Sun protection composition
Through the combination of bis-ethylhexyloxyphenol methoxyphenyltriazine and ethylhexyltriazine and oil with dielectric constant less than 3, the problems of poor solubility and safety risks of chemical sunscreen are solved, and safe and stable sunscreen effects and good user experience are achieved.
Patent Information
- Application Number
- CN202211481632.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2022-11-24
- Publication Date
- 2025-07-22
- Estimated Expiration
- 2042-11-24
AI Technical Summary
Existing chemical sunscreens have problems such as poor solubility, high safety risks and poor user experience, and it is difficult to meet the requirements of safety priority, necessary efficacy and minimal formula for children's sunscreen products.
The combination of bis-ethylhexyloxyphenol methoxyphenyltriazine and ethylhexyltriazine is used as the main sunscreen, and medium polar oils with dielectric constant less than 3 such as dioctyl carbonate are used as solvents to optimize the combination ratio of sunscreen agents, reduce the amount of oil used, and ensure dissolution stability and safety.
It improves the dissolution stability of sunscreen agents, reduces the amount of oil, improves the sense of use, meets the safety and simplicity of children's sunscreen products, and is suitable for use by children and adults.
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Abstract
Description
Technical Field
[0001] The present invention relates to the field of cosmetics, and particularly to a safe, minimalist and stable sunscreen composition, and also relates to a preparation method and an application of the sunscreen composition. Background Art
[0002] Gentle sun protection is the primary consideration for children and sensitive adults when choosing sunscreen products in the sunscreen market. Currently, sunscreen products on the market include physical sunscreens (i.e., using inorganic sunscreens titanium dioxide or zinc oxide), chemical sunscreens (i.e., using organic sunscreens in the list of sunscreens), and a combination of physical and chemical sunscreens. Physical sunscreens have a relatively high safety consensus, but they have relatively weak points in terms of unsatisfactory use experience (difficult to apply, skin appears fake white after application, has a certain astringent feeling, etc.) and difficult to clean. Therefore, chemical sunscreens have considerable advantages in terms of use experience and sun protection efficiency and cannot be replaced by physical sunscreens.
[0003] Regarding the safety and mildness of chemical sunscreens, there have been many controversies in recent years. There are relatively many types of chemical sunscreens. Among the 27 approved sunscreens in China, except for 2 physical sunscreens, the remaining 25 are chemical sunscreens. However, many chemical sunscreens have increasingly faced risks and doubts about human and environmental safety in recent years.
[0004] The traditionally widely used benzophenone-3, ethylhexyl methoxycinnamate, isoamyl p-methoxycinnamate, homosalate, 4-methylbenzylidene camphor have all been suspected of having potential risks of endocrine disruption. Octocrylene, ethylhexyl salicylate, PEG-25 PABA, etc. have also been questioned due to problems such as high skin irritation or high skin permeability. Although butyl methoxydibenzoylmethane, as one of the few UVA band absorbers, has good safety, it has the problem of light instability, which limits its use. As a macromolecular sunscreen with both UVA and UVB absorption, bis-benzotriazolyl tetramethylbutylphenol is not recommended for children's products according to the "Technical Guidelines for Children's Cosmetics" in China because it belongs to nanomaterials.
[0005] Looking at the list of permitted chemical sunscreen agents, considering safety and stability, bis-ethylhexyloxyphenol methoxyphenyl triazine (molecular weight 627 Da) with broad-spectrum UVA and UVB absorption, ethylhexyl triazone (molecular weight 822 Da) in the UVB absorption band, and diethylamino hydroxybenzoyl hexyl benzoate (molecular weight 397 Da) in the UVA absorption band are increasingly being used due to their relatively high molecular weights, molecular stability, and excellent toxicological data to date. Their usage rates have been rising rapidly in recent years in both the adult and children's sunscreen markets. In particular, according to Lipinski's rule of five in drug penetration theory, drugs with a molecular weight above 500 Da are less likely to penetrate. From this perspective, the large-molecule bis-ethylhexyloxyphenol methoxyphenyl triazine and ethylhexyl triazone have a lower penetration risk. Another liquid sunscreen agent, polysiloxane-15, as a polymer, has a relatively large molecular weight, but due to its low UV absorption efficiency, it is not considered as a main sunscreen agent and can be used as an auxiliary sunscreen agent in the application examples.
[0006] These three chemical sunscreen agents with relatively high safety are all crystalline sunscreen agents and need to be dissolved during use to achieve uniform sun protection. However, their solubility, especially that of bis-ethylhexyloxyphenol methoxyphenyl triazine and ethylhexyl triazone, is relatively low. Insufficient dissolution may cause precipitation in the product, thus affecting its use and efficacy.
[0007] Currently, there are usually two solutions: 1) Search for oils with relatively high solubility, usually with relatively high polarity. Low-viscosity oil-soluble liquid sunscreen agents with relatively high polarity (such as ethylhexyl methoxycinnamate, ethylhexyl salicylate, isopentyl p-methoxycinnamate) are widely used to dissolve crystalline sunscreen agents. The high-polarity oils in the following table are also often used as solvents for crystalline sunscreen agents in chemical sunscreen formulations.
[0008] Dielectric constant Butyloctyl salicylate 5.4 Diisobutyl adipate 5.2 Phenethyl benzoate 5.1 Diethylhexyl adipate 4.2 Diethylhexyl sebacate 4 C12-15 alkyl benzoate 3.8
[0009] Note: Dioctyl carbonate is a medium-polarity oil with a dielectric constant of 2.4.
[0010] However, some studies have found that, as published by Y. Schiemanna, *, M. Wegmanna, P. Lerscha, E. Heislerb, M. Farwicka in "Colloids and Surfaces: Physicochemical and Engineering Aspects", Volume 331, Pages 103 - 107, 2008, titled "Enhanced percutaneous penetration of phytosphingosine by polar oils in cosmetic formulations", it can be seen that the high polarity of oils may, to a certain extent, promote penetration. However, the penetration of sunscreen products will increase safety risks and at the same time reduce the efficacy of sun protection. At the same time, the solubility of non - polar oils in crystalline sunscreens is very low. In this sense, choosing oils with medium polarity is a relatively safe choice. Therefore, the present invention innovatively selects dioctyl carbonate as the oil, and its dielectric constant is 2.4.
[0011] 2) Increase the amount of oil used, which is also a commonly used technical means in formulations to ensure that the solvent - type sunscreen does not precipitate in the formulation. In common sunscreen formulations, we can often see the situation where multiple oils are used together. However, increasing the oil content usually not only brings a greasy feeling during use but also increases the formulation's... Therefore, more emulsifiers or stabilizers are required to stabilize the formulation.
[0012] Children's sunscreen is a category that particularly emphasizes safety and mildness. Considering this, in the draft "Technical Guidelines for Children's Cosmetics" promulgated in China in 2022, the principles of "safety first, efficacy essential, and formulation minimalist" were specifically put forward. And for sunscreen products, the requirements of "no more than 3 types of chemical sunscreens and a sun protection factor SPF not exceeding 30" were specifically put forward.
[0013] Based on the above - mentioned background, starting from the principle of "safety first, efficacy essential, and formulation minimalist" for children's sunscreen, the present invention hopes to provide a safe, minimalist, and stable sunscreen composition.
[0014] The present invention unexpectedly discovers that the combination of bis - ethylhexyloxyphenol methoxyphenyl triazine and ethylhexyl triazone in a certain proportion can also increase the solubility of a single sunscreen, play a mutual solubilization role, and thus reduce the minimum amount of oil solvent used. Summary of the Invention
[0015] On the one hand, the present invention provides a safe, minimalist, and stable sunscreen composition, comprising:
[0016] A main sunscreen, wherein the main sunscreen is a combination of bis - ethylhexyloxyphenol methoxyphenyl triazine and ethylhexyl triazone, and the weight ratio of bis - ethylhexyloxyphenol methoxyphenyl triazine to ethylhexyl triazone is 0.5 to 2;
[0017] An oil for a sunscreen agent, the oil being a phenyl-free oil with a dielectric constant less than 3;
[0018] Wherein, the weight ratio of the oil to the main sunscreen agent in the sunscreen composition is 1.5 to 4.
[0019] In a preferred embodiment, the oil is selected from: dicaprylyl carbonate, diethylhexyl carbonate, isopropyl myristate, or a combination thereof.
[0020] In a preferred embodiment, the sunscreen composition further comprises an auxiliary sunscreen agent. In a preferred embodiment, the auxiliary sunscreen agent is a macromolecular chemical sunscreen agent or a physical sunscreen agent with a molecular weight exceeding 500 daltons. In a preferred embodiment, the auxiliary sunscreen agent is selected from: polysiloxane-15, non-nano titanium dioxide or zinc oxide, or a combination thereof. In a preferred embodiment, the total number of sunscreen agents in the sunscreen composition does not exceed 3.
[0021] In a preferred embodiment, the weight ratio of the oil to the main sunscreen agent in the sunscreen composition is 2.3 to 4.
[0022] In a preferred embodiment, the weight ratio of bis-ethylhexyloxyphenol methoxyphenyl triazine to ethylhexyl triazone is 1.25 to 1.75.
[0023] In a preferred embodiment, the total number of oils in the sunscreen agent composition is 1-2.
[0024] On the other hand, the present invention also provides a sunscreen product, which comprises the sunscreen composition of the present invention and a carrier acceptable in the cosmetic field. In a preferred embodiment, the sunscreen product is selected from: sunscreen for infants, sunscreen for children and sensitive adults, sunscreen milk for children and sensitive adults, sunscreen gel for children and sensitive adults, sunscreen spray for children and sensitive adults, sunscreen mousse for children and sensitive adults. Detailed Description
[0025] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, the preferred methods and materials are described herein. For the purposes of the present invention, the following terms are defined below.
[0026] As used herein, the term "about" refers to a quantity, level, value, dimension, size, or amount that can vary by up to 30%, 20%, or 10% compared to the quantity, level, value, dimension, size, or amount of a reference. Percentages used herein, unless otherwise indicated, are by weight.
[0027] Throughout the specification and claims, unless otherwise required, the following words "comprise" and its variants "comprises" and "comprising" shall be understood to mean including the whole or step, or group of wholes or steps, but not excluding any other whole or step, or other group of wholes or steps.
[0028] As used herein, "sunscreen composition" refers to a preparation (e.g., lotion, spray, gel or other topical product) that absorbs and / or reflects some of the sun's ultraviolet (UV) radiation and thus helps prevent the negative effects of sun exposure (e.g., sunburn, premature aging, etc.).
[0029] The present invention selects, formulates and tests the composition from three aspects: safety, simplicity and stability. Safety mainly considers the safety of the sunscreen and the sunscreen oil. The sunscreen strictly selects the combination of bis-ethylhexyloxyphenol methoxyphenyl triazine and ethylhexyl triazone with excellent toxicological data and a molecular weight of more than 500 daltons, and the oil selects medium-polarity oil with good safety. Simplicity mainly focuses on the limitation of the number of compounding ingredients and the research on minimizing the required minimum concentration. In addition to improving mildness, simplicity can also make the product more refreshing and non-greasy, improving the use feeling. Stability is considered from the photo-stability of the sunscreen and the dissolution stability of the sunscreen combination as the evaluation method.
[0030] Sun protection agent
[0031] The present invention takes safety as the primary starting point. According to the principle of formula simplicity, a crystalline macromolecular sunscreen with a molecular weight exceeding 500 daltons is taken as the main research object, and a safe, simple and stable sunscreen composition is provided. In some preferred embodiments, the total number of sunscreens in the sunscreen composition of the present invention does not exceed 3.
[0032] The present invention discovers that the combination of bis-ethylhexyloxyphenol methoxyphenyl triazine and ethylhexyl triazone in a certain proportion can also increase the solubility of a single sunscreen and play a mutual solubilization role, thereby reducing the minimum usage amount of the oil solvent. Therefore, the present invention provides a sunscreen composition comprising bis-ethylhexyloxyphenol methoxyphenyl triazine and ethylhexyl triazone. The sunscreen composition of the present invention selects the combination of bis-ethylhexyloxyphenol methoxyphenyl triazine and ethylhexyl triazone, and by optimizing the ratio of the sunscreen combination, the necessary addition amount of the oil is reduced as much as possible, achieving a multiple balance of safety, simplicity, stability and use feeling.
[0033] The sunscreen composition of the present invention may also comprise other macromolecular chemical sunscreens (e.g., polysiloxane-15) or physical sunscreens (e.g., non-nano titanium dioxide or zinc oxide), and under the premise of meeting safety, the application field is expanded with a simple formula of no more than 3 sunscreens.
[0034] In some embodiments, the weight ratio of bis-ethylhexyloxyphenol methoxyphenyl triazine to ethylhexyl triazone in the sunscreen composition is from 0.5 to 2. In a preferred embodiment, the weight ratio of bis-ethylhexyloxyphenol methoxyphenyl triazine to ethylhexyl triazone in the sunscreen composition is from 0.5 to 0.75. In a preferred embodiment, the weight ratio of bis-ethylhexyloxyphenol methoxyphenyl triazine to ethylhexyl triazone in the sunscreen composition is from 1 to 2. In a preferred embodiment, the weight ratio of bis-ethylhexyloxyphenol methoxyphenyl triazine to ethylhexyl triazone in the sunscreen composition is from 1.25 to 2. In a preferred embodiment, the weight ratio of bis-ethylhexyloxyphenol methoxyphenyl triazine to ethylhexyl triazone in the sunscreen composition is from 1.25 to 1.75. In a preferred embodiment, the weight ratio of bis-ethylhexyloxyphenol methoxyphenyl triazine to ethylhexyl triazone in the sunscreen composition is from 1.5 to 2. In the most preferred embodiment, the weight ratio of bis-ethylhexyloxyphenol methoxyphenyl triazine to ethylhexyl triazone in the sunscreen composition is 1.5.
[0035] In some embodiments, the sunscreen composition comprises at least about 3% by weight of one or more sunscreen agents based on the total weight of the composition. The sunscreen composition may comprise from about 3 to about 35% by weight of one or more sunscreen agents based on the total weight of the composition. The sunscreen composition may comprise from about 3 - 10% by weight of one or more sunscreen agents based on the total weight of the composition.
[0036] Sun protection agent oil
[0037] Regarding the solubility problem of chemical sunscreen agents, oils are usually used to dissolve the sunscreen agents.
[0038] The present invention selects as few mild, non-greasy and non-sticky medium-polarity oils as solvents for the sunscreen agents, and by optimizing the combination ratio of the sunscreen agents, the necessary addition amount of the oils is reduced as much as possible to achieve a multiple balance of safety, simplicity, stability and usability.
[0039] In some embodiments, a single medium-polarity oil with good solubility is selected, and the appropriate addition amount of the oil is confirmed, and then the ratio of the crystalline sunscreen agents bis-ethylhexyloxyphenol methoxyphenyl triazine and ethylhexyl triazone is optimized for dissolution stability. The verification method of dissolution stability adopts the 4-degree Celsius low-temperature tracking test in the common stability standard methods for cosmetics. According to the usual stability requirements, it remains stable without precipitation at 4 degrees Celsius for 12 weeks, that is, it meets the low-temperature stability requirements.
[0040] In some embodiments, the actual formulation of the sunscreen composition further comprises other oils as emollients or dispersants for other components, etc., whereby the number of oils in the sunscreen agent formulation is 1 - 2.
[0041] In some embodiments, the sunscreen composition comprises an oil that does not contain phenyl and has a dielectric constant of less than 6. In a preferred embodiment, the sunscreen composition comprises an oil having a dielectric constant of less than 3. In a preferred embodiment, the sunscreen composition comprises an oil having a dielectric constant of 1-3. In a more preferred embodiment, the sunscreen composition comprises an oil having a dielectric constant of 2-3.
[0042] In some embodiments, the oil in the sunscreen composition is selected from: dicaprylyl carbonate, diethylhexyl carbonate, isopropyl myristate, ethylhexyl salicylate, glyceryl cocoates, isononyl isononanoate, butyl octyl salicylate, diisobutyl adipate, phenethyl benzoate, diethylhexyl adipate, diethylhexyl sebacate, C12-15 alkyl benzoate, or a combination thereof. In a preferred embodiment, the oil in the sunscreen composition is selected from dicaprylyl carbonate, diethylhexyl carbonate, and isopropyl myristate.
[0043] In some embodiments, the weight ratio of the oil to the sunscreen agent in the sunscreen composition is 1.5 to 4. In a preferred embodiment, the weight ratio of the oil to the sunscreen agent in the sunscreen composition is 2.3-4. In some embodiments, the weight ratio of the oil to the sunscreen agent in the sunscreen composition is 6:4. In some embodiments, the weight ratio of the oil to the sunscreen agent in the sunscreen composition is 7:3.
[0044] In some embodiments, the sunscreen composition may comprise about 5-20% by weight of the oil based on the total weight of the composition. The sunscreen composition may comprise about 8-15% by weight of the oil based on the total weight of the composition. The sunscreen composition may comprise about 8-12% by weight of the oil based on the total weight of the composition.
[0045] Sun protection composition
[0046] The safe sun protection of the present invention mainly focuses on the following two aspects: the selection of sunscreen agents and the selection of oils.
[0047] For the selection of sunscreen agents, it should meet the list and scope of use restrictions of "Permitted Sunscreen Agents in Cosmetics" in the "Technical Specifications for Cosmetics Safety". The selection of safe chemical sunscreen agents includes selecting those with a relatively large molecular weight (above 390 daltons) and a green comprehensive rating according to the US Environmental Working Group (EWG). At the same time, the selection of safer physical sunscreen agents includes: 1) using a reasonable test method to characterize that the aggregate particle size of the physical sunscreen agent raw material is above 100 nanometers; and / or 2) if the physical sunscreen agent titanium dioxide is selected, it is required to be rutile type and surface-treated. The chemical sunscreen agent system and physical sunscreen agent system that meet the above requirements for sunscreen agents can be used alone or in combination.
[0048] The oil is preferably a phenyl-free, non-polar, low-polar or medium-polar oil. The identification of the polarity of the oil can refer to the dielectric constant or the polarity classification characterization of professional oil manufacturers.
[0049] The requirement of simplicity in the present invention is mainly reflected in necessity and the quantity of raw materials. The raw materials used must have definite functions from the perspectives of efficacy, stability and safety and cannot be omitted. There are certain limitations on the quantity of raw materials used. The present invention focuses on sunscreen agents and oils, so there are the following two considerations: the limitation on the quantity of sunscreen agents: for children under 12 years old, the quantity of sunscreen agents does not exceed 3; for adult sunscreen, the quantity of sunscreen agents is preferably not more than 5; and the limitation on the quantity of oils: not more than 3.
[0050] The broad-spectrum property of the present invention mainly refers to the requirements in the United States. According to the ISO 24443 method, the critical wavelength is not less than 370 nm. Alternatively, referring to the requirements in the European Union, the UVA-PF / SPF value is not less than 0.33. In a preferred embodiment, the broad-spectrum sunscreen needs to meet both requirements simultaneously.
[0051] A higher UVA protection rate is considered in terms of the ratio of UVA-PF / SPF not less than 0.45.
[0052] In some embodiments, the pH value of the sunscreen composition of the present invention is 6-8. In a preferred embodiment, the pH of the sunscreen composition of the present invention is 6.5-7.5.
[0053] The composition can be prepared using mixing and blending methods well-known in the fields of sunscreen agents and cosmetics.
[0054] The composition can be combined with a "cosmetically acceptable topical carrier", which is a topical carrier that can contain other ingredients dispersed or dissolved therein and has acceptable properties for safe topical use.
[0055] The cosmetically acceptable topical carrier can optionally contain various additional oil-soluble substances and / or oil-dispersible substances, which are commonly used in the composition and are applied to the skin in amounts established in the art. For example, it can include surfactants, emulsifiers, pearlescent agents or opacifiers, thickeners, emollients, conditioners, humectants, chelating agents, exfoliants, preservatives, pH regulators and additives, and the additives enhance the appearance, feel or fragrance of the composition, such as colorants, fragrances, tactile improvers, etc.
[0056] Method of use
[0057] As used herein, "topical application" means directly spraying, rubbing, smearing or spreading on the outer skin or scalp, for example, by hand or with an applicator such as a wipe, roller or sprayer.
[0058] The sunscreen composition can be applied to the skin of the user in any desired manner. In some aspects, the product can be directly applied by hand, or a device such as a cotton pad or other tool can be used to apply the product. The composition is advantageously applied to the skin to facilitate sample absorption. The composition can be left on the applied area for a desired time level, such as about 5 seconds to about 5 minutes. Alternatively, the composition can be left on the applied area and continuously applied until absorbed.
[0059] The compositions of the present invention are sprayable. As used herein, "sprayable" means that when manually actuated or pressurized and released from a dispensing mechanism such as a bottle with a pump spray nozzle or an aerosol can, the composition produces a uniform distribution and reproducible spray pattern over an area of defined shape (e.g., circular, annular) and size. The composition can be sprayable without the use of a propellant, i.e., in a non-aerosol form.
[0060] The present invention will be further illustrated below in connection with specific embodiments. It is necessary to point out here that the embodiments are only used to further illustrate the present invention and should not be construed as limiting the protection scope of the present invention. Those skilled in the art can make some non-essential improvements and adjustments based on the above content of the present invention. The test methods without specific conditions indicated in the following embodiments are generally carried out under conventional conditions or according to the conditions recommended by the manufacturer. Unless otherwise specified, all percentages and parts are by weight.
[0061] Experimental materials:
[0062] Bis-ethylhexyloxyphenol methoxyphenyl triazine, provided by BASF (trade name Tinosorb S), abbreviated as TS;
[0063] Ethylhexyl triazone, provided by BASF (trade name Uvinul T 150), abbreviated as T150;
[0064] Dioctyl carbonate, provided by BASF (trade name Cetiol CC), abbreviated as CC;
[0065] Glycerol cocoates, provided by BASF (trade name 331), abbreviated as 331;
[0066] Isononyl isononanoate, provided by Seppic (trade name Lanol 99), abbreviated as ININ;
[0067] Ethylhexyl salicylate, provided by Ashland (trade name ESCALOL 587), hereinafter referred to as OS.
[0068] Example 1: Investigation of Sunscreen Composition and Its Stability
[0069] Weigh bis-ethylhexyloxyphenol methoxyphenyl triazine and ethylhexyl salicylate according to the mass parts shown in Table 1. While stirring, heat to 85 - 90 °C until completely dissolved, then pour into a glass bottle preheated in an oven at 60 °C, and continue to place it in the oven at 60 °C for heat preservation. Perform the same operation to prepare Samples 2# - 10# according to the mass parts in the following table. After all 10 samples are prepared, place all the samples in an oven at 60 °C for 30 - 60 minutes to ensure that the samples prepared successively are kept at a high temperature of 60 °C for sufficient time. Then take out the samples. After observing that no abnormalities occur, transfer all the samples to an oven at 25 °C.
[0070] Table 1
[0071]
[0072] Observation of stability: Take out the samples to room temperature. Place a flat LED lamp on the desktop at the bottom of the sample, and place the sample on the lamp for visual observation. Placing the LED at the bottom facilitates the discovery of tiny precipitation. Once precipitation occurs in a sample, take out this sample and no longer include it in the scope of stability investigation, denoted by "X".
[0073] Table 2
[0074]
[0075]
[0076]
[0077]
[0078]
[0079] According to the above results, the order of dissolution stability of samples 1-10 from excellent to poor is: 3#, 4#, 5#≈2#, 6#, 7#, 1#, 9#, 10#. Taking the fixed ratio of ethylhexyl salicylate:sunscreen agent of 6 parts by mass:4 parts by mass, the dissolution stability of single sunscreen agents 10# and 1# is not good, while the combined use of the two sunscreen agents in a certain ratio shows better dissolution stability. For example, in the ratio range of bis-ethylhexyloxyphenol methoxyphenyl triazine mass ratio:ethylhexyl triazone mass ratio = 1.25 - 2.00, it shows significantly good dissolution stability. In particular, two samples with bis-ethylhexyloxyphenol methoxyphenyl triazine:ethylhexyl triazone = 1.50 and 1.75 fully meet the standard of 12 weeks (87 days) of low-temperature stability at 4°C for cosmetics, which also shows the good solubility of the highly polar ethylhexyl salicylate in crystalline sunscreen agents.
[0080] Example 2: Sunscreen Composition and Its Stability Investigation
[0081] Weigh bis-ethylhexyloxyphenol methoxyphenyl triazine and glyceryl cocoate according to the parts by mass shown in Table 3. While stirring, heat to 85 - 90°C until completely dissolved, then pour into a glass bottle preheated in an oven at 60°C, and continue to keep it warm in the oven at 60°C. Follow the same operation to prepare samples 12# - 20# according to the parts by mass in the following table. After all 10 samples are prepared, place all the samples in an oven at 60°C for 24 hours to ensure that the samples prepared successively are kept at a constant temperature of 60°C for a sufficient time. Then take out the samples for observation.
[0082] Table 3
[0083]
[0084] Stability Observation: Take out the samples to room temperature. Place a flat LED lamp on the table at the bottom of the sample, and place the sample on the lamp for visual observation. Placing the LED at the bottom is convenient for detecting tiny precipitation. Once precipitation is found in a sample, take out this sample and no longer include it in the scope of stability investigation, denoted by "X".
[0085] Table 4
[0086]
[0087]
[0088] Based on the above results, it can be seen that the order of dissolution stability of samples 11 - 20# from excellent to poor is as follows: 18#≈17#, 15#≈16#≈14#, 13#, 12#, 11#, 19#, 20#. Taking the fixed ratio of coconut oil fatty acid glycerides : sunscreen agent as 6 parts by mass : 4 parts by mass, for single sunscreen agents 20# and 11#, the dissolution stabilities are both not good. However, compared with a certain ratio of the combination of the two sunscreen agents, it shows more excellent dissolution stability. For example, in the ratio range of bis - ethylhexyloxyphenol methoxyphenyl triazine mass ratio : ethylhexyl triazone mass ratio = 0.50 - 0.75, it shows better dissolution stability. It is speculated that this is mainly due to the relative difference in the solubility of coconut oil fatty acid glycerides and ethylhexyl salicylate for ethylhexyl triazone and bis - ethylhexyloxyphenol methoxyphenyl triazine. However, the best samples still cannot meet the stability standard at 4°C for 12 weeks, indicating that the solubility of coconut oil fatty acid glycerides for bis - ethylhexyloxyphenol methoxyphenyl triazine and ethylhexyl triazone is not good.
[0089] Example 3: Sunscreen Composition and Its Stability Investigation
[0090] Weigh bis - ethylhexyloxyphenol methoxyphenyl triazine and dicaprylyl carbonate according to the parts by mass shown in Table 5. While stirring, heat to 85 - 90°C until completely dissolved, then pour it into a glass bottle preheated in an oven at 60°C, and continue to keep it in the 60°C oven for heat preservation. According to the same operation, configure samples 22# - 30# according to the parts by mass in the following table. After all 10 samples are configured, all samples are placed in a 60°C oven and kept at a constant temperature for 60 minutes to ensure that the samples configured successively are all kept at a high temperature of 60°C for sufficient constant temperature. Subsequently, take out the samples for observation.
[0091] Table 5
[0092]
[0093]
[0094] Stability Observation: Take out the samples to room temperature. Place a flat LED lamp on the table at the bottom of the sample, and place the sample on the lamp for visual observation. Placing the LED at the bottom is convenient for detecting tiny precipitation. Once precipitation occurs in the sample, immediately take out this sample and no longer include it in the scope of stability investigation, which is represented by "X".
[0095] Table 6
[0096]
[0097]
[0098]
[0099]
[0100]
[0101] According to the above results, it can be seen that the order of the dissolution stability of samples 21 - 30# from excellent to poor is: 24#, 22#, 23≈25#, 26#, 21#, 27#, 28#, 29#, 30#. Taking the fixed ratio of dicaprylyl carbonate: sunscreen agent of 6 parts by mass: 4 parts by mass, the dissolution stabilities of single sunscreen agents 30# and 21# are both not good, while the combination of the two sunscreen agents shows more excellent dissolution stability in a certain ratio. For example, in the ratio range of bis-ethylhexyloxyphenol methoxyphenyl triazine mass ratio: ethylhexyl triazone mass ratio = 1.00 - 2.00, it shows better dissolution stability, and the bis-ethylhexyloxyphenol methoxyphenyl triazine mass ratio: ethylhexyl triazone mass ratio = 1.50 shows the most excellent performance in this experiment. However, it still cannot meet the stability standard at 4°C for 12 weeks. Comparing the two medium-polarity oils, glyceryl cocoate and dicaprylyl carbonate, neither of them can compare with the polar oil ethylhexyl salicylate in terms of the solubility of bis-ethylhexyloxyphenol methoxyphenyl triazine and ethylhexyl triazone. From this experiment, dicaprylyl carbonate has significantly better solubility than glyceryl cocoate in each ratio range at the bis-ethylhexyloxyphenol methoxyphenyl triazine mass ratio: ethylhexyl triazone mass ratio = 1.50, and dicaprylyl carbonate also feels significantly more refreshing and non-greasy than glyceryl cocoate in terms of the usage feeling, so it has more selection value.
[0102] Example 4: Sunscreen Composition and Its Stability Investigation
[0103] Weigh bis-ethylhexyloxyphenol methoxyphenyl triazine and isononyl isononanoate according to the mass parts shown in Table 7. While stirring, heat them to 85 - 90°C until completely dissolved, then pour them into a glass bottle preheated in an oven at 60°C, and continue to keep it warm in the 60°C oven. Configure samples 32# - 40# according to the mass parts in the following table in the same operation. After all 10 samples are configured, all the samples are placed in the 60°C oven and kept at a constant temperature for 24 hours to ensure that the samples configured successively are kept at a high temperature of 60°C for sufficient constant temperature. Then take out the samples and observe them.
[0104] Table 7
[0105]
[0106] Stability Observation: Take out the samples to room temperature. Place a flat LED lamp on the desktop at the bottom of the samples, and place the samples on the lamp for visual observation. Placing the LED at the bottom is convenient for detecting tiny precipitation. Once precipitation occurs in a sample, immediately take out this sample and no longer include it in the scope of stability investigation, which is represented by "X".
[0107] Table 8
[0108]
[0109]
[0110]
[0111] According to the above results, it can be seen that the order of dissolution stability of samples #31 - 40 from excellent to poor is: #32≈#33, #34, #31, #35≈#37, #36, #38≈#39, #40. Taking the fixed ratio of isononyl isononanoate: sunscreen agent of 6 parts by mass: 4 parts by mass, the dissolution stabilities of single sunscreen agents #40 and #31 are not good, while the combined use of the two sunscreen agents in a certain ratio shows better dissolution stability. For example, in the ratio range of bis - ethylhexyloxyphenol methoxyphenyl triazine mass ratio: ethylhexyl triazone mass ratio = 1.50 - 2.00, it shows better dissolution stability. However, generally speaking, isononyl isononanoate has poor solubility for bis - ethylhexyloxyphenol methoxyphenyl triazine mass ratio and ethylhexyl triazone, showing the worst performance in Experimental Examples 1 - 4.
[0112] According to the results of Experimental Examples 1 - 4, it can be seen that: 1) Bis - ethylhexyloxyphenol methoxyphenyl triazine and ethylhexyl triazone have better dissolution ability under a certain ratio. The ratio between the two has a certain influence on solubility, and the specific optimized ratio will vary with the different dissolution properties of the two sunscreen agents in different oils. 2) The sunscreen agent ethylhexyl salicylate with high - polarity oil has significantly better dissolution ability for crystalline sunscreen agents compared to medium - polarity oils such as dicaprylyl carbonate, isononyl isononanoate, and glyceryl cocoate. Among the three medium - polarity oils, dicaprylyl carbonate shows better dissolution ability for the combination of bis - ethylhexyloxyphenol methoxyphenyl triazine and ethylhexyl triazone compared to isononyl isononanoate and glyceryl cocoate. However, with the ratio of dicaprylyl carbonate: total sunscreen dose = 6:4, it cannot meet the requirements of the dissolution stability of cosmetics. Therefore, it is necessary to increase the relative mass fraction of dicaprylyl carbonate to increase its solubility for sunscreen agents, and the appropriate ratio will be selected in this way in the following experimental examples.
[0113] Example 5: Sunscreen Composition and Its Stability Investigation
[0114] Weigh bis-ethylhexyloxyphenol methoxyphenyl triazine and dioctyl carbonate according to the parts by mass shown in Table 9. While stirring, heat to 85 - 90 °C until completely dissolved, then pour into a glass bottle preheated in an oven at 60 °C, and continue to keep it warm in the oven at 60 °C. Perform the same operation to prepare Samples 41# - 50# according to the parts by mass in the following table. After all 10 samples are prepared, place all the samples in an oven at 60 °C and keep them at a constant temperature for 60 minutes to ensure that the samples prepared successively are kept at a sufficient constant temperature at 60 °C. Then take out the samples for observation.
[0115] Table 9
[0116]
[0117] Observation of stability: Take out the samples to room temperature. Place a flat LED lamp on the desktop at the bottom of the sample, and place the sample on the lamp for visual observation. Placing the LED at the bottom facilitates the discovery of minute precipitation. Once precipitation occurs in a sample, immediately take out this sample and no longer include it in the scope of stability investigation, which is indicated by "X".
[0118] Table 10
[0119]
[0120]
[0121]
[0122]
[0123]
[0124] From the above results, it can be seen that the order of the dissolution stability of Samples 41 - 50# from excellent to poor is: 44#, 43, 46≈47#, 45#, 34#, 42#≈48#, 41#, 49#, 50#. In terms of the ratio of dioctyl carbonate: sunscreen agent being 7 parts by mass: 3 parts by mass, the mass ratio of bis-ethylhexyloxyphenol methoxyphenyl triazine: the mass ratio of ethylhexyl triazone = 0.50 - 2.00 still shows better solubility than a single sunscreen agent. In particular, when the mass ratio of bis-ethylhexyloxyphenol methoxyphenyl triazine: the mass ratio of ethylhexyl triazone = 1.50, it has good low-temperature dissolution stability and can meet the stability requirements of the cosmetic for 12 weeks of stability at 4 °C, which has practical application significance.
[0125] Application Example
[0126] Application scenarios: Sunscreen, sun milk, sun gel, sun spray, sun mousse for children or sensitive adult populations
[0127] Application Example 1: Preparation of sunscreen for infants and young children
[0128]
[0129] Process: Heat phase A to 75°C, disperse it evenly under homogenization, add phase B heated to 75°C, homogenize for 5 minutes after addition, stir and cool to 55°C, add phase C, adjust the pH to 5.0 - 6.0, stir and cool to 50°C, add phase D, homogenize for 3 minutes after addition, stir and cool to 35°C to obtain the product.
[0130] For infants and young children aged 6 months to 2 years, sun protection products with a sun protection factor of around SPF 10 should be selected on the basis of physical sun protection such as clothing and hats. This application example meets the principles of an SPF of 10, two types of chemical sunscreens, and a simple formula. Moreover, all chemical sunscreens are selected as macromolecular sunscreens with a molecular weight > 500, greatly reducing the penetration risk. At the same time, as an oil-in-water product without titanium dioxide and zinc oxide physical sunscreens, it reduces the difficulty of cleaning and is especially suitable for infants and young children.
[0131] Application Example 2: Preparation of Sunscreen for Children and Sensitive Adults
[0132]
[0133]
[0134] Process: Heat phase A to 75°C and disperse it evenly under homogenization; evenly grind and disperse phase C on a three-roll mill for later use; after heating phase B to 75°C, add phase C and mix evenly, then add it to phase A with homogenization turned on. Homogenize for 10 minutes after addition, stir and cool to 55°C, add phase C, adjust the pH to 5.0 - 6.0, stir and cool to 50°C, add phase D, homogenize for 3 minutes after addition, stir and cool to 35°C to obtain the product.
[0135] Application Example 2 is a sunscreen with an SPF of around 25. On the basis of the invention combination, the use of the physical sunscreen zinc oxide (for meeting the sun protection needs of children, non-nano zinc oxide can be selected) is combined. The macromolecular chemical sunscreen is combined with a physical sunscreen with a relatively high safety recognition, which is also a combination with a relatively high safety factor. It also meets the regulatory requirements of children's sun protection products. Compared with pure physical sunscreens, the use of chemical sunscreens improves the efficiency of sunscreens and improves the spreadability to a certain extent. It is suitable for the daily sun protection needs of children and sensitive adults.
[0136] Application Example 3: Preparation of Sunscreen Lotion for Children and Sensitive Adults
[0137]
[0138]
[0139] Process: Phase A is heated to 75°C, dispersed evenly under homogenization, and Phase B heated to 75 - 80°C is added. After addition, homogenize for 5 minutes, stir and cool to 60 - 65°C, add Phase C, adjust the pH to 5.0 - 6.0, add Phase D, after addition, homogenize for 3 minutes, continue to stir and cool to 50°C, add Phase E, homogenize for 2 minutes, and continue to stir and cool to 35°C to obtain the product.
[0140] Application Example 3 is an emulsion with an SPF of around 20 - 30. Based on the invention combination, another macromolecular sunscreen agent, polysiloxane - 15 (a non - crystalline sunscreen agent, but with relatively low sunscreen absorption), is incorporated. It is also a safe sunscreen formulation with all sunscreen agent molecular weights above 500, which also meets the regulatory requirements for children's sunscreen products and is suitable for the daily sunscreen needs of children and sensitive adult populations.
[0141] Application Example 4: Preparation of a sunscreen gel suitable for children and sensitive adults
[0142]
[0143] Process: Phase A is heated to 75°C, dispersed evenly under homogenization, and Phase B heated to 75 - 80°C is added. After addition, homogenize for 5 minutes, stir and cool to 60 - 65°C, add Phase C, after addition, homogenize for 3 minutes, continue to stir and cool to 50°C, add Phase D and Phase E, homogenize for 2 minutes, and continue to stir and cool to 35°C to obtain the product.
[0144] Application Example 4 is a sunscreen gel with an SPF of around 20 - 30. Based on the invention combination, another macromolecular sunscreen agent, polysiloxane - 15 (a non - crystalline sunscreen agent, but with relatively low sunscreen absorption), is incorporated. It is also a safe sunscreen formulation with all sunscreen agent molecular weights above 500, which also meets the regulatory requirements for children's sunscreen products and is suitable for the daily sunscreen needs of children and sensitive adult populations.
[0145] Application Example 5: Preparation of a sunscreen spray suitable for children and sensitive adults
[0146]
[0147] Process: Phase A is heated to 75°C until completely dissolved, and Phase B heated to 75 - 80°C is added under homogenization. After addition, homogenize for 5 minutes, stir and cool to 60 - 65°C, add Phase C, after addition, homogenize for 3 minutes, continue to stir and cool to 50°C, add Phase D and Phase E, homogenize for 2 minutes, and continue to stir and cool to 25°C to obtain the product.
[0148] Application Example 5 is a sunscreen spray with an SPF of around 20 - 30. Based on the invention combination, it is combined with another macromolecular sunscreen, polysiloxane - 15 (a non - crystalline sunscreen, but with relatively low sunscreen absorption). It is also a safe sunscreen formula with all sunscreen agent molecular weights above 500, and it also meets the regulatory requirements for children's sunscreen products, suitable for the daily sunscreen needs of children and sensitive adult populations.
[0149] Application Example 6: Preparation of a sunscreen mousse suitable for children and sensitive adults
[0150]
[0151] Process: Heat phase A to 75°C until completely dissolved, add phase B heated to 75 - 80°C under homogenization. After addition, homogenize for 5 minutes, stir and cool to 60 - 65°C, add phase C. After addition, homogenize for 3 minutes, continue to stir and cool to 50°C, add phases D and E, homogenize for 2 minutes, and continue to stir and cool to 25°C to obtain the liquid part. Fill an appropriate amount of the liquid formula into an aerosol can, fill it with a certain proportion of isobutane and n - propane, and seal it with a lid to obtain the product.
[0152] Application Example 6 is a sunscreen mousse with an SPF of around 20 - 30. Based on the invention combination, it is combined with another macromolecular sunscreen, polysiloxane - 15 (a non - crystalline sunscreen, but with relatively low sunscreen absorption). It is also a safe sunscreen formula with all sunscreen agent molecular weights above 500, and it also meets the regulatory requirements for children's sunscreen products, suitable for the daily sunscreen needs of children and sensitive adult populations.
Claims
1. A safe, simplest and stable sunscreen composition, which is composed of the following components: Sun protection agent, the sun protection agent contains a main sun protection agent, and the main sun protection agent is a combination of bis-ethylhexyloxyphenol methoxyphenyl triazine and ethylhexyl triazone, wherein, The weight ratio of bis-ethylhexyloxyphenol methoxyphenyl triazine to ethylhexyl triazone is 1.5; and A sunscreen grease, and the grease is dicaprylyl carbonate; Wherein, the weight ratio of the grease to the main sunscreen in the sunscreen composition is 7:3, Wherein, the total number of sunscreens in the sunscreen composition does not exceed 3, Wherein, when the total number of sunscreens is 3, an auxiliary sunscreen is further included, and the auxiliary sunscreen is selected from: polysiloxane-15 or non-nano titanium dioxide or zinc oxide.
2. A sunscreen product, which comprises the sunscreen composition according to claim 1 and a carrier acceptable in the cosmetic field.
3. The sunscreen product according to claim 2, wherein the sunscreen product is selected from: sunscreen for infants, sunscreen for children and adults with sensitive skin, sunscreen milk for children and adults with sensitive skin, sunscreen gel for children and adults with sensitive skin, sunscreen spray for children and adults with sensitive skin, sunscreen mousse for children and adults with sensitive skin.
Citation Information
Patent Citations
Agent containing large quantities of UV stabilizers
CN105358221A
Sunscreen composition with high UVA protection effect and application thereof
CN113559003A