CN113749958B

CN113749958B - Sun-proof emulsion composition

Info

Publication number: CN113749958B
Application number: CN202110964193.2A
Authority: CN
Inventors: 刘志威
Original assignee: Budweiser Shanghai Cosmetics Co ltd
Current assignee: Budweiser Shanghai Cosmetics Co ltd
Priority date: 2021-08-21
Filing date: 2021-08-21
Publication date: 2023-08-08
Anticipated expiration: 2041-08-21
Also published as: CN113749958A

Abstract

The invention provides a sun-proof emulsion composition, wherein inorganic sun-proof particles in sun-proof liquid have a core-shell structure, titanium oxide is taken as a core, zinc oxide is taken as a shell, and the sun-proof emulsion composition has higher SPF and PA values, and the sun-proof particles have moisturizing and sun-proof effects through matching with emulsion, are suitable for most skin types, are safe and environment-friendly, and do not cause greasy feeling.

Description

Sun-proof emulsion composition

Technical Field

The invention relates to a sun-proof emulsion composition, and belongs to the technical field of cosmetics.

Background

Ultraviolet light is an important component of sunlight and its energy is about 6% of the total energy of sunlight. The ultraviolet wavelength is 200-400 nm, and is divided into three wave bands of UVC (200-280 nm), UVB (280-320 nm) and UVA (320-400 nm), a small amount of sunlight can strengthen physique of people, and deoxidized sterols in skin can be converted into vitamin D, so that absorption of calcium and other minerals by the human body is facilitated, rickets of children and osteomalacia of adults are prevented, metabolism of the human body is promoted, and immune function is generated. However, if the skin is exposed to sunlight for a long period of time, ultraviolet light waves with huge energy will have adverse effects on the skin. Ultraviolet radiation can cause skin burns and erythema, promote premature skin aging, cause keratitis and cataracts, damage immune cells in the skin, and cause systemic immune function inhibition.

The effect of ultraviolet light on the skin is mainly two: on the one hand due to the ultraviolet light of the UVA region. UVA is called a tanning zone, and after skin is irradiated by the light, tyrosine oxidase in pigment cells of basal layers of epidermis is increased rapidly and tyrosine is polymerized to generate melanin, and the melanin is moved to epidermis so as to darken the skin to prevent and resist invasion of ultraviolet rays into deep skin, so-called tanning is provided, but UVA has a plurality of negative effects on skin structures, such as wrinkling and sagging of skin, irregular and spotted spots, dryness, roughness, relaxation and the like, and serious tissue damage and even skin cancer are caused by long-term irradiation of UVA; on the other hand, UVB is called sunburn area due to ultraviolet rays in UVB region, which penetrates to a small extent, but some rays can penetrate through skin from basal layer of skin to the vicinity of papillary layer, so that capillary vessel is expanded to generate skin inflammation and make epidermal cells generate disorder, and cause acute inflammation of skin, so that skin reddening or blister, erythema and other symptoms are generated, and meanwhile, black skin is generated, and skin blackening is a pathological phenomenon called sunburn. The skin can prematurely age under the prolonged action of UVB radiation.

Among the sunscreen products currently used in the market, organic sunscreens have a large market share, and the main organic sunscreens are:

para aminobenzoic acid (PABA) derivatives: effectively absorbing 280nm-300 nm ultraviolet rays, 4-aminobenzoic acid, monoglyceride of p-aminobenzoic acid, menthyl aminobenzoate, isobutyl para-aminobenzoate, octyl dimethyl para-aminobenzoate, 2-ethyl p-dimethylaminobenzoate and the like. Among them, amyl p-dimethylaminobenzoate, glycerol p-aminobenzoate and the like are all good UVB absorbers.

Anthranilate derivatives: can prevent ultraviolet rays of 290nm-380 nm, has the capability of preventing UVA and UVB rays, such as menthyl anthranilate and homomenthyl anthranilate, and can effectively prevent photochemical carcinogenesis.

Cinnamic acid esters: can prevent ultraviolet rays of 280-310 nm, has high absorptivity, is widely applied, such as ParsolMCX (octyl methoxycinnamate) is the most common sun-screening agent in the world at present, has excellent ultraviolet absorption curve, good safety and good solubility to oily raw materials, and is almost an ideal sun-screening agent.

In addition, there are also salicylates, benzophenones, camphor derivatives, methane derivatives, and organic sunscreens, although they are well compatible with cosmetics, have problems such as increasing the amount of added organic sunscreens in order to protect the skin from uv rays as much as possible, which in turn increases the occurrence of photo-induced cancers and chemical allergies.

The main inorganic sunscreens are now: nano TiO2, znO, fe2O3, siO2, zrO and the like. These nano-semiconductor materials not only inherit the advantages of common materials, but also produce properties that bulk materials do not possess, such as photocatalytic properties, strong ultraviolet absorption properties, reflective properties, and the like. Among them, nano TiO2 is most widely used, and secondly ZnO.

Disclosure of Invention

The invention aims to provide a composition with moisturizing and sun-screening effects, the sun-screening liquid is suitable for most skin types, is safe and environment-friendly, does not cause greasy feel, is convenient to use, and can effectively achieve the moisturizing and sun-screening effects of skin.

A sunscreen emulsion composition comprising in combination:

cetostearyl alcohol ether-6: 1-1.2wt.%;

cetostearyl alcohol ether-25: 1.3-1.5 wt.%;

hydrogenated polyisobutene: 4.5-5 wt.%;

caprylic/capric triglyceride: 2-3wt.%;

ethylhexyl palmitate: 2-4 wt.%;

polydimethyl siloxane: 1.5-2 wt.%;

vitamin E:0.3-0.5 wt.%;

glycerol monostearate: 0.1-0.2wt.%;

ZnO@TiO ₂ ：3-10wt.%；

carbomer: 0.2-0.3wt.%;

glycerol: 4-5wt.%;

propylene glycol: 2-3wt.%;

alpha-mannans: 2-3wt.%;

trehalose: 1-2wt.%;

triethanolamine: 0.2-0.3wt.%;

hyaluronic acid: 0.05-0.1wt.%;

hydrolyzed protein: 0.5-1 wt.%;

essence: 0.01-0.04wt.%;

wherein the ZnO@TiO ₂ The preparation method of (2) is as follows:

(1) Preparing the red gold stone micro-nano sphere titanium oxide in one step: sequentially placing TBT, HCl aqueous solution and PVP in a polytetrafluoroethylene reaction kettle, properly stirring, performing hydrothermal reaction treatment, naturally cooling to obtain a pale yellow precipitate, centrifuging, filtering and washing to obtain a titanium oxide suspension aqueous solution;

(2) Functionalization: adding ammonium sulfate into the suspension of titanium oxide in 40-45 ^o C, stirring at 500-700rpm for 2-3h, and standing at normal temperature for 20-30min;

(3) Adding ethanol solution of zinc acetate into the above solution, and adding zinc acetate into the solution at 70-80 ^o C, stirring at 1000-1500rpm for 20-24h, aging for 2-4h, centrifuging, filtering to obtain 3-10wt.% ZnO@TiO ₂ An aqueous solution;

(4) Carbomer, glycerol, propylene glycol, alpha-manna and trehalose are sequentially added into the mixture, and the mixture is stirred to obtain phase B.

In certain embodiments, the TBT is used in an amount of 0.5 to 1ml, the aqueous HCl is 20ml of 2 to 2.5M, and PVP is 0.1 to 0.15ml.

In certain embodiments, the hydrothermal conditions: 200-210 ^o And C, carrying out hydrothermal reaction for 5-7h.

In certain embodiments, the concentration of the ammonium sulfate in the solution is 0.1-0.5M.

In certain embodiments, the zinc acetate is used in an amount of 10 to 15mM.

The preparation method of the sun-proof emulsion composition comprises the following steps:

(a) Mixing the components of phase A in sequence, and homogenizing for 5-7min;

(c) Mixing the components of the phase B in sequence, and stirring to obtain a stable suspension;

(d) Adding phase B into phase A, and rapidly stirring for 10-15min;

(e) Adding the phase C into the mixed phase in the step (d), and uniformly stirring;

the preparation method of the phase B comprises the following steps:

(2) Functionalization: adding ammonium sulfate into the suspension of titanium oxide in 40-45 ^o C, stirring at 500-700rpm for 2-3h, and standing at normal temperature for 20-30min, wherein the concentration of the ammonium sulfate in the solution is 0.1-0.5M;

(3) Adding ethanol solution of zinc acetate into the above solution, stirring at 70-80 deg.C and 1000-1500rpm for 20-24 hr, aging for 2-4 hr, centrifuging, filtering to obtain 3-10wt.% ZnO@TiO ₂ An aqueous solution;

The phase A contains cetostearyl ether-6, cetostearyl ether-25, hydrogenated polyisobutene, caprylic/capric triglyceride, ethylhexyl palmitate, polydimethylsiloxane, vitamins and glyceryl monostearate.

The phase C comprises carbomer triethanolamine, hyaluronic acid and hydrolyzed protein.

The sun-screening agent adopts an inorganic core-shell structure as a main component, and takes titanium oxide as a core and zinc oxide as a shell.

Firstly, selecting a theoretical basis of compounding titanium oxide and zinc oxide:

nano TiO2 sun protection factorHas high value, good absorption and scattering effects on ultraviolet rays of medium-wave UVB (280-320 nm) and long-wave UVA (320-400 nm), can shield ultraviolet rays, has high transparency, and is nano-scale TiO ₂ The particle size of the catalyst is 1-100 nm, the catalyst has large specific surface area and surface atomic number, the surface energy and the surface tension are increased sharply along with the decrease of the particle size, and the TiO is ₂ The titanium oxide nano particles are very suitable to be used as cores of inorganic sun-screening agents due to the physical and chemical properties, and other sun-screening components are effectively coated on the surfaces of the titanium oxide nano particles through surface modification, so that an effective sun-screening effect is obtained.

The nano ZnO has the capability of shielding ultraviolet rays, is an important and widely used physical sun-screening agent, and has better effect of shielding long UVA (335-380 nm) than nano titanium oxide (TiO) ₂ ). Meanwhile, nano ZnO has antibacterial property, so that the system has astringency and anti-inflammatory property, and has the effect of absorbing grease secreted by human skin.

Based on the physicochemical properties, the invention aims to prepare nano titanium oxide, and the surface of the nano titanium oxide is coated with zinc oxide by surface modification to obtain a core-shell structure.

Titanium oxide: tiO2 is a compound existing in nature, has good thermal stability and nonflammable characteristics, and can be classified into rutile type, anatase type and brookite type according to different crystal structures, and the ultraviolet shielding performance of TiO2 is related to crystal type and granularity. Since the crystal structure of rutile type TiO2 is more stable and compact than that of anatase type TiO2, the refractive index is larger (about 30 percent larger), the photocatalytic effect is small, and the scattering effect is stronger, so that the rutile type nano TiO2 serving as a sun-screening agent is better.

That is, the invention should prepare the red gold stone type titanium oxide, the energy required for preparing the red gold stone is higher, and usually at least high-temperature roasting is needed, but the preparation process for preparing the red gold stone by roasting is generally more loaded, and the red gold stone is obtainedAlthough the crystal form is proper, the external form is generally irregular and is not suitable for being used as an additive of cosmetics, therefore, the invention adopts a one-step hydrothermal method to prepare the red gold titanium oxide, and sequentially places 0.5-1ml TBT, 20ml 2-2.5M HCl aqueous solution and 0.1-0.15ml PVP in a polytetrafluoroethylene reaction kettle, and 200-210 are stirred properly ^o C, carrying out hydrothermal reaction for 5-7h, naturally cooling to obtain a pale yellow precipitate, centrifuging, filtering and washing to obtain a titanium oxide suspension aqueous solution, wherein the titanium oxide prepared by the method is a nano-sized sphere, the size of the nano-sphere is 40-60nm, and the concentration of hydrochloric acid and the hydrothermal temperature are critical to the influence of the formed nano-size, spherical shape and crystal form in the preparation process, and the obtained titanium oxide nano-sphere is shown in the attached figure 1.

In order to effectively form a core-shell structure and improve the adhesion of the core and the shell, the titanium oxide needs to be subjected to surface modification, and the titanium oxide is subjected to SO ₄ ^- Adding ammonium sulfate into the suspension of titanium oxide to 40-45 ^o C, stirring at 500-700rpm for 2-3h, standing at normal temperature for 20-30min, wherein the concentration of the ammonium sulfate in the solution is 0.1-0.5M, and a possible modification basic equation is as follows:

(NH4) ₂ SO ₄ +TiO ₂ →TiOSO ₄ +2NH ₃ +H ₂ O

that is, the titanium oxide is anionized to form TiO-SO ₄ ^- Zinc acetate is added into the solution, and the following reaction occurs on the surface of spherical titanium oxide:

Zn(CH3COO) ₂ + 2TiO-SO ₄ ^- +2H ⁺ →CH3COOH+2TiOSO ₄ ^{- _} Zn(OH) ⁺ the balance is continuously moved by heating, and the titanium oxide surface is directionally coated with the titanium oxide to obtain TiO ₂ The thickness of the zinc oxide obtained is about 20-30nm and the whole TiO ₂ The @ ZnO nano-particles are about 60-100nm, as shown in figure 2, and in addition, figure 3 is a partially-coated failed TiO2@ZnO particle, but the coated core-shell structure is clearly visible, and figures 4 and 6 further verify the core-shell structure.

Carbomer is a high molecular polymer of acrylic acid and allyl sucrose or propenyl pentaerythritol crosslinking, and has the main functions of thickening, suspending, emulsifying and the like, and has certain affinity for skin, so that the carbomer can automatically play a certain role in protecting skin when being added into cosmetics, and the skin is prevented from being damaged by certain chemical components. The dispersion effect of inorganic particles in the solution can be remarkably improved by adding the phase B component into the core-shell inorganic sun-screening particles, the sun-screening emulsion is very stable, and the finally obtained sun-screening emulsion is stable in emulsion state as shown in figure 5.

Beneficial technical effects

(1) The invention is realized by controlling TiO ₂ The morphology of the@ZnO inorganic sun-screening particles is spherical, the particle size is 60-100nm, the size is uniform, the particles can be uniformly dispersed in emulsion, and the stability is good.

(2) By preparing TiO ₂ The inorganic core-shell structure of@ZnO improves the ability of the sun-screening particles to shield different ultraviolet wave bands, and achieves better sun-screening effect and better user experience by matching with emulsion.

Drawings

FIG. 1 is an SEM image of titanium oxide nanospheres prepared by a hydrothermal process according to the present invention.

FIG. 2A TiO according to the invention ₂ SEM image of @ ZnO.

FIG. 3 TiO according to the invention ₂ Incomplete SEM image of the coating of ZnO.

FIG. 4A TiO according to the invention ₂ TEM image of @ ZnO.

FIG. 5 is an optical view of a sunscreen emulsion made in accordance with the present invention.

FIG. 6A TiO according to the invention ₂ XRD pattern of @ ZnO.

Detailed Description

Example 1

A sunscreen emulsion composition prepared by the process of:

(a) Mixing the components of phase A in turn, and homogenizing for 5min.

(c) The components of phase B are mixed in turn and stirred to obtain a stable suspension.

(d) Phase B was added to phase A and stirred rapidly for 10min.

(e) Adding phase C into the mixed phase in the step (d), and uniformly stirring.

The preparation method of the phase B comprises the following steps:

(1) Preparing the red gold stone micro-nano sphere titanium oxide in one step: sequentially placing 0.5ml TBT, 20ml 2M HCl aqueous solution and 0.1ml PVP in a polytetrafluoroethylene reaction kettle, and stirring properly to obtain 200 ^o C, carrying out hydrothermal reaction for 5h, naturally cooling to obtain a pale yellow precipitate, centrifuging, filtering and washing to obtain a titanium oxide suspension aqueous solution.

(2) Functionalization: adding ammonium sulfate into the titanium oxide suspension water solution to obtain a solution of 40 percent ^o C, stirring for 2 hours at 500rpm, and standing for 20 minutes at normal temperature, wherein the concentration of the ammonium sulfate in the solution is 0.1M.

(3) Adding 10mM zinc acetate ethanol solution into the above solution, and adding the solution into 70 ^o C, stirring at 1000rpm for 20h, aging for 2h, centrifuging, filtering to obtain 3wt.% ZnO@TiO ₂ An aqueous solution.

The moisturizing and sun-screening emulsion is characterized by comprising the following components:

phase A:

cetostearyl alcohol ether-6: 1wt.%;

cetostearyl alcohol ether-25: 1.3wt.%;

hydrogenated polyisobutene: 4.5wt.%;

caprylic/capric triglyceride: 2wt.%;

ethylhexyl palmitate: 2wt.%;

polydimethyl siloxane: 1.5wt.%;

vitamin E:0.3wt.%;

glycerol monostearate: 0.1wt.%;

and B phase:

ZnO@TiO ₂ ：3wt.%；

carbomer: 0.2wt.%;

glycerol: 4wt.%;

propylene glycol: 2wt.%;

alpha-mannans: 2wt.%;

trehalose: 1wt.%;

phase C

Triethanolamine: 0.2wt.%;

hyaluronic acid: 0.05wt.%;

hydrolyzed protein: 0.5wt.%;

0.01wt.% of perfume;

deionized water to 100.

Example 2

A preparation method of a moisturizing sun-screening liquid comprises the following steps:

(a) Mixing the components of phase A in turn, and homogenizing for 6min.

(d) Phase B was added to phase A and stirred rapidly for 12.5min.

The preparation method of the phase B comprises the following steps:

(1) Preparing the red gold stone micro-nano sphere titanium oxide in one step: sequentially placing 0.75ml TBT, 20ml 2.25M HCl aqueous solution and 0.125ml PVP in a polytetrafluoroethylene reaction kettle, and stirring properly, 205 ^o C, carrying out hydrothermal reaction for 6 hours, naturally cooling to obtain a pale yellow precipitate, centrifuging, filtering and washing to obtain a titanium oxide suspension aqueous solution.

(2) Functionalization: adding ammonium sulfate into the titanium oxide suspension water solution to make the concentration of the ammonium sulfate be 42.5 ^o C, stirring at 600rpm for 2.5h, and standing at normal temperature for 25min, wherein the concentration of the ammonium sulfate in the solution is 0.13M.

(3) Adding 12.5mM zinc acetate ethanol solution into the above solution, and adding to 75 ^o C stirring at 1250rpm for 22h, aging for 3h, centrifuging, filtering to prepare 7wt.% ZnO@TiO ₂ An aqueous solution.

cetostearyl alcohol ether-6: 1.1wt.%;

cetostearyl alcohol ether-25: 1.4wt.%;

hydrogenated polyisobutene: 4.75wt.%;

caprylic/capric triglyceride: 2.5wt.%;

ethylhexyl palmitate: 3wt.%;

polydimethyl siloxane: 1.75wt.%;

vitamin E:0.4wt.%;

glycerol monostearate: 0.15wt.%;

ZnO@TiO ₂ ：7wt.%；

carbomer: 0.25wt.%;

glycerol: 4.5wt.%;

propylene glycol: 2.5wt.%;

alpha-mannans: 2.5wt.%;

trehalose: 1.5wt.%;

triethanolamine: 0.25wt.%;

hyaluronic acid: 0.075wt.%;

hydrolyzed protein: 0.75wt.%;

0.025wt.% of perfume;

deionized water to 100.

Example 3

(a) Mixing the components of phase A in turn, and homogenizing for 7min.

(d) Phase B was added to phase A and stirred rapidly for 15min.

The preparation method of the phase B comprises the following steps:

(1) Preparing the red gold stone micro-nano sphere titanium oxide in one step: sequentially placing 0.5ml TBT, 20ml 2.5M HCl aqueous solution and 0.15ml PVP in a polytetrafluoroethylene reaction kettle, and stirring properly to obtain 210 ^o C, carrying out hydrothermal reaction for 7h, naturally cooling to obtain a pale yellow precipitate, centrifuging, filtering and washing to obtain a titanium oxide suspension aqueous solution.

(2) Functionalization: adding ammonium sulfate into the titanium oxide suspension water solution, and adding ammonium sulfate into the titanium oxide suspension water solution at 45 DEG C ^o C, stirring at 700rpm for 3 hours, and standing at normal temperature for 30 minutes, wherein the concentration of the ammonium sulfate in the solution is 0.5M.

(3) Adding 10-15mM zinc acetate ethanol solution into the above solution, and adding into 80 ^o C, stirring at 1500rpm for 24 hours, aging for 4 hours, centrifuging, filtering to prepare 10wt.% ZnO@TiO ₂ An aqueous solution.

cetostearyl alcohol ether-6: 1.2wt.%;

cetostearyl alcohol ether-25: 1.5wt.%;

hydrogenated polyisobutene: 5wt.%;

caprylic/capric triglyceride: 3wt.%;

ethylhexyl palmitate: 4wt.%;

polydimethyl siloxane: 2wt.%;

vitamin E:0.5wt.%;

glycerol monostearate: 0.2wt.%;

ZnO@TiO ₂ ：10wt.%；

carbomer: 0.3wt.%;

glycerol: 5wt.%;

propylene glycol: 3wt.%;

alpha-mannans: 3wt.%;

trehalose: 2wt.%;

triethanolamine: 0.3wt.%;

hyaluronic acid: 0.1wt.%;

hydrolyzed protein: 1wt.%;

0.04wt.% of perfume;

deionized water to 100.

Comparative example 1

A moisturizing sun-screening liquid comprises the following components:

cetostearyl alcohol ether-6: 1.1wt.%;

cetostearyl alcohol ether-25: 1.4wt.%;

hydrogenated polyisobutene: 4.75wt.%;

caprylic/capric triglyceride: 2.5wt.%;

ethylhexyl palmitate: 3wt.%;

polydimethyl siloxane: 1.75wt.%;

vitamin E:0.4wt.%;

glycerol monostearate: 0.15wt.%;

carbomer: 0.25wt.%;

glycerol: 4.5wt.%;

propylene glycol: 2.5wt.%;

alpha-mannans: 2.5wt.%;

trehalose: 1.5wt.%;

triethanolamine: 0.25wt.%;

hyaluronic acid: 0.075wt.%;

hydrolyzed protein: 0.75wt.%;

0.025wt.% of perfume;

deionized water to 100.

Comparative example 2

(a) Mixing the components of phase A in turn, and homogenizing for 6min.

(d) Phase B was added to phase A and stirred rapidly for 12.5min.

The preparation method of the phase B comprises the following steps:

(1) One stepPreparation of red Jin Danwei nanosphere titania: sequentially placing 0.75ml TBT, 20ml 2.25M HCl aqueous solution and 0.125ml PVP in a polytetrafluoroethylene reaction kettle, and stirring properly, 205 ^o C, carrying out hydrothermal reaction for 6 hours, naturally cooling to obtain a pale yellow precipitate, centrifuging, filtering and washing to obtain a titanium oxide suspension aqueous solution.

cetostearyl alcohol ether-6: 1.1wt.%;

cetostearyl alcohol ether-25: 1.4wt.%;

hydrogenated polyisobutene: 4.75wt.%;

caprylic/capric triglyceride: 2.5wt.%;

ethylhexyl palmitate: 3wt.%;

polydimethyl siloxane: 1.75wt.%;

vitamin E:0.4wt.%;

glycerol monostearate: 0.15wt.%;

TiO ₂ ：7wt.%；

carbomer: 0.25wt.%;

glycerol: 4.5wt.%;

propylene glycol: 2.5wt.%;

alpha-mannans: 2.5wt.%;

trehalose: 1.5wt.%;

triethanolamine: 0.25wt.%;

hyaluronic acid: 0.075wt.%;

hydrolyzed protein: 0.75wt.%;

0.025wt.% of perfume;

deionized water to 100.

As can be seen from the table, the SPF value of the invention is 47.2+/-0.5, the PA value is 30.2+/-0.5, the sun-proof effect is higher, when the emulsion does not contain inorganic sun-proof particles, the SPF and PA values of the corresponding emulsion are almost not available, as shown in the opposite 1, when only nano titanium oxide is added into the emulsion, the sun-proof capability is improved, but the sun-proof effect is limited, especially the PA value is required to be improved, and the zinc oxide coated on the surface of the titanium oxide can obviously improve the shielding effect of UVA and the sun-proof effect.

The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above examples, and all technical solutions belonging to the concept of the present invention belong to the protection scope of the present invention. It should be noted that modifications and adaptations to the present invention may occur to one skilled in the art without departing from the principles of the present invention and are intended to be within the scope of the present invention.

Claims

1. A sunscreen emulsion composition characterized in that said composition consists of:

cetostearyl alcohol ether-6: 1-1.2wt.%;

cetostearyl alcohol ether-25: 1.3-1.5 wt.%;

hydrogenated polyisobutene: 4.5-5 wt.%;

caprylic/capric triglyceride: 2-3wt.%;

ethylhexyl palmitate: 2-4 wt.%;

polydimethyl siloxane: 1.5-2 wt.%;

vitamin E:0.3-0.5 wt.%;

glycerol monostearate: 0.1-0.2wt.%;

ZnO@TiO ₂ ：3-10wt.%；

carbomer: 0.2-0.3wt.%;

glycerol: 4-5wt.%;

propylene glycol: 2-3wt.%;

alpha-mannans: 2-3wt.%;

trehalose: 1-2wt.%;

triethanolamine: 0.2-0.3wt.%;

hyaluronic acid: 0.05-0.1wt.%;

hydrolyzed protein: 0.5-1 wt.%;

essence: 0.01-0.04wt.%;

deionized water to 100 wt%;

wherein the ZnO@TiO ₂ The preparation method of (2) is as follows:

(1) Preparing the red gold stone micro-nano sphere titanium oxide in one step: placing TBT, aqueous HCl solution and PVP in a polytetrafluoroethylene reaction kettle in sequence, carrying out hydrothermal reaction treatment after proper stirring, naturally cooling to obtain pale yellow precipitate, centrifuging, filtering and washing to obtain a titanium oxide suspension aqueous solution, wherein the dosage of TBT is 0.5-1ml, the dosage of aqueous HCl solution is 20ml of 2-2.5M, and the dosage of PVP is 0.1-0.15ml, and the hydrothermal reaction conditions are as follows: carrying out hydrothermal reaction for 5-7h at 200-210 ℃;

(2) Functionalization: adding ammonium sulfate into the titanium oxide suspension water solution, stirring at the temperature of 40-45 ℃ and the speed of 500-700rpm for 2-3 hours, and standing at normal temperature for 20-30min, wherein the concentration of the ammonium sulfate in the solution is 0.1-0.5M;

(3) Adding zinc acetate ethanol solution into the solution obtained in the step (2), wherein the zinc acetate dosage is 10-15mM, stirring for 20-24h at 70-80 ℃ and 1000-1500rpm, aging for 2-4h, centrifuging, and filtering to obtain 3-10wt.% ZnO@TiO ₂ An aqueous solution.