Novel triazine derivative and salt thereof, and ultraviolet absorbent, external skin agent, and coating composition using the same

Abstract

To provide a 1,3,5-triazine derivative as a novel compound having a suitable ultraviolet absorption action and a salt thereof, and an ultraviolet absorbent and an external skin agent using the same.SOLUTION: The present invention provides a novel hydrophilic triazine derivative having ultraviolet absorption action, for example, represented by the following formula and a salt thereof, and an ultraviolet absorbent, an external skin agent, and a coating composition using the same.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a novel hydrophilic triazine derivative having an ultraviolet absorption action and a salt thereof, and an ultraviolet absorber, a skin external preparation, and a coating composition using the same.

Background Art

[0002] Ultraviolet rays are essential for the biosynthesis of vitamin D and are also used to promote blood circulation and metabolism in the living body and for sterilization and disinfection. On the other hand, when the skin is excessively exposed to ultraviolet rays, it can lead to skin cancer, accelerate skin aging, and cause spots, freckles, and wrinkles. In addition, various synthetic resins and paints such as polyethylene, polypropylene, PVC, and ABS resin will also cause deterioration of these synthetic resins and paints when excessively exposed to ultraviolet rays. Thus, exposure to excessive amounts of ultraviolet rays causes various adverse effects. To prevent such adverse effects, various ultraviolet absorbers have been developed and widely used.

[0003] Near ultraviolet rays, generally called "ultraviolet rays (UV)", can be roughly classified into UVA (wavelength 315 - 400 nm), UVB (wavelength 280 - 315 nm), and UVC (wavelength 200 - 280 nm) based on their wavelengths. Although UVC is UV derived from sunlight, it is significantly absorbed in the ozone layer or the like before reaching the ground, so it usually cannot reach the ground by passing through the ozone layer or the like.

[0004] It is said that UVA and UVB are mainly responsible for the occurrence of skin cancer, skin aging, and deterioration of synthetic resins and paints. Therefore, ultraviolet absorbers have been developed mainly for the purpose of absorbing mainly UVA or UVB.

[0005] As the effects of ultraviolet rays on the skin and the like have become clear, the demand for sunscreen cosmetics with a high ultraviolet ray blocking effect has been increasing. Generally, sunscreen cosmetics use ultraviolet ray scattering agents and ultraviolet ray absorbers for the purpose of blocking ultraviolet ray irradiation to the skin.

[0006] An ultraviolet ray scattering agent shields ultraviolet rays by scattering them, and conventionally, inorganic pigments such as zinc oxide, titanium oxide, kaolin, and calcium carbonate have been used. These can shield ultraviolet rays over a wide band, and since they are inert, they also have high skin safety and are more useful ultraviolet ray shielding agents.

[0007] However, although these inorganic pigments, particularly titanium oxide and zinc oxide, have a high ultraviolet ray shielding effect as described above, on the other hand, they also have a large covering power (hiding power), so when applied to the skin, the cosmetic film becomes white and causes whitening. For this reason, it has been proposed to use particulate titanium oxide and zinc oxide (see, for example, Patent Documents 1 to 3). It is known that the finer these particles are, the higher the ultraviolet ray shielding effect, and the higher the light transmittance in the visible light region, so the transparency increases.

[0008] In addition, these fine particles of inorganic pigments generally have high aggregability, and it is difficult to stably disperse them in a particulate state in a formulation system such as cosmetics. For this reason, the actual situation is that the expected ultraviolet ray shielding effect and transparency have not been obtained. In addition, since these particulate pigments have a high refractive index of light, when used in a large amount, the hiding property increases, and again whitening and the like occur, resulting in an unnatural makeup finish. Furthermore, due to the aggregation of the particles, problems in use such as hindering the spreadability of the cosmetics and causing a scratching feeling when applied to the skin occur. For this reason, the blending amount of these ultraviolet ray scattering agents is naturally limited, and cosmetics having a desired ultraviolet ray shielding effect have not been obtained.

Prior Art Documents

Patent Documents

[0009] [Patent Document 1] Japanese Patent Publication No. 47-42502 [Patent Document 2] Japanese Unexamined Patent Publication No. 49-00450 [Patent Document 3] Japanese Unexamined Patent Publication No. 64-07941 [Summary of the Invention] [Problems to be Solved by the Invention]

[0010] In view of such circumstances, an object of the present invention is to provide a novel 1,3,5-triazine derivative having a suitable ultraviolet absorption effect and a salt thereof.

[0011] Another object of the present invention is to provide an ultraviolet absorber, a skin external preparation, and a coating composition containing the above 1,3,5-triazine derivative and a salt thereof and having a suitable ultraviolet absorption effect. [Means for Solving the Problems]

[0012] As a result of intensive studies to solve the above problems, the present inventors have succeeded in creating a novel triazine derivative and a salt thereof shown below, and have found that the above object can be achieved by the above compound, thus completing the present invention.

[0013] That is, the present invention provides a compound or a salt thereof described below (hereinafter, may also be referred to as "compound" or "compound etc.").

[0014] [1] A 1,3,5-triazine derivative represented by any of general formulas (I) to (IV) or a salt thereof. [Chemical Formula] [Chemical Formula] [Chemical Formula] [Chemical formula] (In general formulas (I) to (IV), G 1 , G 2 , and G 3 each independently represents hydrogen, a linear or branched alkyl group having 1 to 12 carbon atoms which may be substituted, a linear or branched alkenyl group having 1 to 12 carbon atoms which may be substituted, a linear or branched alkynyl group having 1 to 12 carbon atoms which may be substituted, a polyoxyethylene group containing 1 to 8 ethylene oxide units which may be substituted, a polyoxypropylene group containing 1 to 8 propylene oxide units which may be substituted, or -X-Z-Y (wherein Y is present one or more times on Z, and when a plurality of Y are present (when there are a plurality of Y bonded to Z), the plurality of Y may be the same as or different from each other). However, among G 1 , G 2 , and G 3 , at least two of them are -X-Z-Y which may be the same as or different from each other. X is O, N, or S. Y is a sulfonic acid group, a hydroxyl group, a carboxyl group, an amino group, an alkylamino group, an ammonium group, an alkylammonium group, a phosphoric acid group, a phosphonic acid group, or a group corresponding to a salt thereof. Z is a linear or branched alkyl group having 1 to 8 carbon atoms, a linear or branched alkenyl group having 1 to 8 carbon atoms, a linear or branched alkynyl group having 1 to 8 carbon atoms, a polyoxyethylene group containing 1 to 4 ethylene oxide units, or a polyoxypropylene group containing 1 to 4 propylene oxide units. R 1 , R 2 , and R 3 each independently represents a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched alkyl group having 1 to 4 carbon atoms substituted with a hydroxyl group, and l, m, and n are each independently an integer from 0 to 4. When l is 2 or more, the plurality of R 1may be the same or different, and when m is 2 or more, there are a plurality of Rs 2 may be the same or different, and when n is 2 or more, there are a plurality of Rs 3 may be the same or different.)

[0015] [2] The 1,3,5 - triazine derivative or a salt thereof described in [1], represented by the general formula (I).

[0016] [3] The 1,3,5 - triazine derivative or a salt thereof described in [1], represented by the general formula (IV).

[0017] [4] In the above general formulas (I) to (IV), X is N, and Y is a sulfonic acid group, a hydroxyl group, an amino group, an alkylamino group, an ammonium group, an alkylammonium group, a phosphoric acid group, a phosphonic acid group, or a group corresponding to a salt thereof. The 1,3,5 - triazine derivative or a salt thereof described in [1].

[0018] [5] In the above general formula (I), X is N, and Y is a sulfonic acid group, a hydroxyl group, an amino group, an alkylamino group, an ammonium group, an alkylammonium group, a phosphoric acid group, a phosphonic acid group, or a group corresponding to a salt thereof. The 1,3,5 - triazine derivative or a salt thereof described in [2].

[0019] [6] In the above general formulas (I) to (IV), at least one of the one or more Ys present on Z is a hydroxyl group, and Z is a linear or branched alkyl group having 3 to 8 carbon atoms, a linear or branched alkenyl group having 1 to 8 carbon atoms, a linear or branched alkynyl group having 1 to 8 carbon atoms, a polyoxyethylene group containing 2 to 4 ethylene oxide units, or a polyoxypropylene group containing 1 to 4 propylene oxide units. The 1,3,5 - triazine derivative or a salt thereof described in [1].

[0020] [7] In the general formula (I), at least one of the Ys present on Z is a hydroxyl group, and Z is a linear or branched alkyl group having 3 to 8 carbon atoms, a linear or branched alkenyl group having 1 to 8 carbon atoms, a linear or branched alkynyl group having 1 to 8 carbon atoms, a polyoxyethylene group containing 2 to 4 ethylene oxide units, or a polyoxypropylene group containing 1 to 4 propylene oxide units. The 1,3,5-triazine derivative or a salt thereof according to [2].

[0021] [8] In the general formulas (I) to (IV), Y is a sulfonic acid group, a hydroxyl group, a carboxyl group, an alkylamino group, an ammonium group, an alkylammonium group, a phosphoric acid group, a phosphonic acid group, or a group corresponding to a salt thereof. The 1,3,5-triazine derivative or a salt thereof according to [1].

[0022] [9] In the general formula (I), Y is a sulfonic acid group, a hydroxyl group, a carboxyl group, an alkylamino group, an ammonium group, an alkylammonium group, a phosphoric acid group, a phosphonic acid group, or a group corresponding to a salt thereof. The 1,3,5-triazine derivative or a salt thereof according to [2].

[0023]

[10] In the general formulas (I) to (IV), at least one of the Ys present on Z is a group corresponding to a sodium salt, a potassium salt, or a triethanolamine salt. The 1,3,5-triazine derivative or a salt thereof according to [1].

[0024]

[11] In the general formula (I), at least one of the Ys present on Z is a group corresponding to a sodium salt, a potassium salt, or a triethanolamine salt. The 1,3,5-triazine derivative or a salt thereof according to any one of [2].

[0025]

[12] In the above general formulas (I) to (IV), G 1 , G 2 , and G 3 are all -X-Z-Y which are the same as or different from each other, the 1,3,5-triazine derivative or a salt thereof according to [1].

[0026]

[13] In the above general formula (I), G 1 , G 2 , and G 3 are all -X-Z-Y which are the same as or different from each other, the 1,3,5-triazine derivative or a salt thereof according to [2].

[0027]

[14] The 1,3,5-triazine derivative or a salt thereof according to any one of [1] to

[13] , which is water-soluble.

[0028] Further, the present invention provides an ultraviolet absorber described below.

[0029]

[15] An ultraviolet absorber containing the 1,3,5-triazine derivative or a salt thereof according to any one of [1] to

[13] .

[0030] Further, the present invention provides a topical skin composition described below.

[0031]

[16] A topical skin composition containing the 1,3,5-triazine derivative or a salt thereof according to any one of [1] to

[13] .

[0032] Further, the present invention provides a coating composition described below.

[0033]

[17] A coating composition containing the 1,3,5-triazine derivative or a salt thereof according to any one of [1] to

[13] .

[0034]

[18] The coating composition described in

[17] that is water-soluble.

[0035]

[19] The coating composition described in

[17] that contains water.

[0036] Furthermore, the present invention provides a coating layer described below.

[0037]

[20] A coating layer formed using the coating composition described in

[17] .

[0038] Furthermore, the present invention provides a coated body described below.

[21] A coated body that includes the coating layer described in

[20] .

[0039] Furthermore, the present invention provides a method for manufacturing a coating layer described below.

[0040]

[22] A method for manufacturing a coating layer that includes a step of drying the solvent of the coating composition described in

[17] . [Advantages of the Invention]

[0041] The 1,3,5-triazine derivative or a salt thereof of the present invention is a novel compound that is hydrophilic and has excellent ultraviolet absorption properties. It is possible to provide a 1,3,5-triazine derivative or a salt thereof that mainly has strong ultraviolet absorption characteristics in the vicinity of 280 to 315 nm.

[0042] Furthermore, since the ultraviolet absorber, external preparation for skin, and coating composition of the present invention contain the above novel 1,3,5-triazine derivative or a salt thereof, they have excellent hydrophilicity and ultraviolet absorption properties and are useful as an ultraviolet absorber, external preparation for skin, and coating composition. [Modes for Carrying Out the Invention]

[0043] Hereinafter, embodiments of the present invention will be described in detail.

[0044] [1,3,5-Triazine derivative or its salt] The 1,3,5-triazine derivative or its salt of the present invention is characterized by being represented by any one of general formulas (I) to (IV). [Chemical formula] [Chemical formula] [Chemical formula] [Chemical formula] (In general formulas (I) to (IV), G 1 , G 2 , and G 3 each independently represents hydrogen, a linear or branched alkyl group having 1 to 12 carbon atoms which may be substituted, a linear or branched alkenyl group having 1 to 12 carbon atoms which may be substituted, a linear or branched alkynyl group having 1 to 12 carbon atoms which may be substituted, a polyoxyethylene group containing 1 to 8 ethylene oxide units which may be substituted, a polyoxypropylene group containing 1 to 8 propylene oxide units which may be substituted, or -X-Z-Y (where Y exists one or more on Z, and when a plurality of Y exist, the plurality of Y may be the same or different from each other). However, among G 1 , G 2 , and G 3 , at least two of them are -X-Z-Y which may be the same or different from each other. X is O, N, or S. Y is a sulfonic acid group, a hydroxyl group, a carboxyl group, an amino group, an alkylamino group, an ammonium group, an alkylammonium group, a phosphoric acid group, a phosphonic acid group, or a group corresponding to their salts. Z is a linear or branched alkyl group having 1 to 8 carbon atoms, a linear or branched alkenyl group having 1 to 8 carbon atoms, a linear or branched alkynyl group having 1 to 8 carbon atoms, a polyoxyethylene group containing 1 to 4 ethylene oxide units, or a polyoxypropylene group containing 1 to 4 propylene oxide units. R 1 , R 2 , and R 3 each independently represents a linear or branched alkyl group having 1 to 4 carbon atoms or a linear or branched alkyl group having 1 to 4 carbon atoms substituted with a hydroxyl group, and l, m, and n are each independently an integer from 0 to 4. When l is 2 or more, a plurality of R 1 may be the same or different, and when m is 2 or more, a plurality of R 2 may be the same or different, and when n is 2 or more, a plurality of R 3 may be the same or different.)

[0045] As described above, in addition to the fact that cosmetics having a desired ultraviolet ray shielding effect have not been obtained so far, the lipophilic ultraviolet ray absorbers conventionally used in sunscreens and the like have the property of not falling off even when water touches the skin (lipophilicity), and basically a dedicated detergent is required to remove them from the skin. In recent years, as the damage to the skin caused by ultraviolet rays has become apparent, sunscreens have come to be used in daily life, and it has been demanded that sunscreens can be easily washed with water. Furthermore, lipophilic compounds have problems with the effects on products such as solubility and stability in cosmetics, particularly with respect to aqueous solvents, due to an increase in the blending amount.

[0046] On the other hand, according to the 1,3,5-triazine derivative (s-triazine derivative) or a salt thereof of the present invention, since it has the structures represented by the above general formulas (I) to (IV), it is excellent in water solubility, has strong ultraviolet ray absorption characteristics, and is excellent in ultraviolet ray absorption action.

[0047] In the above 1,3,5-triazine derivative or a salt thereof, in general formulas (I) to (IV), G 1, G 2 , and G 3 is, independently of one another, hydrogen, a linear or branched alkyl group having 1 to 12 carbon atoms which may be substituted, a linear or branched alkenyl group having 1 to 12 carbon atoms which may be substituted, a linear or branched alkynyl group having 1 to 12 carbon atoms which may be substituted, a polyoxyethylene group containing 1 to 8 ethylene oxide units which may be substituted, a polyoxypropylene group containing 1 to 8 propylene oxide units which may be substituted, or represents -X-Z-Y (wherein Y is present one or more times on Z, and when a plurality of Y are present, the plurality of Y may be the same as or different from one another). However, among G 1 , G 2 , and G 3 , at least two of them are -X-Z-Y which may be the same as or different from one another. By having the above configuration, it has an excellent ultraviolet absorption effect and becomes excellent in hydrophilicity.

[0048] Examples of the linear or branched alkyl group having 1 to 12 carbon atoms which may be substituted in the above G 1 , G 2 , and G 3 include, for example, methyl group, ethyl group, 1-propyl group, 1-methyl-1-ethyl group, 1-butyl group, 1-methyl-1-propyl group, 1,1-dimethyl-1-ethyl group, 2-methyl-1-propyl group, 1-pentyl group, 2-pentyl group, 1-hexyl group, 2-hexyl group, 1-heptyl group, 2-heptyl group, 1-octyl group, 2-octyl group, 1-nonyl group, 2-nonyl group, 1-decyl group, 2-decyl group, 1-undecyl group, 2-undecyl group, 1-dodecyl group, 2-dodecyl group, 1-tridecyl group, 2-tridecyl group, 1-tetradecyl group, 2-tetradecyl group, etc. From the viewpoint of being able to exhibit a higher absorbance (absorbance of ultraviolet rays per mass), the number of carbon atoms of the alkyl group is preferably an integer of 1 to 8, and more preferably an integer of 1 to 4.

[0049] The above G 1 , G 2 , and G3 As the optionally substituted linear or branched alkenyl group having 1 to 12 carbon atoms in the above, for example, an ethenyl group (ethene group), an allyl group (propene group), a 1-methyl-vinyl group, a 1-butenyl group, a 2-butenyl group, a 2-pentenyl group, etc. can be mentioned. From the viewpoint of being able to exhibit a higher absorbance (absorbance of ultraviolet rays per mass), the number of carbon atoms of the alkenyl group is preferably an integer of 1 to 8, and more preferably an integer of 1 to 4.

[0050] The above G 1 、G 2 、and G 3 As the optionally substituted linear or branched alkynyl group having 1 to 12 carbon atoms in the above, for example, an ethynyl group, a propynyl group, a butynyl group, etc. can be mentioned. From the viewpoint of being able to exhibit a higher absorbance (absorbance of ultraviolet rays per mass), the number of carbon atoms of the alkynyl group is preferably an integer of 1 to 8, and more preferably an integer of 1 to 4.

[0051] The above G 1 、G 2 、and G 3 As the polyoxyethylene group containing 1 to 8 ethylene oxide units which may be substituted in the above G p -H, -(CH2CH2O) p -CH2CH3, -O-(CH2CH2O) p -H, O-(CH2CH2O) p -CH2CH3, etc. can be mentioned. Here, p is an integer of 1 to 8. From the viewpoint of being able to exhibit a higher absorbance (absorbance of ultraviolet rays per mass), p is preferably an integer of 1 to 4, and more preferably an integer of 1 to 3.

[0052] The above G 1 、G 2 、and G 3 As the polyoxypropylene group containing 1 to 8 propylene oxide units which may be substituted in the above, for example, -(CH(CH3)CH2O) q-H, -(CH(CH3)CH2O) q -CH(CH3)CH3, -O-(CH(CH3)CH2O) q -H, O-(CH(CH3)CH2O) q -CH(CH3)CH3, -(CH2CH(CH3)O) q -H, -(CH2CH(CH3)O) q -CH(CH3)CH3, -O-(CH2CH(CH3)O) q -H, O-(CH2CH(CH3)O) q -CH(CH3)CH3 and the like can be mentioned. Here, q is an integer from 1 to 8. From the viewpoint of being able to exhibit a higher absorbance (ultraviolet absorbance per mass), q is preferably an integer from 1 to 4, and more preferably an integer from 1 to 3.

[0053] Also, in the above G 1 , G 2 , and G 3 , at least two of them may be -X-Z-Y which may be the same as or different from each other.

[0054] Also, the above G 1 , G 2 , and G 3 can all be -X-Z-Y which may be the same as or different from each other.

[0055] In the above -X-Z-Y, X is O, N, or S. In a plurality of -X-Z-Y chains, X may be the same as or different from each other.

[0056] In the above -X-Z-Y, Y is a sulfonic acid group, a hydroxyl group, a carboxyl group, an amino group, an alkylamino group, an ammonium group, an alkylammonium group, a phosphate group, a phosphonic acid group, or a group corresponding to a salt thereof. In a plurality of -X-Z-Y chains, Y may be the same as or different from each other.

[0057] Also, there may be a plurality of Ys on Z. As an example of the case where there are a plurality of Ys on Z, for example, when two or three hydroxyl groups (or -O - groups or alkoxide end groups) are bonded (present) on the same Z chain, or when a hydroxyl group and a sulfonic acid group (or sulfonate group) are bonded on the same Z chain, etc. can be cited.

[0058] More specifically, as the above Y, for example, -SO3H, -OH, -COOH, -NH2, -NR 4 R 5 , -PO3H and other alkyl phosphate ester groups, phosphonic acid groups, and -OA, -SO3A, -COOA, -NR 6 R 7 R 8 groups corresponding to their salts such as B can be cited.

[0059] The above A is a counter cation, and for example, a monovalent cation and a divalent cation can be cited. As the above A, typically, alkali metal salts such as sodium and potassium, and triethanolammonium cation can be appropriately used.

[0060] The above B is a counter anion, and for example, a monovalent cation and a divalent cation can be appropriately used. As the above B, typically, hydroxide ion, chloroanion, etc. can be cited.

[0061] In the above -NR 4 R 5 , R 4 and R 5 are, for example, hydrogen or a linear or branched alkyl group having 1 to 4 carbon atoms. When both R 4 and R 5 are hydrogen, it is an amino group, and in other cases, it is an alkylamino group. When both R 4 and R 5As the linear or branched alkyl group having 1 to 4 carbon atoms, for example, a methyl group, an ethyl group, a 1-propyl group, a 1-methyl-1-ethyl group, a 1-butyl group, a 1-methyl-1-propyl group, a 1,1-dimethyl-1-ethyl group, a 2-methyl-1-propyl group, etc. can be mentioned. From the viewpoint of being able to exhibit a higher absorbance (absorbance of ultraviolet rays per mass), R 4 and R 5 are preferably hydrogen or an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 to 2 carbon atoms. R 4 and R 5 may be the same as or different from each other.

[0062] In the above -NR 6 R 7 R 8 B, R 6 , R 7 , and R 8 are, for example, hydrogen or a linear or branched alkyl group having 1 to 4 carbon atoms. When R 6 , R 7 , and R 8 are all hydrogen, it is an ammonium group, and in other cases, it is an alkylammonium group. As the linear or branched alkyl group having 1 to 4 carbon atoms in R 6 , R 7 , and R 8 , for example, a methyl group, an ethyl group, a 1-propyl group, a 1-methyl-1-ethyl group, a 1-butyl group, a 1-methyl-1-propyl group, a 1,1-dimethyl-1-ethyl group, a 2-methyl-1-propyl group, etc. can be mentioned. From the viewpoint of being able to exhibit a higher absorbance (absorbance of ultraviolet rays per mass), R 6 , R 7 , and R 8 are preferably hydrogen or an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 to 2 carbon atoms. R 6 , R 7 , and R 8 may be the same as or different from each other.

[0063] In the above -X-Z-Y, Z is a linear or branched alkyl group having 1 to 8 carbon atoms, a linear or branched alkenyl group having 1 to 8 carbon atoms, a linear or branched alkynyl group having 1 to 8 carbon atoms, a polyoxyethylene group containing 1 to 4 ethylene oxide units, or a polyoxypropylene group containing 1 to 4 propylene oxide units. In a plurality of -X-Z-Y chains, Z may be the same or different from each other.

[0064] Examples of the linear or branched alkyl group having 1 to 8 carbon atoms in the above Z include a methyl group, an ethyl group, a 1 - propyl group, a 1 - methyl - 1 - ethyl group, a 1 - butyl group, a 1 - methyl - 1 - propyl group, a 1,1 - dimethyl - 1 - ethyl group, a 2 - methyl - 1 - propyl group, a 1 - pentyl group, a 2 - pentyl group, a 1 - hexyl group, a 2 - hexyl group, a 1 - heptyl group, a 2 - heptyl group, a 1 - octyl group, a 2 - octyl group, etc. From the viewpoint of exhibiting higher absorbance (absorbance of ultraviolet rays per mass), the number of carbon atoms of the alkyl group is preferably an integer of 1 to 4, and more preferably an integer of 1 to 3.

[0065] Examples of the linear or branched alkenyl group having 1 to 8 carbon atoms in the above Z include an ethenyl group (ethene group), an allyl group (propene group), a 1 - methyl - vinyl group, a 1 - butenyl group, a 2 - butenyl group, a 2 - pentenyl group, etc. From the viewpoint of exhibiting higher absorbance (absorbance of ultraviolet rays per mass), the number of carbon atoms of the alkenyl group is preferably an integer of 1 to 4, and more preferably an integer of 1 to 3.

[0066] Examples of the linear or branched alkynyl group having 1 to 8 carbon atoms in the above Z include an ethynyl group, a propynyl group, a butynyl group, etc. From the viewpoint of exhibiting higher absorbance (absorbance of ultraviolet rays per mass), the number of carbon atoms of the alkynyl group is preferably an integer of 1 to 4, and more preferably an integer of 1 to 3.

[0067] In the above Z, as the polyoxyethylene group containing 1 to 4 ethylene oxide units, for example, -(CH2CH2O) p’ -H, -(CH2CH2O) p’ -CH2CH3, -O-(CH2CH2O) p’ -H, O-(CH2CH2O) p’ -CH2CH3 and the like can be mentioned. Here, p' is an integer of 1 to 4. From the viewpoint of exhibiting higher absorbance (absorbance of ultraviolet rays per mass), p' is preferably an integer of 1 to 3, and more preferably an integer of 1 to 2.

[0068] In the above Z, as the polyoxypropylene group containing 1 to 4 propylene oxide units, for example, -(CH(CH3)CH2O) q’ -H, -(CH(CH3)CH2O) q’ -CH(CH3)CH3, -O-(CH(CH3)CH2O) q’ -H, O-(CH(CH3)CH2O) q’ -CH(CH3)CH3, -(CH2CH(CH3)O) q’ -H, -(CH2CH(CH3)O) q’ -CH(CH3)CH3, -O-(CH2CH(CH3)O) q’ -H, O-(CH2CH(CH3)O) q’ -CH(CH3)CH3 and the like can be mentioned. Here, q' is an integer of 1 to 4. From the viewpoint of exhibiting higher absorbance (absorbance of ultraviolet rays per mass), q' is preferably an integer of 1 to 3, and more preferably an integer of 1 to 2.

[0069] Also, in the above G 1 , G 2 and G 3 R 1 R 2 and R 3each independently represents a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched alkyl group having 1 to 4 carbon atoms substituted with a hydroxyl group; l, m, and n each independently represent an integer from 0 to 4; when l is 2 or more, a plurality of R 1 may be the same or different; when m is 2 or more, a plurality of R 2 may be the same or different; when n is 2 or more, a plurality of R 3 may be the same or different.

[0070] The above R 1 、R 2 、and R 3 Examples of the linear or branched alkyl group having 1 to 4 carbon atoms in 、、and include a methyl group, an ethyl group, a 1-propyl group, a 1-methyl-1-ethyl group, a 1-butyl group, a 1-methyl-1-propyl group, a 1,1-dimethyl-1-ethyl group, and the like. From the viewpoint of exhibiting a higher absorbance (ultraviolet absorbance per mass), the number of carbon atoms of the alkyl group is preferably an integer from 1 to 3, and more preferably an integer from 1 to 2.

[0071] The above R 1 、R 2 、and R 3In the present invention, examples of the linear or branched alkyl group having 1 to 4 carbon atoms substituted with a hydroxyl group include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 2,2-dihydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, a 1,2-dihydroxypropyl group, a 1,3-dihydroxypropyl group, a 2,3-dihydroxypropyl group, a 1,1-dihydroxypropyl group, a 2,2-dihydroxypropyl group, a 3,3-dihydroxypropyl group, a 1-methyl-1-hydroxyethyl group, a 1-methyl-2-hydroxyethyl group, a 1,1-dimethyl-1-hydroxymethyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, a 4-hydroxybutyl group, a 1,2-dihydroxybutyl group, a 1,3-dihydroxybutyl group, a 1,4-dihydroxybutyl group, a 2,3-dihydroxybutyl group, a 2,4-dihydroxybutyl group, a 1,1-dihydroxybutyl group, a 2,2-dihydroxybutyl group, a 3,3-dihydroxybutyl group, a 1-hydroxy-1-methylpropyl group, a 2-hydroxy-1-methylpropyl group, a 3-hydroxy-1-methylpropyl group, a 1-hydroxymethylpropyl group, a 1,1-dimethyl-2-hydroxyethyl group, a 2-methyl-1-hydroxypropyl group, a 2-methyl-2-hydroxypropyl group, a 2-methyl-3-hydroxypropyl group, and the like. From the viewpoint of exhibiting a higher absorbance (absorbance of ultraviolet rays per mass), the number of carbon atoms of the above alkyl group is preferably an integer of 1 to 2.

[0072] In the present invention, examples of the substituent in the case of "optionally substituted" include halogen (fluoro, chloro, bromo, iodo), cyano group, hydroxyl group, amino group, alkoxy group having 1 to 4 carbon atoms, alkyl group having 1 to 4 carbon atoms, alkenyl group having 1 to 4 carbon atoms, alkynyl group having 1 to 4 carbon atoms, cycloalkyl group having 3 to 6 carbon atoms, heteroalkyl group having 1 to 4 carbon atoms, heterocycloalkyl group having 3 to 6 carbon atoms, aryl group, aryloxy group, arylalkyl group, heteroaryl group, and the like. These may be substituted alone or in combination of two or more.

[0073] In the general formulas (I) to (IV) above, X is N, and at least one of the Ys present on Z is a sulfonic acid group, a hydroxyl group, an amino group, an alkylamino group, an ammonium group, an alkylammonium group, a phosphoric acid group, a phosphonic acid group, or a group corresponding to a salt thereof. By having the above configuration, a 1,3,5-triazine derivative or a salt thereof that is hydrophilic, has strong ultraviolet absorption characteristics mainly in the vicinity of 280 to 315 nm, and has excellent ultraviolet absorption action can be obtained.

[0074] In the general formulas (I) to (IV) above, at least one of the Ys present on Z is a hydroxyl group, and Z is a linear or branched alkyl group having 3 to 8 carbon atoms, a linear or branched alkenyl group having 1 to 8 carbon atoms, a linear or branched alkynyl group having 1 to 8 carbon atoms, a polyoxyethylene group containing 2 to 4 ethylene oxide units, or a polyoxypropylene group containing 1 to 4 propylene oxide units. By having the above configuration, a 1,3,5-triazine derivative or a salt thereof that is hydrophilic, has strong ultraviolet absorption characteristics mainly in the vicinity of 280 to 315 nm, and has excellent ultraviolet absorption action can be obtained.

[0075] In the general formulas (I) to (IV) above, at least one of the Ys present on Z can be a sulfonic acid group, a hydroxyl group, a carboxyl group, an amino group, an alkylamino group, an ammonium group, an alkylammonium group, a phosphoric acid group, a phosphonic acid group, or a group corresponding to a salt thereof. By having the above configuration, a 1,3,5-triazine derivative or a salt thereof that is more surely hydrophilic, has strong ultraviolet absorption characteristics mainly in the vicinity of 280 to 315 nm, and has excellent ultraviolet absorption action can be obtained.

[0076] In the general formulas (I) to (IV) above, it is preferable from the viewpoints of synthesis and skin safety, etc. that at least one of the Ys present on Z is a group corresponding to a sodium salt, potassium salt, or triethanolamine salt. By having the above configuration, a 1,3,5-triazine derivative or a salt thereof that is more surely hydrophilic, strongly has ultraviolet absorption characteristics mainly in the vicinity of 280 to 315 nm, and has an excellent ultraviolet absorption effect can be obtained.

[0077] In addition, in the 1,3,5-triazine derivative of the present invention, particularly when it has an acidic group as Y, depending on the pH conditions, a proton dissociates, and an anion (-SO3 - , -COO - , PO3 - etc.) can form a salt structure in which counter cations such as sodium ions, potassium ions, lithium ions, calcium ions, magnesium ions, aluminum ions, triethanolammonium ions, and diethanolammonium ions are bonded. These counter cations may be used alone or in combination of two or more. The acid addition salts of the above 1,3,5-triazine derivative are also included in the present invention.

[0078] In addition, in the 1,3,5-triazine derivative of the present invention, particularly when it has a basic nitrogen atom as Y, it can form a salt structure with an added acid. Examples of the above acid include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and hydrobromic acid, or organic acids such as acetic acid, citric acid, gluconic acid, tartaric acid, lactic acid, maleic acid, fumaric acid, methanesulfonic acid, p-toluenesulfonic acid, and nitrobenzenesulfonic acid. These acids may be used alone or in combination of two or more. The acid addition salts of the above 1,3,5-triazine derivative are also included in the present invention.

[0079] In addition, in the present invention, the absorbance (measured using a quartz cell with an optical path length of 1 cm at a concentration of 5 ppm) of the above 1,3,5-triazine derivative or a salt thereof in the UVB region is usually 0.02 or more, more preferably 0.2 to 1.

[0080] In addition, even when the 1,3,5-triazine derivative or its salt has an absorption ability in the UVA (wavelength 315 to 400 nm) region, it can be appropriately used as an ultraviolet absorber, a skin external preparation, a coating composition, or the like.

[0081] The molecular weight of the 1,3,5-triazine derivative or its salt of the present invention is usually about 450 to 1200, preferably 450 to 1000. When the molecular weight increases, the UV absorption ability per unit weight tends to decrease, and it is necessary to add a larger amount when used as an ultraviolet absorber, a skin external preparation, a coating composition, or the like.

[0082] [Production method of 1,3,5-triazine derivative or its salt] The 1,3,5-triazine derivative or its salt represented by (I) to (IV) of the present invention can be produced by a known reaction using easily available raw materials. Although the schemes (Schemes 1 to 3) of the synthesis examples of the above 1,3,5-triazine derivative or its salt are shown, they are merely examples, and the 1,3,5-triazine derivative or its salt represented by (I) to (IV) of the present invention is not limited to those obtained by the following synthesis examples.

[0083] (Scheme 1) [Chemical formula]

[0084] The 1,3,5-triazine derivative or its salt represented by (I) to (IV) of the present invention can be obtained, for example, by reacting cyanuric chloride, which is a triazine chloride, with a compound containing a group G 1 ~G 3 or the like in the side chain by a nucleophilic substitution reaction or the like.

[0085] For example, as shown in Scheme 1 above, a compound (A) containing a leaving group L and G 1By reacting a compound (B) having a base through a nucleophilic substitution reaction or the like, a compound (C) containing a nitro group can be obtained. In the above reaction, for example, a halogen group such as chlorine is used as L, and G 1 As H, an amine such as diglycolamine can be used. The above reaction can be carried out, for example, in an organic solvent such as methylene chloride or chloroform in the presence of a base such as triethylamine. Also, in the above reaction, when a hydroxyl group or the like is present in G 1 it can also be carried out by appropriately protecting the hydroxyl group or the like with an acetyl group, a benzyl group or the like.

[0086] The leaving group L of the compound (A) in the above Scheme 1 may be, for example, any functional group that can undergo substitution and elimination upon receiving a nucleophilic attack. Examples of the above L include fluoro, chloro, bromo, iodo, or sulfonic acid ester groups such as methanesulfonyl group, p-toluenesulfonyl group, nitrobenzenesulfonyl group, trifluoromethanesulfonyl group, etc. Among them, from the viewpoint of reaction yield and the like, as the above L, chloro, bromo, iodo, methanesulfonyl group, p-toluenesulfonyl group, trifluoromethanesulfonyl group, etc. can be mentioned as preferable ones.

[0087] Also, as the base used in the reaction of the above Scheme 1, a known base can be appropriately used. Examples of the above base include tertiary amines such as trimethylamine, triethylamine, diisopropylethylamine, pyrrolidine, piperidine, and aromatic amines with low nucleophilicity such as pyridine and 4-dimethylaminopyridine. These bases may be used alone or in combination of two or more. In particular, a method of adding an equivalent amount or an excess amount of the above tertiary amine or aromatic amine with low nucleophilicity as an acceptor of chloride ions derived from the leaving group to shift the reaction equilibrium (increase the reaction conversion rate) may also be used.

[0088] Also, in the reaction of the above Scheme 1, for the above G 1 etc. of the compound (B), a compound having a structure corresponding to the target product compound (F) can be appropriately used.

[0089] In the reaction in the above Scheme 1, the molar ratio of compound (B) to compound (A) (mol of compound (B) / mol of compound (A)) can be, for example, 0.5 to 2.0 (mol / mol), and may be 0.8 to 1.3 (mol / mol).

[0090] In the reaction in the above Scheme 1, the above reaction may be appropriately carried out in a solution with each raw material (and catalyst, etc.). When the raw material serves as a solvent, only the raw material may be mixed and used as a reaction solution. As the solvent in the case of using the above solution, a known solvent can be appropriately used. Examples of the above solvent include benzene, toluene, xylene, nitrobenzene, chlorobenzene, dichloroethane, trichloroethane, tetrachloroethane, etc. These solvents may be used alone or in combination of two or more.

[0091] Also, in the reaction in the above Scheme 1, the reaction temperature can be, for example, 0 °C to 80 °C.

[0092] Also, in the reaction in the above Scheme 1, the reaction time can be, for example, 1 to 24 hr.

[0093] (Scheme 2) [Chemical formula]

[0094] Also, as shown in the above Scheme 2, a compound (C) containing a nitro group can be reduced by hydrogenation to obtain a compound (D) containing an amino group.

[0095] For the reduction reaction in the above Scheme 2, a reagent that can reduce the nitro group without reacting with a carbonyl group or the like can be appropriately used. As the above reduction method, hydrogenation using palladium carbon or the like, or reduction using a metal having a reducing action such as iron in acetic acid / aqueous solution or the like may be used.

[0096] In the reaction in Scheme 2 above, the molar ratio of the reducing agent (reagent for the reduction reaction) to compound (C) (mol of reducing agent / mol of compound (C)) can be, for example, 1.0 to 5.0 (mol / mol), and it may also be carried out at 1.0 to 2.0 (mol / mol).

[0097] In the reaction in Scheme 2 above, the reaction may be appropriately carried out in a solution with each raw material (and catalyst, etc.). As the solvent when using such a solution, known solvents can be appropriately used. As the solvent, for example, ethers such as diethyl ether and tetrahydrofuran, alcohols, halogenated solvents such as dichloroethane, trichloroethane, and tetrachloroethane, etc., solvents that do not undergo a reduction action themselves can be used. These solvents may be used alone or in combination of two or more.

[0098] Also, in the reaction in Scheme 2 above, the reaction temperature can be, for example, 0°C to 80°C, and it may also be carried out at 15 to 25°C.

[0099] Also, in the reaction in Scheme 2 above, the reaction time can be, for example, 1 to 24 hours.

[0100] (Scheme 3) [Chemical formula]

[0101] Also, as shown in Scheme 3, the obtained compound (D) containing an amino group can be obtained by reacting it with 3 equivalents with respect to cyanuric chloride (E) by a nucleophilic substitution reaction or the like. Also, then, G 1When protecting hydroxyl groups or the like in a base or the like, a deprotection reaction is appropriately carried out. Further, when obtaining as a salt, a desired salt can be obtained by appropriately carrying out a neutralization reaction as a subsequent step. Further, the deprotection reaction and the neutralization reaction may be appropriately carried out together during the substitution reaction of Scheme 3 above. Thus, the 1,3,5-triazine derivative represented by (I) to (IV) of the present invention or a salt thereof can be obtained.

[0102] In the reaction in Scheme 3 above, the molar ratio of compound (D) to compound (E) (mol of compound (D) / mol of compound (E)) can be, for example, 3.0 to 5.0 (mol / mol), and may be carried out at 3.0 to 3.5 (mol / mol).

[0103] In the reaction in Scheme 3 above, the above reaction may be appropriately carried out in a solution with each raw material (and catalyst, etc.). When the raw material serves as a solvent, only the raw materials may be mixed and used as a reaction solution. As the solvent in the case of using the above solution, a known solvent can be appropriately used. Examples of the above solvent include N-methylpyrrolidone, dimethyl sulfoxide, γ-butyrolactone, dimethylformamide, benzene, toluene, xylene, nitrobenzene, chlorobenzene, dichloroethane, trichloroethane, tetrachloroethane, etc. These solvents may be used alone or in combination of two or more.

[0104] Further, in the reaction in Scheme 3 above, the reaction temperature can be, for example, 0°C to 80°C.

[0105] Further, in the reaction in Scheme 3 above, the reaction time can be, for example, 1 to 24 hours.

[0106] Further, in Schemes 1 to 3 above, although it is an example when X in the -X-Z-Y group in the general formula (I) is N, when X is O or S, the 1,3,5-triazine derivative represented by the general formulas (I) to (IV) of the present invention or a salt thereof can also be obtained in the same manner as appropriate.

[0107] In addition, the deprotection reaction can be appropriately carried out by known methods. For example, reduction reactions with hydrogen or the like, hydrolysis reactions using an acid or a base, or an ion exchange membrane or the like can be appropriately used.

[0108] For the above reduction reaction, reagents or methods that can reduce nitro groups without reacting with carbonyl groups or the like can be appropriately used. As the above reduction method, hydrogenation using palladium carbon or the like, or reduction using a metal having a reducing action such as iron in acetic acid / water system or the like may be carried out.

[0109] As the acid catalyst in the above hydrolysis reaction, known acid catalysts can be appropriately used. Examples of the above acid catalyst include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, formic acid, acetic acid, oxalic acid, maleic acid, fumaric acid, benzoic acid, salicylic acid, phthalic acid, p-toluenesulfonic acid and the like. These acid catalysts may be used alone or in combination of two or more.

[0110] As the basic catalyst in the above hydrolysis reaction, known basic catalysts can be appropriately used. Examples of the above basic catalyst include sodium hydroxide, sodium carbonate, sodium hydrogen carbonate, organic amines such as triethylamine and pyridine, and the like. These basic catalysts may be used alone or in combination of two or more.

[0111] In addition, in each reaction and the like in the above Schemes 1 to 3 of the present invention, the production of the reaction product can be appropriately carried out by known purification methods. Examples of the above purification method include silica gel column chromatography, high performance liquid chromatography, gas chromatography, gel permeation chromatography, recrystallization method, reprecipitation method, solvent extraction method, distillation, vacuum distillation and the like. These purification methods may be used alone or in combination of two or more.

[0112] 〔Use of 1,3,5-triazine derivative or its salt〕 (Ultraviolet absorber) The ultraviolet absorber of the present invention is characterized by containing the above 1,3,5-triazine derivative or its salt as an essential component. Therefore, the ultraviolet absorber of the present invention has excellent hydrophilicity and excellent ultraviolet (mainly ultraviolet B wave) absorption action. In particular, it can be suitably used for aqueous compositions (aqueous solutions, emulsions, etc.). Further, the above ultraviolet absorber may each contain optional components as required. Further, the above 1,3,5-triazine derivative or its salt may be used alone or in combination of two or more kinds.

[0113] In the above ultraviolet absorber, the content of the above 1,3,5-triazine derivative (and its salt) relative to the above ultraviolet absorber (total amount) can be, for example, 0.001 to 100% by mass, more preferably 0.1 to 10% by mass, and still more preferably 0.1 to 1% by mass.

[0114] Examples of the above optional components include known organic ultraviolet absorbers and inorganic powder-based ultraviolet blockers different from the above 1,3,5-triazine derivative or its salt. Further, other optional components may be appropriately added or added to other optional components and used as an ultraviolet absorption composition.

[0115] Examples of other ultraviolet absorbers include benzophenone-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, triazine-based (particularly, hydroxyphenyltriazine-based) ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, etc. These compounds may be used alone or in combination of two or more kinds.

[0116] (External preparation for skin) The external preparation for skin of the present invention is characterized by containing the above-mentioned 1,3,5-triazine derivative or a salt thereof as an essential component. Therefore, it has excellent hydrophilicity and an excellent ultraviolet ray (mainly ultraviolet ray B wave) absorption effect. In particular, it can reduce damage caused by UV exposure at the application sites of the hair and skin of humans and animals. Further, it can be suitably used in an aqueous external preparation for skin (an aqueous solution type or emulsion type external preparation for skin). When washing the application site of the external preparation for skin, it can exhibit high detergency such that the 1,3,5-triazine derivative or a salt thereof can be easily removed by water washing without using a special detergent from the application site. The above-mentioned external preparation for skin can be used, for example, as a cosmetic, a sunscreen composition, etc. Further, the above-mentioned external preparation for skin may each contain optional components as necessary. Further, the above-mentioned 1,3,5-triazine derivative or a salt thereof may be used alone or in combination of two or more kinds.

[0117] In the above-mentioned external preparation for skin, the content of the above-mentioned 1,3,5-triazine derivative (and a salt thereof) with respect to the above-mentioned external preparation for skin (total amount) can be, for example, 0.1 to 100% by mass, more preferably 0.5 to 20% by mass, and even more preferably 1 to 10% by mass.

[0118] The above-mentioned aqueous external preparation for skin refers to an external preparation for skin containing water, for example, in an amount of 30 to 99% by mass per 100% by mass of the composition, such as lotion.

[0119] Further, the above-mentioned external preparation for skin can contain known components without particular limitation.

[0120] The above-mentioned external preparation for skin can be used, in particular, as a sunscreen composition or the like that meets the current needs such as being used in daily life and requiring good detergency.

[0121] In addition, the external preparation for skin of the present invention may contain, for example, the above-mentioned organic ultraviolet absorber, inorganic powder-based ultraviolet blocker, liquid oil, solid oil, wax, hydrocarbon, higher fatty acid, higher alcohol, esters, silicones, anionic surfactant, cationic surfactant, amphoteric surfactant, nonionic surfactant, humectant, water-soluble polymer compound, thickener, film-forming agent, sequestering agent, lower alcohol, polyhydric alcohol, saccharides, amino acids, organic amines, pH adjuster, skin nutrient, vitamins, antioxidant, fragrance, powder, coloring material or water, etc. These optional components may be used alone or in combination of two or more.

[0122] (Coating composition, coating layer) The coating composition of the present invention is characterized by containing the above 1,3,5-triazine derivative or its salt as an essential component. Therefore, it has excellent hydrophilicity and excellent ultraviolet ray (mainly ultraviolet ray B wave) absorption action, and can be suitably used, for example, as a composition containing water-soluble paint, water-soluble adhesive, fabric mist for clothing, etc., water-soluble or environmentally friendly resin, etc. Further, the above coating composition may contain optional components as necessary. Further, the above 1,3,5-triazine derivative or its salt may be used alone or in combination of two or more.

[0123] The above coating composition is particularly preferably water-soluble.

[0124] The above coating composition preferably contains water. Further, depending on the purpose of use and application, other organic solvents, for example, alcohols such as ethanol may be used in combination.

[0125] In the above-mentioned water-soluble coating composition (water-soluble coating composition, aqueous coating composition), it is preferable to contain water, such as in the form of an aqueous solution of the coating composition, in an amount of 0.001 to 99% by mass, for example, per 100% by mass of the composition, and it may also be 0.01 to 90% by mass, 0.1 to 50% by mass, 1 to 50% by mass, 3 to 30% by mass, 5 to 20% by mass, 8 to 10% by mass, etc.

[0126] In the above-mentioned coating composition, depending on the purpose of use and application, the content of the above-mentioned 1,3,5-triazine derivative (and its salt) with respect to the above-mentioned coating composition (total amount) can be, for example, 0.001 to 100% by mass, and can also be 0.01 to 80% by mass, 0.05 to 60% by mass, 0.1 to 50% by mass, 0.5 to 40% by mass, 1 to 30% by mass, 2 to 15% by mass, 3 to 10% by mass, 4 to 5% by mass, etc.

[0127] In the above-mentioned coating composition, from the viewpoints of coating workability and coating film stability of the formed coating layer, etc., depending on the purpose of use and application, for example, the solid content concentration can be 0.001 to 80% by mass, and can also be 0.01 to 60% by mass, 0.05 to 50% by mass, 0.1 to 40% by mass, 1 to 20% by mass, 2 to 10% by mass, 3 to 5% by mass, etc.

[0128] In the above-mentioned coating composition, from the viewpoints of coating workability and coating film stability of the formed coating layer, etc., depending on the purpose of use and application, for example, the viscosity of the coating composition at 20°C can be 0.1 to 100000 mPa·s, and can also be 1 to 10000 mPa·s, 2 to 1000 mPa·s, 10 to 1000 mPa·s, etc.

[0129] In the above-mentioned coating composition, depending on the purpose of use and application, the pH of the above-mentioned coating composition can be, for example, 5 to 11, and can also be 6 to 10, 7 to 8, etc.

[0130] The above coating composition can be used, in particular, as a sunscreen composition or the like that meets the current needs such as being used in daily life and requiring good detergency.

[0131] Moreover, the above coating composition can contain known components without particular limitation. The coating composition of the present invention can contain, for example, the above-mentioned organic ultraviolet absorbers, inorganic powder-based ultraviolet blockers, plasticizers, pigments, dyes, fillers, antioxidants, conductive materials, light stabilizers, peel regulators, softeners, solvents, emulsifiers, liquid fats and oils, solid fats and oils, waxes, hydrocarbons, higher fatty acids, higher alcohols, esters, silicones, anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, humectants, water-soluble polymer compounds, thickeners, film-forming agents, sequestering agents, lower alcohols, polyhydric alcohols, saccharides, amino acids, organic amines, pH adjusters, flame retardants, antioxidants, catalysts, powders, colorants or water, etc. These optional components can be used alone or in combination of two or more.

[0132] Also, the coating layer of the present invention is a coating layer formed using the above coating composition. The coating layer of the present invention is characterized by containing the above 1,3,5-triazine derivative or its salt as an essential component. Therefore, it has an excellent ultraviolet (mainly ultraviolet B wave) absorption effect.

[0133] The thickness of the coating layer can be 10 nm to 3 mm, and may be 10 μm to 2 mm, 30 μm to 1.5 mm, 60 μm to 1.2 mm, or 100 μm to 1 mm, depending on the purpose of use and application.

[0134] In addition, the coated body of the present invention includes the above coating layer. The coating form of the coating layer is not particularly limited. For example, the form of coating a part or all of the coated body with the coating layer, or the surface layer, back surface, and / or intermediate layer of a glass layer or a plastic layer, etc., is not particularly limited.

[0135] The above-mentioned coating is applicable without particular limitation. However, because it has the excellent ultraviolet absorption effect described above, it is preferably used for articles that may be used outdoors, etc., particularly for articles that are exposed to ultraviolet rays such as sunlight. For example, vehicle members such as those for automobiles, airplanes, trains, bicycles, etc., more specifically, each glass such as the front, rear, front door, rear door, rear quarter, sunroof, etc., exterior members such as the front bumper, rear bumper, front grille, spoiler, door mirror, emblem cover, body, etc., interior members such as the center panel, instrument panel, center console, door panel, etc., members of lamps such as headlamps and rear lamps, lens members for in-vehicle cameras, lighting covers, decorative films, and furthermore vehicle members such as various glass substitute members; window glasses of construction machinery, window glasses of buildings, houses, greenhouses, etc., roofs of garages and arcades, etc., floodlights such as lighting and signal lights, signboards, wallpaper surface materials, sanitary products such as bathtubs and washbasins, exterior wall materials for kitchen building materials, flooring materials, cork materials, tiles, cushion floors, interior flooring materials such as linoleum, etc.; electronic devices and electrical products such as mobile phones, portable information terminals, personal computers, OA equipment, solar cells, portable game machines, flat panel displays, touch panels, optical discs such as DVDs and Blu-ray discs, optical components such as lenses, polarizing plates and optical filters, prisms, optical fibers, etc., optical films such as antireflection films and alignment films, retardation films, etc.; cloth products such as clothes and curtains; mechanical parts, agricultural materials, fishery materials, transport containers, packaging containers, toys, playthings, and sundries, etc. can be mentioned.

[0136] In addition, the manufacturing method of the coating layer of the present invention includes a step of drying the solvent of the above coating composition.

[0137] In the above process, the drying of the solvent can be carried out using known means as appropriate. For example, it can be made into a coating layer by heat treatment at room temperature (such as 25 °C) to 250 °C, or 40 °C to 150 °C, ultraviolet rays, infrared irradiation, etc. Further, the formation of the above coating layer can be carried out not only on the already molded substrate, but also by coating the coating composition on the coated body in advance like pre-coating treatment before the molding process.

[0138] As the coating method of the above coating composition, depending on the purpose of use and application, for example, spray coating method, squeegee coating method, flow coating method, bar coating method, spin coating method, dip coating method, die coating method, inkjet method, curtain coating method, screen printing method, gravure printing method, method using a brush or spatula, etc. can be mentioned.

[0139] (Other uses) The 1,3,5-triazine derivative or its salt of the present invention can be blended into products other than external skin preparations and coating compositions, for example, various resins, synthetic rubbers, latexes, packaging materials (films, containers made of synthetic resins, etc.), contact lenses or fibers, etc. to form various compositions or products, and it is also possible to protect these paints, etc. from ultraviolet rays.

Examples

[0140] Hereinafter, examples showing the configuration and effects of the present invention will be specifically described. The evaluation items in the examples, etc. were measured as follows.

[0141] <Measurement of UV spectrum> The measurement of the UV spectrum was carried out using a spectrophotometer (manufactured by Shimadzu Corporation, UV-4250). More specifically, the measurement of each UV spectrum was carried out using ethanol or purified water as the solvent, with a sample solution concentration of 5 ppm and a quartz cell with an optical path length of 1 cm. The absorbance was calculated according to Lambert-beer's law. When Io is the transmitted light intensity of the empty cell and I is the transmitted light intensity of the sample cell, absorbance = -log 10(I / I0) was calculated. Also, the wavelength at which the absorbance in the obtained UV spectrum was maximum was designated as λmax (nm).

[0142] < 1 Measurement of 1H-NMR Spectrum 1 The measurement of the 1H-NMR spectrum was carried out using a nuclear magnetic resonance apparatus (manufactured by JEOL Ltd., JNM-ECP500). More specifically, for each 1 The measurement of the 1H-NMR spectrum was carried out using DMSO-d6 as a solvent and tetramethylsilane as an internal standard.

[0143] <Evaluation of Hydrophilicity> The solubility (g / 100 g of test solvent) of the sample compound in 100 g of the following test solvent was measured. When dissolving, the solution was heated to 60 °C to dissolve it, and then the dissolved state after standing at 25 °C for 12 hours was confirmed.

[0144] (Test Solvent) A mixed solvent containing dipropylene glycol, ethanol, and purified water in amounts of 10% by mass, 10% by mass, and 80% by mass, respectively, was used as the test solvent. However, the total amount of dipropylene glycol, ethanol, and purified water was 100% by mass.

[0145] (Evaluation Method) When the measured solubility was 1.0 (g / 100 g of test solvent) or more, the sample compound was evaluated as having hydrophilicity. On the other hand, when the solubility was less than 1.0 (g / 100 g of test solvent), the sample compound was evaluated as not having hydrophilicity.

[0146] [Example 1] <Synthesis of 1,3,5-trianiolino-p-(carbo-(2-(2-hydroxyethoxy)ethyl)-1-amino)-s-triazine (Synthesis of Compound (1))> [Chemical formula]

[0147] In a 10 L four-necked flask, under a nitrogen stream, 4 L of dichloromethane, 200.0 g (1.90 mol) of diglycolamine, and 202.9 g (2.01 mol) of triethylamine were added at an internal temperature of 5 °C. After that, a solution of 353.4 g (1.90 mol) of 4-nitrobenzoyl chloride in 2 L of dichloromethane was added dropwise at an internal temperature of 15 - 20 °C, and the mixture was stirred at room temperature for 1 hour. Then, 2 L of saturated aqueous sodium bicarbonate was added to the reaction solution and stirred. After that, the organic layer was separated, 1 L of ethyl acetate was added to the aqueous layer, and further re-extraction was performed. The combined organic layers were washed with 2 L of saturated brine, and then the organic layer was distilled off under reduced pressure to obtain 465.0 g (yield 96%) of p-(carbo-(2-(2-hydroxyethoxy)ethyl)-1-amino) nitrobenzene as slightly yellow crystals.

[0148] In a 5 L four-necked flask, under a nitrogen stream, 88.5 g (348.1 mmol) of the obtained p-(carbo-(2-(2-hydroxyethoxy)ethyl)-1-amino) nitrobenzene, 880 mL of tetrahydrofuran, and 14.6 g (366.7 mmol) of sodium hydride (60% dispersion) were added, and the mixture was stirred at room temperature for 1 hour. Then, 40.0 g (377.4 mmol) of benzyl bromide was added dropwise, and the mixture was stirred at 40 °C for 5 hours. Then, 900 mL of saturated aqueous sodium bicarbonate was added to the reaction solution and stirred. After that, the organic layer was separated, washed with 1 L of saturated aqueous sodium bicarbonate, and then the organic layer was distilled off under reduced pressure. The obtained residue was purified using silica gel column chromatography (developing solvent: ethyl acetate / hexane = 1 / 1 → 2 / 1) to obtain 37.6 g (yield 31%) of p-(carbo-(2-(2-benzyloxyethoxy)ethyl)-1-amino) nitrobenzene as a slightly yellow oily substance.

[0149] In a 500 mL four-necked flask, 36.1 g (104.8 mmol) of the obtained p-(carbo-(2-(2-benzyloxyethoxy)ethyl)-1-amino)nitrobenzene, 217 mL of acetic acid, 110 mL of normal water, and 17.0 g of reduced iron were added, and the mixture was stirred at 55 °C for 1.5 hours. Then, the insoluble matter was filtered off with celite and washed with 100 mL of ethyl acetate and 100 mL of normal water. Then, the filtrates were combined, concentrated under reduced pressure, and further 200 mL of normal water and 42.1 g of potassium carbonate were added to adjust the pH to 9. Then, the mixture was extracted three times with 200 mL of ethyl acetate, the organic layers were combined, washed with 200 mL of normal water, and the organic layer was distilled off under reduced pressure to obtain 30.5 g (yield 83%) of p-(carbo-(2-(2-benzyloxyethoxy)ethyl)-1-amino)aniline as a yellow oily substance.

[0150] In a 1 L three-necked flask, 27.6 g (87.8 mmol) of the obtained p-(carbo-(2-(2-benzyloxyethoxy)ethyl)-1-amino)aniline and 200 mL of N-methylpyrrolidone were added, and a solution of 4.6 g (24.9 mmol) of cyanuric chloride in 40 mL of N-methylpyrrolidone was added dropwise, and the mixture was stirred at 50 °C for 1.5 hours. Further, the mixture was stirred at 110 °C for 1 hour, and after the reaction mixture had cooled to room temperature, 350 mL of normal water was added. Then, the mixture was extracted twice with 350 mL of ethyl acetate, the organic layers were combined, and distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (developing solvent: ethyl acetate / acetone = 4 / 1 → 1 / 1) to obtain 23.5 g (yield 93%) of 1,3,5-trianiolino-p-(carbo-(2-(2-benzyloxyethoxy)ethyl)-1-amino)-s-triazine as a colorless oily substance.

[0151] In a 200 mL three-necked flask, 6.5 g (6.4 mmol) of the obtained 1,3,5-trianiolino-p-(carbo-(2-(2-benzyloxyethoxy)ethyl)-1-amino)-s-triazine, 65 mL of tetrahydrofuran, 32.5 mL of ethanol, and 1.3 g of palladium-activated carbon were added. The inside of the flask was replaced with hydrogen gas and stirred at 40 °C for 3 hours. The insoluble matter was filtered off with celite, and after washing the insoluble matter with 10 mL of purified water and 100 mL of ethanol, the filtrate was distilled off under reduced pressure. 50 mL of acetone was added to the obtained residue and stirred, and the precipitated white crystals were collected. The slurry was washed with purified water-acetone to obtain 3.0 g (yield 63%) of 1,3,5-trianiolino-p-(carbo-(2-(2-hydroxyethoxy)ethyl)-1-amino)-s-triazine.

[0152] (Spectral data of compound (1)) UV spectrum: λmax; 306 nm, absorbance; 0.70 (ethanol) 1 H-NMR spectrum: δ [ppm, DMSO-d6] = 3.40 - 3.60 (m, 24H), 4.62 (s, 3H), 7.84 (d, 6H), 7.94 (d, 6H), 8.39 (t, 3H), 9.67 (s, 3H). Solubility; 1.2 (g / 100 g test solvent)… having hydrophilicity.

[0153] [Example 2] (Synthesis of 1,3,5-trianiolino-p-(carbo-2-hydroxy-1,1-bis(hydroxymethyl)ethyl-1-amino)-s-triazine (compound (2))) [Chemical formula]

[0154] In a 2 L three-necked flask, under a nitrogen stream and at an internal temperature of 25°C, 400 mL of N,N-dimethylacetamide, 39.2 g (324 mmol) of tris(hydroxymethyl)aminomethane, and 54.5 g (539 mmol) of triethylamine were added. Then, a solution of 20.0 g (108 mmol) of 4-nitrobenzoyl chloride in 200 mL of N,N-dimethylacetamide was added dropwise at an internal temperature of 2 - 6°C, and the mixture was stirred for 2 hours while maintaining the internal temperature at 2 - 6°C. Further, 110.0 g (1078 mmol) of acetic anhydride was added dropwise, and the mixture was stirred at room temperature for 48 hours. Then, 1.2 L of normal water was added, and the mixture was extracted twice with 600 mL of ethyl acetate. The combined organic layers were washed three times with 600 mL of normal water, and then the organic layer was distilled off under reduced pressure. 100 mL of methanol was added to the obtained residue, and the distillation was repeated twice. 200 mL of n-hexane / ethyl acetate (=9 / 1) was added to the obtained residue and stirred, and 40.9 g (yield 70%) of p-(carbo-2-acetoxy-1,1-bis(acetoxymethyl)ethyl-1-amino)nitrobenzene was obtained as slightly yellow crystals.

[0155] In a 500 mL three-necked flask, 39.0 g (98.4 mmol) of the obtained p-(carbo-2-acetoxy-1,1-bis(acetoxymethyl)ethyl-1-amino)nitrobenzene, 390 mL of methanol, and 3.9 g of palladium-activated carbon were added. The inside of the flask was replaced with hydrogen gas, and the mixture was stirred at room temperature for 2 hours. The insoluble matter was filtered off with celite and washed with 39 mL of purified water. Then, the filtrate was distilled off under reduced pressure. 390 mL of ethyl acetate was added to the obtained residue, and it was further washed with 390 mL of 0.1 mol / L aqueous sodium hydroxide solution and 390 mL of normal water. Then, it was dried over magnesium sulfate, and the organic layer was distilled off under reduced pressure to obtain 25.8 g (yield 72%) of p-(carbo-2-acetoxy-1,1-bis(acetoxymethyl)ethyl-1-amino)aniline.

[0156] In a 300 mL three-necked flask, 10.0 g (27.3 mmol) of the obtained p-(carbo-2-acetoxy-1,1-bis(acetoxymethyl)ethyl-1-amino)aniline and 60 mL of N-methylpyrrolidone were added. A solution of 1.36 g (7.4 mmol) of cyanuric chloride in 10 mL of N-methylpyrrolidone was added dropwise, and the mixture was stirred at 25 °C for 1 hour. Then, it was further stirred at 50 °C for 0.5 hour and at 70 °C for 1 hour. After the reaction mixture cooled to room temperature, 140 mL of ordinary water was added, and the mixture was extracted twice with 70 mL of ethyl acetate. The combined organic layers were distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (developing solvent: ethyl acetate / n-hexane = 10 / 1) to obtain 4.2 g (yield 48%) of 1,3,5-trianiolino-p-(carbo-2-acetoxy-1,1-bis(acetoxymethyl)ethyl-1-amino)-s-triazine as white crystals.

[0157] In a 100 mL three-necked flask, 4.0 g (34.1 mmol) of the obtained 1,3,5-trianiolino-p-(carbo-2-acetoxy-1,1-bis(acetoxymethyl)ethyl-1-amino)-s-triazine and 67 mL of an aqueous methanol solution of 0.5 mol / L potassium carbonate were added, and the mixture was stirred at room temperature for 1 hour. The reaction mixture was distilled off under reduced pressure. 4 mL of ordinary water was added to the obtained residue, and after recovering white crystals, they were washed with methanol as a slurry. Further, recrystallization was performed with isopropanol and purified water to obtain 0.12 g (yield 6.9%) of 1,3,5-trianiolino-p-(carbo-2-hydroxy-1,1-bis(hydroxymethyl)ethyl-1-amino)-s-triazine.

[0158] (Spectral data of compound (2)) UV spectrum: λmax; 307 nm, absorbance; 0.73 (ethanol) 1 H-NMR spectrum: δ [ppm, DMSO-d6] = 3.69 (s, 18H), 7.79 (d, 6H), 7.93 (d, 6H). Solubility; 1.5 (g / 100 g test solvent)… has hydrophilicity.

[0159] [Example 3] <Synthesis of trisodium 1,3,5-trianiolino-p-(3-sulfopropyl-1-oxycarbonyl)-s-triazine (Compound (3))> [Chemical formula]

[0160] In a 100 mL three-necked flask, 2.14 g (4.4 mmol) of 1,3,5-trianiolino-p-hydroxycarbonyl-s-triazine and 15 mL of N,N-dimethylformamide were added, heated to 110 °C and dissolved. Then, 1.77 g (14.5 mmol) of 1,3-propanesultone and 1.54 g (14.5 mmol) of sodium carbonate were added, and the mixture was stirred at 110 °C for 24 hours. Then, 1.77 g (14.5 mmol) of 1,3-propanesultone and 1.54 g (14.5 mmol) of sodium carbonate were further added, and the mixture was stirred at 110 °C for 1 hour. Then, 1.77 g (14.5 mmol) of 1,3-propanesultone was further added, and the mixture was stirred at 110 °C for 1 hour. After the reaction mixture cooled to room temperature, the solvent was distilled off under reduced pressure. Purified water was added to the obtained residue, and purification was performed using HP20 (developing solvent: purified water, acetonitrile) to obtain 1.46 g (yield 36%) of trisodium 1,3,5-trianiolino-p-(3-sulfopropyl-1-oxycarbonyl)-s-triazine as white crystals.

[0161] (Spectral data of Compound (3)) UV spectrum: λmax; 307 nm, absorbance; 0.42 (purified water) 1 H-NMR spectrum: δ [ppm, DMSO-d6] = 1.99 - 2.05 (m, 6H), 2.62 (t, 6H), 4.31 (t, 6H), 7.91 (d, 6H), 7.95 - 8.15 (br, 6H), 9.93 (s, 3H). Solubility; 5.0 (g / 100 g test solvent)… has hydrophilicity.

Claims

1. A 1,3,5-triazine derivative represented by any of general formulas (I) to (IV) or a salt thereof. [Chemical Formula 1] 【Chemical Formula 2】 [Chemical Formula 3] 【Chemical Formula 4】 (In general formulas (I) to (IV), G １ , G ２ , and G ３ are each independently hydrogen, a linear or branched alkyl group having 1 to 12 carbon atoms which may be substituted, a linear or branched alkenyl group having 1 to 12 carbon atoms which may be substituted, a linear or branched alkynyl group having 1 to 12 carbon atoms which may be substituted, a polyoxyethylene group containing 1 to 8 ethylene oxide units which may be substituted, a polyoxypropylene group containing 1 to 8 propylene oxide units which may be substituted, or represents -X-Z-Y (where Y is present one or more times on Z, and when a plurality of Y are present, the plurality of Y are the same or different from each other). However, among G １ , G ２ , and G ３ , at least two of them are -X-Z-Y which are the same as or different from each other. X is O, N, or S. Y is a sulfonic acid group, a hydroxyl group, a carboxyl group, an amino group, an alkylamino group, an ammonium group, an alkylammonium group, a phosphoric acid group, a phosphonic acid group, or a group corresponding to a salt thereof. Z is a linear or branched alkyl group having 1 to 8 carbon atoms, a linear or branched alkenyl group having 1 to 8 carbon atoms, a linear or branched alkynyl group having 1 to 8 carbon atoms, a polyoxyethylene group containing 1 to 4 ethylene oxide units, or a polyoxypropylene group containing 1 to 4 propylene oxide units. R １ , R ２ , and R ３ each independently represents a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched alkyl group having 1 to 4 carbon atoms substituted with a hydroxyl group. l, m, and n are each independently an integer from 0 to 4. When l is 2 or more, a plurality of Rs exist １ which are the same or different. When m is 2 or more, a plurality of R's ２ are the same or different. When n is 2 or more, the plurality of Rs that exist ３ are the same or different.)

2. The 1,3,5-triazine derivative or a salt thereof according to claim 1, represented by general formula (I).

3. The 1,3,5-triazine derivative or a salt thereof according to claim 1, represented by general formula (IV).

4. In the general formulas (I) to (IV), X is N, and Y is a sulfonic acid group, a hydroxyl group, an amino group, an alkylamino group, an ammonium group, an alkylammonium group, a phosphoric acid group, a phosphonic acid group, or a group corresponding to a salt thereof. The 1,3,5-triazine derivative or a salt thereof according to claim 1, characterized in that.

5. In the general formula (I), X is N, and Y is a sulfonic acid group, a hydroxyl group, an amino group, an alkylamino group, an ammonium group, an alkylammonium group, a phosphoric acid group, a phosphonic acid group, or a group corresponding to a salt thereof. The 1,3,5-triazine derivative or a salt thereof according to claim 2, characterized in that.

6. In the general formulas (I) to (IV), at least one of Y existing one or more times on Z is a hydroxyl group, and Z is a linear or branched alkyl group having 3 to 8 carbon atoms, a linear or branched alkenyl group having 1 to 8 carbon atoms, a linear or branched alkynyl group having 1 to 8 carbon atoms, a polyoxyethylene group containing 2 to 4 ethylene oxide units, or a polyoxypropylene group containing 1 to 4 propylene oxide units. The 1,3,5-triazine derivative or a salt thereof according to claim 1, characterized in that.

7. In the general formula (I), at least one of the Ys present on Z is a hydroxyl group, and Z is a linear or branched alkyl group having 3 to 8 carbon atoms, a linear or branched alkenyl group having 1 to 8 carbon atoms, a linear or branched alkynyl group having 1 to 8 carbon atoms, a polyoxyethylene group containing 2 to 4 ethylene oxide units, or a polyoxypropylene group containing 1 to 4 propylene oxide units. The 1,3,5-triazine derivative or a salt thereof according to claim 2, characterized in that.

8. In the general formulas (I) to (IV), Y is a sulfonic acid group, a hydroxyl group, a carboxyl group, an alkylamino group, an ammonium group, an alkylammonium group, a phosphoric acid group, a phosphonic acid group, or a group corresponding to a salt thereof. The 1,3,5-triazine derivative or a salt thereof according to claim 1, characterized in that.

9. In the general formula (I), Y is a sulfonic acid group, a hydroxyl group, a carboxyl group, an alkylamino group, an ammonium group, an alkylammonium group, a phosphoric acid group, a phosphonic acid group, or a group corresponding to a salt thereof. The 1,3,5-triazine derivative or a salt thereof according to claim 2, characterized in that.

10. In the general formulas (I) to (IV), at least one of the Ys present on Z is a group corresponding to a sodium salt, a potassium salt, or a triethanolamine salt. The 1,3,5-triazine derivative or a salt thereof according to claim 1, characterized in that.

11. In the general formula (I), at least one of the Ys present on Z is a group corresponding to a sodium salt, a potassium salt, or a triethanolamine salt. The 1,3,5-triazine derivative or a salt thereof according to any one of claims 2, characterized in that.

12. In the general formulas (I) to (IV) above, G １ , G ２ , and G ３ are each independently -X-Z-Y which are the same as or different from each other, The 1,3,5-triazine derivative or a salt thereof according to claim 1.

13. In the general formula (I), G １ , G ２ , and G ３ are each the same as or different from each other and are -X-Z-Y, and the 1,3,5-triazine derivative or a salt thereof according to claim 2.

14. The 1,3,5-triazine derivative or a salt thereof according to any one of claims 1 to 13, which is water-soluble.

15. An ultraviolet absorber containing the 1,3,5-triazine derivative or a salt thereof according to any one of claims 1 to 13.

16. A topical skin composition containing the 1,3,5-triazine derivative or a salt thereof according to any one of claims 1 to 13.

17. A coating composition containing the 1,3,5-triazine derivative or a salt thereof according to any one of claims 1 to 13.

18. The coating composition according to claim 17, which is water-soluble.

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