Organic p-xylylene dichorsulfonic acid salt for ultraviolet-blocking cosmetic composition and preparation method of organic p-xylylene dichorsulfonic acid salt

Abstract

The present invention relates to an organic salt of p-xylylene dichorsulfonic acid, which can be used in a cosmetic composition for blocking ultraviolet rays, and a preparation method thereof. The invention provides an organic salt of p-xylylene dichorsulfonic acid, which is a neutralization product obtained by combining an organic amine compound with a strongly acidic p-xylylene dichorsulfonic acid aqueous solution with the pH value of 1 in an aqueous solution phase or a powder phase, and the pH value of the organic salt is 5.0-9.0. Therefore, when cosmetics are produced, no extra neutralizer is needed, convenience and safety are achieved, excellent long-term storage stability is achieved, and consistent prescriptions, especially in cosmetic formulas, can be achieved.

Description

Technical Field

[0001] The present invention relates to an organic salt of terephthalylidene dicamphor sulfonic acid that can be used for a cosmetic composition that blocks ultraviolet rays and a preparation method thereof. More specifically, the present invention provides an organic salt of terephthalylidene dicamphor sulfonic acid, which is a neutralized product obtained by combining an organic amine compound with a strongly acidic terephthalylidene dicamphor sulfonic acid aqueous solution having a pH value of 1 in an aqueous solution phase or a powder phase, and the pH value thereof is 5.0 to 9.0. Therefore, the present invention does not require the additional use of a neutralizing agent when producing cosmetics, which is convenient and safe. Therefore, the present invention does not require the additional use of a neutralizing agent when producing cosmetics, which is convenient and safe, and has excellent long-term storage stability, and can achieve a consistent cosmetic formula prescription. Background Art

[0002] As the ozone layer is destroyed due to climate change, ultraviolet rays directly irradiate human skin, causing spots and skin aging. Therefore, ultraviolet blockers are indispensable in cosmetics and are widely used in cosmetics.

[0003] In particular, ultraviolet rays (UVB) in the wavelength range of 280-320 nm can cause erythema (redness) on human skin, while ultraviolet rays (UVA) in the wavelength range of 320-400 nm can cause browning of the skin, cause skin damage, and induce skin cancer.

[0004] Additionally, many countries around the world are tightening regulations regarding skin safety and irritation of sunscreens applied to the skin.

[0005] When light in the ultraviolet range enters the UV blocker, it absorbs the light energy of the ultraviolet light and converts it into heat energy. In other words, the absorbed light ends the life of the light and converts into heat energy. The ultraviolet rays will be absorbed by the UV blocker, blocking the ultraviolet rays from reaching the skin, thereby protecting the skin.

[0006] Currently, terephthalylidene dicamphor sulfonicacid (TDSA, called "Ecamsule" in the United States Pharmacopoeia) is a UV blocker approved by the US FDA. Its blocking performance is in the wavelength range of 320~400 nm, which is equivalent to long-wave ultraviolet rays (UVA).

[0007] With the increasing demand for UV blocking, the application of terephthalylidene dicamphor sulfonic acid is expanding to various fields such as shampoo, medicine, and cosmetics as the market expands.

[0008] Patent Documents 1 and 2 disclose methods for synthesizing terephthalylidene dicamphor sulfonic acid, but it is difficult to remove charged organic impurities, phosphorus chloride, sulfate ions, chloride ions, heavy metals, sodium, etc. generated during the synthesis of terephthalylidene dicamphor sulfonic acid using only known synthesis techniques.

[0009] Therefore, Patent Document 3 discloses a method for purifying terephthalylidene dicamphor sulfonic acid, using a mixed resin containing cations and anions, thereby removing cationic substances and anionic substances generated during synthesis and precipitation, thereby improving the absorbance at the maximum absorption wavelength in ultraviolet spectral analysis.

[0010] However, since terephthalylidene dicamphor sulfonic acid itself has a strong acidity of pH 1 or lower, a neutralizer must be used when used in a cosmetic composition, which brings inconvenience and safety issues to users and requires users to pay attention to them. In particular, even if a neutralizer is used, problems such as pH adjustment and inconsistent formulations may occur in cosmetic applications.

[0011] Furthermore, since terephthalylidene dicamphor sulfonic acid itself is strongly acidic with a pH value of 1 or less, long-term exposure to acidic conditions can lead to a problem in that the purity decreases over time.

[0012] Therefore, by making efforts to solve the above-mentioned problems of using terephthalylidene dicamphor sulfonic acid as a UV blocker in cosmetics, the inventors added an organic amine used in cosmetics to a strongly acidic terephthalylidene dicamphor sulfonic acid aqueous solution with a pH value of 1 to adjust the pH value of the solution to a range of 5.0 to 9.0, and provided an organic salt of terephthalylidene dicamphor sulfonic acid in the form of an aqueous solution or a powder, so that the preparation of cosmetics does not require a separate neutralizer, the preparation of cosmetics is convenient and safe, the prescription is consistent, and the stability of long-term storage is ensured, thereby completing the present invention.

[0013] (Patent Document 1) U.S. Patent Publication No. 4,585,597 (published on April 29, 1986) (Patent Document 2) Chinese Patent Publication No. 106831503 (published on June 13, 2017) (Patent Document 3) Korean Patent Publication No. 10-1937332 (published on January 11, 2019) Summary of the invention Technical issues The object of the present invention is to provide an organic salt of terephthalylidene dicamphor sulfonic acid, which satisfies the convenience and safety requirements in the production of cosmetics by providing a neutralized product formed by combining strongly acidic terephthalylidene dicamphor sulfonic acid with an organic amine compound in a stoichiometric manner.

[0014] Another object of the present invention is to provide a method for preparing an organic salt of terephthalylidene dicamphor sulfonic acid in the form of an aqueous solution or a powder.

[0015] Another object of the present invention is to provide a UV-shielding cosmetic composition containing the organic salt of terephthalylidene dicamphor sulfonic acid.

[0016] Technical Solution To achieve the above-mentioned object, the present invention provides an organic salt of camphor sulfonic acid, which is a neutralization product having a pH value of 5.0 to 9.0 obtained by stoichiometrically combining an organic amine compound with both ends of camphor sulfonic acid, and can be used for a cosmetic composition for blocking ultraviolet rays. Its chemical formula 1 is as follows.

[0017] Chemical formula 1 Wherein, R1, R2 and R3 are the same or different from each other and are independently selected from hydrogen, hydroxyl, amino, carboxyl, C1~C 10 Alkyl, C1~C 10 Hydroxyalkyl, C1~C 10 heteroalkyl, heterocycloalkyl having 20 or less carbon atoms, aryl having 20 or less carbon atoms, C1~C1 containing heterocycloalkyl having 20 or less carbon atoms 10 Alkyl and C1~C2 containing aromatic groups having 20 or fewer carbon atoms 10 One or more substituents in an alkyl group.

[0018] As the organic amine compound, it is preferable to use any one selected from tromethamine, triethanolamine, and 2-amino-2-methyl-1-propanol (AMP).

[0019] As another preferred type of organic amine compound, any one basic amino acid selected from arginine, lysine, histidine, citrulline, and amino acid derivatives in which the carboxyl group of the amino acid is substituted and only the primary amine group remains can be used.

[0020] In addition, another preferred organic amine compound may be used, which is any one polyamine selected from polyethyleneimine, spermidine, spermine, cadaverine and putrescine.

[0021] The organic salt of terephthalylidene dicamphor sulfonic acid can be provided in the form of an aqueous solution or a powder, thereby providing convenience and safety for the production of cosmetics.

[0022] The invention provides a method for preparing an organic salt of terephthalylidene dicamphor sulfonic acid.

[0023] Specifically, the present invention provides a method for preparing an organic salt of terephthalylidene dicamphor sulfonic acid, by dissolving an organic amine compound in a purified terephthalylidene dicamphor sulfonic acid aqueous solution, adjusting the pH value of the solution, and then filtering to obtain a clear aqueous solution.

[0024] In the method of the present invention, the clear aqueous solution obtained above can be further added dropwise into an organic solvent to precipitate crystals, and the crystals are dried in vacuum to obtain a powder form.

[0025] In addition, in the method of the present invention, the clear aqueous solution obtained above can be further freeze-dried to obtain a powder form.

[0026] At this time, when the organic salt of terephthalylidene dicamphor sulfonic acid is an aqueous solution, it can also contain one or more preservatives to maintain the formula, and the preservatives are selected from 1,2-alkanediol, ethylhexylglycerin, hydroxyacetophenone, glycerides, parabens and sodium benzoate.

[0027] Beneficial Effects According to the present invention, an organic salt of terephthalylidene dicamphor sulfonic acid can be provided, which is a neutralization product of strongly acidic terephthalylidene dicamphor sulfonic acid and an organic amine compound. No separate neutralizing agent is required when producing cosmetics, which is convenient and safe, and can ensure long-term storage stability, thereby keeping the formula in cosmetic applications consistent.

[0028] According to the preparation method of the present invention, the organic salt of terephthalylidene dicamphor sulfonic acid can be provided in the form of an aqueous solution or a powder. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 The infrared spectrum results of terephthalylidene dicamphorsulfonic acid 2-tromethamine of the present invention are shown.

[0030] Figure 2 A photograph showing the terephthalylidene dicamphorsulfonic acid·2-tromethamine aqueous solution of the present invention.

[0031] Figure 3 A photograph showing the terephthalylidene dicamphorsulfonic acid·2-tromethamine crystals of the present invention.

[0032] Figure 4 A photograph showing the terephthalylidene dicamphorsulfonic acid·2-tromethamine powder of the present invention. DETAILED DESCRIPTION

[0033] The present invention provides an organic salt of terephthalylidene camphor sulfonic acid, which is a neutralization product having a pH value of 5.0 to 9.0 obtained by stoichiometrically combining an organic amine compound with two ends of terephthalylidene camphor sulfonic acid, as shown in the following chemical formula 1.

[0034] Chemical formula 1 Wherein, R1, R2 and R3 are the same or different from each other and are independently selected from hydrogen, hydroxyl, amino, carboxyl, C1~C 10 Alkyl, C1~C 10 Hydroxyalkyl, C1~C 10 heteroalkyl, heterocycloalkyl having 20 or less carbon atoms, aryl having 20 or less carbon atoms, C1~C1 containing heterocycloalkyl having 20 or less carbon atoms 10 Alkyl and C1~C2 containing aromatic groups having 20 or fewer carbon atoms 10 One or more substituents in an alkyl group.

[0035] Since terephthalylidene dicamphor sulfonic acid can block long-wave ultraviolet rays with a wavelength range of 320 to 400 nm, it is used as a cosmetic material for blocking ultraviolet rays. However, in order to solve the problem of strong acidity of terephthalylidene dicamphor sulfonic acid, terephthalylidene dicamphor sulfonic acid is provided in the form of a salt, thereby ensuring safety during use, providing work convenience, and providing a cosmetic composition with stable ultraviolet blocking ability.

[0036] The organic amine compound used to form the above salts may be an organic amine compound used in cosmetic formulations, a basic amino acid, a biologically derived amine, an organic amine compound used as a food additive, and an organic amine compound used in pharmaceuticals.

[0037] In the organic salt of terephthalylidene dicamphor sulfonic acid of the present invention, the salt used is an organic amine compound designated for pharmaceutical raw materials, food additive raw materials and cosmetic raw materials, so the stability of the raw materials ensures the safety of the final target compound to the human body.

[0038] Specifically, the present invention uses an organic amine for a cosmetic composition, which contains an organic salt of terephthalylidene dicamphor sulfonic acid, which is a neutralization product obtained by combining an organic amine compound with terephthalylidene dicamphor sulfonic acid in an equivalent ratio of 1:2, and has a pH value of 5.0-9.0, preferably a pH value of 6.1-8.0.

[0039] In an embodiment of the present invention, tromethamine, triethanolamine or 2-amino-2-methyl-1-propanol (AMP) is used as a preferred example, but is not limited thereto.

[0040] As another organic amine compound, any one basic amino acid selected from arginine, lysine, histidine, citrulline, and an amino acid derivative in which the carboxyl group of the amino acid is substituted and only the primary amine group remains can be used. As an example of an amino acid derivative, the carboxyl group of the amino acid in N-acetyl-glutamine isostearyl (isostearyl acetyl glutaminate) is substituted and only the primary amine group remains.

[0041] In the embodiments of the present invention, arginine, lysine, and histidine may be used for illustration, but are not limited thereto.

[0042] In addition, as the organic amine compound of the present invention, polyamine is preferably used, and more preferably, any one of polyethyleneimine (PEI), spermidine, spermine, cadaverine, and putrescine can be used.

[0043] Polyethyleneimine is the most well-known polyamine and has the highest cationic density among the existing materials, especially since it is a water-soluble polymer.

[0044] In addition, spermidine is present in various foods such as soybeans, wheat and meat, and spermine is a polyamine with a similar structure to spermidine that performs various physiological functions within cells. Cadaverine is a polyamine found in rotting meat, from which its name is derived, and putrescine is another bioderived polyamine found in various organisms, all of which can be used in the present invention.

[0045] The above organic amine compound is combined with terephthalene dicamphor sulfonic acid in a stoichiometric ratio of two equivalents to form an organic salt of terephthalene dicamphor sulfonic acid.

[0046] Figure 1 The infrared (IR) spectrum result of the terephthalylidene dicamphorsulfonic acid·2-tromethamine organic salt of the present invention is shown, confirming the synthesis of the organic salt.

[0047] The organic salt of terephthalylidene dicamphor sulfonic acid of the present invention can be provided in the form of an aqueous solution or a powder according to the required formula in the cosmetic production process, and can be provided in the form of a stable salt, so that a separate neutralizer is not required in the cosmetic production process, which is convenient and safe, and can also make the prescription of the cosmetic formula consistent.

[0048] In addition, the organic salt of terephthalylidene dicamphor sulfonic acid obtained by the preparation method of the present invention has long-term stability.

[0049] The present invention provides a method for preparing an organic salt of terephthalylidene camphor sulfonic acid. In a first embodiment, the method for preparing an organic salt of terephthalylidene camphor sulfonic acid comprises: dissolving an alkaline organic amine in a purified terephthalylidene camphor sulfonic acid aqueous solution at a temperature lower than or equal to 30°C, adjusting the pH value of the solution, and then filtering the solution with a microfilter to obtain a clear aqueous solution.

[0050] At this time, the pH value of the organic salt of terephthalylidene dicamphor sulfonic acid is finally adjusted to a range of 5.0 to 9.0, and most preferably a range of 6.1 to 8.0.

[0051] An aqueous solution containing a stable formulation of an organic salt of terephthalylidene dicamphor sulfonic acid is provided.

[0052] For example, Figure 2 This is a photograph of the aqueous solution of terephthalylidene dicamphorsulfonic acid and 2-tromethamine in Example 1. The organic salt of terephthalylidene dicamphorsulfonic acid is more stable in a neutral solution than in an acidic solution, and in particular, since it is a neutral solution, it does not deteriorate, and its stability is also improved when a preservative such as 1,2-ethylene glycol is used.

[0053] At this time, the aqueous solution may further contain one or more preservatives selected from 1,2-alkanediol, ethylhexylglycerin, hydroxyacetophenone, glycerides, parabens and sodium benzoate. By further adding preservatives, the formulation stability of the salt can be improved.

[0054] More specifically, for the obtained organic salt of terephthalylidene dicamphor sulfonic acid, the storage stability of the aqueous solution of the organic salt of terephthalylidene dicamphor sulfonic acid can be improved by using 1 to 2.5% of 1,2-hexanediol, 1 to 5% of 1,2-pentanediol, 0.1 to 1% of 1,2-octanediol and 0.1 to 1% of ethylhexylglycerol alone or in combination.

[0055] In the preparation method of the second embodiment of the present invention, a clear aqueous solution of the organic salt of terephthalylidene dicamphor sulfonic acid obtained in the first embodiment is prepared, and the aqueous solution is added dropwise to an organic solvent such as ethanol or acetone or a mixture thereof in an amount four times the volume of the aqueous solution to precipitate crystals, and the crystals are filtered and dried to obtain a powder form after vacuum drying.

[0056] Figure 3This is a photograph of the crystals of terephthalene dicamphor sulfonic acid 2-tromethamine of the present invention. 100 g of the clear aqueous solution of the organic salt of terephthalene dicamphor sulfonic acid obtained in the first embodiment is slowly added dropwise to a four-necked round-bottom flask containing 100 to 500 mL of ethanol or acetone or a mixed solvent thereof while stirring to precipitate the salt. The precipitated crystals are filtered, washed with acetone, and vacuum dried to obtain the organic salt of terephthalene dicamphor sulfonic acid 2-tromethamine.

[0057] Furthermore, in the preparation method of the third embodiment of the present invention, a clear aqueous solution of the organic salt of terephthalylidene dicamphor sulfonic acid obtained in the first embodiment is prepared, and the aqueous solution is freeze-dried to obtain a powder form.

[0058] Figure 4 The powder form of the terephthalylidene dicamphorsulfonic acid 2-tromethamine of the present invention is shown. As described above, the present invention provides an aqueous solution obtained from the method for preparing an organic salt of terephthalylidene dicamphorsulfonic acid, which can be used as it is or in various forms including a crystal form obtained by precipitating the aqueous solution in an organic solvent or a powder form obtained by freeze drying, so as to be selectively used according to the desired formulation when producing cosmetics.

[0059] In particular, the crystals of the organic salt of terephthalylidene dicamphorsulfonic acid exist in a solid form and are therefore more stable than acidic liquids and neutral solutions and can be stored for a long time even at a high temperature such as 45°C.

[0060] The preparation method of the present invention can improve the shortcomings of the traditionally used terephthalylidene dicamphor sulfonic acid, namely, the product stability problem caused by the use of a strong acidic substance with a pH value of 1 or lower, the corrosion of cosmetic production equipment, the heavy metal pollution of cosmetics caused thereby, and the difficulty in stabilizing the product in the cosmetic preparation process. The method also provides safety for the user's body and the work required for cosmetic production.

[0061] Implementation Hereinafter, the present invention will be described in more detail by means of the following examples.

[0062] These Examples are intended to explain the present invention in more detail, and the scope of the present invention is not limited to these Examples.

[0063] <Example 1> According to the analytical method of the United States Pharmacopoeia, 1000 g (0.597 mol) of a 33.6% pure terephthalene dicamphor sulfonic acid (Ecamsule) aqueous solution was placed in a 2 L four-necked round-bottom flask, and 144.64 g (1.194 mol) of tromethamine with a molecular weight of 121.14 g / mol was added while stirring to completely dissolve the solute, and then the pH value of the resulting solution was adjusted to 6.6. The solution was filtered with filter paper to obtain a clear aqueous solution containing terephthalene dicamphor sulfonic acid · 2-tromethamine, whose chemical formula 1-1 is as follows.

[0064] Chemical formula 1-1 <Example 2> 200 g of the terephthalene dicamphorsulfonic acid·2-tromethamine aqueous solution obtained in Example 1 was slowly added dropwise to a beaker containing 800 mL of acetone prepared in advance, and allowed to stand at room temperature for 30 minutes to allow crystals to precipitate. Stirring was continued for two hours until the crystals were completely precipitated, and the crystals were filtered and washed to obtain the target product, i.e., crystals of terephthalene dicamphorsulfonic acid·2-tromethamine. The obtained product was vacuum dried to obtain 79.79 g of the solid target product (yield 95%).

[0065] <Example 3> 200 g of the terephthalylidene dicamphorsulfonic acid·2-tromethamine aqueous solution obtained in Example 1 was placed in a freeze dryer (Lyovapor™ L-300 model) and freeze-dried at ±1°C for 15 hours to obtain 83.98 g of terephthalylidene dicamphorsulfonic acid·2-tromethamine white powdery solid.

[0066] <Example 4> According to the analytical method of the United States Pharmacopoeia, 1000 g (0.597 mol) of a 33.6% pure terephthalene dicamphor sulfonic acid aqueous solution was placed in a 2 L four-necked round-bottom flask, and 178.13 g (1.194 mol) of triethanolamine with a molecular weight of 149.19 g / mol was added while stirring to completely dissolve the solute, and then the pH value of the resulting solution was adjusted to 6.6. The solution was filtered with filter paper to obtain a clear aqueous solution containing terephthalene dicamphor sulfonic acid·2-triethanolamine.

[0067] <Example 5> 200 g of the terephthalylidene dicamphor sulfonic acid·2-triethanolamine aqueous solution obtained in Example 4 was slowly added dropwise to a beaker containing 800 mL of acetone prepared in advance, and allowed to stand at room temperature for 30 minutes to allow crystals to precipitate. Stirring was continued for two hours until the crystals were completely precipitated, and the crystals were filtered and washed to obtain the target product, i.e., crystals of terephthalylidene dicamphor sulfonic acid·2-triethanolamine. The terephthalylidene dicamphor sulfonic acid·2-triethanolamine crystals were vacuum dried to obtain 83.79 g of the target product solid (yield 96%).

[0068] <Example 6> 200 g of the terephthalylidene dicamphorsulfonic acid·2-triethanolamine aqueous solution obtained in Example 4 was placed in a freeze dryer (Lyovapor™ L-300 model) and freeze-dried at ±1°C for 15 hours to obtain 87.19 g of terephthalylidene dicamphorsulfonic acid·2-triethanolamine white powdery solid.

[0069] <Example 7> According to the analytical method of the United States Pharmacopoeia, 1000 g (0.597 mol) of a 33.6% pure terephthalene dicamphor sulfonic acid aqueous solution was placed in a 2 L four-necked round-bottom flask, and 208 g (1.194 mol) of arginine with a molecular weight of 174.21 g / mol was added while stirring to completely dissolve the solute, and then the pH value of the resulting solution was adjusted to 6.6. The solution was filtered with filter paper to obtain a clear terephthalene dicamphor sulfonic acid·2-arginine aqueous solution.

[0070] <Example 8> 200 g of the terephthalylidene dicamphor sulfonic acid·2-arginine aqueous solution obtained in Example 7 was slowly added dropwise to a beaker containing 800 mL of acetone prepared in advance, and allowed to stand at room temperature for 30 minutes to allow crystals to precipitate. Stirring was continued for two hours until the crystals were completely precipitated, and the crystals were filtered and washed to obtain the target product, i.e., crystals of terephthalylidene dicamphor sulfonic acid·2-arginine. The obtained product was vacuum dried to obtain 85.57 g of the solid target product (yield 95%).

[0071] <Example 9> 200 g of the terephthalylidene dicamphorsulfonic acid·2-arginine aqueous solution obtained in Example 7 was placed in a freeze dryer (Lyovapor™ L-300 model) and freeze-dried at ±1°C for 15 hours to obtain 90.07 g of terephthalylidene dicamphorsulfonic acid·2-arginine white powdery solid.

[0072] <Example 10> According to the analytical method of the United States Pharmacopoeia, 1000 g (0.597 mol) of a 33.6% pure terephthalylidene dicamphor sulfonic acid aqueous solution was placed in a 2 L four-necked round-bottom flask, and 106.3 g (1.194 mol) of 2-amino-2-methyl-1-propanol (AMP) with a molecular weight of 89.136 g / mol was added while stirring to completely dissolve the solute, and the pH value of the resulting solution was adjusted to 6.6. The solution was filtered with filter paper to obtain a clear terephthalylidene dicamphor sulfonic acid·2 AMP aqueous solution.

[0073] <Example 11> 200 g of the terephthalylidene dicamphor sulfonic acid·2 AMP aqueous solution obtained in Example 10 was slowly added dropwise to a beaker containing 800 mL of acetone prepared in advance, and allowed to stand at room temperature for 30 minutes to allow crystals to precipitate. Stirring was continued for two hours until the crystals were completely precipitated, and the crystals were filtered and washed to obtain the target product, i.e., terephthalylidene dicamphor sulfonic acid·2 AMP crystals. The obtained product was vacuum dried to obtain 75.97 g of the solid target product (yield 95%).

[0074] <Comparative Example 1> According to the analytical method of the United States Pharmacopoeia, 1000 g (0.597 mol) of a 33.6% pure terephthalylidene dicamphor sulfonic acid aqueous solution was placed in a 2 L four-necked round-bottom flask, and sodium hydroxide was added while stirring to precipitate a white solid. The terephthalylidene dicamphor sulfonic acid·2 Na salt obtained by using NaOH inorganic salt as a neutralizer has a low water solubility at room temperature of only 2~3%, so it is difficult to prepare an aqueous solution of 30% or higher concentration, and the ultraviolet absorption effect will also be reduced, so it is not suitable for use as a UV blocker.

[0075] <Experimental Example 1> Evaluation of the sustained stability of terephthalylidene dicamphor sulfonate The terephthalene dicamphor sulfonic acid · 2-tromethamine aqueous solution of Example 1, the aqueous solution containing the aqueous solution of Example 1 mixed with 2.5% 1,2-hexanediol, and the terephthalene dicamphor sulfonic acid · 2-tromethamine crystals of Example 2 were used. After converting the 33.6% terephthalene dicamphor sulfonic acid (TDSA) aqueous solution into the same equivalent, the content was analyzed by HPLC every 3 months, for a maximum of 12 months, and then every 6 months, for a maximum of 24 months, to evaluate stability. The purity test was performed according to the Ecamsule content test method of the United States Pharmacopoeia 44. At this time, the stability test was performed in a constant temperature chamber at 45°C, protected from light under dark conditions.

[0076] Regarding the HPLC sample preparation method, taking 33.6% terephthalylidene dicamphor sulfonic acid aqueous solution as an example, 300 mg of 33.6% terephthalylidene dicamphor sulfonic acid aqueous solution was placed in a 100-mL volumetric flask, and the volume was adjusted to 100 mL with pure water. Then 5 mL of the resulting solution was placed in a 100-mL volumetric flask, and the volume was adjusted to 100 mL with pure water to prepare the sample.

[0077] In addition, for the aqueous solution of terephthalylidene dicamphorsulfonic acid·2-tromethamine in Example 1 and the aqueous solution containing 2.5% of 1,2-hexanediol in Example 1, samples were prepared in the same manner as above and tested for content.

[0078] 100 mg of the terephthalylidene dicamphorsulfonic acid·2-tromethamine crystals in Example 2 were placed in a 100 mL volumetric flask, and the volume was adjusted to 100 mL with purified water. 5 mL of the resulting solution was placed in a 100 mL volumetric flask, and the volume was adjusted to 100 mL with purified water to prepare a sample. The solution was measured using a Shimadzu high performance liquid chromatograph, and the results are shown in Table 1 below.

[0079] [Table 1] Stability Assessment Results The results shown in Table 1 confirm that the aqueous solution of terephthalylidene dicamphor sulfonic acid is a strong acidic solution and its purity will be reduced if stored at 45°C for a long time.

[0080] On the other hand, it was confirmed that the neutral salt solution of terephthalylidene dicamphorsulfonic acid 2-tromethamine in Example 1 was more stable than the acidic aqueous solution, and furthermore, when added to an aqueous solution containing 1,2-hexanediol, its stability was higher. In addition, it was confirmed that the solid obtained by crystallizing the salt of terephthalylidene dicamphorsulfonic acid 2-tromethamine was stable not only under high temperature conditions of 45°C but also under long-term storage conditions of 24 months, with almost no decrease in content.

[0081] Although the present invention has been described in detail only with respect to the specific embodiments described, it is obvious to those skilled in the art that various modifications and corrections can be made within the technical scope of the present invention. Obviously, these modifications and corrections fall within the scope of the appended claims.

Claims

1. An organic salt of terephthalylidene dicamphor sulfonic acid, as shown in the following chemical formula 1, is a neutralized product obtained by stoichiometrically combining an organic amine compound with the two ends of terephthalylidene dicamphor sulfonic acid, and is used as a cosmetic ingredient for blocking ultraviolet rays: Chemical formula 1 in, R1, R2 and R3 are the same or different from each other and are independently selected from hydrogen, hydroxyl, amino, carboxyl, C1~C 10 Alkyl, C1~C 10 Hydroxyalkyl, C1~C 10 heteroalkyl, heterocycloalkyl having 20 or less carbon atoms, aryl having 20 or less carbon atoms, C1~C1 containing heterocycloalkyl having 20 or less carbon atoms 10 Alkyl and C1~C2 containing aromatic groups having 20 or fewer carbon atoms 10 One or more substituents in an alkyl group. 2 . The organic salt of terephthalylidene dicamphor sulfonic acid according to claim 1 , wherein the organic amine compound is selected from any one of tromethamine, triethanolamine and 2-amino-2-methyl-1-propanol (AMP).

3. The organic salt of terephthalylidene dicamphor sulfonic acid according to claim 1, wherein the organic amine compound is any one basic amino acid selected from arginine, lysine, histidine, citrulline, and an amino acid derivative in which the carboxyl group of the amino acid is substituted and only the primary amine group is retained.

4. The organic salt of terephthalylidene dicamphor sulfonic acid according to claim 1, wherein the organic amine compound is any one polyamine selected from the group consisting of polyethyleneimine, spermidine, spermine, cadaverine and putrescine. 5 . The organic salt of terephthalylidene dicamphor sulfonic acid according to claim 1 , wherein the organic salt of terephthalylidene dicamphor sulfonic acid is in the form of an aqueous solution or a powder.

6. A method for preparing an organic salt of terephthalylidene dicamphor sulfonic acid as shown in the following chemical formula 1, by dissolving an organic amine compound in a purified terephthalylidene dicamphor sulfonic acid aqueous solution, adjusting the pH value of the solution, and then filtering to obtain a clear aqueous solution: Chemical formula 1 in, R1, R2 and R3 are as defined in claim 1.

7. The method according to claim 6, further comprising dropping the obtained clear aqueous solution into an organic solvent to precipitate crystals, and vacuum drying the crystals to obtain a powder form.

8. The method according to claim 6, further comprising freeze-drying the obtained clear aqueous solution to obtain a powder form.

9. The method of claim 6, wherein the aqueous solution further comprises one or more preservatives selected from the group consisting of 1,2-alkanediol, ethylhexylglycerin, hydroxyacetophenone, glycerides, parabens, and sodium benzoate.

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