmethylenemalonamide compound of the present invention has excellent absorbability in the ultraviolet wavelength region where water solubility is extremely high.

Further, visible light of 400 nm or more is not absorbed at all, so it is white, and its aqueous solution is colorless and transparent, so there is no problem of coloring the product.

Furthermore, since it is very water-soluble, it can be incorporated in a large amount in the product, and in this case, the problem of precipitation over time does not occur. In addition, the pH of the blending system is not affected. Therefore, the furylmethylenemalonamide compound of the present invention is used as a water-soluble ultraviolet absorber. It is a very useful compound.

Therefore, the present inventors further examined the effects of skin irritation, photostability, and inorganic powder in order to investigate suitable conditions when the furylmethylenemalonamide compound of the present invention is blended in an external preparation for skin. Went.

[0057] Evaluation 5: Skin irritation test

The test was performed as follows using the same sample as in Evaluation 4 (the blending amount of the UV absorber was 10% by mass). The results are shown in Table 6 below.

A 24-hour occlusion patch test was performed with 20 people per group using fin chambers on the forearm flexion side of healthy male and female volunteers, and judged according to the following criteria.

(Criteria)

Degree of skin reaction Score

No reaction (negative) 0

Mild erythema (negative) 1

Erythema (weak positive) 2

Erythema + edema (moderate positive) 3

Erythema + edema + papules (strongly positive) 4

Large water bubbles (strongest positive) 5

(Judgment)

The average score obtained by dividing the total score of the 20 people by the number of people was determined and judged according to the following criteria.

A: Average score is 0.

B: The average score is greater than 0 and less than 1.

C: The average score is 1 or more and less than 2.

D: The average score is 2 or more.

[0058] [Table 6] Compound Dosage form judgment

(Example 1-1)

2-(2-Furylmethylene) N ¹ , N ³

Bis [2— (2-Hydroxyethoxy)

Echinore] Maron Amid

(Example 1 2)

N ¹ , N ³ —Bis [2— (2-Hydroxy Lotion A Ethoxy) Ethyl] —2 — [(5 Methyl Cream A

_ 2 _furyl) methylene] malonamide Mutsu S Go Lotion A

Cream A

As apparent from Table 6 above, it was confirmed that the external preparation for skin containing the furylmethylenemalonamide compound of the present invention was extremely excellent in safety with no skin irritation in the patch test.

[0060] Review 6: Light stability test

After exposure to an aqueous solution of the furylmethylenemalonamide compound of the present invention in sunlight for 2 weeks (sun exposure 80 Mj / m ² ), the residual rate and appearance change were examined, and the ultraviolet absorption spectrum (solvent: water, concentration 10 ppm, optical path length) lcm) was measured with a spectrophotometer, and the area value was obtained by integrating the range of 290 nm to 400 nm of the ultraviolet absorption spectrum and compared with that before exposure to sunlight. The results are shown in Table 7 below.

(Judgment)

Changes in the residual ratio and the area value of the ultraviolet absorption spectrum were determined according to the following criteria.

A: More than 95% before sun exposure.

B: 90% or more and less than 95% before sun exposure.

C: 70% or more and less than 90% before sun exposure.

D: Less than 70% before sun exposure.

[0061] [Table 7] Compound Residual ratio Appearance UV absorption

Spectral area change

(Example 1-1)

2-(2-Frinolemethylene) N ¹ , N ³

—Bis [2— (2-Hydroxyethoxy)

Echinore] Maronamide

(Example 1 2)

N ¹ , N ³ —Bis [2— (2-Hydroxy A Colorless Transparent A Ethoxy) Ethinole] _2 _ [(5-Methinore

— 2—furyl) methylene] malonamide

(Comparative example)

2 Hydroxy 4-Metoxy 5—

Sunolefosium benzophenone

Sodium

[0062] As is apparent from Table 7 above, the furylmethylenemalonamide compound of the present invention is not decomposed even by exposure to direct sunlight for a long time as compared with the conventional water-soluble ultraviolet absorber, and has a very high residual rate. Indicated.

Also, no coloration or precipitation was observed in the appearance in which the shape and area of the ultraviolet absorption spectrum did not change.

[0063] Evaluation 7: Stability test when combined with inorganic powder external shielding agent

Sunscreen creams with the following formulation were prepared, stored at 50 ° C for 2 months, and visually observed for discoloration to examine the stability when used in combination with inorganic powder UV screening agents. The results are shown in Table 8 below.

"Sunscreen cream"

(1) E chill cellulose 1 - 0 mass ^_0/0

(2) Ethanore 5 · 0

(3) 2-ethylhexyl succinate 24 (4) Titanium dioxide 1.0

(5) Porous anhydrous key powder 1. 0

(6) Spherical nylon powder 1.0

(7) Talc 1.0

(8) Sericite 1 · 0

(9) Boron nitride 1.0

(10) Silicon treatment My power 1.0

(11) UV absorber 10.0

(13) Residual ion exchange water

(14) Preservative appropriate amount

(15) Fragrance proper amount

After (2) was added to (1) and sufficiently swollen, (3) to (; 10) were added and mixed by heating to sufficiently disperse and dissolve. Maintain this dispersion at 70 ° C, gradually add the solution (11) to (15) mixed, and uniformly emulsify with a homomixer, then cool to 30 ° C while stirring well, Got.

[Table 8]

Compound discoloration

(Example 1 1)

2-(2-Frinolemethylene) N ¹ , N ³

—Bis [2— (2-Hydroxyethoxy)

Echinore] Maron Amid

(Example 1 2)

N ¹ , N ³ —Bis [2— (2-Hydroxy

Ethoxy) Ethinole] -2 — [(5-Methinore

-2—Free / Le) methylene] malonamide

(Comparative example)

2 Hydroxy 4-Metoxy 5 Discoloration to deep yellow Sunolefoxime benzophenone sodium

[0065] As is apparent from Table 8 above, the conventional water-soluble ultraviolet absorbers have the ability of yellowing when the inorganic powder is used together, and the skin external preparation containing the furylmethylenemalonamide compound of the present invention is inorganic. No discoloration was observed even when the powder was used in combination.

As described above, the furylmethylenemalonamide compound of the present invention is excellent in light stability with no skin irritation and does not cause discoloration when used in combination with inorganic powder.

Therefore, the ultraviolet absorbent according to the present invention is very useful as an ultraviolet absorbent that can be blended in an external preparation for skin.

Example 2

[0066] Examples of the external preparation for skin of the present invention will be given below, but the present invention is not limited thereto. In addition, all compounding quantities are shown by the mass%.

(Alcohol phase)

Ethanore 10.0 POE (15) Lauryl ether 0 · 5

Preservative appropriate amount

Perfume appropriate amount

(Water phase)

2— (2-furylmethylene) 1 Ν ¹ , Ν ³ bis [2—

(2-Hydroxyethoxy) ethinole] malonamide 10 · 0

2 Phenylbenzimidazole-5 Sulfonic acid 3.0 Sodium hydroxide 0.4

1, 3 Butylene glycol 6.0

Glycerin 4.0

4, 5 Dimorpholino 3 Hydroxypyridazine 0.3 Residue

(Manufacturing method)

After preparing each alcohol phase, it mixed and the target lotion was obtained.

(Alcohol phase)

Ethanore 10. 0

Oleil alcohol 0.1

POE (15) Lauryl ether 0 · 5

Preservative appropriate amount

Perfume appropriate amount

(Water phase)

N ¹ , N ³ bis [2- (2-hydroxyethoxy) ethinole]

—2— [(5 Methyl 2 furyl) methylene] malonamide 5.0

2 Phenylbenzimidazole-5 Sulfonic acid 3.0 Sodium hydroxide 0.4

1, 3 Butylene glycol 6.0 4. 0

Ten

4, 5-Dimorpholino 3-hydroxypyridazine 0.3

Ion exchange water

(Manufacturing method)

An aqueous phase and an alcohol phase were prepared and then mixed to obtain the desired lotion. Method 3: lotion

(Alcohol phase)

Ethanore 10. 0

Paramethoxycinnamic acid 2-ethylhexyl ester 0 · 5

2-Hydroxy mono 4-methoxybenzophenone 0.5

4-tert-butynole 4'-methoxydibenzoinomethane 0.5

2-Ethylhexyl 2-Cyanol 3, 3—

'Tote 0.5

Etenore 0.5

Preservative appropriate amount

Perfume appropriate amount

(Water phase)

Dipropylene glycol 6.0

Sonorebit 4.0

PEG1500 5.0

2— (2-Furylmethylene) one N ¹ , N ³ —Bis [2—

(2-Hydroxyethoxy) ethinole] malonamide 20 · 0

2-Phenylbenzimidazole 5-Sulphonic acid 3. 0 卜 Litananolamine 1. 8 Remaining water

(Manufacturing method)

Mix methylcellulose and quincese into a portion of ion-exchanged water and stir to prepare a viscous liquid. The remainder of the ion exchange water and the other aqueous phase components were mixed and dissolved, and the above viscous liquid was added thereto to obtain a uniform aqueous phase. After preparing the alcohol phase, it was added to the aqueous phase to obtain the desired lotion.

Formulation Example 4: Lotion

(Alcohol phase)

Ethanore 10. 0

Paramethoxycinnamic acid 2-ethylhexyl ester 0.5

4— tert Butinore 4 '-0.5

2 Ethylhexyl 2 Sihano 3, 3- 'Tote 0.5

• n—Tenore 0.5

Preservative appropriate amount

Perfume appropriate amount

(Water phase)

Dipropylene glycol 6.0

Sonorebit 4.0

PEG1500 5.0

2— (2-Furylmethylene) 1 N ¹ , N ³ bis [2—

(2 Hydroxyethoxy) ethyl] malonamide 7 · 0

N ¹ , N ³ bis [2- (2-hydroxyethoxy) ethinole]

—2— [(5 Methyl 2 furyl) methylene] malonamide 7.0

2 Phenylbenzimidazole-5 Sulfonic acid 3.0

卜 Litananolamine 1. 8 Ion exchange water

(Manufacturing method)

Formulation Example 5: Cream

Stearic acid 5.0

Stearino Leano Recone 4 · 0

Isopropyl myristate 18.0

Glycerin monostearate 3.0

Paramethoxycinnamic acid 2-ethylhexyl ester 10

2 Hydroxy 4-methoxybenzophenone 5.0

4 tert Butyl-4'-methoxydibenzoylmethane 3.0

2 Ethylhexyl 2 Cyanol 3, 3—

Diphenino rare tartrate 5.0

Propylene glycol 10.0

2— (2-Furylmethylene) 1 N ¹ , N ³ bis [2—

(2 Hydroxyethoxy) ethyl] malonamide 5 · 0

2-Phenylbenzimidazole 5 sulfonic acid 3.

卜 Litananolamine 1. 8

4, 5 Dimorpholino 3 Hydroxypyridazine 0.2

Potassium hydroxide 0.2

Sodium bisulfite 0. 01

Preservative appropriate amount

Perfume appropriate amount

Ion exchange water (Manufacturing method)

The water phase component was added to ion-exchanged water to dissolve it, and it was heated and kept at 70 ° C (water phase). The other components were mixed, heated and melted and kept at 70 ° C (oil phase). The oil phase was gradually added to the aqueous phase to pre-emulsify it, and the mixture was uniformly emulsified with a homomixer and then cooled to 30 ° C. with stirring to obtain the desired term.

Formulation Example 6: Cream

5. 0

Cornole 4.0

Glance 18.0

3. 0

Paramethoxycinnamic acid 2-ethylhexyl ester 10.0

2-Hydroxy-4-methoxybeh: 5.0

4— tert Butinore 4 '-3.0

2 Ethylhexyl 2 Sihano 3, 3-Diphenino rare tarate 10.

Propylene glycolate 10.0

N ¹ , N ³ bis [2- (2-hydroxyethoxy) ethinole]

—2— [(5 Methyl 2 furyl) methylene] malonamide 3.0

2— (2-Furylmethylene) 1 N ¹ , bis [2—

(2 Hydroxyethoxy) ethyl] malonamide 3 · 0

2 Phenylbenzimidazole-5 Sulfonic acid 3.0

Sodium hydroxide 0.4

Terephthalylidene> 0.5

4, 5—Dimonoreforino 0.2

Potassium hydroxide 0.2

Bisulfite-0.01

Preservative

Fragrance Ion exchange water

(Manufacturing method)

The aqueous phase component was added to ion-exchanged water to dissolve it, and heated to 70 ° C (aqueous phase). The other components were mixed, heated and melted and kept at 70 ° C (oil phase). The oil phase was gradually added to the water phase to pre-emulsify it, and the mixture was uniformly emulsified with a homomixer and then cooled to 30 ° C. with stirring to obtain the desired term.

Formulation Example 7: Cream

Stearic acid 6.0

Sorbitan monostearate 2.0 propylene glycol 10.0

2— (2-Furylmethylene) 1 N ¹ , N ³ bis [2—

(2-Hydroxyethoxy) ethinole] malonamide 10 · 0

2-Phenylbenzimidazole 5 sulfonic acid 3.

Sodium hydroxide 0.4

Glycerin trioctanoate 10 · 0

Squalene 5 · 0

Sodium bisulfite 0. 01

Ethylparaben 0.3

Perfume appropriate amount

Ion exchange water

(Manufacturing method)

Propylene glycol and 2- (2-furylmethylene) N ¹ , N bis [2- (2-hydroxyethoxy) ethinole] malonamide, 2-phenylbenzimidazole-5 sulfonic acid, sodium hydroxide were added to ion-exchanged water. Dissolved and heated to 70 ° C (aqueous phase). The other ingredients were mixed, heated and melted and kept at 70 ° C (oil phase). The oil phase was gradually added to the aqueous phase, pre-emulsified, and uniformly emulsified with a homomixer, and then cooled to 30 ° C. with stirring to obtain the desired cream. Formulation Example 8: Cream

Fragrance

Ion exchange water

(Manufacturing method)

Propylene glycol and N ¹ , N ³ -bis [2- (2-hydroxyethoxy) ethyl] -2-2-[(5 methyl-2-furyl) methylene] malonamide are dissolved in ion-exchanged water, heated to 70 ° C maintained (aqueous phase). The other ingredients were mixed, heated and melted and kept at 70 ° C (oil phase). The oil phase was gradually added to the aqueous phase, pre-emulsified, and uniformly emulsified with a homomixer, and then cooled to 30 ° C with stirring to obtain the desired cream.

Formulation Example 9: Emulsion

Stearic acid 2.5

Cetino Renore = 1 = 1

Vaseline 5.0

Liquid paraffin 10.0

POE (10) Monooleate 2 · 0

Paramethoxycinnamic acid 2 Ethylhexyl ester 3 · 0

2 Hydroxy 4-methoxybenzophenone 2.0

4 tert Butyl-4'-methoxydibenzoylmethane 2.0 2 Ethylhexyl 2 Cyanol 3, 3—

Diphenino rare tartrate 5.0

PEG1500 3.0

Triethanolamine 1 0

2— (2-Furylmethylene) 1 N ¹ , N ³ bis [2—

(2-Hydroxyethoxy) ethinole] malonamide

N ¹ , N ³ —bis [2- (2-hydroxyethoxy) ethyl]

2 -— [(5 Methyl 2 furyl) methylene] malonamide

2-Phenylbenzimidazole 5 sulfonic acid

Sodium hydroxide 0.4

0.5

4, 5-Dimorpholino 3-hydroxypyridazine 0.1

Sodium bisulfite 0. 01

Yechinoreno Raven 0. 3

Carboxybule polymer 0.05

Perfume appropriate amount

Ion exchange water

(Manufacturing method)

Carboxybule polymer was dissolved in a small amount of ion-exchanged water (A phase). The aqueous phase component was added to the remainder of the ion exchange water, dissolved by heating and kept at 70 ° C (aqueous phase). The other ingredients were mixed, heated and melted, and kept at 70 ° C (oil phase). The oil phase was added to the aqueous phase for preliminary emulsification, and the A phase was added and uniformly emulsified with a homomixer, and then cooled to 30 ° C. with stirring to obtain the desired emulsion.

Formulation Example 10: Emulsion

Stearic acid 2.5

Cetino Renore = 1 = 1

Vaseline 5.0 2. 0

Paramethoxycinnamic acid 2 Ethylhexyl ester 3 · 0

2 Hydroxy-4-methoxybe: eh 2. 0

4— tert Butinore 4 '-2. 0

2 Ethylhexyl 2 Sihano 3, 3-Diphenenorea talelate 5.0

PEG1500 3.0

Triethanolamine 0

N ¹ , N ³ bis [2- (2-hydroxyethoxy) ethinole]

—2— [(5 Methyl 2 furyl) methylene] malonamide 3.0

2 Phenylbenzimidazole-5 Sulfonic acid 3.0

Triethanolamine 1.8

0.5

4, 5-Dimorpholino 3-hydroxypyridazine 0.1

Sodium bisulfite 0. 01

Yechinoreno Raven 0. 3

Carboxybule polymer 0.05

Perfume appropriate amount

Ion exchange water

(Manufacturing method)

Carboxybule polymer was dissolved in a small amount of ion-exchanged water (A phase). The aqueous phase component was added and dissolved by heating and kept at 70 ° C (aqueous phase). The other ingredients were mixed, heated and melted, and kept at 70 ° C (oil phase). The oil phase was added to the aqueous phase for preliminary emulsification, and the A phase was added and uniformly emulsified with a homomixer, and then cooled to 30 ° C. with stirring to obtain the desired emulsion.

Formulation Example 11: Gier

95 ^_0/0 Etanonore 10.0

Dipropylene glycol 15.0

Ethenore 2.0 Canolepoxy bininole polymer 1. 0

Sodium hydroxide 0.55

2— (2-Furylmethylene) 1 N ¹ , N ³ bis [2—

(2-Hydroxyethoxy) ethinole] malonamide 1.0

2 Phenylbenzimidazole-5 Sulfonic acid 1.0

Methylparaben 0.1

Perfume appropriate amount

Ion exchange water

(Manufacturing method)

Carboxybule polymer was uniformly dissolved in ion-exchanged water (A phase). POE (50) oleyl ether was dissolved in 95% ethanol and added to Phase A. After adding components other than sodium hydroxide, sodium hydroxide was added to neutralize and thicken to obtain the intended jewel. Formulation Example 12: Gier

95 ^_0/0 Etanonore 10.0

Dipropylene glycol 15.0

POE (50) oleyl ether 2 · 0

Canolepoxy bininole polymer 1. 0

Sodium hydroxide 0.55

N ¹ , N ³ bis [2- (2-hydroxyethoxy) ethinole]

—2— [(5 Methyl 2 furyl) methylene] malonamide 5.0

2— (2-Furylmethylene) 1 N ¹ , N ³ bis [2—

(2 Hydroxyethoxy) ethyl] malonamide 5 · 0

2 Phenylbenzimidazole-5 Sulfonic acid 1.0

Methylparaben 0.2

Perfume appropriate amount

Ion exchange water

(Manufacturing method)

Carboxybule polymer was uniformly dissolved in ion-exchanged water (A phase). 95% ethanol POE (50) oleyl ether was dissolved in the solution and added to Phase A. After adding components other than sodium hydroxide, sodium hydroxide was added to neutralize and thicken to obtain the intended jewel.

(Phase A)

95 ^_0/0 Etanonore 10.0

Paramethoxycinnamic acid 2-ethylhexyl ester 0

2 Hydroxy-4-methoxy bee 0.5

4— tert Butinore 4 0. 5

2 Ethylhexyl 2 Cyannow 3, 3

Eat 0.5

One point 1. 0

Metelparaben 0.15

None

(Phase B)

Potassium hydroxide 0.1

(Phase C)

2— (2-Furylmethylene) one N ¹ , N ³ bis [2

(2-Hydroxyethoxy) ethinole] malonamide 10.0

N ¹ , N ³ bis [2- (2-hydroxyethoxy) ethinole]

—2— [(5 Methyl 2 furyl) methylene] malonamide 10 · 0

2 Phenylbenzimidazole-5 Sulfonic acid 3.0

Sodium hydroxide 0.4

5. 0

Dipropylene glycol 10.0

2. 0

Bisulfite-0.03

Carboxybule polymer 0.2

Remaining water (Manufacturing method)

A phase and C phase were uniformly dissolved, and solubilized by adding A phase to C phase. Next, Phase B was added and mixed to obtain the desired serum.

Formulation Example 14: Essence

(Phase A)

95 ^_0/0 Etanonore 10.0

Paramethoxycinnamic acid 2-ethylhexyl ester 1.0

4— tert Butinore 4 '-0.5

2 Ethylhexyl 2 Cyannow 3, 3

Diphneino Realtari 'Rate 0.5

POE (20) Octinored 'Decanore 1.0

Methylparaben 0.15

Nonteninoleetinoreetenore 0. 1

(Phase B)

Potassium hydroxide 0.1

(Phase C)

N ¹ , N ³ bis [2- (2-hydroxyethoxy) ethinole]

—2— [(5 Methyl 2 furyl) methylene] malonamide 5.0

2 Phenylbenzimidazole-5 Sulfonic acid 3.0

卜 Litananolamine 1. 8

Glycerin 5.0

Dipropylene glycol 10.0 Sodium bisulfite 0.03

Canolepoxy bininole polymer 0.2

Ion exchange water

(Manufacturing method)

A phase and C phase were uniformly dissolved, and solubilized by adding A phase to C phase. Then phase B And mixed to obtain the desired serum.

Formulation Example 15: Self-Tanning Emano Resion

(Part 1)

2 Ethylhexyl 2 Cyanol 3, 3 Diphenyl acrylate 5.0

Stearic acid PEG-5 glycerin 1.0

Stearic acid PEG—60 Glycerin 2 · 0

Cyclomethicone 5.0

Diisopropyl sebacate 5.0

Behenino Reno Conoret 2. 0

Stearnino Reno Conoret 1. 0

Hydrogenated palm oil 2.0

Perfume appropriate amount

(Part 2)

2— (2-Furylmethylene) 1 N ¹ , N ³ bis [2—

(2 Hydroxyethoxy) ethyl] malonamide 5.0

N ¹ , N ³ bis [2- (2-hydroxyethoxy) ethinole]

—2— [(5 Methyl 2 furyl) methylene] malonamide 5 · 0

Dihydroxyacetone 5.0

Dipotassium glycyrrhizinate 0.01

Ethanore 5.0

1, 3 Butylene glycol 5.0

EDTA- 3Na 0.1

Sodium pyrosulfite 0.1

Noraben moderate weight

Ion exchange water

(Manufacturing method)

Part 1 that was uniformly dissolved at 70 ° C was added to part 2 that was uniformly dissolved at 60 ° C, and emulsified. Thereafter, it was cooled to obtain the desired self-tanning emulsion. [0081] Formulation Example 16: Pack

(Phase A)

Dipropylene glycol 5 · 0

POE (60) hydrogenated castor oil 5 0

(Phase B)

Olive oil 5 · 0

Tocopherolate acetate 0.2

Ethylparaben 0.2

Fragrance 0.2

(Phase C)

N ¹ , N ³ —bis [2- (2-hydroxyethoxy) ethyl]

—2— [(5 Methyl 2 furyl) methylene] malonamide 0 · 1

Sodium bisulfite 0.03

Polybunore Norenore (Genity 90, degree of polymerization 2000) 13. 0

Ethanore 7.0

Ion exchange water

(Manufacturing method)

A phase, B phase, and C phase were uniformly dissolved, and B phase was added to A phase to solubilize. This was then added to Phase C and mixed to obtain the desired pack.

[0082] Formulation Example 17: Pack

(Phase A)

Dipropylene glycol 5.0

POE (60) hydrogenated castor oil 5 0

(Phase B)

Olive oil 5 · 0

Tocopherol acetate 0.2

Ethylparaben 0.2

Fragrance 0.2 (c phase)

2— (2-Furylmethylene) 1 N ¹ , N ³ bis [2—

(2-Hydroxyethoxy) ethinole] malonamide 0 · 1

N ¹ , N ³ —bis [2- (2-hydroxyethoxy) ethyl]

—2 [(5-Methyl 2-furyl) methylene] malonamide 0.1

2 Phenylbenzimidazole-5 Sulfonic acid 0.3

Trietanoramine 0. 18

Sodium bisulfite 0.03

Polyvinylidene / Rarenochozore (Ken f90 degree, degree of polymerization 2000) 13. 0

Ethanol 7 0

Ion exchange water

(Manufacturing method)

A phase, B phase, and C phase were uniformly dissolved, and B phase was added to A phase to solubilize. This is then added to Phase C and mixed to obtain the desired

几方 Example 18: Liquid

(Oil phase)

: π

2. 0

Vaseline 2.5

Deodorized liquid lanolin 1.5

Evening primrose oil 2.0

Isopropyl myristate 5.0

Glycerol monooleate 2.0

2 Ethylhexyl 2 Cyan 3, 3- 'enyl attalylate 5.0

P〇E (60) Hardening castor 2.0

Tocopheronole acetate 0. 05

Ethinoreno Raven 0.2

Butinoreparaben 0.1 Fragrance

(Water phase)

N ¹ , N ³ —bis [2- (2-hydroxyethoxy) ethyl]

—2— [(5 Methyl 2 furyl) methylene] malonami ί 5. 0

4, 5-Dimorpholino 3-hydroxypyridazine 0. 05

Bisulfite-0.01

5. 0

0. 01

Canolepoxy bininole polymer 0.2

Potassium hydroxide 0.2

Ion exchange water

(Manufacturing method)

The oil phase and the aqueous phase were each dissolved at 70 ° C. The oil phase was added to the aqueous phase, emulsified with an emulsifier, and then cooled to 30 ° C. with a heat exchanger to obtain the desired emulsion.

因 Introducing Baud 1

15. 0

(2) Sericite 10.0

(3) Spherical nylon powder 10.0

(4) Porous anhydrous anhydride powder 15.0

(5) Boron nitride 5.0

(6) Titanium dioxide 5.0

(7) Iron oxide 3.0

(8) Zinc stearate 5.0

(9) 2— (2 Furylmethylene) one N ¹ , N ³ bis [2.

(2-Hydroxyethoxy) ethinole] malonamide 1.0

(10) Liquid paraffin residue

(11) 2-ethylhexyl 2 cyano 3, 3— 15. 0

. Five

(14) Preservative appropriate amount

(15) Fragrance proper amount

(Manufacturing method)

The components (1) to (8) were mixed and ground. To this, a mixture of the components (9) to (; 15) was added and stirred and mixed. This was molded into a container to obtain the desired solid:

Formulation Example 20: Solid powdery:

15. 0

(2) Sericite 10.0

(3) Spherical nylon powder 10.0

(4) Porous anhydrous anhydride powder 15.0

(5) Boron nitride 5.0

(6) Titanium dioxide 5.0

(7) Iron oxide 3.0

(8) Zinc stearate 5.0

(Θ) Ν ¹ , Ν ³ —Bis [2- (2-hydroxyethoxy) ethyl]

—2— [(5 Methyl 2 furyl) methylene] malonamide 0

(10) 2- (2-Furylmethylene) Ν ¹ , Ν ³ bis [2—

(2-Hydroxyethoxy) ethinole] malonamide 0

(11) Flow remainder

15. 0

1. 5

(14) Preservative appropriate amount

(15) Fragrance proper amount

(Manufacturing method)

The components (1) to (8) were mixed and ground. This is a mixture of the components (9) to (; 15) Were mixed with stirring. This was molded into a container to obtain the desired fixation.

Formulation Example 21: Water-in-oil emulsification foundation

(1) Spherical nylon 10.0

(2) Porous anhydrous anhydride powder 8.0

(3) Titanium mica 2.0

(4) Silicone-treated sericite 2.0

(5) Silicon treatment My power 12.0

(6) Silicone-treated titanium dioxide 5.0

(7) Silicone-treated iron oxide 2.0

(8) Residual ion exchange water

(9) 2— (2 Furylmethylene) 1 Ν ¹ , Ν ³ bis [2—

(2-Hydroxyethoxy) ethinole] malonamide 5.0

18. 0

5. 0

0

(13) Polyoxyethylene-modified dimethylpolysiloxane 2.0

(14) Paramethoxycinnamic acid 2-ethylhexyl ester 3.0

(15) 2-Hydroxy-4-methoxybenzoph 1.0

(16) 4-tert-Butyl-4'-Methoxyjibe: 0.5

0.5

(18) 2-ethylhexyl 2 cyano 3, 3—

Diphneino rare tartrate 0.5

(19) Preservative

(20) Fragrance

(Manufacturing method)

The components (10) to (20) were uniformly mixed and dissolved. : Mixed and crushed hi) to (7) were added and dispersed. To this dispersion, (9) dissolved in (8) was added and emulsified. this Into a container to obtain the desired water-in-oil emulsion foundation,

Formulation Example 22: Water-in-oil emulsion foundation

(1) Spherical nylon 10.0

(2) Porous anhydrous anhydride powder 8.0

(3) Titanium mica 2.0

(4) Silicone-treated sericite 2.0

(5) Silicon treatment My power 12.0

(6) Silicone-treated titanium dioxide 5.0

(7) Silicone-treated iron oxide 2.0

(8) Residual ion exchange water

(Θ) Ν ¹ , Ν ³ —Bis [2- (2-hydroxyethoxy) ethyl]

—2— [(5 Methyl 2 furyl) methylene] malonamide 3.0

(10) 2- (2-Furylmethylene) Ν ¹ , Ν ³ bis [2—

(2-Hydroxyethoxy) ethinole] malonamide 3.0

18. 0

5. 0

0

(14) Polyoxyethylene modified dimethylpolysiloxane 2.0

(15) Paramethoxy-cinnamic acid 2 ethyl ester: xyl distenole 3.0

(16) 2 Hydro: C 4-Methoxyben: / Fueno: 1.0

(17) 4— tert—-Butinole 4′-Methoxy ^ Be, C / Inolemeta: 0.5

(18) terephthalididene strength flusulfo; acid 0., 5

(19) 2-ethylhexyl 2 cyano 3, 3—

Diphneino Rare Talate 0 · 5

(20) Preservative appropriate amount

(21) Fragrance appropriate amount

(Manufacturing method)

The components (11) to (21) were uniformly mixed and dissolved. To this, mixed and crushed (1) to (7) In addition, it was dispersed. To this dispersion, (9) and (10) dissolved in (8) were added and emulsified. This was filled in a container to obtain the desired water-in-oil type emulsion foundation.

(1) Talc residue

(2) Sericite 10

(3) Spherical nylon powder 10.0

(4) Boron nitride 5.0

(5) Iron oxide 3.0

(6) Magnesium carbonate 5.0

(7) Screening 3.0

(8) Glycerin triisooctanoate 2.0

(9) Sorbitan sesquioleate 2.0

(10) 2-ethylhexyl 2 cyano 3, 3—

Diphneino Rare Talate 0 · 5

(11) 2- (2-Furylmethylene) N ¹ , N ³ bis [2—

(2 Hydroxyethoxy) ethyl] malonamide 0 · 5

(12) Preservative appropriate amount

(13) Fragrance proper amount

(Manufacturing method)

The components (1) to (6) were mixed and ground. To this, a mixture of components (7) to (; 13) was added and mixed by stirring to obtain the desired white powder.

Formulation Example 24: Eye Shadow

(3) Spherical nylon powder 10.0

(4) Boron nitride 5.0

(5) Iron oxide 3.0

(6) Titanium oxide coating My strength 5.0 3. 0

(8 2.0

2. 0

(10) 2-ethylhexyl 2 cyano 3, 3-

'Toe 1.0

(11) N ¹ , N "—bis [2- (2-hydroxyethoxy) ethinole]

—2— [(5 Methyl 2 furyl) methylene] malonamide 0 · 3

(12) Preservative appropriate amount

(13) Fragrance proper amount

(Manufacturing method)

The components (1) to (6) were mixed and ground. To this, a mixture of components (7) to (; 13) was added and mixed with stirring to obtain the desired eye shadow.

Formulation Example 25: Lipstick

(1) Carnavalou 0.5

5. 0

10. 0

Remaining

10. 0

20. 0

0.

(8) Paramethoxycinnamic acid 2-ethylhexyl ester

(9) 2 ethino hexino 2 cyan 3, 3—

Diphenino rare tartrate 5.0

(10) 2- (2-Furylmethylene) N ¹ , N ³ bis [2—

(2 Hydroxyethoxy) ethyl] malonamide 3 ·

(11) Macadamia nut oil fatty acid cholesterol ester 4

(12) Synthetic sodium silicate-magnesium 0.

(13) Hydrophobic silica 0.5 '' Water change 2.0

(15) Coloring agent appropriate amount

(16) Preservative appropriate amount

(17) Fragrance appropriate amount

(Manufacturing method)

(12) and (13) were dispersed in (11) heated to 60 ° C., and (10) and (14) were added thereto and stirred sufficiently. This was added to (1) to (9), which had been separately dissolved by heating, and stirred well. Further, (15) to (; 17) were added and dispersed and stirred, and then molded to obtain the desired lipstick.

Formulation Example 26: Lipstick

(I) Kanolena Parou 0/5

5. 0

10. 0

Remaining

10. 0

20. 0

0.5

(8) Paramethoxycinnamic acid 2-ethylhexyl ester 3.0

(9) 2 ethino hexino 2 cyan 3, 3—

Diphenino rare tartrate 5.0

(ΙΟ) Ν ¹ , N ³ bis [2- (2-hydroxyethoxy) ethinole]

—2— [(5 Methyl 2 furyl) methylene] malonamide 2 · 0

(II) 2- (2-Furylmethylene) N ¹ , N ³ bis [2—

(2 Hydroxyethoxy) ethyl] malonamide 3 · 0

(12) 2 Phenylbenzimidazole-5 Sulfonic acid 3 0

(13) Sodium hydroxide 0.4

(14) Macadamia nut oil fatty acid phytosterinole 4.0

(15) Synthetic sodium silicate Magnesium 0.5

(16) Hydrophobic silica 0.5 '' Water change 2.0

(18) Coloring agent appropriate amount

(19) Preservative appropriate amount

(20) Fragrance appropriate amount

(Manufacturing method)

(15) and (16) were dispersed in (14) heated to 60 ° C, and (10), (11), (12), (13), and (17) were added thereto and stirred sufficiently. This was added to (1) to (9), which had been dissolved by heating separately, and stirred sufficiently. Further, (18) to (20) were added, dispersed and stirred, and then molded to obtain the desired lipstick.

Formulation example 27: hair foam

(Stock solution formulation)

(1) Acrylic resin alkanolamine solution (50%) 8.0

(2) Polyoxyethylene hydrogenated castor oil

(3) Flow 5.0

3. 0

(5) Fragrance proper amount

(6) Preservative appropriate amount

(7) Ethanol 15

(8) 2— (2-Furylmethylene) 1 N ¹ , Bis [2—

(2-Hydroxyethoxy) ethyl] malonamide 7 · 0

(9) Residual ion exchange water

(Filling prescription)

(1) Stock solution 90

(2) Liquefied petroleum gas 10.0

(Manufacturing method)

Liquid paraffin was added to a dissolved mixture of glycerin and polyoxyethylene hydrogenated castor oil and uniformly emulsified with a homomixer. This was added to the solution of the other ingredients. For filling, the stock solution was filled into the can, and after filling the valve, gas was filled. [0093] Formulation Example 28: Hair foam

(Stock solution formulation)

(1) Acrylic resin alkanolamine solution (50%) 8.0

(2) Polyoxyethylene hydrogenated castor oil

(3) Liquid paraffin 5

(4) Glycerin 3.0

(5) Fragrance proper amount

(6) Preservative appropriate amount

(7) Ethanol 15.0

(8) Ν ³ -bis [2- (2 hydroxyethoxy) ethynole]

—2— [(5 Methyl 2 furyl) methylene] malonamide 3 · 0

(9) Residual ion exchange water

(Filling prescription)

(1) Stock solution 90.0

(2) Liquefied petroleum gas 10

(Manufacturing method)

Liquid paraffin was added to a dissolved mixture of glycerin and polyoxyethylene hydrogenated castor oil and uniformly emulsified with a homomixer. This was added to the solution of the other ingredients. For filling, the stock solution was filled into the can, and after filling the valve, gas was filled.

[0094] Formulation Example 29: Hair Liquid

(2) Polyoxyethylene hydrogenated castor oil 1.0

(3) Ethanol 50.0

(4) Fragrance proper amount

(5) Preservative appropriate amount

(6) Paramethoxycinnamic acid 2-ethylhexyl ester 2.0

(7) 2-ethylhexyl 2 cyano 3, 3—

5.0 (8) Dye proper amount

(9) 2-(2 Furylmethylene) N ¹ , N ³ bis [2—

(2-Hydroxyethoxy) ethyl] malonamide 2 · 0

(10) Residual ion exchange water

(Manufacturing method)

(1), (2), (4) to (7) were dissolved in (3) (ethanol phase). (8) and (9) were dissolved in (10) (aqueous phase). Add the aqueous phase to the ethanol phase and filter with filter paper to obtain the desired hair liquid

[0095] Formulation Example 30:-

(Stock solution formulation)

(1) Acrylic resin alkanolamine solution (50%) 7.0

(2) Cetino Reano Reconole 0 · 1

(3) Silicone oil 0-3

(4) Ethanol residue

(5) Fragrance proper amount

(6) N ³ —bis [2- (2 hydroxyethoxy) ethynole]

—2— [(5 Methyl 2 furyl) methylene] malonamide 1 · 0

(7) Ion exchange water 3

(Filling prescription)

(1) Stock solution 50

(2) Liquefied petroleum gas 50

(Manufacturing method)

Other components were added to ethanol, dissolved, and filtered. For filling, the stock solution was filled in the can, and after installation, the gas was filled.

[0096] Formulation Example 31: Hair Tonic

(1) 2— (2-Furylmethylene) 1 N ¹ , N ³ bis [2—

(2 Hydroxyethoxy) ethyl] malonamide 3 · 0

(2) Hardened castor oil ethylene oxide (40 mol) adduct 2 · 0 (3) Paramethoxycinnamic acid 2-ethylhexyl ester 3.0

(4) 2 Hydroxy-4-methoxybenzoph 3.0

(5) 4-tert-Butyl-4'-methoxyjibe: 3.0

Ten

(7) 2-ethylhexyl 2 cyano 3, 3—

Diphenino rare tartrate 5.0

(8) 2 Phenylbenzimidazole-5 Sulfonic acid 3

(9) Triethanolamine 1.8

(10) Ethanore 60

(11) Fragrance proper amount

(12) Residual ion exchange water

(Manufacturing method)

( ² ) to ( ⁷ ) were dissolved in (10) (ethanol phase). (1), (8), (9) were dissolved in (12) (aqueous phase). The ethanol phase and the aqueous phase were mixed, and (11) was added to obtain the target heatonic. Formulation Example 32

(1) N ¹ , N ³ —Bis [2- (2-hydroxyethoxy) ethinole]

—2— [(5 Methyl 2 furyl) methylene] malonamide 2. 0

(2) 2— (2-Furylmethylene) 1 N ¹ , N ³ bis [2—

(2-Hydroxyethoxy) ethinole] malonamide 2.0

(3) 2 phenylbenzimidazole-5 sulfonic acid 3.0

(4) Sodium hydroxide 0.4

(5) Hardened castor oil ethylene oxide (40 mol) adduct 2.

(6) Paramethoxycinnamic acid 2 ethylhexyl ester 3

(7) 2 Hydroxy 4-methoxybenzoph: r3.0

(8) 4-tert-Butyl-4'-Methoxyzibe 3.0

(9) 2 ethino hexino 2 cyan 3, 3—

Diphenino rare tartrate

(10) Ethanore 60 (11) Fragrance proper amount

(12) Residual ion exchange water

(Manufacturing method)

(5) to (9) were dissolved in (10) (ethanol phase). (1) to (4) were dissolved in (12) (aqueous phase). The ethanol phase and the aqueous phase were mixed, and (11) was added to obtain the target heatonic.

Claims

Claims [1] A compound represented by the following general formula (1): a compound and a salt thereof.

[Chemical 1]

one two Three

4 5 2 m n 6 6

[2] The compound of claim 1 and a salt thereof, wherein R and R are each represented by the following general formula (2): {(CH 2) 10} 1 H

2 2 2

Compounds and salts thereof.

[Chemical 2]

one two Three

Represents an alkyl group. )

[3] An ultraviolet absorber comprising the furylmethylenemalonamide compound and / or a salt thereof according to claim 1 or 2.

[4] A UV-absorbing composition comprising the furylmethylenemalonamide compound and / or salt thereof according to claim 1 or 2 as an active ingredient.

[5] A skin external preparation comprising the furylmethylenemalonamide compound and / or a salt thereof according to claim 1 or 2. 6. The skin external preparation according to claim 5, further comprising an inorganic powder.