阅读说明：本技术 一种长效且易清洗的防晒霜及其制备方法 (Long-acting and easy-to-clean sunscreen cream and preparation method thereof ) 是由 何花 于 2021-09-02 设计创作，主要内容包括：本发明涉及化妆品领域,公开了一种长效且易清洗的防晒霜及其制备方法。所述防晒霜包括以下质量百分数的组分：二氧化钛@醛基化硫酸软骨素/明胶15～20％,化学防晒剂0～7％,乳化剂3～5％,增稠剂0.5～0.8％,柔润剂3～10％,保湿剂5～10％,余量为水。本发明通过在二氧化钛表面接枝醛基化硫酸软骨素和明胶,一方面能够提高二氧化钛在皮肤表面的附着力,从而延长防晒时间；另一方面还能赋予二氧化钛凉水易清除的特性,只需接触大量凉水即可洗去而确保皮肤表面无残留。(The invention relates to the field of cosmetics, and discloses a long-acting and easy-to-clean sunscreen cream and a preparation method thereof. The sunscreen cream comprises the following components in percentage by mass: 15-20% of titanium dioxide @ formylated chondroitin sulfate/gelatin, 0-7% of a chemical sunscreen agent, 3-5% of an emulsifier, 0.5-0.8% of a thickening agent, 3-10% of a softening agent, 5-10% of a humectant and the balance of water. According to the invention, the surface of titanium dioxide is grafted with aldehyde chondroitin sulfate and gelatin, so that on one hand, the adhesive force of titanium dioxide on the surface of skin can be improved, and the sun-proof time is prolonged; on the other hand, the titanium dioxide can also be endowed with the characteristic of easy removal of cold water, and can be washed away by contacting with a large amount of cold water to ensure no residue on the skin surface.)

1. The long-acting and easy-to-clean sunscreen cream is characterized by comprising the following components in percentage by mass: 15-20% of titanium dioxide @ formylated chondroitin sulfate/gelatin, 0-7% of a chemical sunscreen agent, 3-5% of an emulsifier, 0.5-0.8% of a thickening agent, 3-10% of a softening agent, 5-10% of a humectant and the balance of water.

2. The sunscreen of claim 1 wherein said chemical sunscreen agents comprise a UVB sunscreen agent and a UVA sunscreen agent; the UVB sunscreen comprises at least one of octocrylene, phenylbenzimidazole sulfonic acid, ethylhexyl triazone, and ethylhexyl salicylate; the UVA sunscreen comprises at least one of butyl methoxydibenzoylmethane and bis-ethylhexyloxyphenol methoxyphenyl triazine.

3. The sunscreen of claim 1 wherein said emulsifier comprises at least one of sorbitan sesquioleate, sorbitan stearate, polyhydroxystearic acid, and cetearyl glucoside; the thickening agent comprises at least one of carbomer, tapioca starch and methyl methacrylate cross-linked polymer; the emollient comprises at least one of batyl alcohol, caprylic/capric triglyceride, and squalane; the humectant includes at least one of 1, 2-hexanediol, panthenol, betaine, and sodium hyaluronate.

4. The sunscreen of claim 1 wherein said titanium dioxide @ formylated chondroitin sulfate/gelatin is prepared by the following method:

(A) dropwise adding a sodium periodate solution into a chondroitin sulfate solution while stirring at a temperature of 25-35 ℃ in a dark place, continuously reacting for 3.5-4.5 hours at a temperature of 25-35 ℃ after dropwise adding, adding ethylene glycol to terminate the reaction, and dialyzing to remove the solvent to obtain aldehyde chondroitin sulfate;

(B) adding titanium dioxide into an ethanol water solution, performing ultrasonic dispersion uniformly, then adding dimethyl dimethoxysilane, quaternary ammonium salt-52 and solanesol, mixing uniformly, adjusting the pH to 4-5, reacting at 75-85 ℃ for 2.5-3.5 h, and sequentially centrifuging, washing and drying to obtain cation modified titanium dioxide;

(C) adding cation modified titanium dioxide into water, uniformly dispersing by ultrasonic, then adding aldehyde chondroitin sulfate and gelatin, heating to fully dissolve, stirring for 2-3 h at 40-50 ℃, and sequentially centrifuging, washing and drying to obtain titanium dioxide @ aldehyde chondroitin sulfate/gelatin.

5. The sunscreen cream according to claim 4, wherein in step (A), the concentrations of the chondroitin sulfate solution and the sodium periodate solution are respectively 9 to 13 wt% and 3.5 to 5.5 wt%; the volume ratio of the chondroitin sulfate solution to the sodium periodate solution is 8-10: 1.

6. The sunscreen cream as claimed in claim 4, wherein in the step (B), the mass volume ratio of the titanium dioxide to the dimethyl dimethoxy silane to the ethanol aqueous solution is 1g: 2-3 g: 5-10 mL.

7. The sunscreen cream according to claim 6, wherein in the step (B), the mass ratio of the titanium dioxide to the quaternary ammonium salt-52 is 1: 0.6-0.8; the mass ratio of the titanium dioxide to the solanesol is 1: 0.3-0.5.

8. The sunscreen cream according to claim 4, wherein in the step (C), the mass-to-volume ratio of the cation-modified titanium dioxide, the aldehyde-modified chondroitin sulfate, the gelatin and the water is 1g: 0.3-0.5 g: 0.35-0.45 g: 20-25 mL.

9. The sunscreen cream according to claim 4, wherein in the step (A), the titanium dioxide is added into the ethanol water solution after being subjected to ball milling treatment; the specific process of the high-energy ball milling treatment is as follows: placing titanium dioxide in a ball mill, and ball-milling for 1-3 h at the temperature of 100-200 ℃ and the rotation speed of the ball mill of 300-500 r/min.

10. A method of preparing a sunscreen as claimed in claims 1 to 9 comprising the steps of:

(1) uniformly mixing a chemical sun-screening agent, a softening agent and an emulsifying agent to obtain a phase A;

(2) adding humectant into water, and dissolving to obtain phase B;

(3) and mixing the phase A and the phase B, homogenizing and emulsifying, adding titanium dioxide @ formylated chondroitin sulfate/gelatin, uniformly dispersing, adding a thickening agent, and uniformly mixing to prepare the long-acting and easily-cleaned sunscreen cream.

Technical Field

The invention relates to the field of cosmetics, in particular to a long-acting and easy-to-clean sunscreen cream and a preparation method thereof.

Background

Besides visible light, about 1% of ultraviolet rays with the wavelength of 290-400 nm in sunlight can irradiate the surface of the earth, and the ultraviolet rays are main rays which can damage the skin in the sunlight. The electromagnetic wave with the wavelength of 290-320 nm belongs to medium-wave Ultraviolet (UVB), has an erythema effect on human skin, can reach a corium layer, and can burn the skin by sun, so that the phenomena of desquamation, erythema, suntan and the like are caused; the long-wave Ultraviolet (UVA) in the wavelength band of 320-400 nm is called age ultraviolet and is the most main reason for premature aging of human skin, and can penetrate through the dermis, so that lipid and collagen are damaged, and skin aging and even skin canceration are caused. The loss of ozone in the atmosphere also leads people to pay more and more attention to the damage of ultraviolet rays to the skin, and the sun protection work is well done, so that the sun protection device not only can prevent the skin from being sunburned, but also is an effective mode for delaying the skin aging.

The sunscreen cream can resist the damage of ultraviolet rays after being applied on the skin, mainly because some components capable of blocking or absorbing ultraviolet rays are added, and when the ultraviolet rays irradiate on the skin, the components can scatter or absorb the ultraviolet rays. Nano TiO 2₂Has good absorption, scattering and reflection abilities to ultraviolet rays, and thus is widely used as a physical sunscreen agent. TiO compared to chemical sunscreens₂Although it is preferred to use a physical sunscreen agent having a wide sunscreen wavelength band, good photostability and low susceptibility to allergic reactions, the physical sunscreen agent is also prone to peeling off, has a short skin residence time and is not very durable.

Disclosure of Invention

In order to solve the technical problems, the invention provides a long-acting and easy-to-clean sunscreen cream and a preparation method thereof. According to the invention, the surface of titanium dioxide is grafted with aldehyde chondroitin sulfate and gelatin, so that on one hand, the adhesive force of titanium dioxide on the surface of skin can be improved, and the sun-proof time is prolonged; on the other hand, the titanium dioxide can also be endowed with the characteristic of easy removal of cold water, and can be washed away by contacting with a large amount of cold water to ensure no residue on the skin surface.

The specific technical scheme of the invention is as follows:

a long-acting and easy-to-clean sunscreen cream comprises the following components in percentage by mass: 15-20% of titanium dioxide @ formylated chondroitin sulfate/gelatin, 0-7% of a chemical sunscreen agent, 3-5% of an emulsifier, 0.5-0.8% of a thickening agent, 3-10% of a softening agent, 5-10% of a humectant and the balance of water.

According to the invention, after the titanium dioxide is grafted and modified by using the aldehyde chondroitin sulfate and the gelatin, when the titanium dioxide is smeared on the skin, the hydroxyl, carboxyl, amino and other groups on the surface of the titanium dioxide can be combined with the groups on the surface of the skin, so that the adhesive force of the titanium dioxide on the surface of the skin is improved, and the sunscreen cream can realize lasting sun protection. In addition, the aldehyde chondroitin sulfate and the gelatin can be used as medical adhesives in the prior art, and are used for realizing rapid adhesion between tissues or between tissues and non-tissues in vivo and playing roles in hemostasis and sealing, so that the irritation to the skin is small, and the biological safety is high.

In addition, on the surface of titanium dioxide, the aldehyde chondroitin sulfate and gelatin are mutually crosslinked, and at a higher temperature, the aldehyde chondroitin sulfate and the gelatin tend to be combined with skin surface groups in a covalent bond and non-covalent bond mode, so that better adhesion is provided; when the temperature is reduced, more Schiff base bonds and hydrogen bonds tend to be formed between the aldehyde chondroitin sulfate and the gelatin, the groups combined with the surface of the skin are reduced, and the adhesive force on the skin is reduced, so that the titanium dioxide can be effectively removed only by contacting a large amount of cold water (20 ℃ or below) when the skin is cleaned, and the titanium dioxide is prevented from remaining on the skin.

Preferably, the chemical sunscreen agents include UVB sunscreen agents and UVA sunscreen agents; the UVB sunscreen comprises at least one of octocrylene, phenylbenzimidazole sulfonic acid, ethylhexyl triazone, and ethylhexyl salicylate; the UVA sunscreen comprises at least one of butyl methoxydibenzoylmethane and bis-ethylhexyloxyphenol methoxyphenyl triazine.

Preferably, the emulsifier comprises at least one of sorbitan sesquioleate, sorbitan stearate, polyhydroxystearic acid, and cetearyl glucoside; the thickening agent comprises at least one of carbomer, tapioca starch and methyl methacrylate cross-linked polymer; the emollient comprises at least one of batyl alcohol, caprylic/capric triglyceride, and squalane; the humectant includes at least one of 1, 2-hexanediol, panthenol, betaine, and sodium hyaluronate.

Preferably, the preparation method of the titanium dioxide @ aldehyde chondroitin sulfate/gelatin comprises the following steps:

(A) dropwise adding a sodium periodate solution into a chondroitin sulfate solution while stirring at a temperature of 25-35 ℃ in a dark place, continuously reacting for 3.5-4.5 hours at a temperature of 25-35 ℃ after dropwise adding, adding ethylene glycol to terminate the reaction, and dialyzing to remove the solvent to obtain the aldehyde chondroitin sulfate.

(B) Adding titanium dioxide into an ethanol water solution, performing ultrasonic dispersion uniformly, then adding dimethyl dimethoxysilane, quaternary ammonium salt-52 and solanesol, mixing uniformly, adjusting the pH to 4-5, reacting at 75-85 ℃ for 2.5-3.5 h, and sequentially centrifuging, washing and drying to obtain the cation modified titanium dioxide.

(C) Adding cation modified titanium dioxide into water, uniformly dispersing by ultrasonic, then adding aldehyde chondroitin sulfate and gelatin, heating to fully dissolve, stirring for 2-3 h at 40-50 ℃, and sequentially centrifuging, washing and drying to obtain titanium dioxide @ aldehyde chondroitin sulfate/gelatin.

In the step (A), chondroitin sulfate reacts with sodium periodate, and partial hydroxyl is oxidized into aldehyde group, so that Schiff base bond can be formed between the chondroitin sulfate and gelatin; in the step (B), the dimethyl dimethoxysilane is hydrolyzed to form silicon hydroxyl, dehydration condensation reaction is carried out among the silicon hydroxyl, simultaneously, the silicon hydroxyl reacts with hydroxyl on the surface of the titanium dioxide and hydroxyl in the quaternary ammonium salt-52, so that a positively charged polysiloxane crosslinking network is grafted on the surface of the titanium dioxide, and the solanesol can be grafted to the polysiloxane crosslinking network by utilizing the reaction of the hydroxyl in the titanium dioxide and the silicon hydroxyl; in the step (C), the aldehyde chondroitin sulfate has negative charges and can be combined to a polysiloxane cross-linked network with positive charges through electrostatic attraction, and meanwhile, the gelatin can be combined with the aldehyde chondroitin sulfate through Schiff base bonds and hydrogen bonds, so that grafting of the aldehyde chondroitin sulfate/gelatin cross-linked network on the surface of titanium dioxide is realized.

In the step (B), the purpose of grafting solanesol is: the solanesol can absorb ultraviolet radiation, remove free radicals and inhibit the activity of tyrosinase, so that the sun-screening effect of the sun-screening cream can be improved; in addition, the hydroxyl free radicals generated after the titanium dioxide absorbs ultraviolet light can be removed by grafting the hydroxyl free radicals in a polysiloxane cross-linked network between the titanium dioxide and the aldehyde chondroitin sulfate/gelatin, so that the aldehyde chondroitin sulfate and the gelatin are prevented from being degraded under the action of the ultraviolet light and the titanium dioxide to cause the falling of the titanium dioxide.

Preferably, in the step (A), the concentrations of the chondroitin sulfate solution and the sodium periodate solution are respectively 9-13 wt% and 3.5-5.5 wt%; the volume ratio of the chondroitin sulfate solution to the sodium periodate solution is 8-10: 1.

Preferably, in the step (B), the mass-to-volume ratio of the titanium dioxide to the dimethyl dimethoxy silane to the ethanol aqueous solution is 1g: 2-3 g: 5-10 mL.

Preferably, in the step (B), the mass ratio of the titanium dioxide to the quaternary ammonium salt-52 is 1: 0.6-0.8; the mass ratio of the titanium dioxide to the solanesol is 1: 0.3-0.5.

Preferably, in the step (C), the mass-to-volume ratio of the cation modified titanium dioxide, the aldehyde chondroitin sulfate, the gelatin and the water is 1g: 0.3-0.5 g: 0.35-0.45 g: 20-25 mL.

Preferably, in the step (a), the titanium dioxide is added into an ethanol water solution after being subjected to ball milling treatment; the specific process of the high-energy ball milling treatment is as follows: placing titanium dioxide in a ball mill, and ball-milling for 1-3 h at the temperature of 100-200 ℃ and the rotation speed of the ball mill of 300-500 r/min.

Ball milling is often used for material comminution, and in the present invention is used as an activation process, where the material builds up a large amount of mechanical energy during high speed grinding and impact. In the invention, after the colorant is acted by the mechanical force of the high-energy ball mill, the hydroxyl on the surface of the colorant is activated from the original dormant state, so that the colorant has higher reactivity and is beneficial to the subsequent reaction.

A method of making the sunscreen comprising the steps of:

(1) uniformly mixing a chemical sun-screening agent, a softening agent and an emulsifying agent to obtain a phase A;

(2) adding humectant into water, and dissolving to obtain phase B;

(3) and mixing the phase A and the phase B, homogenizing and emulsifying, adding titanium dioxide @ formylated chondroitin sulfate/gelatin, uniformly dispersing, adding a thickening agent, and uniformly mixing to prepare the long-acting and easily-cleaned sunscreen cream.

Compared with the prior art, the invention has the following advantages:

(1) by grafting the aldehyde chondroitin sulfate and the gelatin on the surface of the titanium dioxide, the adhesive force of the titanium dioxide on the surface of skin can be improved, so that the sun-screening time of the sun-screening cream is prolonged, and the titanium dioxide can be removed by contacting a large amount of cold water during face washing;

(2) solanesol is grafted in a polysiloxane cross-linked network between titanium dioxide and the aldehyde chondroitin sulfate/gelatin, so that the aldehyde chondroitin sulfate and the gelatin can be prevented from being degraded after the titanium dioxide absorbs ultraviolet light, and the sun-proof time is prolonged.

Detailed Description

The present invention will be further described with reference to the following examples. The following examples are intended only to illustrate the invention in detail and are not intended to limit the scope of the invention in any way.

Example 1

A long-acting and easy-to-clean sunscreen cream comprises the following components in percentage by mass: 15% of titanium dioxide @ formylated chondroitin sulfate/gelatin, 3% of octocrylene, 1% of ethylhexyl triazone, 3% of butyl methoxy dibenzoylmethane, 3% of sorbitan sesquioleate, 0.5% of methyl methacrylate cross-linked polymer, 1.5% of batyl alcohol, 1.5% of caprylic/capric triglyceride, 1.5% of panthenol, 2.5% of betaine, 6% of sodium hyaluronate and the balance of water.

The preparation method of the titanium dioxide @ aldehyde chondroitin sulfate/gelatin comprises the following steps:

(A) placing titanium dioxide in a ball mill, and carrying out ball milling for 3h under the conditions that the temperature is 100 ℃ and the rotating speed of the ball mill is 500r/min to obtain pretreated titanium dioxide;

(B) dropwise adding 5.5 wt% sodium periodate solution into 9 wt% chondroitin sulfate solution while stirring at a temperature of 25 ℃ in a dark place, wherein the volume ratio of the chondroitin sulfate solution to the sodium periodate solution is 10:1, continuously reacting for 4.5 hours at 25 ℃ after dropwise adding, adding ethylene glycol to terminate the reaction, and dialyzing to remove the solvent to obtain aldehyde chondroitin sulfate;

(C) adding pretreated titanium dioxide into an ethanol water solution, performing ultrasonic dispersion uniformly, then adding dimethyl dimethoxy silane, quaternary ammonium salt-52 and solanesol, wherein the mass-volume ratio of the pretreated titanium dioxide to the dimethyl dimethoxy silane to the quaternary ammonium salt-52 to the solanesol to the ethanol water solution is 1g:2g:0.6g:0.3g:5mL, after uniform mixing, adjusting the pH value to 5, reacting for 2.5h at 85 ℃, and sequentially performing centrifugation, washing and drying to obtain cation modified titanium dioxide;

(D) adding cation modified titanium dioxide into water, uniformly dispersing by ultrasonic, then adding aldehyde chondroitin sulfate and gelatin, wherein the mass volume ratio of the cation modified titanium dioxide to the aldehyde chondroitin sulfate to the gelatin to the water is 1g:0.3g:0.35g:20mL, heating to fully dissolve, stirring for 3 hours at 40 ℃, and sequentially centrifuging, washing and drying to obtain the titanium dioxide @ aldehyde chondroitin sulfate/gelatin.

A method of making the sunscreen comprising the steps of:

(1) uniformly mixing octocrylene, ethylhexyl triazone, butyl methoxy dibenzoyl methane, batyl alcohol, caprylic/capric triglyceride and sorbitan sesquioleate to obtain phase A;

(2) adding panthenol, betaine and sodium hyaluronate into water, and dissolving to obtain phase B;

(3) and mixing the phase A and the phase B, homogenizing and emulsifying, adding titanium dioxide @ formylated chondroitin sulfate/gelatin, dispersing uniformly, adding a methyl methacrylate cross-linked polymer, and mixing uniformly to prepare the long-acting and easily-cleaned sunscreen cream.

Example 2

A long-acting and easy-to-clean sunscreen cream comprises the following components in percentage by mass: 18% of titanium dioxide @ formylated chondroitin sulfate/gelatin, 0.6% of phenylbenzimidazole sulfonic acid, 1% of ethylhexyl salicylate, 1.9% of bis-ethylhexyloxyphenol methoxyphenyl triazine, 4% of polyhydroxystearic acid, 0.6% of tapioca starch, 2.5% of caprylic/capric triglyceride, 4% of squalane, 1, 2-hexanediol, 1% of betaine, 3.5% of sodium hyaluronate, and the balance of water.

The preparation method of the titanium dioxide @ aldehyde chondroitin sulfate/gelatin comprises the following steps:

(A) placing titanium dioxide in a ball mill, and carrying out ball milling for 2h under the conditions that the temperature is 150 ℃ and the rotating speed of the ball mill is 400r/min to obtain pretreated titanium dioxide;

(B) dropwise adding 4.5 wt% sodium periodate solution into 11 wt% chondroitin sulfate solution while stirring at a dark place and a temperature of 30 ℃, wherein the volume ratio of the chondroitin sulfate solution to the sodium periodate solution is 9:1, continuing to react for 4 hours at a temperature of 30 ℃ after the dropwise addition is finished, adding ethylene glycol to terminate the reaction, and dialyzing to remove the solvent to obtain aldehyde chondroitin sulfate;

(C) adding pretreated titanium dioxide into an ethanol water solution, performing ultrasonic dispersion uniformly, then adding dimethyl dimethoxy silane, quaternary ammonium salt-52 and solanesol, wherein the mass-volume ratio of the pretreated titanium dioxide to the dimethyl dimethoxy silane to the quaternary ammonium salt-52 to the solanesol to the ethanol water solution is 1g:2.5g:0.7g:0.4g:8mL, mixing uniformly, adjusting the pH value to 4.5, reacting at 80 ℃ for 3h, and sequentially performing centrifugation, washing and drying to obtain cation modified titanium dioxide;

(D) adding cation modified titanium dioxide into water, uniformly dispersing by ultrasonic, then adding aldehyde chondroitin sulfate and gelatin, wherein the mass volume ratio of the cation modified titanium dioxide to the aldehyde chondroitin sulfate to the gelatin to the water is 1g:0.4g:0.4g:25mL, heating to fully dissolve, stirring for 2.5 hours at 45 ℃, and sequentially centrifuging, washing and drying to obtain titanium dioxide @ aldehyde chondroitin sulfate/gelatin.

A method of making the sunscreen comprising the steps of:

(1) uniformly mixing phenyl benzimidazole sulfonic acid, ethylhexyl salicylate, bis-ethylhexyloxyphenol methoxyphenyl triazine, caprylic/capric triglyceride, squalane and polyhydroxystearic acid to prepare a phase A;

(2) adding 1, 2-hexanediol, betaine and sodium hyaluronate into water, and fully dissolving to obtain phase B;

(3) and mixing the phase A and the phase B, homogenizing and emulsifying, adding titanium dioxide @ formylated chondroitin sulfate/gelatin, dispersing uniformly, adding cassava starch, and mixing uniformly to prepare the long-acting and easily-cleaned sunscreen cream.

Example 3

A long-acting and easy-to-clean sunscreen cream comprises the following components in percentage by mass: titanium dioxide @ formylated chondroitin sulfate/gelatin 20%, cetearyl glucoside 5%, carbomer 0.8%, batyl alcohol 4%, caprylic/capric triglyceride 2.6%, squalane 3.4%, panthenol 1.5%, betaine 3.5%, and the balance water.

The preparation method of the titanium dioxide @ aldehyde chondroitin sulfate/gelatin comprises the following steps:

(A) placing titanium dioxide in a ball mill, and carrying out ball milling for 1h under the conditions that the temperature is 200 ℃ and the rotating speed of the ball mill is 300r/min to obtain pretreated titanium dioxide;

(B) dropwise adding 3.5 wt% sodium periodate solution into 13 wt% chondroitin sulfate solution while stirring at a temperature of 35 ℃ in a dark place, wherein the volume ratio of the chondroitin sulfate solution to the sodium periodate solution is 8:1, continuing to react for 3.5 hours at 35 ℃ after the dropwise addition is finished, adding ethylene glycol to terminate the reaction, and dialyzing to remove the solvent to obtain aldehyde-based chondroitin sulfate;

(C) adding pretreated titanium dioxide into an ethanol water solution, performing ultrasonic dispersion uniformly, then adding dimethyl dimethoxy silane, quaternary ammonium salt-52 and solanesol, wherein the mass-volume ratio of the pretreated titanium dioxide to the dimethyl dimethoxy silane to the quaternary ammonium salt-52 to the solanesol to the ethanol water solution is 1g to 3g to 0.8g to 0.5g to 10mL, mixing uniformly, adjusting the pH value to 4, reacting for 3.5h at 75 ℃, and sequentially performing centrifugation, washing and drying to obtain cation modified titanium dioxide;

(D) adding cation modified titanium dioxide into water, uniformly dispersing by ultrasonic, then adding aldehyde chondroitin sulfate and gelatin, wherein the mass volume ratio of the cation modified titanium dioxide to the aldehyde chondroitin sulfate to the gelatin to the water is 1g:0.5g:0.45g:25mL, heating to fully dissolve, stirring for 2 hours at 50 ℃, and sequentially centrifuging, washing and drying to obtain the titanium dioxide @ aldehyde chondroitin sulfate/gelatin.

A method of making the sunscreen comprising the steps of:

(1) mixing batyl alcohol, caprylic/capric triglyceride, squalane and cetearyl glucoside uniformly to obtain phase A;

(2) adding panthenol and betaine into water, and dissolving to obtain phase B;

(3) and mixing the phase A and the phase B, homogenizing and emulsifying, adding titanium dioxide @ formylated chondroitin sulfate/gelatin, dispersing uniformly, adding carbomer, and mixing uniformly to obtain the long-acting and easily-cleaned sunscreen cream.

Example 4

A long-acting and easy-to-clean sunscreen cream comprises the following components in percentage by mass: 15% of titanium dioxide @ formylated chondroitin sulfate/gelatin, 3% of octocrylene, 1% of ethylhexyl triazone, 3% of butyl methoxy dibenzoylmethane, 3% of sorbitan sesquioleate, 0.5% of methyl methacrylate cross-linked polymer, 1.5% of batyl alcohol, 1.5% of caprylic/capric triglyceride, 1.5% of panthenol, 2.5% of betaine, 6% of sodium hyaluronate and the balance of water.

The preparation method of the titanium dioxide @ aldehyde chondroitin sulfate/gelatin comprises the following steps:

(A) dropwise adding 5.5 wt% sodium periodate solution into 9 wt% chondroitin sulfate solution while stirring at a temperature of 25 ℃ in a dark place, wherein the volume ratio of the chondroitin sulfate solution to the sodium periodate solution is 10:1, continuously reacting for 4.5 hours at 25 ℃ after dropwise adding, adding ethylene glycol to terminate the reaction, and dialyzing to remove the solvent to obtain aldehyde chondroitin sulfate;

(B) adding titanium dioxide into an ethanol water solution, performing ultrasonic dispersion uniformly, then adding dimethyl dimethoxy silane, quaternary ammonium salt-52 and solanesol, wherein the mass volume ratio of the titanium dioxide to the dimethyl dimethoxy silane to the quaternary ammonium salt-52 to the solanesol to the ethanol water solution is 1g to 2g to 0.6g to 0.3g to 5mL, mixing uniformly, adjusting the pH value to 5, reacting at 85 ℃ for 2.5h, and sequentially performing centrifugation, washing and drying to obtain cation modified titanium dioxide;

(C) adding cation modified titanium dioxide into water, uniformly dispersing by ultrasonic, then adding aldehyde chondroitin sulfate and gelatin, wherein the mass volume ratio of the cation modified titanium dioxide to the aldehyde chondroitin sulfate to the gelatin to the water is 1g:0.3g:0.35g:20mL, heating to fully dissolve, stirring for 3 hours at 40 ℃, and sequentially centrifuging, washing and drying to obtain the titanium dioxide @ aldehyde chondroitin sulfate/gelatin.

A method of making the sunscreen comprising the steps of:

(1) uniformly mixing octocrylene, ethylhexyl triazone, butyl methoxy dibenzoyl methane, batyl alcohol, caprylic/capric triglyceride and sorbitan sesquioleate to obtain phase A;

(2) adding panthenol, betaine and sodium hyaluronate into water, and dissolving to obtain phase B;

(3) and mixing the phase A and the phase B, homogenizing and emulsifying, adding titanium dioxide @ formylated chondroitin sulfate/gelatin, dispersing uniformly, adding a methyl methacrylate cross-linked polymer, and mixing uniformly to prepare the long-acting and easily-cleaned sunscreen cream.

Comparative example 1

A long-acting and easy-to-clean sunscreen cream comprises the following components in percentage by mass: 15% of titanium dioxide, 3% of octocrylene, 1% of ethylhexyl triazone, 3% of butyl methoxy dibenzoyl methane, 3% of sorbitan sesquioleate, 0.5% of methyl methacrylate cross-linked polymer, 1.5% of batyl alcohol, 1.5% of caprylic/capric triglyceride, 1.5% of panthenol, 2.5% of betaine, 6% of sodium hyaluronate and the balance of water.

A method of making the sunscreen comprising the steps of:

(1) uniformly mixing octocrylene, ethylhexyl triazone, butyl methoxy dibenzoyl methane, batyl alcohol, caprylic/capric triglyceride and sorbitan sesquioleate to obtain phase A;

(2) adding panthenol, betaine and sodium hyaluronate into water, and dissolving to obtain phase B;

(3) mixing the phase A and the phase B, homogenizing and emulsifying, adding the methyl methacrylate cross-linked polymer, and uniformly mixing to prepare the long-acting easy-to-clean sunscreen cream.

Comparative example 2

A long-acting and easy-to-clean sunscreen cream comprises the following components in percentage by mass: 15% of titanium dioxide @ formylated chondroitin sulfate, 3% of octocrylene, 1% of ethylhexyl triazone, 3% of butyl methoxy dibenzoylmethane, 3% of sorbitan sesquioleate, 0.5% of methyl methacrylate cross-linked polymer, 1.5% of batyl alcohol, 1.5% of caprylic/capric triglyceride, 1.5% of panthenol, 2.5% of betaine, 6% of sodium hyaluronate and the balance of water.

The preparation method of the titanium dioxide @ aldehyde chondroitin sulfate comprises the following steps:

(A) placing titanium dioxide in a ball mill, and carrying out ball milling for 3h under the conditions that the temperature is 100 ℃ and the rotating speed of the ball mill is 500r/min to obtain pretreated titanium dioxide;

(B) dropwise adding 5.5 wt% sodium periodate solution into 9 wt% chondroitin sulfate solution while stirring at a temperature of 25 ℃ in a dark place, wherein the volume ratio of the chondroitin sulfate solution to the sodium periodate solution is 10:1, continuously reacting for 4.5 hours at 25 ℃ after dropwise adding, adding ethylene glycol to terminate the reaction, and dialyzing to remove the solvent to obtain aldehyde chondroitin sulfate;

(C) adding pretreated titanium dioxide into an ethanol water solution, performing ultrasonic dispersion uniformly, then adding dimethyl dimethoxy silane, quaternary ammonium salt-52 and solanesol, wherein the mass-volume ratio of the pretreated titanium dioxide to the dimethyl dimethoxy silane to the quaternary ammonium salt-52 to the solanesol to the ethanol water solution is 1g:2g:0.6g:0.3g:5mL, after uniform mixing, adjusting the pH value to 5, reacting for 2.5h at 85 ℃, and sequentially performing centrifugation, washing and drying to obtain cation modified titanium dioxide;

(D) adding cation modified titanium dioxide into water, uniformly dispersing by ultrasonic, then adding aldehyde chondroitin sulfate, wherein the mass volume ratio of the cation modified titanium dioxide to the aldehyde chondroitin sulfate to gelatin to water is 1g:0.65g:20mL, heating to fully dissolve, stirring for 3h at 40 ℃, and sequentially centrifuging, washing and drying to obtain the titanium dioxide @ aldehyde chondroitin sulfate.

A method of making the sunscreen comprising the steps of:

(1) uniformly mixing octocrylene, ethylhexyl triazone, butyl methoxy dibenzoyl methane, batyl alcohol, caprylic/capric triglyceride and sorbitan sesquioleate to obtain phase A;

(2) adding panthenol, betaine and sodium hyaluronate into water, and dissolving to obtain phase B;

(3) and mixing the phase A and the phase B, homogenizing and emulsifying, adding titanium dioxide @ formylated chondroitin sulfate, dispersing uniformly, adding a methyl methacrylate cross-linked polymer, and mixing uniformly to prepare the long-acting and easily-cleaned sunscreen cream.

Comparative example 3

A long-acting and easy-to-clean sunscreen cream comprises the following components in percentage by mass: 15% of titanium dioxide @ chondroitin sulfate/gelatin, 3% of octocrylene, 1% of ethylhexyl triazone, 3% of butyl methoxydibenzoylmethane, 3% of sorbitan sesquioleate, 0.5% of methyl methacrylate cross-linked polymer, 1.5% of batyl alcohol, 1.5% of caprylic/capric triglyceride, 1.5% of panthenol, 2.5% of betaine, 6% of sodium hyaluronate and the balance of water.

The preparation method of the titanium dioxide @ chondroitin sulfate/gelatin comprises the following steps:

(A) placing titanium dioxide in a ball mill, and carrying out ball milling for 3h under the conditions that the temperature is 100 ℃ and the rotating speed of the ball mill is 500r/min to obtain pretreated titanium dioxide;

(B) adding pretreated titanium dioxide into an ethanol water solution, performing ultrasonic dispersion uniformly, then adding dimethyl dimethoxy silane, quaternary ammonium salt-52 and solanesol, wherein the mass-volume ratio of the pretreated titanium dioxide to the dimethyl dimethoxy silane to the quaternary ammonium salt-52 to the solanesol to the ethanol water solution is 1g:2g:0.6g:0.3g:5mL, after uniform mixing, adjusting the pH value to 5, reacting for 2.5h at 85 ℃, and sequentially performing centrifugation, washing and drying to obtain cation modified titanium dioxide;

(C) adding cation modified titanium dioxide into water, uniformly dispersing by using ultrasonic waves, then adding chondroitin sulfate and gelatin, wherein the mass volume ratio of the cation modified titanium dioxide to the chondroitin sulfate to the gelatin to the water is 1g:0.3g:0.35g:20mL, heating to fully dissolve, stirring for 3 hours at 40 ℃, and sequentially centrifuging, washing and drying to obtain the titanium dioxide @ chondroitin sulfate/gelatin.

A method of making the sunscreen comprising the steps of:

(1) uniformly mixing octocrylene, ethylhexyl triazone, butyl methoxy dibenzoyl methane, batyl alcohol, caprylic/capric triglyceride and sorbitan sesquioleate to obtain phase A;

(2) adding panthenol, betaine and sodium hyaluronate into water, and dissolving to obtain phase B;

(3) and mixing the phase A and the phase B, homogenizing and emulsifying, adding titanium dioxide @ chondroitin sulfate/gelatin, dispersing uniformly, adding a methyl methacrylate cross-linked polymer, and mixing uniformly to obtain the long-acting and easily-cleaned sunscreen cream.

Comparative example 4

A long-acting and easy-to-clean sunscreen cream comprises the following components in percentage by mass: 15% of titanium dioxide @ formylated chondroitin sulfate/gelatin, 3% of octocrylene, 1% of ethylhexyl triazone, 3% of butyl methoxy dibenzoylmethane, 3% of sorbitan sesquioleate, 0.5% of methyl methacrylate cross-linked polymer, 1.5% of batyl alcohol, 1.5% of caprylic/capric triglyceride, 1.5% of panthenol, 2.5% of betaine, 6% of sodium hyaluronate and the balance of water.

The preparation method of the titanium dioxide @ aldehyde chondroitin sulfate/gelatin comprises the following steps:

(A) placing titanium dioxide in a ball mill, and carrying out ball milling for 3h under the conditions that the temperature is 100 ℃ and the rotating speed of the ball mill is 500r/min to obtain pretreated titanium dioxide;

(B) dropwise adding 5.5 wt% sodium periodate solution into 9 wt% chondroitin sulfate solution while stirring at a temperature of 25 ℃ in a dark place, wherein the volume ratio of the chondroitin sulfate solution to the sodium periodate solution is 10:1, continuously reacting for 4.5 hours at 25 ℃ after dropwise adding, adding ethylene glycol to terminate the reaction, and dialyzing to remove the solvent to obtain aldehyde chondroitin sulfate;

(C) adding pretreated titanium dioxide into an ethanol water solution, performing ultrasonic dispersion uniformly, then adding dimethyl dimethoxy silane and quaternary ammonium salt-52, wherein the mass-volume ratio of the pretreated titanium dioxide to the dimethyl dimethoxy silane to the quaternary ammonium salt-52 to the ethanol water solution is 1g:2g:0.6g:5mL, mixing uniformly, adjusting the pH value to 5, reacting at 85 ℃ for 2.5h, and sequentially performing centrifugation, washing and drying to obtain cation modified titanium dioxide;

(D) adding cation modified titanium dioxide into water, uniformly dispersing by ultrasonic, then adding aldehyde chondroitin sulfate and gelatin, wherein the mass volume ratio of the cation modified titanium dioxide to the aldehyde chondroitin sulfate to the gelatin to the water is 1g:0.3g:0.35g:20mL, heating to fully dissolve, stirring for 3 hours at 40 ℃, and sequentially centrifuging, washing and drying to obtain the titanium dioxide @ aldehyde chondroitin sulfate/gelatin.

A method of making the sunscreen comprising the steps of:

(1) uniformly mixing octocrylene, ethylhexyl triazone, butyl methoxy dibenzoyl methane, batyl alcohol, caprylic/capric triglyceride and sorbitan sesquioleate to obtain phase A;

(2) adding panthenol, betaine and sodium hyaluronate into water, and dissolving to obtain phase B;

(3) and mixing the phase A and the phase B, homogenizing and emulsifying, adding titanium dioxide @ formylated chondroitin sulfate/gelatin, dispersing uniformly, adding a methyl methacrylate cross-linked polymer, and mixing uniformly to prepare the long-acting and easily-cleaned sunscreen cream.

Comparative example 5

A long-acting and easy-to-clean sunscreen cream comprises the following components in percentage by mass: 11.6% of titanium dioxide @ formylated chondroitin sulfate/gelatin, 3.4% of solanesol, 3% of octocrylene, 1% of ethylhexyl triazone, 3% of butyl methoxy dibenzoyl methane, 3% of sorbitan sesquioleate, 0.5% of methyl methacrylate cross-linked polymer, 1.5% of batyl alcohol, 1.5% of caprylic/capric triglyceride, 1.5% of panthenol, 2.5% of betaine, 6% of sodium hyaluronate and the balance of water. 1.3

The preparation method of the titanium dioxide @ aldehyde chondroitin sulfate/gelatin comprises the following steps:

(A) placing titanium dioxide in a ball mill, and carrying out ball milling for 3h under the conditions that the temperature is 100 ℃ and the rotating speed of the ball mill is 500r/min to obtain pretreated titanium dioxide;

(B) dropwise adding 5.5 wt% sodium periodate solution into 9 wt% chondroitin sulfate solution while stirring at a temperature of 25 ℃ in a dark place, wherein the volume ratio of the chondroitin sulfate solution to the sodium periodate solution is 10:1, continuously reacting for 4.5 hours at 25 ℃ after dropwise adding, adding ethylene glycol to terminate the reaction, and dialyzing to remove the solvent to obtain aldehyde chondroitin sulfate;

(C) adding pretreated titanium dioxide into an ethanol water solution, performing ultrasonic dispersion uniformly, then adding dimethyl dimethoxy silane and quaternary ammonium salt-52, wherein the mass-volume ratio of the pretreated titanium dioxide to the dimethyl dimethoxy silane to the quaternary ammonium salt-52 to the ethanol water solution is 1g:2g:0.6g:5mL, mixing uniformly, adjusting the pH value to 5, reacting at 85 ℃ for 2.5h, and sequentially performing centrifugation, washing and drying to obtain cation modified titanium dioxide;

(D) adding cation modified titanium dioxide into water, uniformly dispersing by ultrasonic, then adding aldehyde chondroitin sulfate and gelatin, wherein the mass volume ratio of the cation modified titanium dioxide to the aldehyde chondroitin sulfate to the gelatin to the water is 1g:0.3g:0.35g:20mL, heating to fully dissolve, stirring for 3 hours at 40 ℃, and sequentially centrifuging, washing and drying to obtain the titanium dioxide @ aldehyde chondroitin sulfate/gelatin.

A method of making the sunscreen comprising the steps of:

(1) uniformly mixing octocrylene, ethylhexyl triazone, butyl methoxy dibenzoyl methane, batyl alcohol, caprylic/capric triglyceride and sorbitan sesquioleate to obtain phase A;

(2) adding panthenol, betaine and sodium hyaluronate into water, and dissolving to obtain phase B;

(3) and mixing the phase A and the phase B, homogenizing and emulsifying, adding titanium dioxide @ formylated chondroitin sulfate/gelatin, dispersing uniformly, adding a methyl methacrylate cross-linked polymer, and mixing uniformly to prepare the long-acting and easily-cleaned sunscreen cream.

The SPF value and PFA value of the sunscreen creams of examples 1-4 and comparative examples 1-5 immediately after application, the SPF value and PFA value after 5h application, and the SPF value and PFA value after 20s flushing with cold water of 20 + -2 ℃ and warm water of 35 + -2 ℃ respectively at the same flow rate after application were measured by the method in the technical Specification for safety of cosmetics (2015 edition) in China, and the SPF value reduction rate and PFA value reduction rate after 5h application and 20s flushing with cold water and warm water were calculated, and the results are shown in Table 1.

TABLE 1

The SPF value and the PFA value reduction rate of the sunscreen cream washed by cold water in the embodiments 1 to 4 are both larger than those of the sunscreen cream washed by warm water, which shows that the titanium dioxide @ chondroitin sulfate/gelatin of the present invention has a lower adhesive force on the skin surface at a lower temperature and a higher adhesive force on the skin surface at a higher temperature.

Compared with the comparative example 1, the sunscreen effect and the durability of the sunscreen cream are obviously higher in the example 1 in which the titanium dioxide is modified by adopting the method of the invention than in the comparative example 1, because the hydroxyl, carboxyl, amino and other groups on the surface of the titanium dioxide can be combined with the groups on the surface of the skin when the titanium dioxide is coated on the skin after the titanium dioxide is subjected to graft modification by using the aldehyde chondroitin sulfate and the gelatin, so that the adhesive force of the titanium dioxide on the surface of the skin is improved, and the sunscreen cream has better sunscreen effect and longer sunscreen time.

Compared with example 1, in example 4, in the process of preparing titanium dioxide @ formylated chondroitin sulfate/gelatin, the titanium dioxide is not subjected to ball milling, and the sun-screening effect and durability of the sun-screening cream are obviously lower than those of example 1, because the hydroxyl on the surface of the titanium dioxide is activated from the original dormant state after the titanium dioxide is subjected to the mechanical force of the ball mill, the titanium dioxide has higher reaction activity, so that the subsequent reaction is facilitated, and more formylated chondroitin sulfate, gelatin and solanesol are grafted on the titanium dioxide.

The easy cleaning of the sunscreen of comparative examples 2 and 3 was significantly lower than that of example 1, using titanium dioxide @ formylated chondroitin sulfate in comparative example 2 and titanium dioxide @ chondroitin sulfate/gelatin in comparative example 3 compared to example 1. The aldehyde chondroitin sulfate and the gelatin are mutually crosslinked on the surface of the titanium dioxide, and the two are combined with skin surface groups in a covalent bond and non-covalent bond mode at a higher temperature to provide better adhesive force; when the temperature is reduced, more Schiff base bonds and hydrogen bonds are formed between the aldehyde chondroitin sulfate and the gelatin, the groups combined with the surface of the skin are reduced, and the adhesive force on the skin is reduced, so that the titanium dioxide can be effectively removed by contacting a large amount of cold water.

Compared with the example 1, in the comparative example 4, in the process of preparing titanium dioxide @ formylated chondroitin sulfate/gelatin, solanesol is not added, and the sun-screening effect and the durability of the sun-screening cream are obviously lower than those of the example 1, because the solanesol can absorb ultraviolet radiation, remove free radicals and inhibit the activity of tyrosinase, the sun-screening effect of the sun-screening cream can be improved; and the hydroxyl free radicals generated after the titanium dioxide absorbs ultraviolet light can be removed by grafting the hydroxyl free radicals in a polysiloxane cross-linked network between the titanium dioxide and the aldehyde chondroitin sulfate/gelatin, so that the aldehyde chondroitin sulfate and the gelatin are prevented from being degraded under the action of the ultraviolet light and the titanium dioxide to cause the shedding of the titanium dioxide.

Comparative example 5, in which solanesol was dispersedly added with titanium dioxide @ formylated chondroitin sulfate/gelatin without being grafted to titanium dioxide, showed significantly lower durability of sunscreen than example 1, compared to example 1, because solanesol hardly prevents the formylated chondroitin sulfate and gelatin from contacting hydroxyl radicals generated after the titanium dioxide absorbs uv light when solanesol was dispersedly added with titanium dioxide @ formylated chondroitin sulfate/gelatin.

Although the present invention has been described in detail with reference to the embodiments, it will be understood by those skilled in the art that the embodiments may be modified or changed without departing from the spirit of the present invention within the scope of the appended claims.