CN115813793A

CN115813793A - Sunscreen composition

Info

Publication number: CN115813793A
Application number: CN202211481632.5A
Authority: CN
Inventors: 王鞠骏; 洪菁
Original assignee: Shanghai Jahwa United Co Ltd
Current assignee: Shanghai Jahwa United Co Ltd
Priority date: 2022-11-24
Filing date: 2022-11-24
Publication date: 2023-03-21

Abstract

The present invention provides a safe, simple and stable sunscreen composition comprising: a primary sunscreen agent which is a combination of bis-ethylhexyloxyphenol methoxyphenyl triazine and ethylhexyl triazone, wherein the weight ratio of bis-ethylhexyloxyphenol methoxyphenyl triazine and ethylhexyl triazone is 0.5 to 2; an oil or fat for sunscreen agents, which contains no phenyl group and has a dielectric constant of less than 3; wherein the weight ratio of the grease to the main sunscreen agent in the sunscreen composition is 1.5 to 4. The invention also provides a safe, simple and stable sunscreen product.

Description

Sunscreen composition

Technical Field

The invention relates to the field of cosmetics, in particular to a safe, simple and stable sunscreen composition, and relates to a preparation method and application of the sunscreen composition.

Background

Mild sun protection is a primary consideration in the choice of sun protection products for both children and adults susceptible to sun protection in the sun protection market. The sunscreen products currently on the market include physical sunscreens (i.e. using the inorganic sunscreens titanium dioxide or zinc oxide), chemical sunscreens (i.e. using the organic sunscreens of the sunscreen list) and physicochemical combinations of the three types. Physical sunscreens have a high safety consensus, but they have the relative weakness of an unsatisfactory use experience (difficulty in application, false white skin after application, certain astringency, etc.) and difficulty in cleaning. Therefore, chemical sun protection has considerable advantages in use experience and sun protection efficiency, and cannot be replaced by physical sun protection.

The safety and mildness of the sunscreen composition as a chemical sunscreen agent are more controversial in recent years. The chemical sun-screening agents have a relatively large variety, and in 27 standard sun-screening agents in China, except 2 physical sun-screening agents, the other 25 sun-screening agents belong to chemical sun-screening agents. However, many chemical sunscreens have been increasingly confronted in recent years with human and environmental safety risks and challenges.

Traditionally widely used benzophenone-3, ethylhexyl methoxycinnamate, isoamyl p-methoxycinnamate, homosalate, and 4-methylbenzylidene camphor have all been suspected of presenting potential risks of endocrine disruption. Problems such as skin irritation and high skin permeability are also suspected for octocrylene, ethylhexyl salicylate, PEG-25 p-aminobenzoic acid, and the like. Butyl methoxydibenzoylmethane, which is a few UVA band absorbers, is not safe, but has a problem of unstable illumination, and thus its use is limited. Methylene bis-benzotriazolyl tetramethyl butyl phenol is taken as a macromolecular sun-screening agent with UVA and UVB absorption at the same time, and is not recommended to be used in children products according to the technical guidance principle of children cosmetics in China because of belonging to nano materials.

Throughout the list of standard chemical sunscreens, from the safety and stability points of view, bis-ethylhexyloxyphenol methoxyphenyl triazine (molecular weight 627 dalton), ethylhexyl triazone (molecular weight 822 dalton) and diethylaminooxybenzoyl hexyl benzoate (molecular weight 397 dalton), both of which absorb in the UVA and UVB broad spectrum, are increasingly used due to their higher molecular weight, molecular stability and excellent toxicological data up to now, the rate of use in the market for both adult and child sunscreens rising rapidly in recent years. In particular, according to the Ribes-King's rule on the theory of drug permeation, it is mentioned that drugs with a component of more than 500 daltons are not easily permeated, and from this point of view, the macromolecular bis-ethylhexyloxyphenol methoxyphenyl triazine and ethylhexyl triazone have lower permeation risks. The other liquid type sunscreen agent polysiloxane-15 has a relatively large molecular weight as a polymer, but is not considered as a main sunscreen agent because of its low ultraviolet absorption efficiency, and can be used as an auxiliary sunscreen agent in application examples.

The three types of chemical sun-screening agents with higher safety are all crystalline sun-screening agents, and need to be dissolved for use when in use so as to play a role in uniformly screening sun. However, the solubility of bis-ethylhexyloxyphenol methoxyphenyl triazine and ethylhexyl triazone, especially, is low, the dissolution is not enough, the precipitation in the product is possible, the use and the efficacy are affected, and the situation is also complained on the market in the past.

There are generally two types of current solutions: 1) While oils with relatively high solubility have been sought, low viscosity oil-soluble liquid sunscreens with relatively high polarity (e.g., ethylhexyl methoxycinnamate, ethylhexyl salicylate, isoamyl p-methoxycinnamate) are generally widely used to solubilize crystalline sunscreens, the highly polar oils in the following table are also commonly used in chemical sunscreen formulations as solvents for crystalline sunscreens.

	Dielectric constant
		Butyl octanol salicylate	5.4
Adipic acid diisobutyl ester	5.2
		Benzoic acid phenethyl ester	5.1
Diethylhexyladipate	4.2
		Diethylhexylsebacate	4
Benzoic acid C12-15-alcohol esters	3.8

Note: the dioctyl carbonate is medium polar grease, and the dielectric constant is 2.4.

However, some studies found, for example, in y.schiemanna, ×, m.wegmanna, p.lerscha, e.heislerb, m.farwicka, in "colloids and surfaces: the physicochemical and engineering fields, journal 2008, p.331, 103-107, published in the text "biological activity of a polar oil-and-fat-enhanced phytosphingosine transdermal penetrant in cosmetic formulations", from which it can be seen that the high polarity of oil and fat may have an effect of promoting penetration to some extent, and penetration as a sunscreen product may increase the safety risk and also reduce the sunscreen efficacy. At the same time, the solubility of the nonpolar oils in crystalline sunscreens is very low. In this sense, the selection of medium polarity grease is a safer choice. Therefore, the invention innovatively selects the dioctyl carbonate as the grease, and the dielectric constant of the dioctyl carbonate is 2.4.

2) The use amount of the grease is increased, which is a common technical means of the formula, so as to ensure that the solvent type sunscreen agent is not separated out in the formula. In common sunscreen formulations, we can often see the use of multiple oils together. However, an increase in the fat content generally not only leads to a greasy use sensation, but also increases the formulation and therefore requires more emulsifiers or stabilizers to stabilize the formulation.

The sun protection for children is a category which particularly emphasizes safety and mildness. Based on the consideration, the principle of ' safety priority, necessary efficacy and extremely simple formula ' is particularly proposed in the research draft of ' technical guide principle of children cosmetics ' issued in 2022 in China, and the requirements that the types of chemical sun-screening agents are not more than 3 and the sun-screening index SPF is not more than 30 ' are particularly proposed for sun-screening products.

In view of the above background, the present invention is based on the principle of "safety first, efficacy necessary and formulation extremely simple" of children sunscreen, and it is desirable to provide a safe, simple and stable sunscreen composition.

The invention surprisingly discovers that the solubility of a single sun-screening agent can be increased by compounding bis-ethylhexyloxyphenol methoxyphenyl triazine and ethylhexyl triazone according to a certain proportion, so that mutual solubilization is realized, and the minimum usage amount of an oil solvent is reduced.

Disclosure of Invention

In one aspect, the present invention provides a safe, simple, and stable sunscreen composition comprising:

a primary sunscreen agent which is a combination of bis-ethylhexyloxyphenol methoxyphenyl triazine and ethylhexyl triazone, wherein the weight ratio of bis-ethylhexyloxyphenol methoxyphenyl triazine and ethylhexyl triazone is 0.5 to 2;

an oil or fat for sunscreen agents, which contains no phenyl group and has a dielectric constant of less than 3;

wherein the weight ratio of the grease to the main sunscreen agent in the sunscreen composition is 1.5-4.

In a preferred embodiment, the grease is selected from: dioctyl carbonate, diethylhexyl carbonate, isopropyl myristate, or combinations thereof.

In a preferred embodiment, the sunscreen composition further comprises an auxiliary sunscreen. In a preferred embodiment, the auxiliary sunscreen agent is a macromolecular chemical sunscreen agent or physical sunscreen agent having a molecular weight of more than 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.

In a preferred embodiment, the weight ratio of oil to primary sunscreen in the sunscreen composition is from 2.3 to 4.

In a preferred embodiment, the weight ratio of bis-ethylhexyloxyphenol methoxyphenyl triazine to ethylhexyl triazone is from 1.25 to 1.75.

In a preferred embodiment, the total amount of oil and fat in the sunscreen composition is from 1 to 2.

In another aspect, the present invention also provides a sunscreen product comprising the sunscreen composition of the present invention and a cosmetically acceptable carrier. In a preferred embodiment, the sunscreen product is selected from: the sunscreen cream for infants, the sunscreen cream for children and adult sensitive people, the sunscreen gel for children and adult sensitive people, the sunscreen spray for children and adult sensitive people and the sunscreen mousse for children and adult sensitive people.

Detailed Description

Unless defined otherwise, 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.

The term "about" as used herein refers to an amount, level, value, dimension, size, or amount that differs by up to 30%, 20%, or 10% as compared to the amount, level, value, dimension, size, or amount of a reference. The percentages used herein are by weight unless otherwise indicated.

Throughout the specification and claims, unless the context requires otherwise, the word "comprise", and variations such as "comprises" and "comprising", will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integers or steps.

As used herein, "sunscreen composition" refers to a formulation (e.g., lotion, spray, gel, or other topical product) that absorbs and/or reflects some of the Ultraviolet (UV) radiation of the sun and thus helps prevent the negative effects of sun exposure (e.g., sunburn, premature aging, etc.).

The invention selects, mixes and tests the composition from three aspects of safety, simplicity and stability. Safety is mainly aimed at safety considerations for the selection of sunscreens and sunscreens oils. The sun-screening agent is a combination of bis-ethylhexyloxyphenol methoxyphenyl triazine and ethylhexyl triazone which has excellent toxicological data and molecular weight of more than 500 daltons, and the grease is medium-polarity grease with good safety. To this end, studies have been undertaken primarily with regard to the number limitations of the formulation ingredients and the minimum concentration required to minimize them. So as to improve the mildness, and simultaneously, the product is more refreshing and not greasy, and the use feeling is improved. Stabilization is the selection of sunscreen from the photostability of the sunscreen, and is considered from the solubility stability of the sunscreen combination as a means of evaluation.

Sunscreen agent

The invention takes safety as the first starting point, takes a crystal type macromolecular sun-screening agent with the molecular weight of more than 500 daltons as a main research object according to the principle from a formula to a simple principle, and provides a safe, simple and stable sun-screening composition. In some preferred embodiments, the total number of sunscreens in the sunscreen compositions of this invention is no more than 3.

The invention discovers that the solubility of a single sun-screening agent can be increased by compounding bis-ethylhexyloxyphenol methoxyphenyl triazine and ethylhexyl triazone according to a certain proportion, and mutual solubilization is realized, so that the minimum usage amount of the grease solvent is reduced. Accordingly, the present invention provides a sunscreen composition comprising bis-ethylhexyloxyphenol methoxyphenyl triazine and ethylhexyl triazone. The sunscreen composition disclosed by the invention selects the combination of bis-ethylhexyloxyphenol methoxyphenyl triazine and ethylhexyl triazone, and the necessary addition amount of grease is reduced as much as possible by optimizing the combination ratio of the sunscreen agent, so that multiple balance of safety, simplicity and stability in use is achieved.

The sunscreen compositions of the present invention may also contain other macromolecular chemical sunscreens (e.g., polysiloxane-15) or physical sunscreens (e.g., non-nano titanium dioxide or zinc oxide) to extend the field of application in a simple formulation of no more than 3 sunscreens while meeting safety requirements.

In some embodiments, the weight ratio of bis-ethylhexyloxyphenol methoxyphenyl triazine and ethylhexyl triazone in the sunscreen composition is from 0.5 to 2. In a preferred embodiment, the weight ratio of bis-ethylhexyloxyphenol methoxyphenyl triazine and 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 and ethylhexyl triazone in the sunscreen composition is from 1 to 2. In a preferred embodiment, the weight ratio of bis-ethylhexyloxyphenol methoxyphenyl triazine and ethylhexyl triazone in the sunscreen composition is from 1.25 to 2. In a preferred embodiment, the weight ratio of bis-ethylhexyloxyphenol methoxyphenyl triazine and 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 and ethylhexyl triazone in the sunscreen composition is from 1.5 to 2. In a most preferred embodiment, the weight ratio of bis-ethylhexyloxyphenol methoxyphenyl triazine and ethylhexyl triazone in the sunscreen composition is 1.5.

In some embodiments, the sunscreen composition comprises at least about 3% by weight of one or more sunscreens, based on the total weight of the composition. The sunscreen composition may comprise from about 3 to about 35 weight percent of one or more sunscreen agents, based on the total weight of the composition. The sunscreen composition may comprise from about 3 to about 10 wt% of one or more sunscreen agents, based on the total weight of the composition.

Sunscreen oils and fats

To address the solubility problem of chemical sunscreens, oils are often used to solubilize the sunscreen.

According to the invention, the medium-polarity oil which is as mild, non-greasy and non-greasy as possible is selected as the solvent of the sunscreen agent, and the necessary addition amount of the oil is reduced as much as possible by optimizing the combination ratio of the sunscreen agent, so that multiple balance of safety, simplicity and stability in use is achieved.

In some embodiments, a single medium polarity grease with good solubility is selected, a proper grease adding amount is confirmed, and then the optimal selection of the dissolution stability of the ratio of the crystallization type sunscreen agent bis-ethylhexyloxyphenol methoxyphenyl triazine to ethylhexyltriazone is carried out. The method for verifying the dissolution stability adopts a low-temperature tracking test at 4 ℃ in a common stability standard method for cosmetics, and the low-temperature stability requirement is met by keeping the stability for 12 weeks at the low temperature of 4 ℃ without precipitation according to the common stability requirement.

In some embodiments, the actual formulation of the sunscreen composition may also include other oils as emollients or other ingredient dispersants, etc., whereby the amount of oil in the sunscreen formulation is from 1 to 2.

In some embodiments, the sunscreen composition comprises a lipid having a dielectric constant of less than 6 that is free of phenyl groups. 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 from 1 to 3. In a more preferred embodiment, the sunscreen composition comprises an oil having a dielectric constant of from 2 to 3.

In some embodiments, the oil or fat in the sunscreen composition is selected from the group consisting of: dioctyl carbonate, diethylhexyl carbonate, isopropyl myristate, ethylhexyl salicylate, glyceryl cocoate, isononyl isononanoate, butyl octanol salicylate, diisobutyl adipate, phenethyl benzoate, diethylhexyl adipate, diethylhexyl sebacate, C12-15 alcohol benzoate, or combinations thereof. In a preferred embodiment, the oil or fat in the sunscreen composition is selected from the group consisting of dioctyl carbonate, diethylhexyl carbonate, isopropyl myristate.

In some embodiments, the weight ratio of oil to sunscreen in the sunscreen composition is from 1.5 to 4. In a preferred embodiment, the weight ratio of oil to sunscreen in the sunscreen composition is from 2.3 to 4. In some embodiments, the weight ratio of oil to sunscreen in the sunscreen composition is 6:4. In some embodiments, the weight ratio of oil to sunscreen in the sunscreen composition is 7:3.

In some embodiments, the sunscreen composition may comprise from about 5% to about 20% by weight of the oil, based on the total weight of the composition. The sunscreen composition may comprise from about 8 wt% to about 15 wt% of the oil, based on the total weight of the composition. The sunscreen composition may comprise from about 8 wt% to about 12 wt% of the oil based on the total weight of the composition.

Sunscreen composition

The safety sun protection of the invention mainly focuses on the following two aspects: the choice of sunscreen and the choice of oil.

The selection of the sunscreen agent should meet the list and limited range of cosmetic safety technical specifications. The selection of safe chemical sunscreens included selecting chemical sunscreens with a relatively large molecular weight (above 390 daltons) and a green color according to the american Environmental Working Group EWG (Environmental Working Group) composite score. Also, safer physical sunscreen options include: 1) A reasonable test method is adopted to represent that the aggregation state particle size of the physical sun-screening agent raw material is more than 100 nanometers; and/or 2) if the physical sunscreen titanium dioxide is selected, it is desirably of the rutile type and is surface treated. Chemical sunscreen systems and physical sunscreen systems that meet the above sunscreen requirements can be used alone or in combination.

The oil or fat is preferably selected from non-phenyl, non-polar, low-polar or medium-polar oils or fats. The identity of the polarity of the grease may be characterized by reference to the dielectric constant or the polarity classification of a professional grease manufacturer.

The invention relates to the simple requirements mainly reflected in the necessity and the quantity of raw materials. The raw materials used must have certain functions from the viewpoint of efficacy, stability and safety, and cannot be omitted. The amount of raw materials used is limited. The present invention focuses on sunscreens and greases, and therefore has two considerations: sunscreen number limitation: for children aged 12 years and younger to sun screen, the number of sunscreens does not exceed 3; for adult sunscreens, the number of sunscreens is recommended to be no more than 5; and grease quantity limitation: not more than 3.

The invention has broad spectrum and is mainly referred to the American requirement, and the critical wavelength is not lower than 370 nanometers according to the method of ISO 24443. Alternatively, the UVA-PF/SPF value is not less than 0.33, as referred to European Union requirements. In a preferred embodiment, broad spectrum sunscreen is required to meet both requirements.

Higher UVA protection rates are considered in the aspect that the ratio of UVA-PF/SPF is not lower than 0.45.

In some embodiments, the sunscreen compositions of the present invention have a pH of 6 to 8. In a preferred embodiment, the pH of the sunscreen composition of the present invention is from 6.5 to 7.5.

The compositions may be prepared using mixing and blending methods well known in the sunscreen and cosmetic arts.

The composition may be combined with a "cosmetically acceptable topical carrier", i.e., a topical carrier capable of containing other ingredients dispersed or dissolved therein and having acceptable properties that render it safe for topical use.

The cosmetically acceptable topical carrier may optionally include a wide variety of additional oil-soluble and/or oil-dispersible materials commonly used in compositions for application to the skin at levels established in the art. For example, surfactants, emulsifiers, pearlizing or opacifying agents, thickeners, emollients, conditioning agents, humectants, chelating agents, exfoliants, preservatives, pH adjusters, and additives that enhance the appearance, feel, or fragrance of the composition, such as colorants, fragrances, tactile modifiers, and the like, may be included.

Application method

As used herein, "topically applying" means spraying, wiping, spreading or spreading directly on the outer skin or scalp, for example, by hand or by an applicator such as a wipe, roller or sprayer.

The sunscreen composition may be applied to the skin of the user in any desired manner. In some aspects, the product may be applied directly by hand, or the product may be applied using a device such as a cosmetic cotton swab or other implement. The composition is advantageously applied to the skin in order to facilitate sample absorption. The composition may be left on the area to be applied for a desired level of time, such as from about 5 seconds to about 5 minutes. Alternatively, the composition may be left on the area of application and continued to be applied until absorption.

The compositions of the present invention are sprayable. As used herein, "sprayable" means that the composition, when manually actuated or released by pressurization from a dispensing mechanism such as a bottle or aerosol can having a pump spray nozzle, produces an evenly distributed and reproducible spray pattern over an area of defined shape (e.g., circular, annular) and size. The composition may be sprayable without the use of a propellant, i.e., in a non-aerosol form.

The invention will be further illustrated by the following specific examples. It should be noted that the examples are given solely for the purpose of illustration and are not to be construed as limitations on the scope of the invention, as many insubstantial modifications and variations of the invention may be made by those skilled in the art in light of the above teachings. Test methods in which specific conditions are not specified in the following examples are generally carried out under conventional conditions or under conditions recommended by the manufacturer. All percentages and parts are by weight unless otherwise indicated.

Experimental materials:

bis-ethylhexyloxyphenol methoxyphenyl triazine, supplied by BASF (trade name Tinosorb S), abbreviated as TS;

ethylhexyl triazone, supplied by BASF (trade name Uvinul T150), abbreviated T150;

dioctyl carbonate, supplied by BASF (trade name Cetiol CC), abbreviated CC;

cocoglycerides, supplied by BASF (trade name: BASF)

331 331 for short;

isononyl isononanoate, supplied by Seppic (trade name Lanol 99), abbreviated as ININ;

ethylhexyl salicylate, ashland (trade name escanol 587), OS for short.

Example 1: sunscreen composition and stability study thereof

Weighing bis-ethylhexyloxyphenol methoxyphenyl triazine and ethylhexyl salicylate according to the mass parts shown in Table 1, heating to 85-90 ℃ while stirring until the bis-ethylhexyloxyphenol methoxyphenyl triazine and the ethylhexyl salicylate are completely dissolved, pouring into a glass bottle preheated in a 60 ℃ oven, and continuously placing in the 60 ℃ oven for heat preservation. And (3) preparing samples No. 2-10 according to the mass parts in the following table by the same operation, and after 10 samples are prepared, putting all the samples into a 60 ℃ oven together for constant temperature for 30-60 minutes to keep the samples prepared in sequence at the high temperature of 60 ℃ and at the sufficient constant temperature. The samples were then removed and, after observing that no abnormalities occurred, all samples were transferred to an oven at 25 ℃.

TABLE 1

And (3) observing stability: taking out the sample to room temperature, placing a flat LED lamp on the desktop at the bottom of the sample, placing the sample on the lamp for visual observation, and placing the bottom for placing the LED so as to find micro precipitation. Once a sample is deposited, the sample is removed and no stability considerations are included, indicated by an "X".

TABLE 2

According to the results, the dissolution stability of the samples # 1-10 is sequentially from excellent to inferior: 3#, 4#, 5#, 2#, 6#, 7#, 1#, 9#, 10#. Based on the fixed ratio of 6 parts by mass of ethylhexyl salicylate to 4 parts by mass of sunscreen agent, the single sunscreen agents 10# and 1# have poor dissolution stability, and compared with a certain ratio, the combination of the two sunscreen agents has more excellent dissolution stability, for example, the ratio of the mass ratio of bis-ethylhexyloxyphenol methoxyphenyl triazine to the mass ratio of ethylhexyltriazinone = 1.25-2.00 shows significantly good dissolution stability, particularly, the ratio of bis-ethylhexyloxyphenol methoxyphenyl triazine: both samples, ethylhexyl triazone =1.50 and 1.75, fully met the criterion of low temperature stability of the cosmetic at 4 ℃ for 12 weeks (87 days), and also showed good solubility of the more polar ethylhexyl salicylate for the crystalline sunscreen.

Example 2: sunscreen composition and stability study thereof

Weighing bis-ethylhexyloxyphenol methoxyphenyl triazine and cocoglyceride according to the mass parts shown in table 3, heating to 85-90 ℃ while stirring until the bis-ethylhexyloxyphenol methoxyphenyl triazine and the cocoglyceride are completely dissolved, pouring into a glass bottle preheated in a 60 ℃ oven, and continuously placing in the 60 ℃ oven for heat preservation. In the same way, samples No. 12-20 are prepared according to the mass parts in the following table, and after 10 samples are prepared, all the samples are put in a 60 ℃ oven together for 24 hours to keep the samples prepared in sequence at a high temperature of 60 ℃ and at a sufficient constant temperature. The sample was then removed and observed.

TABLE 3

And (3) observing stability: taking out the sample to room temperature, placing a flat LED lamp on the desktop at the bottom of the sample, placing the sample on the lamp for visual observation, and placing the bottom to place the LED so as to find micro precipitation. Once a sample is deposited, the sample is removed and no stability considerations are included, indicated by an "X".

TABLE 4

According to the results, the sequence from good to bad of the dissolution stability of the samples No. 11-20 is as follows: 18# -17 #, 15# -16 # -14 #, 13#, 12#, 11#, 19#, 20#. Based on the fixed ratio of 6 parts by mass of the coco glyceride to 4 parts by mass of the sunscreen, the single sunscreens 20# and 11# have poor dissolution stability, and compared with a certain ratio, the combination of the two sunscreens has more excellent dissolution stability, for example, the ratio of the mass ratio of the bis-ethylhexyl phenol methoxyphenyl triazine to the mass ratio of the ethylhexyl triazone = 0.50-0.75 shows better dissolution stability, which is supposed to be mainly caused by the different solubility differences of the coco glyceride and the ethylhexyl salicylate between the ethylhexyl triazone and the bis-ethylhexyl phenol methoxyphenyl triazine. However, the best samples also failed to meet the stability criterion of 12 weeks at 4 ℃, and it was found that the solubility of cocoglycerides in bis-ethylhexyloxyphenol methoxyphenyl triazine and ethylhexyl triazone was poor.

Example 3: sunscreen composition and stability study thereof

Weighing bis-ethylhexyloxyphenol methoxyphenyl triazine and dioctyl carbonate according to the mass parts shown in Table 5, heating to 85-90 ℃ while stirring until the bis-ethylhexyloxyphenol methoxyphenyl triazine and the dioctyl carbonate are completely dissolved, pouring into a glass bottle preheated in a 60 ℃ oven, and continuously placing in the 60 ℃ oven for heat preservation. In the same way, samples 22# to 30# are prepared according to the parts by mass in the following table, and after 10 samples are prepared, all the samples are placed in a 60 ℃ oven together for constant temperature for 60 minutes so as to keep the samples prepared successively at a high temperature of 60 ℃ and at a sufficient constant temperature. The sample was then removed and observed.

TABLE 5

TABLE 6

According to the results, the dissolution stability of the samples # 21-30 is sequentially from excellent to inferior: 24#, 22#, 23 # -25 #, 26#, 21#, 27#, 28#, 29#, 30#. Using dioctyl carbonate: for the fixed ratio of 6 parts by mass of the sunscreen agent to 4 parts by mass of the sunscreen agent, the single sunscreen agents 30# and 21# have poor dissolution stability, and the combination of the two sunscreen agents has more excellent dissolution stability compared with a certain ratio, for example, the ratio of the mass ratio of the bis-ethylhexyloxyphenol methoxyphenyl triazine to the mass ratio of the ethylhexyl triazone =1.00 to 2.00 shows better dissolution stability, and the ratio of the mass ratio of the bis-ethylhexyloxyphenol methoxyphenyl triazine: ethylhexyl triazone mass ratio =1.50 performs most well in this experiment. But still fails to meet the 12-week stability criterion at 4 ℃. Comparing two medium polarity oils, cocoglycerides, with dioctyl carbonate, neither compares in solubility with the polar oil, ethylhexyl salicylate, in bis-ethylhexyloxyphenol methoxyphenyl triazine and ethylhexyl triazone. From the experiment, the mass ratio of the dioctyl carbonate to the bis-ethylhexyloxyphenol methoxyphenyl triazine is shown as follows: the mass ratio of ethylhexyl triazone =1.50 is obviously superior to that of the cocoglyceride in each proportion, and the dioctyl carbonate is obviously fresher and less sticky than the cocoglyceride in use feeling, so the dioctyl carbonate has a high selection value.

Example 4: sunscreen composition and stability study thereof

Weighing bis-ethylhexyloxyphenol methoxyphenyl triazine and isononyl isononanoate according to the mass parts shown in Table 7, heating to 85-90 ℃ while stirring until the materials are completely dissolved, pouring the materials into a glass bottle preheated in a 60 ℃ oven, and continuously placing the glass bottle in the 60 ℃ oven for heat preservation. In the same way, samples No. 32-40 are prepared according to the parts by mass in the following table, and after 10 samples are prepared, all the samples are put in a 60 ℃ oven together to be kept at a constant temperature for 24 hours so as to keep the samples prepared successively at a high temperature of 60 ℃ and at a sufficiently constant temperature. The sample was then removed and observed.

TABLE 7

TABLE 8

According to the results, the dissolution stability of the 31-40 # samples is sequentially from excellent to inferior: 32#, 33#, 34#, 31#, 35#, 37#, 36#, 38#, 39#, and 40#. Isononyl isononanoate: for the fixed ratio of 6 parts by mass to 4 parts by mass of the sunscreen agent, the single sunscreen agents 40# and 31# have poor dissolution stability, and the combination of the two sunscreen agents has more excellent dissolution stability compared with a certain ratio, for example, the ratio of the mass ratio of bis-ethylhexyloxyphenol methoxyphenyl triazine to the mass ratio of ethylhexyl triazone = 1.50-2.00 shows better dissolution stability. However, in general, the mass ratio of isononyl isononanoate to bis-ethylhexyloxyphenol methoxyphenyl triazine and the solubility of ethylhexyl triazone were not good, and they were the worst in examples 1 to 4.

According to the results of experimental examples 1-4, 1) bis-ethylhexyloxyphenol methoxyphenyl triazine and ethylhexyl triazone have better dissolving capacity under a certain proportion, the proportion of the bis-ethylhexyloxyphenol methoxyphenyl triazine and the ethylhexyl triazone has certain influence on the solubility, and the specific optimized proportion can be different along with the different dissolving performances of different oils and fats on two sunscreens. 2) The ethylhexyl salicylate as a high-polarity oil sunscreen has obviously better dissolving capacity for crystal sunscreens than the dioctyl carbonate, isononyl isononanoate and glyceryl cocoate as medium-polarity oils; in three medium-polarity oils, dioctyl carbonate has better dissolving capacity for the combination of bis-ethylhexyloxyphenol methoxyphenyl triazine and ethylhexyl triazone compared with isononyl isononanoate and coco glyceride; but in the form of dioctyl carbonate: total sunscreen dose =6:4, the requirement of the dissolution stability of the cosmetic cannot be met, so that the relative mass part of the dioctyl carbonate needs to be increased to increase the solubility of the dioctyl carbonate to the sunscreen, and a proper proportion is selected in the following experimental examples.

Example 5: sunscreen composition and stability study thereof

Weighing bis-ethylhexyloxyphenol methoxyphenyl triazine and dioctyl carbonate according to the mass parts shown in Table 9, heating to 85-90 ℃ while stirring until the bis-ethylhexyloxyphenol methoxyphenyl triazine and the dioctyl carbonate are completely dissolved, pouring into a glass bottle preheated in a 60 ℃ oven, and continuously placing in the 60 ℃ oven for heat preservation. In the same way, samples No. 41 to 50 are prepared according to the mass parts in the following table, and after 10 samples are prepared, all the samples are placed in a 60 ℃ oven together for constant temperature for 60 minutes so as to keep the samples prepared in sequence at the high temperature of 60 ℃ and at the sufficient constant temperature. The sample was then removed and observed.

TABLE 9

And (3) stability observation: taking out the sample to room temperature, placing a flat LED lamp on the desktop at the bottom of the sample, placing the sample on the lamp for visual observation, and placing the bottom for placing the LED so as to find micro precipitation. Once a sample is deposited, the sample is removed and no stability considerations are included, indicated by an "X".

Watch 10

According to the results, the order of the dissolution stability of the samples No. 41-50 from good to bad is as follows: 44#, 43, 46 #, 45#, 34#, 42#, 48#, 41#, 49#, 50#. Using dioctyl carbonate: the sun-screening agent comprises 7 parts by mass: in the aspect of 3 parts by mass of the ratio, the mass ratio of the bis-ethylhexyloxyphenol methoxyphenyl triazine is as follows: ethylhexyl triazone mass ratio =0.50 to 2.00 still shows better solubility than the single sunscreen agent, in particular bis-ethylhexyloxyphenol methoxyphenyl triazine mass ratio: the mass ratio of the ethylhexyl triazone =1.50 has better low-temperature dissolution stability, can meet the stability requirement of cosmetics stable for 12 weeks at the low temperature of 4 ℃, and has practical use significance.

Application example

Application scenarios: sunscreen cream, sunscreen emulsion, sunscreen gel, sunscreen spray and sunscreen mousse for children or adult sensitive people

Application example 1: preparation of baby sunscreen cream

The process comprises the following steps: heating phase A to 75 ℃, uniformly dispersing under homogenization, adding phase B heated to 75 ℃, homogenizing for 5 minutes after adding, stirring and cooling to 55 ℃, adding phase C, adjusting pH to 5.0-6.0, stirring and cooling to 50 ℃, adding phase D, homogenizing for 3 minutes after adding, stirring, and cooling to 35 ℃ to obtain the final product.

According to the professional season of the State drug administration and the guidance of professional doctors, the sun protection of infants between 6 months and 2 years old is realized by selecting physical sun protection such as clothes and caps and matching with sun protection products with sun protection index SPF of about 10. The application example meets the principle that the SPF is 10, the types of the chemical sunscreens are 2, the formula is simple, and the chemical sunscreens are macromolecular sunscreens with the molecular weight of more than 500, so that the penetration risk is greatly reduced. Meanwhile, as an oil-in-water product without titanium dioxide and zinc oxide physical sunscreens, the cleaning difficulty is reduced, and the water-in-oil type sunscreen lotion is particularly suitable for infants.

Application example 2: preparation of sunscreen cream suitable for children and adult sensitive people

The process comprises the following steps: heating phase A to 75 ℃, and uniformly dispersing under homogenization; uniformly grinding and dispersing the phase C on a three-roller grinder for later use; heating phase B to 75 deg.C, adding phase C, mixing, and adding phase A under the condition of opening homogenization. Homogenizing for 10 min after adding, stirring and cooling to 55 ℃, adding the phase C, adjusting the pH to 5.0-6.0, stirring and cooling to 50 ℃, adding the phase D, homogenizing for 3 min after adding, stirring and cooling to 35 ℃ to obtain the final product.

The second application example is a sunscreen cream with the SPF 25 or so, the invention is combined with the use of a physical sunscreen agent zinc oxide (zinc oxide can be selected from non-nano grade in order to meet the sunscreen requirement of children), and the macromolecular chemical sunscreen is combined with a physical sunscreen agent with higher safety acceptance, so that the invention is also a collocation with higher safety factor. Also meets the requirements of the children sunscreen product. Compared with pure physical sun protection, the use of the chemical sun protection agent improves the efficiency of the sun protection agent and improves the spreadability to a certain extent. Is suitable for daily sun protection requirements of children and sensitive adults.

Application example 3: preparation of sunscreen lotion suitable for children and adult sensitive people

The process comprises the following steps: heating phase A to 75 ℃, uniformly dispersing under homogenization, adding phase B heated to 75-80 ℃, homogenizing for 5 minutes after adding, stirring and cooling to 60-65 ℃, adding phase C, adjusting pH to 5.0-6.0, adding phase D, homogenizing for 3 minutes after adding, continuously stirring and cooling to 50 ℃, adding phase E, homogenizing for 2 minutes, continuously stirring and cooling to 35 ℃ to obtain the final product.

The third application example is an emulsion with the SPF of about 20-30, and is matched with another macromolecular sun-screening agent polysiloxane-15 (a non-crystalline sun-screening agent, but the relatively sun-screening absorption is not high) on the basis of the invention combination, and is also a safe sun-screening formula with the molecular weight of all sun-screening agents being more than 500, so that the third application example also meets the regulation requirements of children sun-screening products, and is suitable for daily sun-screening requirements of children and sensitive adults.

Application example 4: preparation of sunscreen gel suitable for children and adults

The process comprises the following steps: heating phase A to 75 ℃, uniformly dispersing under homogenization, adding phase B heated to 75-80 ℃, homogenizing for 5 minutes after adding, stirring and cooling to 60-65 ℃, adding phase C, homogenizing for 3 minutes after adding, continuously stirring and cooling to 50 ℃, adding phase D and phase E, homogenizing for 2 minutes, and continuously stirring and cooling to 35 ℃ to obtain the final product.

The fourth application example is a sunscreen gel with the SPF of about 20-30, and the invention is matched with another macromolecular sunscreen polysiloxane-15 (a non-crystalline sunscreen agent, but the relative sunscreen absorption is not high) on the basis of the combination, and is also a safe sunscreen formula with the molecular weight of all sunscreen agents above 500, so that the sunscreen gel also meets the regulation requirements of children sunscreen products, and is suitable for daily sunscreen requirements of children and sensitive adults.

Application example 5: preparation of sunscreen spray suitable for children and adult sensitive people

The process comprises the following steps: heating phase A to 75 ℃ to completely dissolve, adding phase B which is heated to 75-80 ℃ under the condition of homogenization, homogenizing for 5 minutes after the addition is finished, stirring and cooling to 60-65 ℃, adding phase C, homogenizing for 3 minutes after the addition is finished, continuously stirring and cooling to 50 ℃, adding phase D and phase E, homogenizing for 2 minutes, continuously stirring and cooling to 25 ℃ to obtain the final product.

The fifth application example is a sunscreen spray with the SPF of about 20-30, and is matched with another macromolecular sunscreen polysiloxane-15 (a non-crystalline sunscreen agent, but the relative sunscreen absorption is not high) on the basis of the invention combination, and is also a safe sunscreen formula with the molecular weight of all sunscreen agents above 500, so that the fifth application example also meets the regulation requirements of children sunscreen products, and is suitable for daily sunscreen requirements of children and sensitive adults.

Application example 6: preparation of sun-proof mousse suitable for children and adult sensitive people

The process comprises the following steps: heating phase A to 75 ℃ to completely dissolve, adding phase B which is heated to 75-80 ℃ under homogenization, homogenizing for 5 minutes after adding, stirring and cooling to 60-65 ℃, adding phase C, homogenizing for 3 minutes after adding, continuing stirring and cooling to 50 ℃, adding phase D and phase E, homogenizing for 2 minutes, continuing stirring and cooling to 25 ℃ to obtain a liquid part. Filling a proper amount of the liquid formula into an aerosol can, filling a certain proportion of isobutane and n-propane, and covering and sealing to obtain the product.

The sixth application example is a sun-protection mousse with an SPF of about 20-30, and is matched with another macromolecular sun-protection agent polysiloxane-15 (a non-crystalline sun-protection agent, but the relative sun-protection absorption is not high) on the basis of the invention combination, and is also a safe sun-protection formula with the molecular weight of all sun-protection agents above 500, so that the sun-protection mousse also meets the regulation requirements of children sun-protection products, and is suitable for daily sun-protection requirements of children and sensitive adults.

Claims

1. A safe, to simple, stable sunscreen composition comprising:

a primary sunscreen which is a combination of bis-ethylhexyloxyphenol methoxyphenyl triazine and ethylhexyl triazone, wherein the weight ratio of bis-ethylhexyloxyphenol methoxyphenyl triazine to ethylhexyl triazone is from 0.5 to 2;

2. A sunscreen composition according to claim 1, wherein said oil is selected from the group consisting of: dioctyl carbonate, diethylhexyl carbonate, isopropyl myristate, or combinations thereof.

3. The sunscreen composition of claim 1, wherein the composition further comprises an auxiliary sunscreen.

4. A sunscreen composition according to claim 3, wherein the auxiliary sunscreen is a macromolecular chemical sunscreen or physical sunscreen having a molecular weight of more than 500 daltons.

5. A sunscreen composition according to claim 3, wherein said auxiliary sunscreen is selected from the group consisting of: polysiloxane-15, non-nano titanium dioxide or zinc oxide, or a combination thereof.

6. A sunscreen composition according to claim 1, wherein the total number of sunscreens in the composition is no more than 3.

7. A sunscreen composition according to claim 1 wherein the weight ratio of oil to primary sunscreen in the composition is from 2.3 to 4.

8. A sunscreen composition according to claim 1 wherein the weight ratio of bis-ethylhexyloxyphenol methoxyphenyl triazine to ethylhexyl triazone is from 1.25 to 1.75.

9. The sunscreen composition of claim 1, wherein the total amount of oil and fat in the sunscreen composition is from 1 to 2.

10. A sunscreen product comprising the sunscreen composition of any of claims 1-9 and a cosmetically acceptable carrier.

11. A sunscreen product according to claim 10 selected from the group consisting of: the sunscreen cream for infants, the sunscreen cream for children and adult sensitive people, the sunscreen gel for children and adult sensitive people, the sunscreen spray for children and adult sensitive people and the sunscreen mousse for children and adult sensitive people.