CN110613619B - Fullerene-containing biological sunscreen composition and aerosol - Google Patents

Fullerene-containing biological sunscreen composition and aerosol Download PDF

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CN110613619B
CN110613619B CN201910975190.1A CN201910975190A CN110613619B CN 110613619 B CN110613619 B CN 110613619B CN 201910975190 A CN201910975190 A CN 201910975190A CN 110613619 B CN110613619 B CN 110613619B
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fullerene
parts
sunscreen
aerosol
containing biological
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CN110613619A (en
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温俊帆
陈楚光
龚一帆
潘塨芷
张为敬
梁高健
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Zhongshan Tentop Fine Chemical Co ltd
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04Dispersions; Emulsions
    • A61K8/046Aerosols; Foams
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/37Esters of carboxylic acids
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/494Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
    • A61K8/4966Triazines or their condensed derivatives
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/60Sugars; Derivatives thereof
    • A61K8/602Glycosides, e.g. rutin
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89Polysiloxanes
    • A61K8/891Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q15/00Anti-perspirants or body deodorants
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    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • A61Q19/004Aftersun preparations
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • A61Q19/08Anti-ageing preparations

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Abstract

The invention belongs to the technical field of sunscreen and skin care products, and particularly relates to a fullerene-containing biological sunscreen composition and aerosol. The biological sunscreen composition comprises the following preparation raw materials: fullerene, glucosylrutin, p-methoxy isoamyl cinnamate, polysiloxane-15, ethylhexyl triazone, diethylamino hydroxybenzoyl hexyl benzoate and bis-ethylhexyloxyphenol methoxyphenyl triazine. The raw material components of the biological sunscreen composition are green, environment-friendly, safe and harmless, and all bands of UVB, UVA, visible light and IRA can be comprehensively and effectively protected through the cooperation of all the raw materials, so that various skin problems such as skin diseases and skin injuries induced by sunlight can be effectively prevented, and the health and the good life of people can be better guaranteed.

Description

Fullerene-containing biological sunscreen composition and aerosol
Technical Field
The invention belongs to the technical field of sunscreen and skin care products, and particularly relates to a fullerene-containing biological sunscreen composition and aerosol.
Background
With the increasingly thinner ozone layer, the ultraviolet rays reaching the ground are increasing, which has attracted a wide global attention. Ultraviolet rays in sunlight are classified into three types: ultraviolet C (100 to 280nm), ultraviolet B (280 to 320nm), and ultraviolet A (320 to 400 nm). UVC is completely absorbed by the earth's atmosphere, UVB is only partially absorbed by the atmospheric ozone layer, and UVA is not absorbed by the atmosphere. UVB mainly causes cutaneous erythema response, DNA damage and immunosuppression, and UVA mainly causes immunosuppression. Clearly, it is well established that ultraviolet radiation has many adverse effects on human health.
In recent years, the effects of visible and infrared light on the skin have also become more and more interesting. Visible light (400-700 nm) carries less energy, mainly generates free radicals and color deposition to hurt the skin, accelerates skin aging, wherein the blue light wave band (400-500 nm) can cause skin color deposition to increase, and the color deposition induced by the blue light is more stubborn than the color deposition induced by UVB, and red light (500-700 nm) can hardly cause color deposition. The infrared ray has an influence on the skin in a wavelength band of 700-1000 nm (near infrared ray, IRA for short), and the near infrared ray can accelerate skin aging. Therefore, sun protection is important to reduce the damage caused by solar radiation, and the use of sun protection agents is the most common protection measure at present. However, most of the sunscreen products on the market currently only have the efficacy of protecting ultraviolet UVB and UVA, and the sunscreen products capable of completely protecting UVB, UVA, visible light and IRA are rarely seen, so that the development of a sunscreen product having the efficacy of protecting all bands of sunlight is needed.
Sunscreens are classified into chemical absorbers and physical screening agents according to their mechanism of action. Uv chemical absorbers are mostly carbonyl-bound aromatic compounds, and such chemical structures allow molecules to absorb high-energy uv rays and release energy in the form of low-energy rays, thereby preventing uv-induced skin damage. Chemical sunscreens of limited use in cosmetics include camphor, salicylic acids, benzoates, benzophenones, triazines, and the like. Currently, many studies on ultraviolet chemical absorbers have been reported, but no effective absorber or shielding agent has been developed yet for visible light and near infrared rays.
In addition, with the development of society and the increased awareness of sun protection, the characteristics, applications and safety of sun protection agents are also receiving more and more attention. In addition to the wide application of chemical and physical sunscreens in raw materials, some biological agents such as tea polyphenol, polydatin and the like are also researched in the aspect of sunscreen at present, so that the biological sunscreen technology is also an important subject in the field of research on skin protection.
Patent document CN106176566A discloses a cosmetic composition with whitening effect, which contains glucosyl rutin, and indicates that glucosyl rutin has strong absorption effect on ultraviolet rays and super light resistance, and can be added into the composition without adding any chemical sunscreen agent to significantly reduce the stimulation of ultraviolet rays to skin. The fullerene is a closed cage structure consisting of 12 five-membered rings formed by carbon atoms and a certain number of six-membered rings, is the 3 rd allotrope of carbon, and researches show that the fullerene has antioxidant activity, cell protection effect, antibacterial activity and antiviral effect, and is increasingly applied to sunscreen products in recent years. However, no fullerene, glucosyl rutin and ultraviolet chemical absorbent are found to be compounded for protecting the whole wave band of sunlight at present through retrieval.
Disclosure of Invention
In order to fill the blank of the prior art, the invention firstly provides a fullerene-containing biological sunscreen composition, which reduces the dosage of a chemical sunscreen agent through the synergistic effect of the components, has the effect of comprehensively protecting UVB, UVA, visible light and IRA, and effectively prevents various skin problems such as sunlight-induced skin diseases, skin injuries and the like.
The biological sunscreen composition containing fullerene provided by the invention comprises the following preparation raw materials in parts by weight: 0.01 to 0.05 part of fullerene, 0.1 to 0.4 part of glucosyl rutin, 2.0 to 3.0 parts of p-methoxy isoamyl cinnamate, 151.0 to 2.0 parts of polysiloxane, 1.5 to 2.5 parts of ethylhexyl triazone, 2.0 to 3.0 parts of diethylamino hydroxybenzoyl hexyl benzoate and 3.0 to 4.0 parts of bis-ethylhexyloxyphenol methoxyphenyl triazine.
Preferably, the fullerene-containing biological sunscreen composition comprises the following preparation raw materials in parts by weight: 0.02 part of fullerene, 0.25 part of glucosyl rutin, 2.5 parts of p-methoxy isoamyl cinnamate, 151.5 parts of polysiloxane, 2.0 parts of ethylhexyl triazone, 2.5 parts of diethylamino hydroxybenzoyl hexyl benzoate and 3.5 parts of bis-ethylhexyloxyphenol methoxyphenyl triazine.
The invention selects four ultraviolet chemical absorbers of p-methoxy cinnamic acid isoamyl ester, ethylhexyl triazone, diethylamino hydroxybenzoyl hexyl benzoate and bis-ethylhexyloxyphenol methoxyphenyl triazine, and can synergistically generate broad-spectrum strong absorption within the ultraviolet wavelength ranges of UVA and UVB of 280-400 nm; and polysiloxane-15 is a chain structure with large molecular weight, has polymerization and adsorption effects on other sunscreen agent colored groups, and can adsorb sunscreen agents deposited in skin concave seams to play a sunscreen synergy effect. The maximum absorption wavelength region of glucosyl rutin is 430-450 nm, and part of blue light can be absorbed within the wavelength range of blue light; the ethylhexyl triazone and the bis-ethylhexyl phenol methoxyphenyl triazine can also absorb part of visible light, but the product is easy to yellow after absorbing the visible light, and the problem of the product yellowing caused by the visible light absorption of the product can be solved under the compounding of glucosyl rutin. The fullerene has strong oxidation resistance, can quench active oxygen free radicals strongly, and protect the skin from being damaged by free radicals induced by visible light and oxidative stress reaction, and meanwhile, the fullerene and glucosyl rutin are cooperated to inhibit the expression of matrix metalloproteinase-1 induced by near infrared to play a role in resisting photoaging, and the fullerene is cooperated with an ultraviolet chemical absorbent to improve the absorption capacity of ultraviolet rays. In addition, the fullerene has no consumption loss in the process of scavenging free radicals, can stably exist on the surface of the skin, and continuously exerts the capability of scavenging the free radicals, thereby establishing a long-acting biological sun-screening mechanism for quenching active oxygen free radicals, preventing oxidative stress damage of the free radicals and resisting photoaging for the skin.
In order to ensure the stable exertion of the efficacy of the biological sunscreen composition, the invention provides the biological sunscreen aerosol containing fullerene, the aerosol can exert excellent sunlight all-band protection effect, has excellent waterproof and sweat resistance, and is green, safe and environment-friendly in a formula system.
The invention provides a biological sunscreen aerosol containing fullerene, which comprises the following preparation raw materials in percentage by weight: the composition comprises 10-14% of dioctyl carbonate, 3-7% of octyl methicone, 2-4% of squalane, 0.05-0.2% of bisabolol, 0.03-0.08% of hemp seed oil, 17-22% of solvent, 4-7% of film forming agent and 48-52% of propellant.
Preferably, the solvent is isododecane.
Preferably, the film forming agent is at least one of hydrogenated polydimethylsiloxane, polymethyl methacrylate and trimethylsiloxysilicate.
Preferably, the film-forming agent consists of hydrogenated polydimethylsiloxane, polymethyl methacrylate and trimethylsiloxysilicate.
Preferably, the weight ratio of the hydrogenated polydimethylsiloxane to the polymethyl methacrylate to the trimethylsiloxysilicate is (3-5): 5: 1.
Preferably, the propellant is dimethyl ether.
Correspondingly, the invention also provides a preparation method of the fullerene-containing biological sunscreen aerosol, which specifically comprises the following steps:
s1, putting p-methoxy isoamyl cinnamate, polysiloxane-15, ethylhexyl triazone, diethylamino hydroxybenzoyl hexyl benzoate, bis-ethyl hexyloxyphenol methoxyphenyl triazine and dioctyl carbonate into a stirring tank according to the formula amount, heating to 80-83 ℃, and keeping the temperature and stirring uniformly;
s2, cooling naturally under stirring, adding the octyl polymethylsiloxane and the film-forming agent according to the formula amount when the temperature is reduced to 40 ℃, uniformly stirring, then adding the solvent, the glucosyl rutin, the fullerene, the squalane, the bisabolol and the hemp seed oil according to the formula amount, uniformly stirring, sampling, inspecting, and discharging qualified materials;
s3, discharging, canning, sealing, adding a propellant in a formula amount, and inspecting to obtain the fullerene-containing biological sunscreen aerosol.
The fullerene-containing biological sunscreen aerosol takes the composition as a main sunscreen component, and has the effects of relieving, calming, repairing and resisting inflammation on skin by matching with the bisabolol and the hemp seed oil, so that the aims of resisting solar radiation, quenching active oxygen free radicals for a long time, preventing oxidative stress damage of the free radicals, resisting photoaging and repairing after sunburn are fulfilled. Meanwhile, hydrogenated polydimethylsiloxane, polymethyl methacrylate and trimethylsiloxy silicate are selected to be compounded as a film forming agent, and the film forming agent is cooperated with polysiloxane-15 to jointly improve the forming speed and the waterproof and sweat-resistant performance of the sunscreen film.
Therefore, compared with the prior art, the invention has the advantages that:
(1) the raw material components of the biological sun-screening composition containing fullerene belong to the 1-2 green grade of EWG (American environmental group), do not cause harm to marine coral reefs, have extremely high safety coefficient to human bodies and environment, and are a green, environment-friendly, safe and harmless formula system.
(2) The fullerene-containing biological sunscreen composition reduces the use of chemical sunscreen agents, and can effectively protect all bands of UVB, UVA, visible light and IRA, thereby effectively preventing various skin problems such as sunlight-induced skin diseases, skin injuries and the like, and better ensuring the health and the beautiful life of people.
(3) The formula system of the fullerene-containing biological sunscreen aerosol is safe, mild and stable, does not contain alcohol, essence and preservative, has excellent sunlight full-wave-band protection effect and excellent waterproof and sweat-resistant performance, establishes a long-acting biological sunscreen mechanism for quenching active oxygen free radicals, preventing oxidative stress damage of the free radicals, resisting photoaging and repairing after sun exposure for skin, has simple preparation method and stable process, can be industrially produced, is convenient to carry and use, can be popularized and applied, and has good market prospect.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Examples 1 to 4 Fullerene-containing biological sunscreen compositions of the present invention
Examples 1-4 formulations of fullerene containing biological sunscreen compositions are shown in table 1 below.
TABLE 1 EXAMPLES 1 TO 4 formulation of Fullerene-containing biological sunscreen composition
Raw materials Example 1 Example 2 Example 3 Example 4
Fullerene 0.01g 0.05g 0.02g 0.01g
Glucosyl rutin 0.40g 0.10g 0.25g 0.10g
p-methoxy cinnamic acid isoamyl ester 2.0g 3.0g 2.5g 2.0g
Polysiloxane-15 1.0g 2.0g 1.5g 1.0g
Ethyl hexyl triazone 2.5g 1.5g 2.0g 1.5g
Diethylamino hydroxybenzoyl hexyl benzoate 2.0g 3.0g 2.5g 2.0g
Bis-ethylhexyloxyphenol methoxyphenyl triazine 4.0g 3.0g 3.5g 3.0g
Examples 5 to 8 Fullerene-containing biological sunscreen aerosol of the present invention
Examples 5-8 formulations of fullerene containing bio-sunscreen aerosols are shown in table 2 below.
TABLE 2 EXAMPLES 5-8 Fullerene-containing biological sunscreen aerosol formulations
Figure BDA0002233373230000041
Figure BDA0002233373230000051
Examples 5 to 8 preparation methods of fullerene-containing bio-sunscreen aerosols are as follows:
s1, putting p-methoxy isoamyl cinnamate, polysiloxane-15, ethylhexyl triazone, diethylamino hydroxybenzoyl hexyl benzoate, bis-ethyl hexyloxyphenol methoxyphenyl triazine and dioctyl carbonate into a stirring tank according to the formula amount, heating to 80-83 ℃, and keeping the temperature and stirring uniformly;
s2, cooling naturally under stirring, adding octyl polymethylsiloxane, hydrogenated polydimethylsiloxane, polymethyl methacrylate and trimethylsiloxy silicate according to the formula when the temperature is reduced to 40 ℃, stirring uniformly, adding isododecane, glucosyl rutin, fullerene, squalane, bisabolol and hemp seed oil according to the formula, stirring uniformly, sampling, inspecting, and discharging qualified materials;
s3, discharging, canning, sealing, adding dimethyl ether according to the formula amount, and inspecting to obtain the fullerene-containing biological sunscreen aerosol.
Comparative example 1
The comparative example differs from example 7 only in that: the product does not contain fullerene, glucosylrutin and polysiloxane-15, correspondingly increases the content of p-methoxy isoamyl cinnamate to 3.0g, the content of ethylhexyl triazone to 2.27g, the content of diethylamino hydroxybenzoyl hexyl benzoate to 3.0g and the content of bis-ethylhexyloxyphenol methoxyphenyl triazine to 4.0g
Comparative example 2
The comparative example differs from example 7 only in that: without polysiloxane-15, the content of p-methoxycinnamic acid isoamyl ester was correspondingly increased to 3.0g, the content of diethylamino hydroxybenzoyl hexyl benzoate was increased to 3.0g, and the content of bis-ethylhexyloxyphenol methoxyphenyl triazine was increased to 4.0 g.
Comparative example 3
The comparative example differs from example 7 only in that: does not contain fullerene, and correspondingly increases the content of glucosyl rutin to 0.27 g.
Comparative example 4
The comparative example differs from example 7 only in that: does not contain glucosyl rutin, and correspondingly increases the content of fullerene to 0.27 g.
Test example I, physicochemical indexes and stability of the fullerene-containing biological sunscreen composition and aerosol of the present invention
The results of the physical and chemical indexes and stability of the biological sunscreen aerosols of examples 5-8 are shown in table 3 below.
Table 3 detection results of physical and chemical indexes and stability of biological sunscreen aerosol in examples 5-8
Item Examples 5 to 8 biological sunscreen Aerosol
Appearance of liquid agent Light yellow transparent liquid
Product appearance In the form of fine mist when sprayed
Discharge Rate (25 ℃ C.) ≥95%
Internal pressure (25 ℃ C.) 0.40~0.60MPa
Heat resistance The temperature is 40 +/-2 ℃, the temperature is 4 hours, and the normal use can be realized after the temperature is restored to the room temperature (25℃)
Cold resistance The temperature is between minus 5 ℃ plus or minus 2 ℃, the temperature is 24 hours, and the normal use can be realized after the temperature is restored to the room temperature (25℃)
And (II) spraying the aerosol of the embodiments 5-8 and the aerosol of the comparative example 4 into transparent glass cups to enable the liquid to uniformly cover the cup walls, observing that the liquid is light yellow, then placing the glass cups under natural illumination for 10 hours (7 to 17 points), wherein compared with the liquid before illumination, the liquid color of the aerosol of the embodiments 5-8 is still light yellow without obvious change, while the liquid color of the aerosol of the comparative example 4 is deepened and becomes dark yellow, which prompts that the glucosyl rutin in the invention can solve the problem of yellowing of products caused by the absorption of visible light by ethylhexyl triazone and bis-ethylhexyl phenol methoxyphenyl triazine.
Test example II, the detection of the protective efficacy of the fullerene-containing biological sunscreen composition and the aerosol of the present invention
Measurement of SPF value and PFA value
The products of examples 5 to 8 and comparative examples 1 to 3 were tested for their sunscreen effect according to the method for measuring sunscreen factor (SPF value) of sunscreen cosmetics and the method for measuring long-wave ultraviolet protection index (PFA value) of sunscreen cosmetics in the technical standards for safety of cosmetics (2015 edition), and the test results are shown in table 4 below.
Wherein 2 < PFA <4 is PA +, 4 < PFA <8 is PA + +, 8 < PFA < 16 is PA + + +, and PFA >16 is PA + + +.
TABLE 4 measurement results of SPF value and PFA value
Aerosol formulation SPF value PFA value UVA protection class
Example 5 51.7 16.4 PA++++
Example 6 53.0 16.7 PA++++
Example 7 53.8 17.2 PA++++
Example 8 50.5 16.0 PA++++
Comparative example 1 26.3 7.9 PA++
Comparative example 2 33.4 10.5 PA+++
Comparative example 3 37.8 12.1 PA+++
As can be seen from table 4 above, the biological sunscreen composition and the aerosol of the present invention have a UVB sunscreen value of SPF50+, and a UVA sunscreen value of PA + + +, which have significant protection against uv UVB and UVA. However, the comparative examples 1 to 3 lack certain components, and the SPF value and the PFA value of the biological sunscreen composition and the aerosol are reduced to different degrees, which indicates that the components of the biological sunscreen composition and the aerosol are synergistic to effectively improve the resistance of the skin to ultraviolet UVB and UVA.
(II) measurement of antioxidant Capacity
The oxidation resistance of the compositions of examples 1 to 4 and comparative example 3 and the product of example 7 was tested according to the following test methods, wherein the compositions of examples 1 to 4 and comparative example 3 were prepared into a solution with a mass concentration of 5% as a sample, and the product of example 7 was prepared into a solution with a mass concentration of 50% using a stock solution as a sample. The test results are shown in table 5 below.
(1)ABTS+Determination of clearance
Adding 2mL of 7.4mmol/L ABTS solution and 1mL of sample into a test tube, mixing uniformly, standing at room temperature for 10min, measuring the absorbance Ai at 734nm, repeating for 3 times, taking the average value, and calculating the clearance rate, wherein the formula is as follows: ABTS+Clearance ═ 1-Ai/A0) × 100% where Ai is the absorbance value of the added sample, A0The absorbance value of the sample was replaced with ethanol.
(2) Determination of OH clearance
Referring to the Fenton reaction system, 2mL of 0.02mol/L ethanol salicylic acid solution and 0.009mol/L Fe solution were added to the test tube2SO42mL of solution, 2mL of sample and 0.088mol/L of H2O22mL of the solution was reacted at 37 ℃ for 30min, and the absorbance Ai was measured at 517nm, and the measurement was repeated 3 times, and the clearance was calculated by taking the average value, as follows: OH clearance ═ 1- (Ai-Aj)/A0]× 100% where Ai is the absorbance value of the sample, Aj is the absorbance value of the sample without salicylic acid, A0Absorbance values without sample addition.
(3)·O2 -Determination of clearance
Adding 5mL of 0.05mol/L Tris-HCl solution, 2mL of sample and 0.5mL of 0.005mol/L pyrogallol solution into a test tube, reacting for 4min at room temperature, stopping the reaction by using HCl, measuring the absorbance Ai at 320nm, repeating for 3 times, taking an average value, and calculating the clearance rate by the following formula: o2 -Clearance rate is [1- (Ai-Aj)/A0]× 100% where Ai is the absorbance value of the added sample, Aj is the absorbance value of the pyrogallol replaced by hydrochloric acid, A0The absorbance value of the sample was replaced with pure water.
TABLE 5 test results for antioxidant Performance
Item ABTS+Clearance rate OH clearance ·O2 -Clearance rate
Example 1 92.2% 84.0% 90.8%
Example 2 96.4% 83.8% 92.7%
Example 3 96.0% 83.5% 92.6%
Example 4 90.5% 77.3% 87.9%
Example 7 96.2% 85.1% 93.4%
Comparative example 3 10.5% 8.2% 5.6%
From table 5 above, it can be seen that: the biological sunscreen composition and the aerosol of the invention have ABTS+-,. OH and. O2 -The scavenging rate of free radicals is high, and the antioxidant effect is remarkable. The composition of comparative example 3, which does not contain fullerene, has a significantly reduced oxidation resistance. The biological sunscreen composition and the aerosol provided by the invention are strong in oxidation resistance, can quench active oxygen free radicals strongly, and protect the skin from being damaged by free radicals induced by visible light and oxidative stress reaction, so that the damage of the visible light to the skin is prevented.
(III) determination of the Effect on matrix Metalloproteinase-1 (MMP-1)
(1) Test materials: adult dermal fibroblasts (purchased from Guangzhou Yuanjing Biotechnology Limited), were cultured after revival, and 4 days were taken according to the growth curve for subsequent experiments. Compositions of examples 1-3, comparative example 3 and comparative example 4.
(2) The grouping and processing method of the test are shown in the following Table 6, wherein 8-methoxypsoralen is abbreviated as 8-MOP, the wavelength of IRA irradiation is 720-1200 nm, and the light intensity is 360J/cm2
TABLE 6 test grouping and processing methods
Figure BDA0002233373230000091
(3) Test items and results: randomly selecting 5 slices in each group, randomly selecting 4 visual fields in each slice, and performing image analysis by using an image analyzer in a blind method under 400 times, and detecting: absorbance (reflecting the depth of staining); ② the ratio of positive reaction region to negative reaction region (PN-area). The test results are shown in table 7 below.
Immunohistochemical staining results show that positive MMP-1 products are present in cytoplasm of each component fibroblast, and the positive MMP-1 products are brown yellow particles, are expressed most strongly in 60 hours, then gradually weaken and gradually recover in 84 hours.
TABLE 760 h respective component fibroblast MMP-1 immunohistochemical staining Absorbance and PN-area (. about.P <0.05)
Group of Absorbance of the solution PN-area
Normal control group 0.052±0.030* 9.01±1.34*
Positive control group 0.198±0.036 92.35±17.60
EXAMPLE 1 group 0.109±0.062* 41.27±9.40*
EXAMPLE 2 group 0.114±0.069* 44.95±10.58*
EXAMPLE 3 group 0.105±0.050* 38.13±9.08*
Comparative example 3 group 0.157±0.082 81.08±10.40
Comparative example 4 group 0.179±0.079 85.33±11.64
As can be seen from the above Table 7, the biological sunscreen composition of the present invention has an obvious inhibitory effect on the expression of near-infrared induced human dermal fibroblast MMP-1, suggesting that the biological sunscreen composition of the present invention has the efficacy of anti-photoaging. While comparative example 3 and comparative example 4 lack fullerene and glucosylrutin, respectively, and accordingly have a reduced inhibitory effect on the expression of MMP-1, suggesting that fullerene and glucosylrutin synergistically enhance the anti-photoaging efficacy in the present invention.
Test example III test of Water and sweat resistance of Fullerene-containing biological sunscreen Aerosol
The waterproof effects of the products of examples 5 to 8 and comparative example 2 were tested according to the method for measuring the waterproof performance of sunscreen cosmetics in technical safety standards for cosmetics (2015 edition), and the test results are shown in table 8 below.
TABLE 8 measurement results of Water repellency
Aerosol formulation SPF value SPF value after 100min test
Example 5 51.7 46.7
Example 6 53.0 49.6
Example 7 53.8 50.7
Example 8 50.5 46.0
Comparative example 2 33.4 17.3
From table 8 above, it can be seen that: after the fullerene-containing biological sunscreen aerosol is subjected to a water resistance test for 100min, the SPF value can still be maintained to be more than 46, and the fullerene-containing biological sunscreen aerosol has excellent water resistance and sweat resistance and is suitable for outdoor activities such as summer or swimming. The aerosol of comparative example 2 does not contain polysiloxane-15, and the SPF value is obviously reduced after 100min test, which indicates that the special molecular structure of polysiloxane-15 can be cooperated with hydrogenated polydimethylsiloxane, polymethyl methacrylate and trimethylsiloxysilicate to improve the waterproof and sweat resistance of the sun-proof film.
Test example four, safety test of fullerene-containing bio-sunscreen aerosol of the present invention
The safety of the fullerene-containing biological sunscreen aerosol of examples 5 to 8 was evaluated by referring to the human skin patch test in the technical standards for cosmetic safety (2015 th edition).
The experimental results are as follows: each group of subjects pass the repetitive open smearing test of the aerosol of the embodiment 5-8, and the skin reaction is observed after 7 days, wherein 0 case has adverse skin reaction (negative reaction), which indicates that the biological sunscreen aerosol is safe, mild and non-irritant.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.

Claims (4)

1. A biological sunscreen aerosol containing fullerene is characterized by being prepared from the following raw materials in percentage by weight: 10-14% of fullerene-containing biological sunscreen composition, 3-7% of dioctyl carbonate, 3-7% of octyl polymethylsiloxane, 2-4% of squalane, 0.05-0.2% of bisabolol, 0.03-0.08% of hemp seed oil, 17-22% of solvent, 4-7% of film forming agent and 48-52% of propellant;
the fullerene-containing biological sunscreen composition is prepared from the following raw materials in parts by weight: 0.01 to 0.05 part of fullerene, 0.1 to 0.4 part of glucosyl rutin, 2.0 to 3.0 parts of p-methoxy isoamyl cinnamate, 151.0 to 2.0 parts of polysiloxane, 1.5 to 2.5 parts of ethylhexyl triazone, 2.0 to 3.0 parts of diethylamino hydroxybenzoyl hexyl benzoate and 3.0 to 4.0 parts of bis-ethylhexyloxyphenol methoxyphenyl triazine;
the solvent is isododecane;
the film forming agent consists of hydrogenated polydimethylsiloxane, polymethyl methacrylate and trimethylsiloxy silicate;
the propellant is dimethyl ether.
2. The fullerene-containing biological sunscreen aerosol according to claim 1, wherein the fullerene-containing biological sunscreen composition is prepared from the following raw materials in parts by weight: 0.02 part of fullerene, 0.25 part of glucosyl rutin, 2.5 parts of p-methoxy isoamyl cinnamate, 151.5 parts of polysiloxane, 2.0 parts of ethylhexyl triazone, 2.5 parts of diethylamino hydroxybenzoyl hexyl benzoate and 3.5 parts of bis-ethylhexyloxyphenol methoxyphenyl triazine.
3. The fullerene-containing bio-sunscreen aerosol according to claim 1, wherein the hydrogenated polydimethylsiloxane, the polymethyl methacrylate and the trimethylsiloxysilicate are present in a weight ratio of (3-5): 5: 1.
4. A method for preparing a fullerene-containing bio-sunscreen aerosol according to any one of claims 1 to 3, comprising the steps of:
s1, putting p-methoxy isoamyl cinnamate, polysiloxane-15, ethylhexyl triazone, diethylamino hydroxybenzoyl hexyl benzoate, bis-ethyl hexyloxyphenol methoxyphenyl triazine and dioctyl carbonate into a stirring tank according to the formula amount, heating to 80-83 ℃, and keeping the temperature and stirring uniformly;
s2, cooling naturally under stirring, adding the octyl polymethylsiloxane and the film-forming agent according to the formula amount when the temperature is reduced to 40 ℃, uniformly stirring, then adding the solvent, the glucosyl rutin, the fullerene, the squalane, the bisabolol and the hemp seed oil according to the formula amount, uniformly stirring, sampling, inspecting, and discharging qualified materials;
s3, discharging, canning, sealing, adding a propellant in a formula amount, and inspecting to obtain the fullerene-containing biological sunscreen aerosol.
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