CN113749958A

CN113749958A - Sunscreen emulsion composition

Info

Publication number: CN113749958A
Application number: CN202110964193.2A
Authority: CN
Inventors: 刘志威
Original assignee: Individual
Current assignee: Budweiser Shanghai Cosmetics Co ltd
Priority date: 2021-08-21
Filing date: 2021-08-21
Publication date: 2021-12-07
Anticipated expiration: 2041-08-21
Also published as: CN113749958B

Abstract

The invention provides a sunscreen emulsion composition, wherein inorganic sunscreen particles in sunscreen liquid have a core-shell structure, titanium oxide is used as a core, zinc oxide is used as a shell, and the sunscreen liquid has high SPF (specific pathogen free) and PA (polyamide) values.

Description

Sunscreen emulsion composition

Technical Field

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

Background

Ultraviolet rays are an important component of sunlight, and the energy of the ultraviolet rays accounts for about 6 percent of the total energy of the sunlight. The ultraviolet wavelength is 200-400 nm, the ultraviolet 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 enhance the physique of a human body, deoxysterol in the skin can be converted into vitamin D, and therefore the vitamin D can be beneficial to the absorption of calcium and other minerals by the human body, the occurrence of infantile rickets and adult osteomalacia can be prevented, the metabolism of the human body can be promoted, and the immune function can be generated. However, if the skin is exposed to sunlight for a long time, ultraviolet light waves with large 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 suppression.

The effect of ultraviolet light on skin is mainly two-fold: on the one hand, due to the ultraviolet radiation in the UVA region. UVA is called a tanning area, after the skin is irradiated by the light, tyrosine oxidase in pigment cells of an epidermal basal layer is increased rapidly and tyrosine is polymerized to generate melanin, and the melanin is moved to the epidermis so as to darken the skin and prevent and resist the invasion of ultraviolet rays to the deep part of the skin, and the UVA has a protective effect, namely the tanning, but the UVA has a plurality of negative effects on the skin structure, such as wrinkling, sinking, generation of irregularity and spots, dryness, roughness, looseness and the like, and serious tissue damage can be caused by long-time irradiation of the UVA, and even skin cancer can be caused; on the other hand, the ultraviolet rays in the UVB region are caused, and the UVB is called a sunburn region, and the penetration degree is not deep, but the part of the rays can penetrate through the skin, penetrate from a skin basal layer to the vicinity of a papillary layer, so that the part of capillaries is expanded to generate skin inflammation, and epidermal cells are obstructed, so that the acute inflammation of the skin is caused, the skin is reddened, or the symptoms such as blisters and erythema are generated, and the skin is blackened, which is a pathological phenomenon of the skin and is called sunburn. Skin is prematurely aged by prolonged exposure to UVB radiation.

Organic sunscreen agents in the sunscreen products used in the current market have a large market share, and the main organic sunscreen agents are:

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

Anthranilate derivatives: can prevent 290-380 nm ultraviolet ray and UVA and UVB ray, such as anthranilic acid menthol ester and anthranilic acid high menthol ester, and can effectively prevent photochemical carcinogenesis.

Cinnamic acid esters: the sunscreen composition can prevent ultraviolet rays with the wavelength of 280 nm-310 nm, and has high absorptivity, so the sunscreen composition is widely applied, for example, ParsolMCX (octyl methoxycinnamate) is the most common sunscreen composition in the world at present, has an excellent ultraviolet light absorption curve, is good in safety, has good solubility to oily raw materials, and is almost an ideal sunscreen composition.

In addition, salicylic acid esters, benzophenone compounds, camphor derivatives, methane derivatives, and organic sunscreens are well compatible with cosmetics, but have problems such as increase in the amount of the sunscreen added to protect the skin from ultraviolet rays as much as possible, which in turn increases the incidence of cancer and chemical allergy.

The main inorganic sunscreens used today are: nano TiO2, ZnO, Fe2O3, SiO2, ZrO and the like. The nanometer semiconductor materials not only inherit the advantages of common materials, but also produce the properties which are not possessed by bulk materials, such as photocatalysis performance, strong ultraviolet absorption performance, reflection performance and the like. Among them, nano TiO2 is most widely used, and ZnO is the second choice.

Disclosure of Invention

The invention aims to provide a composition with moisturizing and sunscreen effects, the sunscreen lotion is suitable for most of skin types, is safe and environment-friendly, does not bring greasy feeling, is convenient to use, and effectively achieves the moisturizing and sunscreen effects of skin.

A sunscreen emulsion composition comprising, in combination:

ceteareth-6: 1-1.2 wt.%;

ceteareth-25: 1.3-1.5 wt.%;

hydrogenated polyisobutene: 4.5-5 wt.%;

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

ethylhexyl palmitate: 2-4 wt.%;

polydimethylsiloxane: 1.5-2 wt.%;

vitamin E: 0.3-0.5 wt.%;

glyceryl monostearate: 0.1-0.2 wt.%;

ZnO@TiO₂：3-10wt.%；

carbomer: 0.2-0.3 wt.%;

glycerol: 4-5 wt.%;

propylene glycol: 2-3 wt.%;

α -mannan: 2-3 wt.%;

trehalose: 1-2 wt.%;

triethanolamine: 0.2-0.3 wt.%;

hyaluronic acid: 0.05-0.1 wt.%;

hydrolyzing protein: 0.5-1 wt.%;

essence: 0.01-0.04 wt.%;

wherein the ZnO @ TiO₂The preparation method comprises the following steps:

(1) preparing the rutile micro-nano sphere titanium oxide by one step: sequentially placing TBT, HCl aqueous solution and PVP in a polytetrafluoroethylene reaction kettle, carrying out hydrothermal reaction treatment after proper stirring, naturally cooling to obtain light yellow precipitate, centrifuging, filtering and washing to obtain titanium oxide suspension aqueous solution;

(2) functionalization: adding ammonium sulfate into the titanium oxide suspension aqueous solution at 40-45 deg.C^oC, stirring at 500-700rpm for 2-3h, and standing at normal temperature for 20-30 min;

(3) adding zinc acetate ethanol solution into the above solution, and dissolving at 70-80 deg.C^oC, stirring at 1500rpm for 20-24h, aging for 2-4h, centrifuging, filtering, and preparing into 3-10wt.% ZnO @ TiO₂An aqueous solution;

(4) adding carbomer, glycerol, propylene glycol, alpha-mannan, and trehalose, and stirring to obtain phase B.

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

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

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

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

The preparation method of the sunscreen emulsion composition comprises the following steps:

(a) mixing the phase A components 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 10-15 min;

(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 titanium oxide suspension aqueous solution at 40-45 deg.C^oC, 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;

(3) adding an ethanol solution of zinc acetate into the solution, stirring at 1500rpm at 70-80 ℃ for 20-24h, aging for 2-4h, centrifuging, filtering, and preparing into 3-10wt.% ZnO @ TiO₂An aqueous solution;

The phase A contains ceteareth-6, ceteareth-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-proof main component adopted by the invention is an inorganic core-shell structure, titanium oxide is used as a core, and zinc oxide is used as a shell.

Firstly, the composite theoretical basis of titanium oxide and zinc oxide is selected:

the nano TiO2 has high sun protection factor, good absorption and scattering effects on ultraviolet rays of medium-wave UVB (280-320 nm) and long-wave UVA (320-400 nm), ultraviolet shielding performance and high transparency, and in addition, the nano TiO2 has high sun protection factor₂Has a large specific surface area and a large number of surface atoms, and the surface energy and surface tension thereof are sharply increased with the decrease of the particle diameter, and TiO is used as a binder for a polyurethane₂The titanium oxide nanoparticles are very suitable for being used as the core of an inorganic sunscreen agent due to the physical and chemical properties, and other sunscreen components are effectively coated on the surfaces of the particles through surface modification, so that an effective sunscreen 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 on blocking long UVA (335 nm-380 nm) than nano titanium oxide (TiO)₂). And in addition, due to the higher specific surface area and the broad-spectrum absorption of ultraviolet wavelength of the nano ZnO, the nano ZnO can be better dispersed in the formula of the sunscreen cream, so that more ultraviolet rays can be absorbed.

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

Titanium oxide: TiO2 is a compound existing in nature, has good thermal stability and incombustibility, and can be classified into rutile type, anatase type and brookite type according to the crystal structure, and the shielding property of TiO2 against ultraviolet rays is related to the crystal form and particle size. Rutile type TiO2 is better as a sunscreen agent because the crystal structure of rutile type TiO2 is more stable and compact than anatase type TiO2, the refractive index is larger (about 30 percent larger), the photocatalysis is smaller, and the scattering effect is stronger.

Namely, the invention should prepare the rutile type titanium oxide, the energy required for preparing the rutile is high, at least high-temperature roasting is usually required, but the preparation process for preparing the rutile by roasting is generally relatively loaded, and the obtained rutile is proper in crystal form, but the external form of the rutile is generally irregular and is not suitable for being used as an additive of cosmetics, so the invention adopts a one-step hydrothermal method to prepare the rutile type titanium oxide, and 0.5-1ml of TBT, 20ml of 2-2.5M HCl aqueous solution and 0.1-0.15ml of PVP are sequentially placed in a polytetrafluoroethylene reaction kettle, and after proper stirring, 200-210 materials are added^oC, carrying out hydrothermal reaction for 5-7h, naturally cooling to obtain a light yellow precipitate, centrifuging, filtering and washing to obtain a titanium oxide suspension water solution, wherein the titanium oxide prepared by the method is a nano-sized sphere, the size of the nanosphere is 40-60nm, the influence of the concentration of hydrochloric acid and the hydrothermal temperature on the formed nano size, spherical shape and crystal form is critical in the preparation process, and the obtained titanium oxide nanosphere is shown in figure 1.

In order to effectively form a core-shell structure and improve the adhesion between a core and a shell, the titanium oxide needs to be subjected to surface modification, and the titanium oxide is subjected to SO₄ ^-Dissolving, adding ammonium sulfate into the titanium oxide suspension water solution, and dissolving at 40-45 deg.C^oC, 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 the possible modification basic equation is as follows:

(NH4)₂SO₄+TiO₂→TiOSO₄+2NH₃+H₂O

that is, the titanium oxide is anionized to form TiO-SO₄ ^-Adding zinc acetate into the solution, and carrying out the following reaction on the surface of the spherical titanium oxide:

Zn(CH3COO)₂+ 2TiO-SO₄ ^-+2H⁺→CH3COOH+2TiOSO₄ ^{- _}Zn(OH)⁺the titanium oxide is directionally coated on the surface by continuously moving the balance through heating to obtain TiO₂@ ZnO, obtaining zinc oxide of thickness approximately 20-30nm, TiO as a whole₂About 60-100nm for @ ZnO nanoparticles, as shown in figure 2, and in addition, figure 3 shows TiO2@ ZnO particles with partial coating failure, but the coating core-shell structure is clear and visible, and figures 4 and 6 further verify the core-shell structure.

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

Advantageous technical effects

(1) The invention controls TiO₂The @ ZnO inorganic sunscreen particles are spherical in shape, have the particle size of 60-100nm, are uniform in size, can be uniformly dispersed in the emulsion, and are good in stability.

(2) By preparing TiO₂The @ ZnO inorganic core-shell structure improves the capability of the sunscreen particles for shielding different ultraviolet wave bands, and achieves better sunscreen effect and better user experience by matching with the emulsion.

Drawings

FIG. 1 is an SEM image of the titanium oxide nanospheres prepared by the hydrothermal method of the present invention.

FIG. 2 shows TiO prepared according to the invention₂SEM image of @ ZnO.

FIG. 3 shows TiO prepared according to the invention₂Incomplete SEM image of coating of @ ZnO.

FIG. 4 shows TiO prepared according to the invention₂TEM image of @ ZnO.

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

FIG. 6 shows TiO prepared according to the invention₂The XRD pattern of @ ZnO.

Detailed Description

Example 1

A sunscreen emulsion composition prepared by the process of:

(a) mixing the phase A components in sequence, and homogenizing for 5 min.

(c) And mixing the components of the phase B in sequence, and stirring to obtain a stable suspension.

(d) Add phase B to phase a and stir rapidly for 10 min.

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

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

(1) preparing the rutile micro-nano sphere titanium oxide by one step: placing 0.5ml TBT, 20ml 2M HCl aqueous solution and 0.1ml PVP in sequence in a polytetrafluoroethylene reaction kettle, stirring properly, and then 200^oAnd C, carrying out hydrothermal reaction for 5 hours, naturally cooling to obtain a light yellow precipitate, centrifuging, filtering and washing to obtain a titanium oxide suspension water solution.

(2) Functionalization: adding ammonium sulfate into the titanium oxide suspension aqueous solution at 40 deg.C^oAnd C, stirring at 500rpm for 2 hours, standing at normal temperature for 20min, wherein the concentration of the ammonium sulfate in the solution is 0.1M.

(3) To the above solution was added 10mM zinc acetate in ethanol at 70 deg.C^oC, stirring at 1000rpm for 20h, aging for 2h, centrifuging, filtering, and preparing into 3wt.% ZnO @ TiO₂An aqueous solution.

The moisturizing sunscreen emulsion is characterized by comprising the following components:

phase A:

ceteareth-6: 1 wt.%;

ceteareth-25: 1.3 wt.%;

hydrogenated polyisobutene: 4.5 wt.%;

caprylic/capric triglyceride: 2 wt.%;

ethylhexyl palmitate: 2 wt.%;

polydimethylsiloxane: 1.5 wt.%;

vitamin E: 0.3 wt.%;

glyceryl monostearate: 0.1 wt.%;

phase B:

ZnO@TiO₂：3wt.%；

carbomer: 0.2 wt.%;

glycerol: 4 wt.%;

propylene glycol: 2 wt.%;

α -mannan: 2 wt.%;

trehalose: 1 wt.%;

phase C

Triethanolamine: 0.2 wt.%;

hyaluronic acid: 0.05 wt.%;

hydrolyzing protein: 0.5 wt.%;

0.01wt.% perfume;

deionized water to 100.

Example 2

A preparation method of the moisturizing sunscreen liquid comprises the following steps:

(a) mixing the phase A components in sequence, and homogenizing for 6 min.

(d) Add phase B to phase a and stir rapidly for 12.5 min.

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

(1) preparing the rutile micro-nano sphere titanium oxide by one step: 0.75ml of TBT, 20ml of 2.25M HCl aqueous solution and 0.125ml of PVP are sequentially placed in a polytetrafluoroethylene reaction kettle, properly stirred and then 205 ml of PVP is added^oC, carrying out hydrothermal reaction for 6h, naturally cooling to obtain light yellow precipitate, centrifuging, filtering, washing to obtainTo obtain the titanium oxide suspension water solution.

(2) Functionalization: ammonium sulfate was added to the above titanium oxide suspension aqueous solution at 42.5^oC, stirring at 600rpm for 2.5h, standing at normal temperature for 25min, wherein the concentration of the ammonium sulfate in the solution is 0.13M.

(3) To the above solution was added 12.5mM zinc acetate in ethanol at 75^oC, stirring at 1250rpm for 22h, aging for 3h, centrifuging, filtering to prepare 7wt.% ZnO @ TiO₂An aqueous solution.

ceteareth-6: 1.1 wt.%;

ceteareth-25: 1.4 wt.%;

hydrogenated polyisobutene: 4.75 wt.%;

caprylic/capric triglyceride: 2.5 wt.%;

ethylhexyl palmitate: 3 wt.%;

polydimethylsiloxane: 1.75 wt.%;

vitamin E: 0.4 wt.%;

glyceryl monostearate: 0.15 wt.%;

ZnO@TiO₂：7wt.%；

carbomer: 0.25 wt.%;

glycerol: 4.5 wt.%;

propylene glycol: 2.5 wt.%;

α -mannan: 2.5 wt.%;

trehalose: 1.5 wt.%;

triethanolamine: 0.25 wt.%;

hyaluronic acid: 0.075 wt.%;

hydrolyzing protein: 0.75 wt.%;

0.025wt.% perfume;

deionized water to 100.

Example 3

(a) mixing the phase A components in sequence, and homogenizing for 7 min.

(d) Add phase B to phase a and stir rapidly for 15 min.

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

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

(2) Functionalization: adding ammonium sulfate to the titanium oxide suspension aqueous solution at 45 deg.C^oAnd C, stirring at 700rpm for 3 hours, standing at normal temperature for 30min, 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 dissolving in 80 deg.C^oC, stirring at 1500rpm for 24 hours, aging for 4 hours, centrifuging, filtering, and preparing into 10wt.% ZnO @ TiO₂An aqueous solution.

ceteareth-6: 1.2 wt.%;

ceteareth-25: 1.5 wt.%;

hydrogenated polyisobutene: 5 wt.%;

caprylic/capric triglyceride: 3 wt.%;

ethylhexyl palmitate: 4 wt.%;

polydimethylsiloxane: 2 wt.%;

vitamin E: 0.5 wt.%;

glyceryl monostearate: 0.2 wt.%;

ZnO@TiO₂：10wt.%；

carbomer: 0.3 wt.%;

glycerol: 5 wt.%;

propylene glycol: 3 wt.%;

α -mannan: 3 wt.%;

trehalose: 2 wt.%;

triethanolamine: 0.3 wt.%;

hyaluronic acid: 0.1 wt.%;

hydrolyzing protein: 1 wt.%;

0.04wt.% perfume;

deionized water to 100.

Comparative example 1

A moisturizing sunscreen liquid comprises the following components:

ceteareth-6: 1.1 wt.%;

ceteareth-25: 1.4 wt.%;

hydrogenated polyisobutene: 4.75 wt.%;

caprylic/capric triglyceride: 2.5 wt.%;

ethylhexyl palmitate: 3 wt.%;

polydimethylsiloxane: 1.75 wt.%;

vitamin E: 0.4 wt.%;

glyceryl monostearate: 0.15 wt.%;

carbomer: 0.25 wt.%;

glycerol: 4.5 wt.%;

propylene glycol: 2.5 wt.%;

α -mannan: 2.5 wt.%;

trehalose: 1.5 wt.%;

triethanolamine: 0.25 wt.%;

hyaluronic acid: 0.075 wt.%;

hydrolyzing protein: 0.75 wt.%;

0.025wt.% perfume;

deionized water to 100.

Comparative example 2

(a) mixing the phase A components in sequence, and homogenizing for 6 min.

(d) Add phase B to phase a and stir rapidly for 12.5 min.

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

(1) preparing the rutile micro-nano sphere titanium oxide by one step: 0.75ml of TBT, 20ml of 2.25M HCl aqueous solution and 0.125ml of PVP are sequentially placed in a polytetrafluoroethylene reaction kettle, properly stirred and then 205 ml of PVP is added^oAnd C, carrying out hydrothermal reaction for 6h, naturally cooling to obtain a light yellow precipitate, centrifuging, filtering and washing to obtain a titanium oxide suspension aqueous solution.

ceteareth-6: 1.1 wt.%;

ceteareth-25: 1.4 wt.%;

hydrogenated polyisobutene: 4.75 wt.%;

caprylic/capric triglyceride: 2.5 wt.%;

ethylhexyl palmitate: 3 wt.%;

polydimethylsiloxane: 1.75 wt.%;

vitamin E: 0.4 wt.%;

glyceryl monostearate: 0.15 wt.%;

TiO₂：7wt.%；

carbomer: 0.25 wt.%;

glycerol: 4.5 wt.%;

propylene glycol: 2.5 wt.%;

α -mannan: 2.5 wt.%;

trehalose: 1.5 wt.%;

triethanolamine: 0.25 wt.%;

hyaluronic acid: 0.075 wt.%;

hydrolyzing protein: 0.75 wt.%;

0.025wt.% perfume;

deionized water to 100.

As can be seen from the above table, the SPF value of the present invention is 47.2 ± 0.5, the PA value is 30.2 ± 0.5, and the sunscreen effect is high, and when the emulsion does not contain inorganic sunscreen particles, the SPF and PA values corresponding to the emulsion are almost not present, as shown in contrast 1, when only nano titanium oxide is added, the sunscreen ability is improved, but the sunscreen effect is limited, especially the PA value is to be improved, and the coating of zinc oxide on the surface of titanium oxide can significantly improve the screening effect of UVA, and improve the sunscreen 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 embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may occur to those skilled in the art without departing from the principle of the invention, and are considered to be within the scope of the invention.

Claims

1. A sunscreen emulsion composition characterized in that said combination comprises the following components:

ceteareth-6: 1-1.2 wt.%;

ceteareth-25: 1.3-1.5 wt.%;

hydrogenated polyisobutene: 4.5-5 wt.%;

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

ethylhexyl palmitate: 2-4 wt.%;

polydimethylsiloxane: 1.5-2 wt.%;

vitamin E: 0.3-0.5 wt.%;

glyceryl monostearate: 0.1-0.2 wt.%;

ZnO@TiO₂：3-10wt.%；

carbomer: 0.2-0.3 wt.%;

glycerol: 4-5 wt.%;

propylene glycol: 2-3 wt.%;

α -mannan: 2-3 wt.%;

trehalose: 1-2 wt.%;

triethanolamine: 0.2-0.3 wt.%;

hyaluronic acid: 0.05-0.1 wt.%;

hydrolyzing protein: 0.5-1 wt.%;

essence: 0.01-0.04 wt.%;

wherein the ZnO @ TiO₂The preparation method comprises the following steps:

(3) adding zinc acetate ethanol solution into the above solution, and dissolving at 70-80 deg.C^oC, stirring at 1500rpm for 20-24h, aging for 2-4h, centrifuging, filtering, and preparing into 3-10wt.% ZnO @ TiO₂An aqueous solution.

2. A sunscreen emulsion composition as claimed in claim 1 wherein TBT is used in an amount of 0.5 to 1ml, aqueous HCl in an amount of 20ml 2 to 2.5M, PVP in an amount of 0.1 to 0.15 ml.

3. A sunscreen emulsion composition as claimed in claim 1 wherein said hydrothermal conditions are: 200-210^oC, carrying out hydrothermal reaction for 5-7 h.

4. A sunscreen emulsion composition as claimed in claim 1 wherein said ammonium sulfate is present in solution at a concentration of 0.1 to 0.5M.

5. A sunscreen emulsion composition according to claim 1 wherein said zinc acetate is present in an amount of 10 to 15 mM.