WO2022082940A1 - Sunscreen composition, sunscreen gel comprising same, and preparation method therefor - Google Patents

Abstract

A sunscreen composition, a sunscreen gel comprising same and a preparation method therefor. The sunscreen composition comprises an ultraviolet absorber and a photoprotective additive, wherein the ultraviolet absorber comprises microsphere particles loaded with a chemical sunscreen agent; and the ultraviolet absorber further comprises a free chemical sunscreen agent. The sunscreen gel comprises the sunscreen composition, a thickener, a polyol, a preservative, a pH regulator, and water. The sunscreen gel can provide protection against UVA, UVB, HEV and IRA, prevent photoaging and improve the barrier function and resistance of the skin, makes the skin moisturized and smooth, is mild and non-irritant, and avoids "sunscreen holes" during application, and also has broad development prospects in the field of sunscreen skin care products.

Description

Sunscreen composition, sunscreen gel containing the same, and preparation method thereof technical field

The present application relates to the technical field of cosmetics, and relates to a sunscreen composition, a sunscreen gel containing the same, and a preparation method thereof.

Background technique

Ultraviolet (UV) is a part of the electromagnetic spectrum (light) that reaches the earth from the sun. The wavelength is shorter than that of visible light and invisible to the naked eye. According to the wavelength, ultraviolet rays can be divided into long-wave ultraviolet (Ultraviolet A, UVA), medium-wave ultraviolet (Ultraviolet B, UVB) and short-wave ultraviolet (Ultraviolet C, UVC), most of which are absorbed by the ozone layer and do not reach the earth. Scientific research has proved that excessive exposure to ultraviolet rays will damage the human immune system, accelerate skin aging, and lead to various skin diseases and even skin cancer.

Blue light, also known as High Energy Visible Light (HEV), is light with high energy with a wavelength between 400 and 500 nm. It exists in sunlight, but mainly comes from the screens of electronic products. Scientific research has shown that blue light can promote the production of reactive oxygen species, which can cause cell damage, and the melanosis caused by blue light is more difficult to remove than that caused by ultraviolet radiation.

The wavelength of near-infrared light (Infrared A, IRA) is between 700 and 1400 nm, and most of the IRA can reach the dermis, causing DNA damage and oxidative stress damage, and up-regulating the expression of matrix metalloproteinase-1 (MMP-1) in vivo , thereby destroying collagen, causing the skin to sag and lose its elasticity.

Traditional sunscreen usually refers to the protection of UVA and UVB. The protection methods include the use of physical sunscreens to reflect and scatter ultraviolet rays, but there are problems such as whitening and poor skin feel; and the use of chemical sunscreens to absorb ultraviolet rays. The water-soluble chemical sunscreens used in the cosmetics industry mainly include phenylbenzimidazole sulfonic acid, terephthalimide dicamphor sulfonic acid, and benzophenone-4. It has been reported that phenylbenzimidazole sulfonic acid is exposed to sunlight. Free radicals will be generated under the sun, which will damage the skin DNA, terephthalmethylene dicamphor sulfonic acid can be decomposed by 40% after two hours of exposure to sunlight, and benzophenone-4 is irritating to the skin and eyes. Among oil-soluble sunscreens, bis-ethylhexyloxyphenol methoxyphenyl triazine is the most effective broad-spectrum UV absorber in the industry at present, with high absorption for both UVA and UVB, and strong photostability.

With the increasing frequency of daily use of electronic products and the further improvement of awareness of light pollution, the protection of HEV and IRA has gradually attracted people's attention.

CN109077974A discloses a waterproof and anti-sweat type full-band sunscreen skin care product, the sunscreen skin care product includes sunscreen agent and grease, emulsifier, film-forming agent, thickener, polyol, preservative, pH adjuster, cosmetic additives and Water, with high SPF and PA protection value, up to SPF50 and PA+++, can protect the skin for a long time against infrared light, but cannot protect against HEV, and cannot improve the skin's barrier function and ability to resist ultraviolet rays.

CN111616982A discloses an NMN-containing anti-blue light sunscreen formulation and a preparation method thereof. The sunscreen formulation comprises: glycerin, acrylamide dimethyl taurate/acrylamide copolymer, carbomer, propylene glycol, pentylene glycol, p-Hydroxyacetophenone, alpha-bisabolol, ionic surfactant, ester emulsifier, ethylhexyl methoxycinnamate, cetyl PEG/PPG-10/1 dimethicone Alkane, aloe vera extract and cactus extract, etc., can prevent blue light, and repair skin aging caused by blue light and ultraviolet rays, and can protect against UVA, UVB and HEV at the same time, but not for IRA protection.

CN110840794A discloses an anti-blue light and anti-infrared sunscreen composition. The composition includes Flos chinensis extract, acicular titanium dioxide and polysiloxane 15, which can achieve the effect of resisting UVA, UVB, HEV and IRA, but does not have the Solve the problem of whitening and greasy skin during use.

In summary, a sunscreen composition is provided, which has UVA, UVB, HEV and IRA protective effects, feels refreshing, moisturizing, non-greasy, non-heavy, and does not cause whitening, and can improve skin barrier function and protect against ultraviolet rays. The ability to prevent photoaging is of great significance to the field of sunscreen skin care products.

SUMMARY OF THE INVENTION

The present application provides a sunscreen composition, a sunscreen gel containing the same, and a preparation method thereof, the sunscreen composition can protect against UVA, UVB, HEV and IRA, and the sunscreen gel containing the sunscreen composition has a skin feel Moisturizing and silky, mild and non-irritating, it can improve the skin's barrier function and resistance, and prevent photoaging.

In a first aspect, the present application provides a sunscreen composition, the sunscreen composition includes a UV absorber and a photoprotective additive, the UV absorber includes microsphere particles loaded with a chemical sunscreen agent, and the UV absorber further includes a free Chemical sunscreens.

In the sunscreen composition of the present application, the chemical sunscreen agent is loaded on the microsphere particles, so that the oil-soluble chemical sunscreen agent can be added in the water phase and cooperate with the free chemical sunscreen agent in the oil phase, thereby balancing the sunscreen condensation The chemical sunscreens in the water phase and oil phase in the invention protect against UVA and UVB. In addition, the microsphere particle structure can cause scattering and refraction of light, thereby increasing the contact between chemical sunscreens and light, and further enhancing the sunscreen effect. Photoprotective additives can protect HEV and IRA, improve skin barrier function and ability to resist ultraviolet rays, prevent photoaging, and cooperate with ultraviolet absorbers to achieve full-band protection of UVA, UVB, HEV and IRA.

Preferably, the mass ratio of the chemical sunscreen agent-loaded microsphere particles, the free chemical sunscreen agent and the photoprotective additive is 1:(0.2-8.8):(0.05-2), including but not limited to 1:0.5:0.1, 1:1.5:0.5, 1:3.5:1.1, 1:5.5:1.4, or 1:7.5:1.8.

In this application, chemical sunscreens may be bis-ethylhexyloxyphenol methoxyphenyl triazine, diethylaminohydroxybenzoyl hexyl benzoate, 4-methylbenzylidene camphor, ethylhexyl triazine Any one or a combination of at least two of ketone, isoamyl p-methoxycinnamate, or ethylhexyl methoxycinnamate.

Preferably, the chemical sunscreen-loaded microsphere particles comprise chemical sunscreen-loaded silica, preferably bis-ethylhexyloxyphenol methoxyphenyltriazine-loaded silica.

In this application, chemical sunscreens, especially bis-ethylhexyloxyphenol methoxyphenyl triazine, are loaded on silica, so that oil-soluble chemical sunscreens can be added in the water phase, and the chemical sunscreens freed in the oil phase can be added to the water. The chemical sunscreens in the water phase and the oil phase in the sunscreen gel are balanced, so as to avoid "sunscreen leaks" when applying, and the microsphere particle structure of silica can cause light scattering and refraction, thereby increasing the chemical sunscreens The contact with the light further enhances the sun protection effect.

Preferably, the silica loaded with bis-ethylhexyloxyphenol methoxyphenyl triazine comprises 24% to 35% of bis-ethylhexyloxyphenol methoxyphenyl triazine by mass, including but not limited to 25% , 26%, 27%, 30%, 32, 33%, or 34%, and silica 65% to 76%, including but not limited to 66%, 67%, 68%, 69%, 72%, 74%, or 75% %.

Preferably, the particle size of the silica is 6-9 μm, including but not limited to 6.5 μm, 7 μm, 7.5 μm or 8 μm.

Preferably, the free chemical sunscreens include bis-ethylhexyloxyphenol methoxyphenyl triazine, diethylaminohydroxybenzoyl hexyl benzoate, 4-methylbenzylidene camphor, ethylhexyl triazine Any one or a combination of at least two of oxazinone, isoamyl p-methoxycinnamate, or ethylhexyl methoxycinnamate, wherein typical but non-limiting combinations include: bis-ethylhexyloxy A combination of phenol methoxyphenyl triazine and diethylaminohydroxybenzoylhexylbenzoate, a combination of diethylaminohydroxybenzoylhexylbenzoate and ethylhexylmethoxycinnamate, 4-methyl A combination of benzylidene camphor and ethylhexyl triazinone or a combination of isoamyl p-methoxycinnamate and ethylhexyl methoxycinnamate.

Preferably, the photoprotective additives include carnosine, hydrolyzed yeast protein and ascorbyl tetraisopalmitate.

In this application, the photoprotective additives include carnosine, hydrolyzed yeast protein and ascorbyl tetraisopalmitate. Carnosine has the effect of quenching active oxygen free radicals, and can prevent the active oxygen free radicals induced by HEV from causing damage to the skin, Promote collagen production, inhibit IRA-induced MMP-1 production; hydrolyzed yeast protein can increase the expression of caspase-14, which is related to keratinization and hydration, and Participates in the synthesis of Natural Moisturizing Factor (NMF), improves the expression of filaggrin (precursor of NMF), enhances the skin's ability to resist UV, and reduces skin damage caused by UV; ascorbyl tetraisopalmitate has excellent After being absorbed by the skin, it is converted into vitamin C through the catalytic action of enzymes, which can prevent UV-induced DNA damage, inhibit UV radiation and reactive oxygen free radical damage to cells, and promote collagen production. Synergistically, it can protect HEV and IRA, improve the barrier function of the skin, enhance the ability to lock water and moisturizing, improve the ability of the skin to resist ultraviolet rays, reduce skin damage caused by ultraviolet rays, and prevent photoaging.

In a second aspect, the present application provides a sunscreen gel comprising the sunscreen composition of the first aspect.

Preferably, the mass percentage of the sunscreen composition in the sunscreen gel is 5.0% to 37%, including but not limited to 6.0%, 8.0%, 10.0%, 15.0%, 20.0%, 25.0%, 30.0% or 35.0%.

Preferably, the sunscreen gel also includes thickeners, polyols, preservatives, pH adjusters and water.

Preferably, the mass percentage of the chemical sunscreen-loaded microsphere particles in the sunscreen condensation is 2.5% to 10.0%, including but not limited to 2.6%, 2.9%, 3.5%, 5.0%, 6.0%, 7.0% %, 7.5%, 8.0%, 8.5%, 9.0% or 9.5%.

Preferably, the mass percentage of the free chemical sunscreen agent in the sunscreen gel is 2.0% to 22.0%, including but not limited to 2.6%, 2.9%, 3.5%, 5.0%, 10.0%, 13.0%, 15.0% %, 16.0%, 17.5%, 19.0% or 21.0%.

Preferably, the mass percentage of the photoprotective additive in the sunscreen condensation is 0.5% to 5.0%, including but not limited to 0.5%, 0.9%, 1.5%, 2.0%, 3.5% or 4.0%.

Preferably, the mass percentage of the thickener in the sunscreen gel is 0.2% to 0.5%, including but not limited to 0.3%, 0.35% or 0.4%.

Preferably, the mass percentage of the polyol in the sunscreen condensation is 8.0% to 18.0%, including but not limited to 8.2%, 8.6%, 8.8%, 9.5%, 10.0%, 12.0%, 14.0% or 16.0% %.

Preferably, the mass percentage of the preservative in the sunscreen gel is 0.5% to 1.0%, including but not limited to 0.6%, 0.7%, 0.8% or 0.9%.

Preferably, the mass percentage of the pH adjusting agent in the sunscreen gel is 0.12%-0.5%, including but not limited to 0.15%, 0.2%, 0.25%, 0.3%, 0.35% or 0.4%.

Preferably, the mass percentage of the water in the sunscreen condensation is 45.0% to 85.0%, including but not limited to 55%, 60%, 65%, 70%, 75%, 80% or 84%.

Preferably, the sunscreen gel further comprises grease.

Preferably, the mass percentage of the oil in the sunscreen gel is 0% to 20.0%, including but not limited to 0.5%, 1.0%, 5.0%, 10%, 11%, 13%, 15% or 18% .

Preferably, the sunscreen gel comprises by mass percentage: 2.5%-10.0% of microsphere particles loaded with chemical sunscreen agent, 2.0%-22.0% of free chemical sunscreen agent, 0.5%-5.0% of photoprotective additive, thickener 0.2% to 0.5%, polyol 8.0% to 18.0%, preservative 0.5% to 1.0%, pH adjuster 0.12% to 0.5%, oil 0% to 20.0%, and the balance is water.

Preferably, the thickener comprises acrylic acid (ester)/C10-C30 alkanol acrylate cross-linked polymer.

Preferably, the thickener further comprises any one or a combination of at least two of carbomer, xanthan gum, sodium polyacrylate or hydroxyethyl acrylate/sodium acryloyldimethyl taurate copolymer.

Preferably, the polyol comprises any one or a combination of at least two of glycerol, butanediol, 1,3-propanediol or 1,2-hexanediol, wherein typical but non-limiting combinations include: glycerol and A combination of butanediol, a combination of butanediol and 1,3-propanediol, or a combination of butanediol and 1,2-hexanediol.

Preferably, the preservatives include p-hydroxyacetophenone and/or phenoxyethanol.

Preferably, the pH adjuster includes aminomethyl propanol and/or triethanolamine.

Preferably, the grease comprises any one or at least two of dioctyl carbonate, C12-C15 alcohol benzoate, isohexadecane, undecane/tridecane or octylmethicone combinations, wherein typical but non-limiting combinations include: a combination of dioctyl carbonate and C12-C15 alcohol benzoate, a combination of isohexadecane and octylmethicone, undecane/decane A combination of trioxane and C12-C15 alcohol benzoate or a combination of dioctyl carbonate and isohexadecane.

In a third aspect, the present application provides a preparation method of the sunscreen condensation dew described in the second aspect, the preparation method comprising the following steps:

(1) mixing water, thickener, polyol and microsphere particles loaded with chemical sunscreen agent to obtain phase A;

(2) heating the free chemical sunscreen agent, followed by cooling to obtain the B phase;

(3) Phase B is added to Phase A and mixed;

(4) Add preservatives, photoprotective additives and pH regulators, and mix;

(5) vacuuming and defoaming to obtain the sunscreen condensation.

Preferably, the mixing in step (1) is carried out in an emulsifying pot.

Preferably, the mixing temperature in step (1) is 30-45°C, including but not limited to 32°C, 34°C, 36°C, 38°C, 40°C, 42°C or 44°C.

Preferably, the heating temperature in step (2) is 60-80°C, including but not limited to 62°C, 64°C, 66°C, 70°C, 75°C or 78°C.

Preferably, the temperature for cooling in step (2) is 30-45°C, including but not limited to 32°C, 34°C, 36°C, 38°C, 40°C, 42°C or 44°C.

Preferably, the mixing time in step (3) is 10-15 min, including but not limited to 11 min, 12 min, 13 min or 14 min.

Preferably, the preservative in step (4) is pre-dissolved with polyol.

Preferably, the mixing time in step (4) is 10-15 min, including but not limited to 11 min, 12 min, 13 min or 14 min.

Preferably, the temperature of vacuum degassing in step (5) is 30-37°C, including but not limited to 32°C, 34°C, 35°C or 36°C.

As a preferred technical scheme, the preparation method of the sunscreen gel comprises the following steps:

(1) Control the temperature to 30-45°C, add water, thickener, polyol and chemical sunscreen-loaded microsphere particles to the emulsification pot, and mix them evenly to obtain phase A;

(2) heating the free chemical sunscreen agent and grease to 60-80°C, mixing evenly, and cooling to 30-45°C to obtain phase B;

(3) add phase B to phase A and mix for 10～15min;

(4) Add preservatives, photoprotective additives and pH adjusters dissolved in polyol in advance, and mix for 10 to 15 minutes;

(5) Vacuuming and defoaming at 30-37° C. to obtain the sunscreen condensation.

Compared with the prior art, the present application at least has the following beneficial effects:

(1) In the sunscreen composition of the present application, the chemical sunscreen agent-loaded microsphere particles enable the oil-soluble chemical sunscreen agent to be added to the water phase and cooperate with the free chemical sunscreen agent in the oil phase, thereby balancing the sunscreen. The chemical sunscreens in the water and oil phases in the condensation protect against UVA and UVB. In addition, the microsphere particle structure can cause scattering and refraction of light, thereby increasing the contact between chemical sunscreens and light, and further enhancing the sunscreen effect. The photoprotective additive can protect HEV and IRA, improve the barrier function of the skin, enhance the ability of locking water and moisturizing, enhance the ability of the skin to resist ultraviolet rays, reduce skin damage caused by ultraviolet rays, prevent photoaging, and cooperate with ultraviolet absorbers. Achieve full-band protection from UVA, UVB, HEV and IRA;

(2) The sunscreen gel of the present application comprises the sunscreen composition, which can protect against UVA, UVB, HEV and IRA, and can improve the barrier function and resistance of the skin. Compared with the products, the sunscreen gel of the present application can increase the SPF value by more than 20%, the PFA value by more than 17%, the pigmentation inhibition rate is higher than 91%, and the highest is 99.5%; the MMP-1 inhibition rate is higher than 90%, The highest is 98.6%; the reduction rate of TEWL rising value is higher than 70.5%, and the highest is 80.6%; the reduction rate of sunburn cells is higher than 54%, and the highest is 63.8%; and it is mild and non-irritating, and the skin feels moist, which is suitable for sunscreen skin care products. The field has broad prospects for development;

(3) The preparation method of the present application has simple operation, mild conditions and high efficiency, and is suitable for large-scale production.

Detailed ways

In order to facilitate the understanding of the present application, the present application lists the following examples. It should be understood by those skilled in the art that the embodiments are only for helping the understanding of the present application, and should not be regarded as a specific limitation of the present application.

If no specific technique or condition is indicated in the examples, the technique or condition described in the literature in the field or the product specification is used. The reagents or instruments used without the manufacturer's indication are conventional products that can be purchased through regular channels.

Example 1

This example provides a sunscreen composition, and the ingredients of the sunscreen composition are shown in Table 1.

The total mass of the sunscreen composition is 100 grams.

Table 1

The mass ratio of bis-ethylhexyloxyphenol methoxyphenyl triazine and silica in the bis-ethylhexyloxyphenol methoxyphenyl triazine/silica is 2.4:7.6.

The preparation method includes the following steps:

(1) Put the B phase into the emulsification pot, heat to 80°C, stir and disperse evenly, and then cool down to 30°C;

(2) slowly and uniformly add phase A to phase B, stir and homogenize for 15min;

(3) add C phase to the emulsifying pot again, stir and homogenize for 10min;

(4) Vacuuming and defoaming at 30° C., discharging, and standing to obtain the sunscreen composition.

Example 2

This example provides a sunscreen composition, and the ingredients of the sunscreen composition are shown in Table 2.

The total mass of the sunscreen composition was 15 grams.

Table 2

The mass ratio of bis-ethylhexyloxyphenol methoxyphenyl triazine and silica in the bis-ethylhexyloxyphenol methoxyphenyl triazine/silica is 3.5:6.5.

The preparation method includes the following steps:

(1) Put the B phase into the emulsification pot, heat to 80°C, stir and disperse evenly, and then cool down to 30°C;

(2) slowly and uniformly add phase A to phase B, stir and homogenize for 15min;

(3) add C phase to the emulsifying pot again, stir and homogenize for 10min;

(4) Vacuuming and defoaming at 30° C., discharging, and standing to obtain the sunscreen composition.

Example 3

This embodiment provides a sunscreen gel, and the ingredients of the sunscreen gel are shown in Table 3.

table 3

The mass ratio of bis-ethylhexyloxyphenol methoxyphenyl triazine and silica in the bis-ethylhexyloxyphenol methoxyphenyl triazine/silica is 3:7.

The preparation method includes the following steps:

(1) heating and dissolving p-hydroxyacetophenone and phenoxyethanol with an appropriate amount of butanediol in advance;

(2) Put the A phase into the emulsification pot, stir and disperse evenly at 30°C;

(3) heating phase B to 80°C, stirring and dispersing evenly, and then cooling to 30°C;

(4) slowly and uniformly add phase B to phase A, stir and homogenize for 15min;

(5) add C phase to the emulsification pot again, stir and homogenize for 10min;

(6) Vacuuming and defoaming at 30° C., discharging, and standing to obtain the sunscreen condensation.

Example 4

This embodiment provides a sunscreen gel, and the ingredients of the sunscreen gel are shown in Table 4.

Table 4

The mass ratio of bis-ethylhexyloxyphenol methoxyphenyl triazine and silica in the bis-ethylhexyloxyphenol methoxyphenyl triazine/silica is 3:7.

The preparation method includes the following steps:

(1) Heat and dissolve p-hydroxyacetophenone with an appropriate amount of 1,2-hexanediol in advance;

(2) put the A phase into the emulsification pot, stir and disperse evenly at 45°C;

(3) heating phase B to 75°C, stirring and dispersing evenly, then cooling to 45°C;

(4) slowly and uniformly add phase B to phase A, stir and homogenize for 10min;

(5) add C phase to the emulsification pot again, stir and homogenize for 15min;

(6) Vacuuming and defoaming at 37° C., discharging, and standing to obtain the sunscreen condensation.

Example 5

This embodiment provides a sunscreen gel, and the ingredients of the sunscreen gel are shown in Table 5.

table 5

The mass ratio of bis-ethylhexyloxyphenol methoxyphenyl triazine and silica in the bis-ethylhexyloxyphenol methoxyphenyl triazine/silica is 3:7.

The preparation method includes the following steps:

(1) heating and dissolving p-hydroxyacetophenone and phenoxyethanol with an appropriate amount of butanediol in advance;

(2) put the A phase into the emulsification pot, stir and disperse evenly at 30°C;

(3) heating phase B to 70°C, stirring and dispersing evenly, and then cooling to 30°C;

(4) slowly and uniformly add phase B to phase A, stir and homogenize for 15min;

(5) add C phase to the emulsification pot again, stir and homogenize for 10min;

(6) Vacuuming and defoaming at 30° C., discharging, and standing to obtain the sunscreen condensation.

Example 6

This embodiment provides a sunscreen gel, and the ingredients of the sunscreen gel are shown in Table 6.

Table 6

In the described bis-ethylhexyloxyphenol methoxyphenyl triazine/silica, the mass ratio of bis-ethylhexyloxyphenol methoxyphenyl triazine and silica is 3:7, and the undecane/tridecane The mass ratio of undecane and tridecane is 7:3.

The preparation method includes the following steps:

(1) Heat and dissolve p-hydroxyacetophenone with an appropriate amount of 1,2-hexanediol in advance;

(2) Put the A phase into the emulsification pot, stir and disperse evenly at 30°C;

(3) heating phase B to 60°C, stirring and dispersing evenly, and then cooling to 30°C;

(4) slowly and uniformly add phase B to phase A, stir and homogenize for 15min;

(5) add C phase to the emulsification pot again, stir and homogenize for 10min;

(6) Vacuuming and defoaming at 30° C., discharging, and standing to obtain the sunscreen condensation.

Example 7

This embodiment provides a sunscreen gel, and the ingredients of the sunscreen gel are shown in Table 7.

Table 7

The mass ratio of bis-ethylhexyloxyphenol methoxyphenyl triazine and silica in the bis-ethylhexyloxyphenol methoxyphenyl triazine/silica is 3:7.

The preparation method includes the following steps:

(1) heating and dissolving p-hydroxyacetophenone and phenoxyethanol with an appropriate amount of butanediol in advance;

(2) Put the A phase into the emulsification pot, stir and disperse evenly at 30°C;

(3) heating phase B to 80°C, stirring and dispersing evenly, and then cooling to 30°C;

(4) slowly and uniformly add phase B to phase A, stir and homogenize for 15min;

(5) add C phase to the emulsification pot again, stir and homogenize for 10min;

(6) Vacuuming and defoaming at 30° C., discharging, and standing to obtain the sunscreen condensation.

Comparative Example 1

This comparative example provides a sunscreen gel that does not contain microsphere particles loaded with chemical sunscreen agents, and the content of the chemical sunscreen agent is the same as that of Example 3. The ingredients of the sunscreen gel are shown in Table 8.

Table 8

The mass ratio of bis-ethylhexyloxyphenol methoxyphenyl triazine and silica in the bis-ethylhexyloxyphenol methoxyphenyl triazine/silica is 3:7.

The preparation method is the same as in Example 3.

Comparative Example 2

This comparative example provides a sunscreen gel, which does not contain microsphere particles loaded with chemical sunscreen agents, and the chemical sunscreen agent content is the same as that of Example 4, which is higher than that of Example 3. The ingredients of the sunscreen gel are shown in Table 9. Show.

Table 9

The mass ratio of bis-ethylhexyloxyphenol methoxyphenyl triazine and silica in the bis-ethylhexyloxyphenol methoxyphenyl triazine/silica is 3:7.

The preparation method is the same as in Example 4.

Comparative Example 3

This comparative example provides a sunscreen gel, and the photoprotective additives are carnosine and ascorbyl tetraisopalmitate, and the ingredients of the sunscreen gel are shown in Table 10.

Table 10

The mass ratio of bis-ethylhexyloxyphenol methoxyphenyl triazine and silica in the bis-ethylhexyloxyphenol methoxyphenyl triazine/silica is 3:7.

The preparation method is the same as in Example 5.

Comparative Example 4

This comparative example provides a sunscreen gel, and the photoprotective additives are hydrolyzed yeast protein and ascorbic acid tetraisopalmitate, and the ingredients of the sunscreen gel are shown in Table 11.

Table 11

In the described bis-ethylhexyloxyphenol methoxyphenyl triazine/silica, the mass ratio of bis-ethylhexyloxyphenol methoxyphenyl triazine and silica is 3:7, and the undecane/tridecane The mass ratio of undecane and tridecane is 7:3.

The preparation method is the same as in Example 6.

Comparative Example 5

This comparative example provides a sunscreen gel, and the photoprotective additives are carnosine and hydrolyzed yeast protein, and the ingredients of the sunscreen gel are shown in Table 12.

Table 12

The mass ratio of bis-ethylhexyloxyphenol methoxyphenyl triazine and silica in the bis-ethylhexyloxyphenol methoxyphenyl triazine/silica is 3:7.

The preparation method is the same as in Example 7.

Comparative Example 6

This comparative example provides a sunscreen gel, and the photoprotective additive is only ascorbic acid tetraisopalmitate, and the ingredients of the sunscreen gel are shown in Table 13.

Table 13

The mass ratio of bis-ethylhexyloxyphenol methoxyphenyl triazine and silica in the bis-ethylhexyloxyphenol methoxyphenyl triazine/silica is 3:7.

The preparation method is the same as in Example 5.

Comparative Example 7

This comparative example provides a sunscreen gel, and the photoprotective additive is only hydrolyzed yeast protein, and the ingredients of the sunscreen gel are shown in Table 14.

Table 14

The mass ratio of bis-ethylhexyloxyphenol methoxyphenyl triazine and silica in the bis-ethylhexyloxyphenol methoxyphenyl triazine/silica is 3:7.

The preparation method is the same as in Example 6.

Comparative Example 8

This comparative example provides a sunscreen gel, the light protection additive is only carnosine, and the ingredients of the sunscreen gel are shown in Table 15.

Table 15

The mass ratio of bis-ethylhexyloxyphenol methoxyphenyl triazine and silica in the bis-ethylhexyloxyphenol methoxyphenyl triazine/silica is 3:7.

The preparation method is the same as in Example 7.

Test Example 1 Sunscreen Effect Test

Sun Protection Factor (SPF) is also known as the sun protection factor, which indicates the level of sun protection effect that sunscreen products can exert. SPF is suitable for evaluating the protection effect of sunscreen cosmetics against UVB. The larger the SPF value, the better the sunscreen effect. SPF is determined according to the skin's minimum erythema dose (Minimum Erythema Dose, MED), as shown in formula (1).

The long-wave ultraviolet protection index (Protection Factor of UVA, PFA) of sunscreen cosmetics is also called UVA protection index. UVA in sunlight irradiates the skin, which mainly produces the physiological effect of skin blackening. This effect is measured by the minimum continuous blackening dose (Minimal Persistent Pigment Darkening Dose, MPPD). MPPD is 2 to 4 hours after irradiation. The minimum ultraviolet irradiation dose or the shortest irradiation time required to produce slight blackening, the PFA calculation formula is shown in formula (2).

The samples prepared in Examples 1-7 and Comparative Examples 1 and 2 were selected, and the sunscreen effect of the samples was tested according to the Sunscreen Cosmetics Sunscreen Index Test Method (Human Body Method) in "Technical Specification for Cosmetics Safety" (2015 Edition). The test results are shown in Table 16. Show.

Table 16

test group	SPF	PFA
Example 1	39.4	15.8
Example 2	31.6	10.1
Example 3	30.8	12.8
Example 4	37.6	11.5
Example 5	59.1	19.4
Example 6	12.2	10.7
Example 7	32.3	11.6
Comparative Example 1	25.1	10.9
Comparative Example 2	31.3	9.7

It can be seen from Table 16 that the chemical sunscreen agents of Examples 1-7 are loaded on silica, and the sunscreen performance is good. 3. The difference between Comparative Example 2 and Example 4 is that bis-ethylhexyloxyphenol methoxyphenyl triazine/silica is not added to the water phase, but an equal amount of bis-ethylhexyloxyphenol is added to the oil phase. Methoxyphenyl triazine, to ensure the same content of chemical sunscreens, to exclude the effects of different chemical sunscreens on SPF and PFA, as can be seen from Table 13, Example 3 is compared to Comparative Example 1, and Example 4 is compared to Comparative Example 2. The SPF is increased by more than 20.0%, and the PFA is increased by more than 17%, indicating that the application uses the microsphere particles loaded with chemical sunscreens to balance the chemical sunscreens of the water phase and the oil phase, which can improve the sunscreen effect, and thus can not affect the sunscreen effect. In the case of sunscreen effect, reduce the addition amount of chemical sunscreen agent. It should be noted that the addition amount of chemical sunscreen agent can significantly affect SPF and PFA, which is positively correlated, that is, the higher the amount of chemical sunscreen agent added, the greater the SPF and PFA values. , and the lower the added amount of chemical sunscreen agent, the lower the SPF and PFA values. The chemical sunscreen agent in Example 6 is added in a lower amount, so its SPF value and PFA value are also lower.

Test Example 2 Blue light-induced pigmentation inhibition rate experiment

The samples prepared in Examples 1-7 and Comparative Examples 3-8 were taken for testing, and blank matrix products without photoprotective additives were used as blank controls.

A 3D artificial skin model was used to conduct a blue light-induced pigmentation inhibition test. An equal amount of each sample was smeared on the artificial skin model, and the test was repeated using 2 holes for each sample. The skin model was continuously exposed to LED blue light (476nm, 1000lux) every day. Irradiate for 1 hour and continue for 7 days, then use 1mol/L NaOH solution (containing 10% dimethyl sulfoxide) to extract the melanin in the model, take a water bath at 80°C for 0.5h, and centrifuge after the melanin particles are completely dissolved, take the The supernatant was measured at the wavelength of 405nm OD value, and the melanin content in the model was calculated by the standard curve of melanin. Taking the blank control as a reference, the pigmentation inhibition rate was calculated according to formula (3). The experimental results are shown in Table 17.

Inhibition rate (%) = (blank control melanin content - sample melanin content)/blank control melanin content × 100% (3)

Test Example 3 Near-infrared (IRA)-induced MMP-1 expression inhibition experiment

IRA radiation destroys collagen-1 by upregulating the expression of matrix metalloproteinase 1 (MMP-1), resulting in loss of skin elasticity. The human dermal fibroblast method was used to evaluate the inhibitory effect of the samples on the expression of MMP-1 induced by IRA, so as to evaluate the protective effect of IRA.

The samples prepared in Examples 1-7 and Comparative Examples 3-8 were tested, and the blank matrix products without photoprotective additives were used as blank controls. Human dermal fibroblasts were cultured with culture medium, and washed with PBS solution after 24 hours. Then add an appropriate amount of PBS solution, irradiate with infrared rays (IRA: 760-1400nm, 360J/cm ² ), add each sample (diluted 10 times), then extract RNA and carry out PCR, using MMP-1/18S rRNA for quantitative analysis , and the blank control was used as a reference to calculate the MMP-1 inhibition rate according to formula (4). The experimental results are shown in Table 17.

MMP-1 inhibition rate (%) = (expression of MMP-1 in blank control - expression of MMP-1 in sample)/expression of MMP-1 in blank control × 100% (4)

Table 17

test group	Pigmentation inhibition rate (%)	MMP-1 inhibition rate (%)
Example 1	99.5	98.6
Example 2	91.4	90.1
Example 3	97.8	97.2
Example 4	95.1	93.7
Example 5	94.2	92.0
Example 6	96.5	94.3
Example 7	92.4	91.2
Comparative Example 3	75.7	72.6
Comparative Example 4	40.6	51.3
Comparative Example 5	70.8	62.8
Comparative Example 6	30.3	34.9

Comparative Example 7	20.4	30.8
Comparative Example 8	61.7	60.4

It can be seen from Table 17 that the samples prepared in Examples 1-7 also contain three photoprotective additives, carnosine, hydrolyzed yeast protein and ascorbic acid tetraisopalmitate, and the pigmentation inhibition rate and MMP-1 inhibition rate are both above 90%, That is to say, it has better protection effect of HEV and IRA; in contrast, the samples prepared in Comparative Examples 3-8 did not add carnosine, hydrolyzed yeast protein and ascorbyl tetraisopalmitate at the same time, the pigmentation inhibition rate and MMP-1 inhibition rate The highest inhibition rate of pigmentation is only 75.7%, the highest inhibition rate of MMP-1 is only 72.6%, and the protective effect of HEV and IRA is poor; Three photoprotective additives, hydrolyzed yeast protein and ascorbyl tetraisopalmitate, make each component play a synergistic role, thereby achieving stronger HEV and IRA protection effect.

Test Example 4 UV Damage Experiment

Scientific research shows that after UV exposure, the skin's Trans Epidermal Water Loss (TEWL) increases, the barrier function is damaged, the skin becomes dry, and sunburn cells are produced. In this test example, the samples prepared in Examples 1-7 and Comparative Examples 3-8 are used for testing, and the blank matrix products without photoprotective additives are used as blank controls.

30 volunteers aged 23 to 34 were selected for human testing. First, the thigh skin was selected to test TEWL, and then the test samples and blank control samples were used respectively, twice a day, once in the morning and once in the evening, for 15 days, according to the lowest erythema dose of the volunteers' skin The thigh skin was irradiated with full spectrum for 6 hours, and TEWL was tested. The blank control was used as a reference, and the reduction rate of TEWL rise was calculated according to formula (5). The results are shown in Table 18. The sunburn cells were observed and counted under a focus microscope, and the reduction rate of the sunburn cells was calculated according to formula (6). The results are shown in Table 18.

TEWL rising value reduction rate (%) = (blank control TEWL value difference - sample TEWL value difference)/blank control TEWL value difference × 100% (5)

Sunburn cell reduction rate (%) = (the number of sunburned cells in the blank control - the number of sunburned cells in the sample)/the number of sunburned cells in the blank control × 100% (6)

Table 18

test group	TEWL rising value reduction rate (%)	Sunburn cell reduction rate (%)
Example 1	80.6	63.8
Example 2	70.9	54.1

Example 3	76.3	61.5
Example 4	72.4	57.2
Example 5	71.7	56.6
Example 6	73.6	59.4
Example 7	71.1	55.3
Comparative Example 3	28.3	30.7
Comparative Example 4	57.1	44.2
Comparative Example 5	45.4	32.5
Comparative Example 6	22.6	23.9
Comparative Example 7	54.5	38.1
Comparative Example 8	17.7	18.2

It can be seen from Table 18 that the samples prepared in Examples 1-7 also contain three kinds of photoprotective additives: carnosine, hydrolyzed yeast protein and ascorbic acid tetraisopalmitate. higher than 54.1%, that is, it can improve the barrier function of the skin, enhance the ability to lock water and moisturizing, and improve the ability of the skin to resist ultraviolet rays; in contrast, the samples prepared in Comparative Examples 3-8 did not add carnosine and hydrolyzed yeast protein at the same time. and ascorbyl tetraisopalmitate, the highest reduction rate of TEWL rising value is only 57.1%, and the highest reduction rate of sunburn cells is only 44.2%; it shows that the sunscreen composition of the present application uses carnosine, hydrolyzed yeast protein and ascorbic acid at the same time The three photoprotective additives of tetraisopalmitate make each component play a synergistic role, which can significantly improve the skin's barrier function, enhance the ability to lock water and moisturizing, improve the skin's ability to resist ultraviolet rays, and reduce skin damage caused by ultraviolet rays, Prevent photoaging.

Test Example 5 Patch Test

The samples prepared in Examples 1-7 were taken for patch test to detect the potential of causing adverse reactions in human skin.

According to the method of human skin patch test in "Cosmetics Safety Technical Specifications" (2015 edition), 30 volunteers aged 18-60 who met the test requirements were selected as subjects (15 males and 15 males). Add each sample into the patch tester respectively, the dosage is 0.020～0.025g, and the blank control does not add any substance. The patch tester is applied to the flexor side of the subject's forearm with non-irritating tape, and lightly pressed with the palm of the hand to make it uniform. Apply it to the skin, mark the test site for observation, apply it once every 24 hours, 30 minutes after the patch is removed, and observe the skin reaction after the indentation disappears. The tester stops the patch test; if it is a negative reaction, then continue to perform the above patch test at the same test site of the subject, repeat the patch test 6 times in total, record the test group response results according to Table 19, test The results are shown in Table 20.

Table 19

grade	symbol	Identification standard
0	-	Negative reaction: no irritation, no erythema
1	±	Suspected reaction: mild erythema
2	+	Weak positive reaction: erythema
3	++	Strong positive reaction: erythema, papules, vesicles
4	+++	Strong positive reaction: severe edema, bullae

Table 20

Table 20 shows that the sunscreen composition and sunscreen gel prepared in the present application do not cause skin allergy and irritation, and have good mildness.

Test Example 6 Skin Feel Test

In order to evaluate the skin feel of the present application, the samples prepared in Examples 3-7 and Comparative Examples 1 and 2 were selected as test samples, and skin feel evaluation was carried out. Select 10 women aged 25 to 35 years old (sensory test training qualified) to conduct product sensory evaluation test, under the independent environment of constant temperature (22±1℃) and relative humidity (50±5%), test after resting for 1h, scoring system : The score ranges from 1 to 10. The higher the score, the stronger the characteristic of the item. The results are shown in Table 21 below.

Table 21

test group	Hydration	greasy feeling	lightness
Example 3	9.5	0.55	9.25
Example 4	9.3	0.65	9.1
Example 5	9.6	0.4	9.35
Example 6	9.8	0.35	9.5
Example 7	9.1	0.8	9.05
Comparative Example 1	7.6	2.8	7.2
Comparative Example 2	7.2	3.2	7.0

As can be seen from Table 21, the skin feel test results of the samples prepared in Examples 3-7 are all better than those prepared in Comparative Examples 1 and 2, indicating that in this application, chemical sunscreens, especially bis-ethylhexyloxyphenol methyl Oxyphenyltriazine is loaded in silica, so that oil-soluble chemical sunscreens can be added to the water phase and cooperate with the free chemical sunscreens in the oil phase, thus balancing the chemical properties of the water and oil phases in the sunscreen condensation. Sunscreen agent, and silica has good oil absorption properties, which can reduce greasiness and enhance hydration and lightness.

To sum up, in the sunscreen composition of the present application, the chemical sunscreen agent-loaded microsphere particles allow the oil-soluble chemical sunscreen agent to be added to the water phase and cooperate with the free chemical sunscreen agent in the oil phase, thereby balancing In addition, the microsphere particle structure can cause light scattering and refraction, thereby increasing the contact between chemical sunscreen agents and light, and further improving sun protection. The photoprotective additive can protect HEV and IRA, improve the barrier function of the skin, enhance the ability of locking water and moisturizing, improve the ability of the skin to resist ultraviolet rays, reduce skin damage caused by ultraviolet rays, and cooperate with ultraviolet absorbers to achieve UVA , UVB, HEV and IRA full band protection. The sunscreen gel containing the sunscreen composition can protect against UVA, UVB, HEV and IRA, and can improve the barrier function and resistance of the skin. development prospects.

The applicant declares that this application illustrates the detailed process equipment and process flow of the application through the above-mentioned embodiments, but the application is not limited to the above-mentioned detailed process equipment and process flow, that is, it does not mean that the application must rely on the above-mentioned detailed process equipment and process flow. Process flow can be implemented. Those skilled in the art should understand that any improvement to the application, the equivalent replacement of each raw material of the product of the application, the addition of auxiliary components, the selection of specific methods, etc., all fall within the scope of protection and disclosure of the application.

Claims (15)

1. A sunscreen composition comprising a UV absorber and a photoprotective additive;

   wherein the UV absorber comprises chemical sunscreen-loaded microsphere particles; and

   The UV absorbers also include free chemical sunscreens.
2. The sunscreen composition according to claim 1, wherein the mass ratio of the chemical sunscreen agent-loaded microsphere particles, the free chemical sunscreen agent and the photoprotective additive is 1:(0.2-8.8):(0.05-2) .
3. The sunscreen composition according to claim 1 or 2, wherein the chemical sunscreen-loaded microsphere particles comprise chemical sunscreen-loaded silica, preferably bis-ethylhexyloxyphenol methoxyphenyltriazine-loaded silica.
4. The sunscreen composition according to any one of claims 1 to 3, wherein the bis-ethylhexyloxyphenolmethoxyphenyltriazine-loaded silica comprises bis-ethylhexyloxyphenolmethoxyphenyltriazine by mass percentage Phenyltriazine 24% to 35% and silica 65% to 76%;

   Preferably, the particle size of the silica is 6-9 μm.
5. The sunscreen composition of any one of claims 1 to 4, wherein the free chemical sunscreen agent comprises bis-ethylhexyloxyphenol methoxyphenyl triazine, diethylaminohydroxybenzoylbenzoic acid Any one or a combination of at least two of hexyl ester, 4-methylbenzylidene camphor, ethylhexyl triazinone, isoamyl p-methoxycinnamate, or ethylhexyl methoxycinnamate.
6. The sunscreen composition of any one of claims 1 to 5, wherein the photoprotective additive comprises carnosine, hydrolyzed yeast protein, and ascorbyl tetraisopalmitate.
7. A sunscreen gel comprising the sunscreen composition of any one of claims 1-6.
8. The sunscreen gel according to claim 7, wherein the mass percentage of the sunscreen composition in the sunscreen gel is 5.0% to 37.0%;

   Optionally, the sunscreen gel also includes thickeners, polyols, preservatives, pH adjusters and water.
9. The sunscreen gel according to claim 7 or 8, wherein the mass percentage of the chemical sunscreen-loaded microsphere particles in the sunscreen gel is 2.5% to 10.0%;

   Preferably, the mass percentage of the free chemical sunscreen agent in the sunscreen condensation is 2.0% to 22.0%;

   Preferably, the mass percentage of the photoprotective additive in the sunscreen condensation is 0.5% to 5.0%;

   Preferably, the mass percentage of the thickener in the sunscreen gel is 0.2% to 0.5%;

   Preferably, the mass percentage of the polyol in the sunscreen condensation is 8.0% to 18.0%;

   Preferably, the mass percentage of the preservative in the sunscreen gel is 0.5% to 1.0%;

   Preferably, the mass percentage of the pH adjuster in the sunscreen condensation is 0.12% to 0.5%;

   Preferably, the mass percentage of the water in the sunscreen condensation is 45.0% to 85.0%;

   Preferably, the sunscreen gel also includes grease;

   Preferably, the mass percentage of the oil in the sunscreen gel is 0% to 20.0%.
10. The sunscreen gel according to any one of claims 7 to 9, wherein the sunscreen gel comprises by mass percentage: 2.5%-10.0% of microsphere particles loaded with chemical sunscreen agent, 2.0%-22.0% of chemical sunscreen agent %, photoprotective additive 0.5%～5.0%, thickener 0.2%～0.5%, polyol 8.0%～18.0%, preservative 0.5%～1.0%, pH adjuster 0.12%～0.5% and grease 0%～20.0 %, the balance is water.
11. The sunscreen gel according to any one of claims 7 to 10, wherein the thickener comprises acrylic acid or acrylates/C10-C30 alkanol acrylate crosspolymer; and/or

    The thickening agent also includes any one or a combination of at least two of carbomer, xanthan gum, sodium polyacrylate or hydroxyethyl acrylate/sodium acryloyldimethyltaurate copolymer.
12. The sunscreen gel according to any one of claims 7 to 11, wherein the polyhydric alcohol comprises any one or at least two of glycerol, butanediol, 1,3-propanediol or 1,2-hexanediol a combination of species;

    Preferably, the preservative comprises p-hydroxyacetophenone and/or phenoxyethanol;

    Preferably, the pH adjusting agent comprises aminomethyl propanol and/or triethanolamine;

    Preferably, the grease comprises any one or at least two of dioctyl carbonate, C12-C15 alcohol benzoate, isohexadecane, undecane/tridecane or octylmethicone The combination.
13. A preparation method of the sunscreen condensation dew described in any one of claims 7 to 12, comprising the following steps:

    (1) mixing water, thickener, polyol and microsphere particles loaded with chemical sunscreen agent to obtain phase A;

    (2) heating the free chemical sunscreen agent, followed by cooling to obtain the B phase;

    (3) Phase B is added to Phase A and mixed;

    (4) Add preservatives, photoprotective additives and pH regulators, and mix;

    (5) vacuuming and defoaming to obtain the sunscreen condensation.
14. The preparation method according to claim 13, wherein the mixing in step (1) is carried out in an emulsifying pot;

    Preferably, the mixing temperature in step (1) is 30-45°C;

    Preferably, the heating temperature in step (2) is 60-80°C;

    Preferably, the temperature of step (2) cooling is 30～45 ℃;

    Preferably, the mixing time in step (3) is 10-15 min;

    Preferably, the preservative in step (4) is pre-dissolved with polyol;

    Preferably, the mixing time in step (4) is 10-15 min;

    Preferably, the temperature of vacuum degassing in step (5) is 30-37°C.
15. The preparation method according to claim 13 or 14, wherein the preparation method comprises the following steps:

    (1) Control the temperature to 30-45°C, add water, thickener, polyol and chemical sunscreen-loaded microsphere particles to the emulsifying pot, and mix them evenly to obtain phase A;

    (2) heating the free chemical sunscreen agent and grease to 60-80°C, mixing evenly, and cooling to 30-45°C to obtain phase B;

    (3) add phase B to phase A and mix for 10～15min;

    (4) Add preservatives, photoprotective additives and pH adjusters dissolved in polyol in advance, and mix for 10 to 15 minutes;

    (5) Vacuuming and defoaming at 30-37° C. to obtain the sunscreen condensation.