SPF-enhancing polymer having excellent feeling of use

Abstract

Provided are: an SPF-enhancing polymer which exhibits an excellent feeling of use that is not sticky while having an SPF-enhancing effect; and an ultraviolet-blocking composition comprising the same. A cosmetic composition for blocking ultraviolet rays, which contains the amphiphilic copolymer of the present invention, corresponds to or exhibits an excellent value compared to a conventional SPF-enhancing film-forming agent, and exhibits a low stickiness and an excellent feeling of use compared to a dosage form in which a conventional film-forming agent is used. Thus, the polymer can be usefully used in a cosmetic composition for blocking ultraviolet rays as a polymer for enhancing SPF in the field of cosmetics.

Description

Technical Field

[0001] This invention relates to a polymer for SPF reinforcement, and more specifically, to a polymer for SPF reinforcement with excellent user experience. Background Technology

[0002] UV blockers contain chemical and physical components that protect the skin by absorbing or reflecting ultraviolet (UV) rays, blocking both UVA and UVB rays. To improve the physical properties and UV-blocking ability of UV blockers, polymers are sometimes used, primarily to stabilize the UV-blocking components, improve spreadability, enhance durability, form a protective film on the skin, and improve the feel and experience.

[0003] In sunscreen / makeup products, increasing the amount of UV-blocking agents used to improve UV protection can lead to a sticky and heavy feel, as well as a reduced user experience due to emulsifiers used to stabilize the UV-blocking ingredients.

[0004] To compensate for these shortcomings, amphiphilic or water-soluble polymers are sometimes used to improve formulation stability and user experience. However, existing polymers used for this purpose do not have an SPF-enhancing effect. Furthermore, film-forming agents are sometimes used as oil-soluble polymers. Although this can exhibit an SPF-enhancing effect, it has the disadvantage of causing the product to feel heavy and pilling due to the film formed after the formulation dries.

[0005] Therefore, what is needed is an SPF-enhancing material that can improve the SPF value without reducing the user experience when applied to products. Summary of the Invention

[0006] The problem to be solved

[0007] The problem to be solved by the present invention is to provide an SPF-enhancing polymer that exhibits excellent user experience while having an SPF-enhancing effect.

[0008] Furthermore, the problem solved by the present invention is to provide an ultraviolet blocking composition comprising the above-mentioned SPF-enhancing polymer.

[0009] The problems to be solved by the present invention are not limited to those mentioned above. Those skilled in the art should be able to clearly understand other technical problems not mentioned through the following description.

[0010] Solution to the problem

[0011] In order to achieve the above-mentioned problem, according to one aspect of the present invention, an amphiphilic copolymer represented by the following chemical formula 1 is provided.

[0012] <Chemical Formula 1>

[0013]

[0014] In the above formula,

[0015] A is C 12-22 Alkyl acrylate or C 12-22 Alkyl methacrylates,

[0016] B is 2-acrylamido-2-methyl-1-propanesulfonic acid.

[0017] X and Y represent the weight percentage (%) of each monomer in the copolymer.

[0018] X ranges from 0.001% by weight to 99.999% by weight.

[0019] Y ranges from 0.001% by weight to 99.999% by weight.

[0020] The amphiphilic copolymer of the present invention is composed of C as a hydrophobic monomer. 12-22 Alkyl acrylate or C 12-22 Alkyl methacrylates and 2-acrylamido-2-methyl-1-propanesulfonic acid (taurate series), which is a hydrophilic monomer, exhibit amphiphilic properties.

[0021] In one implementation, X is 50% to 99.999% by weight, Y is 0.001% to 50% by weight, preferably X is 60% to 99.999% by weight, Y is 0.001% to 40% by weight, more preferably X is 80% to 99.999% by weight, Y is 0.001% to 20% by weight, and most preferably X is 85% to 99.999% by weight, Y is 0.001% to 15% by weight.

[0022] Furthermore, in one implementation example, X can be 85% to 95% by weight and Y can be 5% to 15% by weight; or X can be 80% to 90% by weight and Y can be 10% to 20% by weight.

[0023] In one implementation, the molecular weight of the amphiphilic copolymer can be 10 to 100 kDa, preferably 20 to 80 kDa, more preferably 30 to 60 kDa, and most preferably 40 to 50 kDa, but is not limited thereto.

[0024] In one implementation, the melting point of the amphiphilic copolymer according to the present invention can be 40 to 45°C, but is not limited to this. Within the above melting point range, the user experience can be even better.

[0025] In one implementation example, the amphiphilic copolymer of the above chemical formula 1 can be an amphiphilic copolymer of the following chemical formula 2.

[0026] <Chemical Formula 2>

[0027]

[0028] In the above formula,

[0029] R1 is hydrogen or methyl, R2 is C 12-22 alkyl,

[0030] X and Y represent the weight percentage (%) of each monomer in the copolymer.

[0031] X ranges from 0.001% by weight to 99.999% by weight.

[0032] Y ranges from 0.001% by weight to 99.999% by weight.

[0033] The amphiphilic copolymer of the present invention, represented by the following chemical formula 1, can be manufactured by a manufacturing method including the step of reacting monomer A and monomer B in a reaction solvent, wherein monomer A is C. 12-22 Alkyl acrylate or C 12-22 Alkyl methacrylate, wherein monomer B is 2-acrylamido-2-methyl-1-propanesulfonic acid.

[0034] <Chemical Formula 1>

[0035]

[0036] In the above formula,

[0037] X and Y represent the weight percentage (%) of each monomer in the copolymer.

[0038] X ranges from 0.001% by weight to 99.999% by weight.

[0039] Y ranges from 0.001% by weight to 99.999% by weight.

[0040] In the method for manufacturing the amphiphilic copolymer of the present invention, reaction solvents and reaction conditions commonly used in copolymer synthesis methods can be used, and preferably, the copolymer can be manufactured as follows.

[0041] Add an appropriate amount (e.g., about 6 times the weight of the monomer) of a reaction solvent commonly used in polymer synthesis methods (e.g., t-BuOH, etc.). After adding the monomer to the solvent according to its respective weight ratio, add an appropriate amount (e.g., 0.33 times the weight of the monomer) of an auxiliary solvent for dissolving the monomer (e.g., ammonia water (25-28 wt%) for dissolving AMPS) as needed. After heating to a temperature suitable for the polymer-forming reaction (e.g., 75°C) to dissolve the monomer, add an appropriate amount (e.g., 1.625% of the monomer weight, dissolved in about 20 times the weight of the initiator in acetone) of polymerization initiator (e.g., ACVA[4,4'-Azobis(4-cyanovaleric acid), 4,4'-azobis(4-cyanovaleric acid)) and maintain an appropriate temperature (e.g., 70-75°C) for an appropriate time (e.g., 4 hours). Add an appropriate solvent (e.g., ethanol) at about 3 times the weight of the reaction solvent to obtain a precipitate, thereby obtaining the final polymer.

[0042] According to another aspect of the present invention, a cosmetic composition for blocking ultraviolet rays comprising the above-described amphiphilic copolymer is provided. The amphiphilic copolymer of the present invention is contained in the oil phase of the above-described cosmetic composition for blocking ultraviolet rays, and the final formulation is preferably an O / W type.

[0043] The cosmetic composition for ultraviolet blocking of the present invention may contain an effective ultraviolet blocking ingredient. As the aforementioned effective ultraviolet blocking ingredient, it may include inorganic ultraviolet blocking agents and / or organic ultraviolet blocking agents.

[0044] The aforementioned inorganic ultraviolet blocking agent can be any one or more selected from the group consisting of titanium dioxide and zinc oxide.

[0045] The aforementioned organic ultraviolet blocking agent may be any one or more selected from the group consisting of ethylhexyl methoxycinnamate, ethylhexyl salicylate, octocrylene, butyl methoxydibenzoylmethane, oxybenzophenone, octyl triazine ketone, menthol anthranilate, methylene bis-benzotriazolyl tetramethylbutylphenol, humosasulfate, ethylhexyl triazine ketone, 3,4-methylbenzyl methylene camphor, p-methoxycinnamate isoamyl ester, bis-ethylhexyloxyphenol methoxyphenyl triazine, polysiloxane-15, diethylaminohydroxybenzoylhexyl benzoate, and phenylbenzimidazole sulfonic acid.

[0046] The cosmetic composition may include 2 to 30% by weight of the aforementioned inorganic UV blocker, preferably 3 to 25% by weight, more preferably 5 to 20% by weight, relative to the total weight of the composition.

[0047] The cosmetic composition may include 1 to 30% by weight of the aforementioned organic UV blocker, preferably 3 to 25% by weight, more preferably 5 to 20% by weight, relative to the total weight of the composition.

[0048] The cosmetic composition for UV blocking according to the present invention may contain the above-mentioned amphiphilic copolymer and the above-mentioned UV blocking active ingredient in a ratio of 1:100 by weight. Preferably, it may contain them in a ratio of 1:80 to 1:60, and more preferably, in a ratio of 1:40 to 1:20. Within the above ratio range, the effect according to the present invention is even better.

[0049] The UV-blocking cosmetic compositions containing the amphiphilic copolymer of the present invention correspond to or outperform SPF-enhancing film-forming agents conventionally used in the industry. Therefore, it has been confirmed that the amphiphilic copolymer of the present invention can be used as a polymer for SPF enhancement.

[0050] Furthermore, it has been confirmed that the UV-blocking cosmetic composition containing the amphiphilic copolymer of the present invention exhibits lower stickiness and superior user experience compared to formulations using existing SPF-enhancing film-forming agents, and demonstrates excellent non-stickiness while achieving an SPF-enhancing effect. This solves the problem of user experience being hindered by UV-blocking raw materials and emulsifiers used together, demonstrating an SPF-enhancing effect that achieves the desired SPF effect while using a smaller amount of UV-blocking raw material.

[0051] In this instruction manual, "SPF" refers to the standard ultraviolet blocking index used in the cosmetics industry, which can be measured using the following method: A subject's skin area is exposed to ultraviolet light without the application of an ultraviolet blocking product, and erythema in the skin area is assessed over a period of 16 to 24 hours. Then, an ultraviolet blocking product is applied to the subject's skin area, followed by exposure to ultraviolet light, and erythema in the skin area is assessed again over a period of 16 to 24 hours. Next, the ratio of the ultraviolet radiation dose at which minimal erythema occurs in the skin area with the product applied to the ultraviolet radiation dose at which minimal erythema occurs in the skin area without the product applied is calculated and expressed as the SPF.

[0052] In this specification, "SPF enhancement" refers to further increasing the SPF value of the UV blocker calculated as described above. That is, SPF enhancement of the present invention means that a second SPF value measured when applying a cosmetic composition for UV blocking containing the amphiphilic copolymer according to the present invention is greater than a first SPF value measured when applying a cosmetic composition for UV blocking that does not contain the amphiphilic copolymer according to the present invention.

[0053] The cosmetic compositions according to the invention may also contain all kinds of additives that can be used in conventional cosmetics, such as preservatives, fragrances, pigments, powders, thickeners, opacifiers, binders, viscosity modifiers, colorants, scenting agents, film-forming agents, etc. These are readily available commercially and can be used.

[0054] All ingredients described in this invention preferably do not exceed the maximum usage limits specified in relevant regulations and standards in Korea, China, Europe, Japan, etc. (e.g., regulations related to cosmetic safety standards (Korea), cosmetic safety technical specifications (China), hygiene standards (China)). That is, preferably, the cosmetic composition according to this invention contains the ingredients according to this invention within the content limits permitted by the relevant regulations and standards of each country.

[0055] The method for manufacturing the ultraviolet-blocking cosmetic composition of the present invention can be manufactured by conventional methods used in the industry for manufacturing ultraviolet-blocking compositions.

[0056] Furthermore, the amount of the ultraviolet-blocking cosmetic composition applied to the skin according to one embodiment of the present invention can be selected in various ways depending on the skin condition, the skin's reaction to ultraviolet light, the ultraviolet index, etc. It can be applied once a day or in multiple applications.

[0057] The dosage form of the ultraviolet blocking cosmetic composition according to one embodiment of the present invention is not particularly limited, and it can be used on the skin, for example, in the form of skin care or body care cosmetics including lotions, serums, creams, gels, ointments, masks, sheets, etc.; facial or body makeup cosmetics including primers, makeup bases, liquid foundations, concealers, etc.; or color makeup cosmetics including lip glosses, blushes, etc.

[0058] Invention Effects

[0059] It has been confirmed that the UV-blocking cosmetic composition containing the amphiphilic copolymer of the present invention corresponds to or exhibits a superior SPF value compared to the SPF-enhancing film-forming agents used in the conventional industry, thus enabling it to be used as an SPF-enhancing polymer. It has also been confirmed that compared to formulations using existing film-forming agents, it has a lower stickiness and exhibits a superior user experience, thus providing an excellent non-sticky user experience while achieving an SPF-enhancing effect.

[0060] Therefore, the amphiphilic copolymer of the present invention can be usefully used in the cosmetic field as an SPF-enhancing polymer in cosmetic compositions for UV blocking.

[0061] The effects of this invention are not limited to those described above, but should be understood to include all effects that can be inferred from the composition of the invention as described in the description or claims. Detailed Implementation

[0062] The present invention will now be described in more detail through embodiments. However, the following embodiments are merely illustrative of the invention, and the scope of the invention is not limited thereto.

[0063] Example 1. Synthesis of SPF-enhancing polymers

[0064] Add t-BuOH (6 times the weight of the monomer) as the reaction solvent. Add the monomer to the solvent according to the weight standard: 85% SMA (stearyl methacrylate) and 15% AMPS (2-acrylamido-2-methyl-1-propanesulfonic acid) or HEA (hydroxyethyl acrylate). To dissolve the AMPS, add 0.33 times the weight of the AMPS monomer (25-28% by weight of ammonia) (do not add ammonia when adding HEA). Heat to 75°C to confirm whether the monomer has dissolved.

[0065] The initiator ACVA [4,4'-Azobis(4-cyanovaleric acid), 4,4'-azobis(4-cyanovaleric acid)] (1.625% relative to the monomer weight) was dissolved in acetone at 20 times its weight relative to the initiator and slowly added. The reaction was carried out at 70–75°C for 4 hours. Ethanol at 3 times the amount of t-BuOH used was then added to obtain a precipitate. The components used in the polymerization are shown in Table 1 below.

[0066] [Table 1]

[0067]

[0068] Example 2. Molecular weight measurement of polymerized polymers

[0069] The molecular weight was determined using gel permeation chromatography (GPC), as shown below.

[0070] The polymer was mixed into tetrahydrofuran to a concentration of 10 mg / ml. The mixture (sample) was placed in a 54°C oven for 10 minutes, followed by a shaker for 60 minutes to promote dissolution. Upon close visual inspection, the sample appeared to be completely dissolved in the solvent.

[0071] The prepared samples were analyzed using two Polypore 300 × 7.5 mm columns (manufactured by Agilent Technologies), a Waters 2695 chromatograph, tetrahydrofuran mobile phase, and refractive index-based detection. Samples were filtered through a 0.45 μm nylon filter before being injected into the HPLC system. The Agilent Technologies Easi Vial polystyrene (PS) standard was used for calibration. Polystyrene standards ranging from 2,520,000 to 162 Daltons were used for calibration.

[0072] The system is equipped with a PSS SECcurity 1260 RI detector. The average molecular weight was determined using a polystyrene calibration curve.

[0073] The spectrum was recorded and various molecular weights were determined using the Win GPC Unichrom 81 program.

[0074] Measurements showed that the average molecular weight of the polymer with a ratio of 85% SMA and 15% AMPS was 46 kDa.

[0075] Example 3. Melting point measurement of monomers and polymers

[0076] Melting point was measured using a differential scanning calorimeter (DSC), as shown below.

[0077] Five mg of polymer samples (SMA 95% / AMPS 5%; SMA 90% / AMPS 10%; SMA 85% / AMPS 15%) placed in a crucible were exposed to a first temperature rise from -20°C to 100°C at a heating rate of 10°C / min, followed by cooling from 100°C to -20°C at a cooling rate of 10°C / min, and finally exposed to a second temperature rise from -20°C to 100°C at a heating rate of 5°C / min. During the second temperature rise, the difference in force absorbed through the empty crucible and through the crucible containing the polymer sample was measured as a function of temperature. The melting point of the compounds (monomers and polymers) is the temperature value corresponding to the peak of the curve expressed as a function of temperature.

[0078] The melting point measurement results are shown in Table 2 below.

[0079] [Table 2]

[0080]

[0081] Example 4. Measurement of SPF enhancement effect

[0082] The synthesized polymer was applied to a UV-blocking cream formulation, and the SPF enhancement effect was measured by in vitro testing.

[0083] Specifically, the experimental sample was prepared at 1.3 mg / cm³. 2 The in vitro SPF was measured using an SPF-290AS (Solar Light, USA) after being applied to a PMMA plate (HelioScreen Labs, HD6) and dried at room temperature for 15 minutes.

[0084] The formulations of each dosage form in the experiment are as follows. The aqueous phase was uniformly mixed and dissolved, the oil phase was uniformly mixed and dissolved by heating, the oil phase was added to the aqueous phase, and the mixture was processed and emulsified using a homogeneous mixer, followed by degassing, to produce the following dosage forms.

[0085] A: No SPF-reinforced polymer added (control group)

[0086] B: Tego SP 13-1 (INCI: Poly C10-30 Alkyl Acrylate)

[0087] C: Tego SP 13-6 (INCI: Poly C10-30 Alkyl Acrylate)

[0088] D: A copolymer of 85% Stearyl methacrylate and 15% AMPS

[0089] E: A copolymer of 85% Stearyl methacrylate and 15% HEA.

[0090] [Table 3]

[0091]

[0092] As shown in Table 3 above, it was confirmed that formulations D and E using synthetic polymers have the same or higher SPF enhancement effect compared to previously used SPF film-forming agents (B, C).

[0093] Example 5. User Experience Measurement

[0094] The synthesized polymer was applied to a UV-blocking cream formulation (such as the formulation in Example 4), and user experience testing was conducted.

[0095] A panel of 20 participants applied formulas B, D, and E to their skin and then conducted a sensory evaluation. The evaluation criteria for user experience are as follows, and the average user experience scores are shown in Table 5 below.

[0096] [Evaluation Criteria]

[0097] 1 point: Very poor

[0098] 2 points: Poor

[0099] 3 points: Average

[0100] 4 points: Good

[0101] 5 points: Excellent

[0102] [Table 4]

[0103]

[0104] As shown in Table 4, the formulation using the copolymer polymer of SMA and AMPS exhibited a superior user experience compared to formulations using existing film-forming agents. Furthermore, it was confirmed that AMPS, being the hydrophilic group, had a lower stickiness compared to HEA, demonstrating a superior user experience.

[0105] Example 6. Confirmation of SPF enhancement effect in dosage forms based on AMPS content

[0106] The SPF-enhancing effect was confirmed by including a polymer with the AMPS monomer content changed to 5-15% in the same dosage form as in Example 4 above. The formulation is shown in Table 5 below.

[0107] A: Control group (no polymer added)

[0108] F: SMA 95%, AMPS 5%

[0109] G: SMA 90%, AMPS 10%

[0110] D: SMA 85%, AMPS 15%

[0111] [Table 5]

[0112]

[0113] As shown in Table 5, the results of confirming the SPF enhancement effect include polymers with AMPS monomer content changed to 5-15%, confirming that the SPF enhancement effect was exhibited within this polymer content range.

[0114] The foregoing description of the present invention is illustrative, and those skilled in the art should understand that it can be readily modified into other specific forms without altering the technical concept or essential features of the invention. Therefore, it must be understood that the embodiments described above are exemplary in all respects and not limiting. For example, the individual components described as a single type may also be implemented separately, and similarly, the components described as separate may be implemented in a combined form.

[0115] The scope of this invention is defined by the claims described below, and it should be interpreted that all modifications or variations derived from the meaning and scope of the claims and their equivalents are included within the scope of this invention.

Claims

1. An amphiphilic copolymer represented by the following chemical formula 1: <Chemical Formula 1> In the above formula, A is C 12-22 Alkyl acrylate or C 12-22 Alkyl methacrylates, B is 2-acrylamido-2-methyl-1-propanesulfonic acid. X and Y represent the weight percentage (%) of each monomer in the copolymer. X ranges from 0.001% by weight to 99.999% by weight. Y ranges from 0.001% by weight to 99.999% by weight.

2. The amphiphilic copolymer according to claim 1, characterized in that, X is from 50% to 99.999% by weight, and Y is from 0.001% to 50% by weight.

3. The amphiphilic copolymer according to claim 1, characterized in that, The molecular weight of the amphiphilic copolymer is 10 to 100 kDa.

4. The amphiphilic copolymer according to claim 1, characterized in that, The amphiphilic copolymer has a melting point of 40 to 45°C.

5. The amphiphilic copolymer according to claim 1, characterized in that, The chemical formula 1 is the following chemical formula 2. <Chemical Formula 2> In the above formula, R1 is hydrogen or methyl, R2 is C 12-22 alkyl, X and Y represent the weight percentage (%) of each monomer in the copolymer. X ranges from 0.001% by weight to 99.999% by weight. Y ranges from 0.001% by weight to 99.999% by weight.

6. A cosmetic composition for blocking ultraviolet light, comprising the amphiphilic copolymer as described in any one of claims 1 to 5.

7. The cosmetic composition for ultraviolet blocking according to claim 6, characterized in that, It also contains effective UV-blocking ingredients.

8. A method for manufacturing an amphiphilic copolymer represented by the following chemical formula 1, comprising: The step of reacting monomer A and monomer B in a reaction solvent, wherein monomer A is C 12-22 Alkyl acrylate or C 12-22 Alkyl methacrylate, wherein monomer B is 2-acrylamido-2-methyl-1-propanesulfonic acid. <Chemical Formula 1> In the above formula, X and Y represent the weight percentage (%) of each monomer in the copolymer. X ranges from 0.001% by weight to 99.999% by weight. Y ranges from 0.001% by weight to 99.999% by weight.

9. The manufacturing method according to claim 8, characterized in that, The reaction solvent is t-BuOH.

10. The manufacturing method according to claim 8, characterized in that, 4,4'-azobis(4-cyanopentanoic acid) was used as the initiator.

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