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

Abstract

The present invention relates to providing a novel compound, specifically a 1,3,5-triazine derivative and salt thereof, which has a suitable ultraviolet absorption action, and to an ultraviolet absorbent and external skin agent using the same.　The present invention is the 1,3,5-triazine derivative or salt thereof represented by general formula (I), etc. (In the general formula, G1, G2, and G3 each independently represent hydrogen, a straight or branched chain alkyl group, etc. having 1-12 carbon atoms which may be substituted, or -X-Z-Y. However, at least two of G1, G2, and G3 may be -X-Z-Y, which may be identical or different from each other.　X is O, N, or S.　Y is a sulfonic acid group, a hydroxyl group, or a carboxyl group, etc., or a group corresponding to a salt thereof.　Z is a straight or branched chain alkyl group, etc. having 1-8 carbon atoms.　R1, R2, and R3 each independently represent a straight or branched chain alkyl group, etc. having 1-4 carbon atoms, and l, m, and n each independently represent an integer from 0 to 4.)

Description

Novel triazine derivatives and salts thereof, and ultraviolet absorbers, topical skin preparations, and coating compositions using the same

[0001] The present invention relates to novel hydrophilic triazine derivatives and salts thereof that have ultraviolet absorbing properties, as well as ultraviolet absorbers, topical skin preparations, and coating compositions that use the same.

[0002] Ultraviolet rays are essential for the biosynthesis of vitamin D and are used to promote blood circulation and metabolism in the body, as well as for sterilization and disinfection. However, excessive exposure of the skin to ultraviolet rays can lead to the development of skin cancer and accelerate skin aging, causing age spots, freckles, wrinkles, and other problems. Furthermore, excessive exposure to ultraviolet rays can cause the deterioration of various synthetic resins and paints, such as polyethylene, polypropylene, PVC, and ABS resin. Thus, excessive exposure to ultraviolet rays can cause various adverse effects. To prevent these adverse effects, various ultraviolet absorbers have been developed and are widely used.

[0003] Near-ultraviolet rays, commonly called "ultraviolet rays (UV)," can be broadly classified based on their wavelength into UVA (wavelength 315-400 nm), UVB (wavelength 280-315 nm), and UVC (wavelength 200-280 nm). Note that UVC is UV derived from sunlight, but is significantly absorbed by the ozone layer and the like before reaching the ground, and therefore does not normally pass through the ozone layer and the like to reach the ground.

[0004] UVA and UVB are believed to be the main causes of skin cancer, skin aging, and deterioration of synthetic resins and paints. For this reason, ultraviolet absorbers have been developed primarily for the purpose of absorbing UVA or UVB.

[0005] As the effects of ultraviolet light on the skin and the like have become more apparent, there has been an increasing demand for sunscreen cosmetics with a high ultraviolet light blocking effect. Generally, sunscreen cosmetics contain ultraviolet light scattering agents and ultraviolet light absorbing agents for the purpose of blocking ultraviolet light from reaching the skin.

[0006] UV scattering agents shield UV rays by scattering them, and inorganic pigments such as zinc oxide, titanium oxide, kaolin, calcium carbonate, etc. have been used conventionally. These are capable of shielding UV rays over a wide range and, because they are inactive, are highly safe for the skin, making them more useful UV screening agents.

[0007] However, although these inorganic pigments, particularly titanium oxide and zinc oxide, have a high UV-shielding effect as described above, they also have a high covering power (hiding power), which causes the cosmetic film to turn white when applied to the skin, resulting in a white cast. For this reason, the use of finely divided titanium oxide and zinc oxide has been proposed (see, for example, Patent Documents 1 to 3). It is known that the finer these particles are, the higher the UV-shielding effect and the higher the light transmittance in the visible light range, resulting in higher transparency.

[0008] Furthermore, these inorganic pigment fine particles generally have a high tendency to aggregate, making it difficult to stably disperse them in a fine particle state in formulations such as cosmetics. As a result, the expected UV-shielding effect and transparency are not achieved. Furthermore, because these fine particle pigments have a high refractive index, using them in large quantities increases the hiding power, resulting in a whitish cast and an unnatural cosmetic finish. Furthermore, particle aggregation hinders the spreadability of the cosmetic and causes problems in use, such as a squeaky feeling when applied to the skin. For this reason, the amount of these UV scattering agents that can be incorporated is naturally limited, and cosmetics with the desired UV-shielding effect have not been obtained.

[0009] Japanese Patent Publication No. 47-42502 Publication No. 49-00450 Japanese Patent Publication No. 64-07941

[0010] In view of the above circumstances, an object of the present invention is to provide 1,3,5-triazine derivatives and salts thereof, which are novel compounds having a suitable ultraviolet absorbing effect.

[0011] Another object of the present invention is to provide an ultraviolet absorber, an external skin preparation, and a coating composition that contain the above-mentioned 1,3,5-triazine derivative and its salt and have a suitable ultraviolet absorbing effect.

[0012] As a result of intensive investigations to solve the above problems, the present inventors have succeeded in creating the following novel triazine derivatives and salts thereof, and have found that the above objects can be achieved by using these compounds, thereby completing the present invention.

[0013] That is, the present invention provides the following compounds or salts thereof (hereinafter, sometimes referred to as "compounds" or "compounds, etc.").

[0014] [1] A 1,3,5-triazine derivative or a salt thereof represented by any one of general formulas (I) to (IV): (In general formulas (I) to (IV), G １ , G ２ , and G ３ each independently represents hydrogen, an optionally substituted linear or branched alkyl group having 1 to 12 carbon atoms, an optionally substituted linear or branched alkenyl group having 1 to 12 carbon atoms, an optionally substituted linear or branched alkynyl group having 1 to 12 carbon atoms, an optionally substituted polyoxyethylene group containing 1 to 8 ethylene oxide units, an optionally substituted polyoxypropylene group containing 1 to 8 propylene oxide units, or -X-Z-Y (wherein one or more Ys are present on Z, and when there are more than one Ys bonded to Z), the multiple Ys may be the same or different). However, G １ , G ２ , and G ３At least two of the groups are -X-Z-Y, which may be the same or different. 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 phosphate group, a phosphonate 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 each independently represent an integer of 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.)

[0015] [2] The 1,3,5-triazine derivative or salt thereof according to [1], represented by general formula (I):

[0016] [3] The 1,3,5-triazine derivative or salt thereof according to [1], represented by general formula (IV):

[0017] [4] The 1,3,5-triazine derivative or salt thereof according to [1], wherein in the general formulae (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.

[0018] [5] The 1,3,5-triazine derivative or salt thereof according to [2], wherein 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.

[0019] [6] The 1,3,5-triazine derivative or salt thereof according to [1], wherein in the general formulae (I) to (IV), 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.

[0020] [7] The 1,3,5-triazine derivative or salt thereof according to [2], wherein in the general formula (I), 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.

[0021] [8] The 1,3,5-triazine derivative or salt thereof according to [1], wherein in the general formulae (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.

[0022] [9] The 1,3,5-triazine derivative or salt thereof according to [2], wherein 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.

[0023]

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

[0024]

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

[0025]

[12] In the above general formulas (I) to (IV), G １ , G ２ , and G ３ are all the same or different -X-Z-Y, or a salt thereof.

[0026]

[13] In the above general formula (I), G １ , G ２ , and G ３ are all the same or different -X-Z-Y, or a salt thereof.

[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] The present invention also provides the following ultraviolet absorbents.

[0029]

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

[13] .

[0030] The present invention also provides the following external skin compositions.

[0031]

[16] A composition for external use on skin, comprising the 1,3,5-triazine derivative or salt thereof according to any one of [1] to

[13] .

[0032] The present invention also provides the following coating compositions.

[0033]

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

[13] .

[0034]

[18] The coating composition according to

[17] , which is water-soluble.

[0035]

[19] The coating composition according to

[17] , which contains water.

[0036] The present invention also provides the following coating layer.

[0037]

[20] A coating layer formed using the coating composition according to

[17] .

[0038] The present invention also provides the following coated body:

[21] A coated body comprising the coating layer according to

[20] .

[0039] The present invention also provides the following method for producing a coating layer.

[0040]

[22] A method for producing a coating layer, comprising a step of drying the solvent of the coating composition according to

[17] .

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

[0042] Furthermore, the ultraviolet absorber, topical skin preparation, and coating composition of the present invention contain the novel 1,3,5-triazine derivative or a salt thereof, and therefore have excellent hydrophilicity and ultraviolet absorbing properties, and are useful as ultraviolet absorbers, topical skin preparations, and coating compositions.

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

[0044] [1,3,5-Triazine Derivative or Salt Thereof] The 1,3,5-triazine derivative or salt thereof of the present invention is characterized by being represented by any one of general formulas (I) to (IV). (In general formulas (I) to (IV), G １ , G ２ , and G ３ each independently represents hydrogen, an optionally substituted linear or branched alkyl group having 1 to 12 carbon atoms, an optionally substituted linear or branched alkenyl group having 1 to 12 carbon atoms, an optionally substituted linear or branched alkynyl group having 1 to 12 carbon atoms, an optionally substituted polyoxyethylene group containing 1 to 8 ethylene oxide units, an optionally substituted polyoxypropylene group containing 1 to 8 propylene oxide units, or -X-Z-Y (wherein one or more Ys are present on Z, and when more than one Y is present, the multiple Ys may be the same or different). However, G １ , G ２ , and G ３ At least two of the groups are -X-Z-Y, which may be the same or different. 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 phosphate group, a phosphonate 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 each independently represent an integer of 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 R３ may be the same or different.)

[0045] As described above, cosmetics and the like having the desired UV-shielding effect have not been obtained to date. In addition, lipophilic UV absorbers used in conventional sunscreens and the like have the property of not coming off even when water comes into contact with the skin (lipophilicity), and basically require dedicated cleansers to remove them from the skin. In recent years, as damage to the skin caused by UV rays has become more apparent, sunscreens have become more commonly used in daily life, and there is a demand for sunscreens that can be easily washed off with water. Furthermore, as the amount of lipophilic compounds added increases, problems arise in terms of the impact on products, such as solubility and stability in cosmetics, particularly in aqueous solvents.

[0046] In contrast, the 1,3,5-triazine derivative (s-triazine derivative) or salt thereof of the present invention has a structure represented by any one of the general formulae (I) to (IV) above, and therefore has excellent water solubility, strong ultraviolet absorption properties, and excellent ultraviolet absorption action.

[0047] In the above 1,3,5-triazine derivative or salt thereof, G １ , G ２ , and G ３ each independently represents hydrogen, an optionally substituted linear or branched alkyl group having 1 to 12 carbon atoms, an optionally substituted linear or branched alkenyl group having 1 to 12 carbon atoms, an optionally substituted linear or branched alkynyl group having 1 to 12 carbon atoms, an optionally substituted polyoxyethylene group containing 1 to 8 ethylene oxide units, an optionally substituted polyoxypropylene group containing 1 to 8 propylene oxide units, or -X-Z-Y (wherein one or more Ys are present on Z, and when more than one Y is present, the multiple Ys may be the same or different). However, G １ , G ２ , and G ３ At least two of the groups -X-Z-Y may be the same or different. By having the above structure, the composition has excellent ultraviolet absorbing properties and is more hydrophilic.

[0048] Above G １ , G ２ , and G ３ Examples of the optionally substituted linear or branched alkyl group having 1 to 12 carbon atoms in the formula (I) 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, a 1-nonyl group, a 2-nonyl group, a 1-decyl group, a 2-decyl group, a 1-undecyl group, a 2-undecyl group, a 1-dodecyl group, a 2-dodecyl group, a 1-tridecyl group, a 2-tridecyl group, a 1-tetradecyl group, and a 2-tetradecyl group. From the viewpoint of being able to exhibit higher absorbance (ultraviolet absorbance per mass), the number of carbon atoms in the alkyl group is preferably an integer of 1 to 8, and more preferably an integer of 1 to 4.

[0049] Above G １ , G ２ , and G ３ In the formula (I), examples of the optionally substituted linear or branched alkenyl group having 1 to 12 carbon atoms include ethenyl (ethene), allyl (propene), 1-methyl-vinyl, 1-butenyl, 2-butenyl, and 2-pentenyl. From the viewpoint of being able to exhibit higher absorbance (ultraviolet absorbance per mass), the number of carbon atoms in the alkenyl group is preferably an integer of 1 to 8, and more preferably an integer of 1 to 4.

[0050] Above G １ , G ２ , and G ３ In the formula (I), examples of the optionally substituted linear or branched alkynyl group having 1 to 12 carbon atoms include an ethynyl group, a propynyl group, a butynyl group, etc. From the viewpoint of being able to exhibit higher absorbance (ultraviolet absorbance per mass), the number of carbon atoms in the alkynyl group is preferably an integer of 1 to 8, and more preferably an integer of 1 to 4.

[0051] Above G １ , G ２ , and G ３ Examples of the optionally substituted polyoxyethylene group containing 1 to 8 ethylene oxide units in the above formula include -(CH ２ CH ２ O) ｐ -H, -(CH ２ CH ２ O) ｐ -CH ２ CH ３ , —O—(CH ２ CH ２ O) ｐ -H, O-(CH ２ CH ２ O) ｐ -CH ２ CH ３ Here, p is an integer of 1 to 8. From the viewpoint of being able to exhibit higher absorbance (ultraviolet absorbance per mass), p is preferably an integer of 1 to 4, and more preferably an integer of 1 to 3.

[0052] Above G １ , G ２ , and G ３ In the above formula, examples of the polyoxypropylene group containing 1 to 8 propylene oxide units which may be substituted include -(CH(CH ３ ) CH ２ O) ｑ -H, -(CH(CH ３ ) CH ２ O) ｑ -CH(CH ３ ) CH ３ , -O-(CH(CH ３ ) CH ２ O) ｑ -H, O-(CH(CH ３ ) CH ２ O) ｑ -CH(CH ３ ) CH ３ , -(CH ２ CH (CH ３ ) O) ｑ -H, -(CH ２ CH (CH ３ ) O) ｑ -CH(CH３ ) CH ３ , —O—(CH ２ CH (CH ３ ) O) ｑ -H, O-(CH ２ CH (CH ３ ) O) ｑ -CH(CH ３ ) CH ３ Here, q is an integer of 1 to 8. From the viewpoint of being able to exhibit higher absorbance (ultraviolet absorbance per mass), q is preferably an integer of 1 to 4, and more preferably an integer of 1 to 3.

[0053] Also, the above G １ , G ２ , and G ３ In the formula, at least two are -XZY, which may be the same or different.

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

[0055] In the above -XZY, X is O, N, or S. In multiple -XZY chains, X may be the same or different.

[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 phosphoric acid group, a phosphonic acid group, or a group corresponding to a salt thereof. In multiple -X-Z-Y chains, Y may be the same or different.

[0057] In addition, a plurality of Y's may be present on Z. When a plurality of Y's are present on Z, for example, two or three hydroxyl groups (or -O) may be present on the same Z chain. － Examples of such a case include a case where a hydroxyl group and a sulfonic acid group (or sulfonate salt group) are bonded (present) to the same Z chain.

[0058] More specifically, Y is, for example, —SO ３ H, -OH, -COOH, -NH ２ , -NR ４ R ５ , -PO ３ In addition to H, phosphate alkyl ester groups, phosphonic acid groups, and -OA, -SO ３ A, -COOA, -NR ６ R ７ R ８ Examples of the groups include groups corresponding to salts of these groups such as B.

[0059] The A is a counter cation, and examples thereof include monovalent cations and divalent cations. Representative examples of A include alkali metal salts such as sodium and potassium, and triethanolammonium cations.

[0060] The above B is a counter anion, and for example, a monovalent cation or a divalent cation can be appropriately used. Representative examples of the above B include a hydroxide ion and a chlorine anion.

[0061] Above -NR ４ R ５ In this case, R ４ and R ５ is, for example, hydrogen or a linear or branched alkyl group having 1 to 4 carbon atoms. ４ and R ５ When all of R are hydrogen atoms, it is an amino group, otherwise it is an alkylamino group. ４ and R ５ Examples of the linear or branched alkyl group having 1 to 4 carbon atoms in R 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 a 2-methyl-1-propyl group. From the viewpoint of exhibiting higher absorbance (ultraviolet absorbance per mass), R ４ and R ５ is hydrogen, or the number of carbon atoms in the alkyl group is preferably an integer of 1 to 3, more preferably an integer of 1 or 2. ４ and R５ may be the same or different from each other.

[0062] Above -NR ６ R ７ R ８ In B, R ６ , R ７ , and R ８ is, for example, hydrogen or a linear or branched alkyl group having 1 to 4 carbon atoms. ６ , R ７ , and R ８ When R is all hydrogen, it is an ammonium group, otherwise it is an alkylammonium group. ６ , R ７ , and R ８ Examples of the linear or branched alkyl group having 1 to 4 carbon atoms in R 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 a 2-methyl-1-propyl group. From the viewpoint of exhibiting higher absorbance (ultraviolet absorbance per mass), R ６ , R ７ , and R ８ is hydrogen, or the number of carbon atoms in the alkyl group is preferably an integer of 1 to 3, more preferably an integer of 1 or 2. ６ , R ７ , and R ８ may be the same 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 multiple -X-Z-Y chains, Z may be the same or different.

[0064] Examples of the linear or branched alkyl group having 1 to 8 carbon atoms for 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 being able to exhibit higher absorbance (ultraviolet absorbance per mass), the number of carbon atoms in 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 Z include ethenyl (ethene), allyl (propene), 1-methyl-vinyl, 1-butenyl, 2-butenyl, and 2-pentenyl. From the viewpoint of exhibiting higher absorbance (ultraviolet absorbance per mass), the number of carbon atoms in 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 Z include an ethynyl group, a propynyl group, and a butynyl group. From the viewpoint of being able to exhibit higher absorbance (ultraviolet absorbance per mass), the number of carbon atoms in the alkynyl group is preferably an integer of 1 to 4, and more preferably an integer of 1 to 3.

[0067] The polyoxyethylene group containing 1 to 4 ethylene oxide units in Z is, for example, —(CH ２ CH ２ O) ｐ’ -H, -(CH ２ CH ２ O) ｐ’ -CH ２ CH ３ , —O—(CH ２ CH ２ O) ｐ’ -H, O-(CH ２ CH ２ O) ｐ’ -CH ２CH ３ Here, p' is an integer of 1 to 4. From the viewpoint of being able to exhibit higher absorbance (ultraviolet absorbance per mass), p' is preferably an integer of 1 to 3, and more preferably an integer of 1 or 2.

[0068] The polyoxypropylene group containing 1 to 4 propylene oxide units in Z includes, for example, —(CH(CH ３ ) CH ２ O) ｑ’ -H, -(CH(CH ３ ) CH ２ O) ｑ’ -CH(CH ３ ) CH ３ , -O-(CH(CH ３ ) CH ２ O) ｑ’ -H, O-(CH(CH ３ ) CH ２ O) ｑ’ -CH(CH ３ ) CH ３ , -(CH ２ CH (CH ３ ) O) ｑ’ -H, -(CH ２ CH (CH ３ ) O) ｑ’ -CH(CH ３ ) CH ３ , —O—(CH ２ CH (CH ３ ) O) ｑ’ -H, O-(CH ２ CH (CH ３ ) O) ｑ’ -CH(CH ３ ) CH ３ Here, q' is an integer of 1 to 4. From the viewpoint of being able to exhibit higher absorbance (ultraviolet absorbance per mass), q' is preferably an integer of 1 to 3, and more preferably an integer of 1 or 2.

[0069] Also, the above G １ , G ２ , and G ３ In this case, 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 of 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.

[0070] The above R １ , R ２ , and R ３ In the formula (I), examples of the linear or branched alkyl group having 1 to 4 carbon atoms 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, etc. From the viewpoint of being able to exhibit higher absorbance (ultraviolet absorbance per mass), the number of carbon atoms in the alkyl group is preferably an integer of 1 to 3, and more preferably an integer of 1 or 2.

[0071] The above R １ , R ２ , and R ３In the above, 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 ... Examples of suitable alkyl groups include methyl, 3-hydroxybutyl, 4-hydroxybutyl, 1,2-dihydroxybutyl, 1,3-dihydroxybutyl, 1,4-dihydroxybutyl, 2,3-dihydroxybutyl, 2,4-dihydroxybutyl, 1,1-dihydroxybutyl, 2,2-dihydroxybutyl, 3,3-dihydroxybutyl, 1-hydroxy-1-methylpropyl, 2-hydroxy-1-methylpropyl, 3-hydroxy-1-methylpropyl, 1-hydroxymethylpropyl, 1,1-dimethyl-2-hydroxyethyl, 2-methyl-1-hydroxypropyl, 2-methyl-2-hydroxypropyl, and 2-methyl-3-hydroxypropyl groups. From the viewpoint of exhibiting higher absorbance (ultraviolet absorbance per mass), the number of carbon atoms in the 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, etc. These may be substituted alone or in combination of two or more.

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

[0074] In the above general formulas (I) to (IV), at least one of the Ys present on Z may be a hydroxyl group, and Z may be 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. This configuration allows for the production of a 1,3,5-triazine derivative or a salt thereof that is hydrophilic, has strong ultraviolet absorption properties mainly in the vicinity of 280 to 315 nm, and exhibits excellent ultraviolet absorption properties.

[0075] In the above general formulas (I) to (IV), at least one of the Ys present on Z may be 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 phosphonate group, or a group corresponding to a salt thereof. By having the above structure, it is possible to more reliably obtain a 1,3,5-triazine derivative or a salt thereof that is hydrophilic, has strong ultraviolet absorption properties mainly in the vicinity of 280 to 315 nm, and has excellent ultraviolet absorption properties.

[0076] In addition, in the above general formulas (I) to (IV), it is preferable that at least one of the one or more Ys present on Z is a group corresponding to a sodium salt, a potassium salt, or a triethanolamine salt from the viewpoints of synthesis and safety to the skin, etc. By having the above-mentioned constitution, it is possible to more reliably obtain a 1,3,5-triazine derivative or a salt thereof that is hydrophilic, has strong ultraviolet absorption properties mainly in the vicinity of 280 to 315 nm, and has excellent ultraviolet absorption properties.

[0077] In addition, in the 1,3,5-triazine derivative of the present invention, particularly when Y has an acidic group, depending on the pH conditions, the proton dissociates and the resulting anion (-SO ３ － , -COO － , P.O. ３ － The 1,3,5-triazine derivative may have a salt structure in which a counter cation such as a sodium ion, a potassium ion, a lithium ion, a calcium ion, a magnesium ion, an aluminum ion, a triethanolammonium ion, or a diethanolammonium ion is bonded to the 1,3,5-triazine derivative. These counter cations may be used alone or in combination of two or more. The present invention also includes acid addition salts of the above 1,3,5-triazine derivatives.

[0078] Furthermore, the 1,3,5-triazine derivative of the present invention, particularly when Y has a basic nitrogen atom, can take a salt structure by addition of an acid. Examples of the acid include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and hydrobromic acid, and 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 present invention also includes acid addition salts of the above 1,3,5-triazine derivatives.

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

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

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

[0082] [Method for Producing 1,3,5-Triazine Derivatives or Salts Thereof] The 1,3,5-triazine derivatives represented by (I) to (IV) of the present invention or salts thereof can be produced by known reactions using readily available raw materials. The schemes (Schemes 1 to 3) of synthesis examples of the 1,3,5-triazine derivatives or salts thereof are shown above, but these are merely examples, and the 1,3,5-triazine derivatives represented by (I) to (IV) of the present invention or salts thereof are not limited to those obtained by the synthesis examples below.

[0083] (Scheme 1)

[0084] The 1,3,5-triazine derivatives or salts thereof represented by (I) to (IV) of the present invention can be prepared by, for example, providing a triazine chloride such as cyanuric chloride with a G group corresponding to a side chain. １ ~G ３ The compound can be obtained by reacting a compound containing a group or the like 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 a compound (G １ The compound (B) having a nitro group can be reacted by a nucleophilic substitution reaction or the like to obtain the compound (C) having a nitro group. For example, the reaction can be carried out by using a halogen group such as chlorine as L, １As 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. １ When a hydroxyl group or the like is present in the reaction product, the hydroxyl group or the like can be protected with an acetyl group, a benzyl group or the like as appropriate.

[0086] The leaving group L of the compound (A) in Scheme 1 may be, for example, a functional group that can be substituted and eliminated by nucleophilic attack. Examples of L include fluoro, chloro, bromo, iodo, and sulfonate groups such as methanesulfonyl, p-toluenesulfonyl, nitrobenzenesulfonyl, and trifluoromethanesulfonyl. Among these, from the viewpoint of reaction yield and the like, chloro, bromo, iodo, methanesulfonyl, p-toluenesulfonyl, and trifluoromethanesulfonyl are preferred as L.

[0087] Furthermore, known bases can be used appropriately as the base used in the reaction of Scheme 1 above. Examples of the base include tertiary amines such as trimethylamine, triethylamine, diisopropylethylamine, pyrrolidine, and 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 may be used in which the above-mentioned tertiary amines or aromatic amines with low nucleophilicity are added in an equal or excess amount as acceptors for chloride ions derived from the leaving group, thereby shifting the reaction equilibrium (increasing the reaction conversion rate).

[0088] In the reaction of the above scheme 1, the above G of the above compound (B) １ For the above, a compound having a structure corresponding to the target product, compound (F), can be used as appropriate.

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

[0090] In the reaction in Scheme 1, the reaction may be carried out in a suitable solution of each raw material (and catalyst, etc.), or when the raw materials serve as a solvent, only the raw materials may be mixed and used as a reaction solution. A known solvent can be used as a solvent when preparing the solution. Examples of the solvent include benzene, toluene, xylene, nitrobenzene, chlorobenzene, dichloroethane, trichloroethane, and tetrachloroethane. These solvents may be used alone or in combination of two or more.

[0091] In addition, the reaction in the above Scheme 1 can be carried out at a reaction temperature of, for example, 0°C to 80°C.

[0092] In addition, in the reaction in Scheme 1, the reaction time can be, for example, 1 to 24 hours.

[0093] (Scheme 2)

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

[0095] In the reduction reaction in Scheme 2, a reagent capable of reducing a nitro group without reacting with a carbonyl group, etc., can be appropriately used. The reduction method may include hydrogenation using palladium carbon, etc., or reduction using a metal having a reducing action, such as iron, in an acetic acid / water system, etc.

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

[0097] In the reaction in Scheme 2, the reaction may be carried out in a suitable solution of each raw material (and catalyst, etc.). A known solvent can be used as the solvent for the solution. Examples of the solvent include ethers such as diethyl ether and tetrahydrofuran, alcohols, and halogenated solvents such as dichloroethane, trichloroethane, and tetrachloroethane, which are not subject to reduction. These solvents may be used alone or in combination of two or more.

[0098] In addition, the reaction in the above Scheme 2 can be carried out at a reaction temperature of, for example, 0°C to 80°C, or may be carried out at 15°C to 25°C.

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

[0100] (Scheme 3)

[0101] As shown in Scheme 3, the resulting amino group-containing compound (D) can be reacted with 3 equivalents of cyanuric chloride (E) by a nucleophilic substitution reaction or the like to obtain a compound (D). １ When a hydroxyl group or the like is protected in a group or the like, a deprotection reaction is appropriately carried out. When a salt is obtained, the desired salt can be obtained by appropriately carrying out a neutralization reaction as a post-step. Furthermore, the deprotection reaction or neutralization reaction may be appropriately carried out in conjunction with the substitution reaction of Scheme 3 above. In this way, the 1,3,5-triazine derivatives of the present invention represented by (I) to (IV) or salts thereof can be obtained.

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

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

[0104] In addition, the reaction in the above Scheme 3 can be carried out at a reaction temperature of, for example, 0°C to 80°C.

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

[0106] In addition, the above schemes 1 to 3 are examples where X in the -X-Z-Y group in general formula (I) is N. However, even when X is O or S, the 1,3,5-triazine derivatives or salts thereof represented by the general formulae (I) to (IV) of the present invention can be obtained in the same manner as above.

[0107] The deprotection reaction can be carried out by any known method, such as a reduction reaction using hydrogen or the like, or a hydrolysis reaction using an acid, a base, or an ion exchange membrane.

[0108] In the reduction reaction, a reagent or method that can reduce a nitro group without reacting with a carbonyl group, etc., can be appropriately used. The reduction method may include hydrogenation using palladium carbon, etc., or reduction using a metal with a reducing action, such as iron, in an acetic acid / water system, etc.

[0109] As the acid catalyst for the hydrolysis reaction, known acid catalysts can be appropriately used. Examples of the 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, and p-toluenesulfonic acid. These acid catalysts may be used alone or in combination of two or more.

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

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

[0112] [Uses of 1,3,5-triazine derivative or salt thereof] (Ultraviolet absorber) The ultraviolet absorber of the present invention is characterized by containing the above-mentioned 1,3,5-triazine derivative or salt thereof as an essential component. As a result, the ultraviolet absorber of the present invention has excellent hydrophilicity and also has excellent ultraviolet (mainly ultraviolet-B) absorbing properties. In particular, it is suitable for use in aqueous compositions (such as aqueous solutions and emulsions). Furthermore, the above-mentioned ultraviolet absorbers may each contain optional components as necessary. Furthermore, the above-mentioned 1,3,5-triazine derivative or salt thereof may be used alone or in combination of two or more.

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

[0114] Examples of the optional components include known organic ultraviolet absorbers and inorganic powder ultraviolet screening agents other than the 1,3,5-triazine derivatives or salts thereof. Furthermore, the composition may be used as an ultraviolet absorbing composition by adding other optional components as appropriate or by adding the optional components to other optional components.

[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.

[0116] (External Skin Preparation) The external skin preparation of the present invention is characterized by containing the above-mentioned 1,3,5-triazine derivative or its salt as an essential ingredient. As a result, it has excellent hydrophilicity and excellent ultraviolet (primarily ultraviolet-B) absorption properties, and is particularly capable of reducing damage caused by UV exposure at the application site of human and animal hair and skin. Furthermore, it can be suitably used in aqueous external skin compositions (aqueous solution-type or emulsion-type external skin compositions), and exhibits high cleansing properties that allow the 1,3,5-triazine derivative or its salt to be easily removed from the application site by rinsing with water without the need for special detergents when washing the application site of the external skin preparation. The external skin preparation can be used, for example, as a cosmetic, a sunscreen composition, etc. Furthermore, the external skin preparation may each contain optional ingredients as needed. Furthermore, the above-mentioned 1,3,5-triazine derivative or its salt may be used alone or in combination of two or more.

[0117] In the topical skin preparation, the content of the 1,3,5-triazine derivative (and its salt) relative to the total amount of the topical skin preparation 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 aqueous skin external composition refers to a skin external composition such as a lotion, which contains water in an amount of, for example, 30 to 99% by mass per 100% by mass of the composition.

[0119] Furthermore, the above-mentioned external skin preparation can contain known ingredients without any particular limitations.

[0120] The above-mentioned external preparation for skin can be used as a sunscreen composition that meets current needs, particularly those used in daily life, for which good cleansing properties are required.

[0121] The topical skin preparation of the present invention may contain, for example, the above-mentioned organic ultraviolet absorbers and inorganic powder-based ultraviolet screening agents, liquid oils and fats, solid oils and fats, waxes, hydrocarbons, higher fatty acids, higher alcohols, esters, silicones, anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, moisturizers, water-soluble polymeric compounds, thickeners, film-forming agents, sequestering agents, lower alcohols, polyhydric alcohols, sugars, amino acids, organic amines, pH adjusters, skin nutrients, vitamins, antioxidants, fragrances, powders, coloring materials, 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-mentioned 1,3,5-triazine derivative or a salt thereof as an essential component. As a result, the coating composition has excellent hydrophilicity and excellent ultraviolet (mainly ultraviolet-B) absorption properties, and can be suitably used, for example, as a composition containing a water-soluble or environmentally friendly resin, such as a water-soluble paint, a water-soluble adhesive, or a fabric mist for clothing. Furthermore, the above-mentioned coating composition may contain optional components as necessary. Furthermore, the above-mentioned 1,3,5-triazine derivative or a salt thereof may be used alone, or two or more types may be mixed and used.

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

[0124] The coating composition preferably contains water, and may contain other organic solvents, such as alcohols such as ethanol, depending on the purpose and application.

[0125] The above-mentioned water-soluble coating composition (water-soluble coating composition, water-based coating composition) preferably contains water in an amount of, for example, 0.001 to 99% by mass, per 100% by mass of the composition, such as an aqueous coating composition solution, and may also contain water in an amount of 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 coating composition, the content of the 1,3,5-triazine derivative (and salt thereof) relative to the total amount of the coating composition can be, for example, 0.001 to 100% by mass, 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., depending on the purpose and application of the coating composition.

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

[0128] In the coating composition, the viscosity at 20°C of the coating composition may be, for example, 0.1 to 100,000 mPa·s, 1 to 10,000 mPa·s, 2 to 1,000 mPa·s, 10 to 1,000 mPa·s, etc., depending on the purpose and application, from the viewpoints of coating workability, film stability of the coating layer to be formed, and the like.

[0129] The coating composition may have a pH of, for example, 5 to 11, 6 to 10, 7 to 8, etc., depending on the intended use and application.

[0130] The coating composition can be used as a sunscreen composition that meets current needs, particularly those used in daily life, where good washability is required.

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

[0132] The coating layer of the present invention is formed using the coating composition. The coating layer of the present invention is characterized by containing the 1,3,5-triazine derivative or a salt thereof as an essential component. As a result, the coating layer has excellent ultraviolet (mainly ultraviolet-B) absorption properties.

[0133] The thickness of the coating layer can be 10 nm to 3 mm, or 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 and application.

[0134] The coated body of the present invention includes the above-described coating layer. The coating form of the coating layer is not particularly limited, and may be, for example, a form in which the coated body is partially or entirely covered with the coating layer, or a form in which the coated body is covered with the coating layer on the surface or back surface of a glass layer or a plastic layer, and / or an intermediate layer.

[0135] The above-mentioned covering body is not particularly limited and can be applied, but because it has the above-mentioned excellent ultraviolet absorbing effect, it is preferably used for, for example, articles that may be used outdoors, particularly for articles that are exposed to ultraviolet rays such as sunlight.For example, it can be used for vehicle components such as automobiles, aircraft, trains, bicycles, etc., more specifically, for each glass such as front, rear, front door, rear door, rear quarter, sunroof, etc., front bumper, rear bumper, front grill, spoiler, door mirror, emblem cover, body, etc. exterior components, center panel, instrument panel, center console, door panel, etc. interior components, headlamp, rear lamp, etc. lamp components, lens components for in-vehicle cameras, lighting covers, decorative films, and various glass substitutes, etc.; window glass for construction machinery, window glass for buildings, houses, greenhouses, etc., roofs of garages and arcades, etc., lighting fixtures, traffic lights, etc., signboards, Examples include building materials such as wallpaper coverings, sanitary products such as bathtubs and washbasins, kitchen building materials, exterior wall materials, flooring materials, cork materials, tiles, cushion flooring, and interior flooring materials such as linoleum; electronic devices and electrical products such as mobile phones, personal digital assistants, personal computers, office equipment, solar cells, portable game consoles, flat panel displays, touch panels, optical discs such as DVDs and Blu-ray discs, lenses, optical components such as polarizing plates, optical filters, prisms, optical fibers, and optical films such as anti-reflection films, alignment films, polarizing films, and retardation films; fabric products such as clothing and curtains; machine parts, agricultural materials, fishing materials, transport containers, packaging containers, toys, play equipment, and miscellaneous goods.

[0136] The method for producing a coating layer of the present invention also includes a step of drying the solvent from the coating composition.

[0137] In the above step, the solvent can be dried using a known method as appropriate. For example, a coating layer can be formed by heat treatment at room temperature (e.g., 25°C) to 250°C or 40°C to 150°C, ultraviolet or infrared irradiation, or the like. Furthermore, the coating layer can be formed not only on an already molded substrate, but also on a coated body in advance before molding, as in a precoat treatment.

[0138] Examples of the method for applying (coating) the coating composition include spray coating, squeegee coating, flow coating, bar coating, spin coating, dip coating, die coating, inkjet coating, curtain coating, screen printing, gravure printing, and methods using a brush or spatula, depending on the purpose and application.

[0139] (Other Uses) The 1,3,5-triazine derivative or a salt thereof of the present invention can be incorporated into products other than topical skin preparations and coating compositions, such as various resins, synthetic rubber, latex, packaging materials (films, synthetic resin containers, etc.), contact lenses, fibers, etc., to form various compositions or products, and these coatings, etc. can be protected from ultraviolet rays.

[0140] Examples that specifically illustrate the configuration and effects of the present invention will be described below. The evaluation items in the examples were measured as follows.

[0141] <Measurement of UV Spectra> UV spectra were measured using a spectrophotometer (Shimadzu Corporation, UV-4250). More specifically, each UV spectrum was measured using ethanol or purified water as the solvent, 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 the Lambert-Beer law, where Io is the transmitted light intensity of an empty cell and I is the transmitted light intensity of a sample cell, as follows: absorbance = -log １０ (I / I ０ The wavelength at which the absorbance in the obtained UV spectrum was maximum was defined as λmax (nm).

[0142] < １ Measurement of H-NMR spectrum> １ The H-NMR spectrum was measured using a nuclear magnetic resonance spectrometer (manufactured by JEOL Ltd., JNM-ECP500). １ The H-NMR spectrum was measured using DMSO-d ６ and tetramethylsilane as an internal standard.

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

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

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

[0146] Example 1 Synthesis of 1,3,5-trianilino-p-(carbo-(2-(2-hydroxyethoxy)ethyl)-1-amino)-s-triazine (compound (1))

[0147] In a 10 L four-neck flask, 4 L of dichloromethane, 200.0 g (1.90 mol) of diglycolamine, and 202.9 g (2.01 mol) of triethylamine were added under a nitrogen stream at an internal temperature of 5°C, and then 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 to 20°C, followed by stirring at room temperature for 1 hour. Subsequently, 2 L of saturated aqueous sodium bicarbonate was added to the reaction solution and stirred, after which the organic layer was separated, and 1 L of ethyl acetate was added to the aqueous layer, followed by further re-extraction. The organic layers were combined and washed with 2 L of saturated brine, and then the organic layer was distilled under reduced pressure to obtain 465.0 g (yield 96%) of p-(carbo-(2-(2-hydroxyethoxy)ethyl)-1-amino)nitrobenzene as pale yellow crystals.

[0148] In a 5 L four-neck flask, 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 under a nitrogen stream, and the mixture was stirred at room temperature for 1 hour. Thereafter, 40.0 g (377.4 mmol) of benzyl bromide was added dropwise, and the mixture was stirred at 40°C for 5 hours. Thereafter, 900 mL of saturated aqueous sodium bicarbonate was added to the reaction solution, and the mixture was stirred. Thereafter, the organic layer was separated and washed with 1 L of saturated aqueous sodium bicarbonate, and then the organic layer was distilled off under reduced pressure. The resulting 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 pale yellow oily substance.

[0149] Into a 500 mL four-neck 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 ordinary water, and 17.0 g of reduced iron were added, and the mixture was stirred at 55°C for 1.5 hours. Thereafter, insoluble matter was removed by filtration using Celite, and the mixture was washed with 100 mL of ethyl acetate and 100 mL of ordinary water. Thereafter, the filtrates were combined and concentrated under reduced pressure, and then 200 mL of ordinary water and 42.1 g of potassium carbonate were added, and the pH was adjusted to 9. Thereafter, the mixture was extracted three times with 200 mL of ethyl acetate, and the organic layers were combined and washed with 200 mL of ordinary water, and then the organic layer was distilled 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] Into a 1 L three-neck 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, followed by stirring at 50°C for 1.5 hours. The mixture was further stirred at 110°C for 1 hour, and after the reaction mixture had cooled to room temperature, 350 mL of ordinary water was added. Thereafter, the mixture was extracted twice with 350 mL of ethyl acetate, and the organic layers were combined and distilled under reduced pressure. The resulting residue was purified using silica gel column chromatography (developing solvent: ethyl acetate / acetone=4 / 1→1 / 1) to obtain 23.5 g (yield 93%) of 1,3,5-trianilino-p-(carbo-(2-(2-benzyloxyethoxy)ethyl)-1-amino)-s-triazine as a colorless oil.

[0151] Into a 200 mL three-neck flask were added 6.5 g (6.4 mmol) of the obtained 1,3,5-trianilino-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 on activated carbon. The atmosphere in the flask was replaced with hydrogen gas, and the mixture was stirred at 40°C for 3 hours. Insoluble matter was removed by filtration through Celite, and the insoluble matter was washed with 10 mL of purified water and 100 mL of ethanol, and the filtrate was then distilled off under reduced pressure. 50 mL of acetone was added to the obtained residue, and the mixture was stirred, and the precipitated white crystals were collected. The mixture was slurry-washed with purified water-acetone, and 3.0 g (yield 63%) of 1,3,5-trianilino-p-(carbo-(2-(2-hydroxyethoxy)ethyl)-1-amino)-s-triazine was obtained.

[0152] (Spectral data of compound (1)) UV spectrum: λmax; 306 nm, absorbance; 0.70 (ethanol) １ H-NMR spectrum: δ [ppm, DMSO-d ６ ] = 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 / 100g test solvent)...Hydrophilic.

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

[0154] In a 2 L three-neck flask, under a nitrogen stream, 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 at an internal temperature of 25°C. 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 to 6°C, and the mixture was stirred for 2 hours while maintaining the internal temperature at 2 to 6°C. Furthermore, 110.0 g (1078 mmol) of acetic anhydride was added dropwise, and the mixture was stirred at room temperature for 48 hours. After that, 1.2 L of ordinary water was added, followed by extraction twice with 600 mL of ethyl acetate. The organic layers were combined and washed three times with 600 mL of ordinary water, and the organic layer was then distilled off under reduced pressure. 100 mL of methanol was added to the obtained residue and the mixture was distilled off twice. 200 mL of n-hexane / ethyl acetate (=9 / 1) was added to the obtained residue and stirred to obtain 40.9 g (yield 70%) of p-(carbo-2-acetoxy-1,1-bis(acetoxymethyl)ethyl-1-amino)nitrobenzene as pale yellow crystals.

[0155] Into a 500 mL three-neck flask were added 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 on activated carbon. The atmosphere in the flask was replaced with hydrogen gas, and the mixture was stirred at room temperature for 2 hours. Insoluble matter was removed by filtration through Celite, and the insoluble matter was washed with 39 mL of purified water, and the filtrate was then evaporated under reduced pressure. 390 mL of ethyl acetate was added to the resulting residue, which was then washed with 390 mL of 0.1 mol / L aqueous sodium hydroxide solution and 390 mL of ordinary water. The mixture was then dried over magnesium sulfate, and the organic layer was evaporated under reduced pressure to obtain 25.8 g of p-(carbo-2-acetoxy-1,1-bis(acetoxymethyl)ethyl-1-amino)aniline (yield: 72%).

[0156] Into a 300 mL three-neck 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, and a solution of 1.36 g (7.4 mmol) of cyanuric chloride in 10 mL of N-methylpyrrolidone was added dropwise, followed by stirring at 25°C for 1 hour. Thereafter, the mixture was stirred for an additional 0.5 hour at 50°C, and then for an additional 1 hour at 70°C. After the reaction mixture had cooled to room temperature, 140 mL of ordinary water was added, followed by extraction twice with 70 mL of ethyl acetate, and the organic layers were combined and evaporated under reduced pressure. The obtained residue was purified using silica gel column chromatography (developing solvent: ethyl acetate / n-hexane=10 / 1) to obtain 4.2 g (yield 48%) of 1,3,5-trianilino-p-(carbo-2-acetoxy-1,1-bis(acetoxymethyl)ethyl-1-amino)-s-triazine as white crystals.

[0157] Into a 100 mL three-neck flask, 4.0 g (34.1 mmol) of the obtained 1,3,5-trianilino-p-(carbo-2-acetoxy-1,1-bis(acetoxymethyl)ethyl-1-amino)-s-triazine and 67 mL of a 0.5 mol / L aqueous methanol solution of potassium carbonate were added, and the mixture was stirred at room temperature for 1 hour. The reaction mixture was distilled under reduced pressure, and 4 mL of ordinary water was added to the resulting residue. White crystals were recovered and then slurry-washed with methanol. Further, the crystals were recrystallized from isopropanol and purified water to obtain 0.12 g (yield 6.9%) of 1,3,5-trianilino-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-d ６ ] = 3.69 (s, 18H), 7.79 (d, 6H), 7.93 (d, 6H). Solubility: 1.5 (g / 100g test solvent)...Hydrophilic.

[0159] Example 3 Synthesis of 1,3,5-trianilino-p-(carbo-3-sulfopropyl-1-oxy)-s-triazine trisodium salt (compound (3))

[0160] Into a 100 mL three-neck flask, 2.14 g (4.4 mmol) of 1,3,5-trianilino-p-hydroxycarbonyl-s-triazine and 15 mL of N,N-dimethylformamide were added and heated to 110°C to dissolve the mixture. Then, 1.77 g (14.5 mmol) of 1,3-propane sultone and 1.54 g (14.5 mmol) of sodium carbonate were added and the mixture was stirred at 110°C for 24 hours. Subsequently, 1.77 g (14.5 mmol) of 1,3-propane sultone and 1.54 g (14.5 mmol) of sodium carbonate were further added and the mixture was stirred at 110°C for 1 hour. Subsequently, 1.77 g (14.5 mmol) of 1,3-propane sultone was further added and the mixture was stirred at 110°C for 1 hour. After the reaction mixture was cooled to room temperature, the solvent was distilled off under reduced pressure. Purified water was added to the obtained residue, and the mixture was purified using HP20 (developing solvent: purified water, acetonitrile) to obtain 1.46 g (yield 36%) of 1,3,5-trianilino-p-(carbo-3-sulfopropyl-1-oxy)-s-triazine trisodium salt 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-d ６ ] = 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 / 100g test solvent)...Hydrophilic.

Claims

1. A 1,3,5-triazine derivative or a salt thereof represented by any one of general formulas (I) to (IV): (In general formulas (I) to (IV), G １ , G ２ , and G ３ each independently represents hydrogen, an optionally substituted linear or branched alkyl group having 1 to 12 carbon atoms, an optionally substituted linear or branched alkenyl group having 1 to 12 carbon atoms, an optionally substituted linear or branched alkynyl group having 1 to 12 carbon atoms, an optionally substituted polyoxyethylene group containing 1 to 8 ethylene oxide units, an optionally substituted polyoxypropylene group containing 1 to 8 propylene oxide units, or -X-Z-Y (wherein one or more Y's are present on Z, and when more than one Y's are present, the multiple Y's present are the same or different from each other), provided that G １ , G ２ , and G ３ Among these, at least two are -X-Z-Y, which may be the same or different. 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 each independently represent an integer of 0 to 4. When l is 2 or more, a plurality of R １ are the same or different. When m is 2 or more, there are multiple R ２ are the same or different. When n is 2 or more, there are multiple R ３ are the same or different.) 2. The 1,3,5-triazine derivative or its salt according to claim 1, represented by general formula (I):

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

4. The 1,3,5-triazine derivative or salt thereof according to claim 1, characterized in that 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.

5. The 1,3,5-triazine derivative or salt thereof according to claim 2, characterized in that in said 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 any of these salts.

6. The 1,3,5-triazine derivative or salt thereof according to claim 1, characterized in that in said general formulas (I) to (IV), at least one of the Y's 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.

7. The 1,3,5-triazine derivative or salt thereof according to claim 2, characterized in that in said general formula (I), at least one of the Y's 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.

8. The 1,3,5-triazine derivative or salt thereof according to claim 1, wherein 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 salt thereof.

9. The 1,3,5-triazine derivative or salt thereof according to claim 2, wherein in 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 salt thereof.

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

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

12. In the above general formulas (I) to (IV), G １ , G ２ , and G ３ are all the same or different -X-Z-Y, or a salt thereof.

13. In the general formula (I), G １ , G ２ , and G ３ are all the same or different -X-Z-Y, or a salt thereof.

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 comprising the 1,3,5-triazine derivative or its salt according to any one of claims 1 to 13.

16. A composition for external application to the skin, comprising the 1,3,5-triazine derivative or its salt according to any one of claims 1 to 13.

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

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

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