CN110251411B - Transparent aqueous sunscreen spray and preparation method thereof - Google Patents

Abstract

The invention discloses a transparent aqueous sunscreen spray and a preparation method thereof. The transparent aqueous agent sunscreen spray comprises the following components in percentage by mass: 0.1-5% of troxerutin, 10-40% of cerium oxide, 0.01-0.05% of coastal cress, 0.01-2.5% of thickening agent, 1-15% of humectant, 1-10% of skin conditioner, 0.01-0.8% of pH regulator, 0.3-1% of preservative and the balance of water. The transparent aqueous sunscreen spray has good ultraviolet absorption capacity, can effectively resist the deterioration or damage to objects/human bodies caused by ultraviolet rays, and has an obvious sunscreen effect. And the system has stable property, can form a transparent and uniform aqueous solution system, and has no obvious character difference and good stability through heat resistance and cold resistance tests.

Description

Transparent aqueous sunscreen spray and preparation method thereof

Technical Field

The invention belongs to the technical field of cosmetics, and particularly relates to a transparent aqueous sunscreen spray and a preparation method thereof.

Background

With the improvement of living standard, more and more people use the sunscreen product every day. Sunscreen sprays are preferred by consumers for their convenience of use. Currently marketed sunscreen sprays are divided into two categories: opaque products and clear aqueous products. Transparent aqueous products are generally added with water-soluble chemical sunscreen agents, opaque products mostly contain chemical sunscreen agents and physical sunscreen agents, titanium dioxide and zinc oxide, the safety of the chemical sunscreen agents is controversial, and the detection of the chemical sunscreen agents in blood after sunscreen cream is used has been reported recently to cause panic of consumers. In 2016, it was reported that the use of chemical sunscreens endangered the marine environment, that oxybenzone and octyl methoxycinnamate blocked the growth of coral larvae, and that oxybenzone was toxic to seven coral species. In the market, a plurality of pure physical sun-screening agent products are also available, in order to pursue sun-screening effect and transparency, the titanium dioxide used for physical sun-screening is nano-scale, the nano-scale titanium dioxide can generate photoactivity under ultraviolet light, and is converted into photocatalyst, so that a large amount of free radicals are generated, strong oxidative destruction is realized, the generated free radicals can seriously threaten the skin, and the skin aging is accelerated.

At present, the difficulty of developing a safe and effective transparent water agent sunscreen spray is very high.

Troxerutin, also known as vitamin P4 and hydroxyethyl rutin, is one of the derivatives of flavonoid rutin, and can be extracted from plants or synthesized by processing rutin. Troxerutin has excellent bioactivity, and can resist thrombosis, erythrocyte and fibrinolysis, inhibit telangiectasia, improve vascular injury, protect endothelial cells, etc., and is used for treating thrombosis.

Chinese patent application publication No. CN 107184441 a discloses a sunscreen composition without chemical sunscreen, which contains physical sunscreen agent nano titanium dioxide and has potential photo-activity.

The Chinese patent application with the publication number of CN 102727400A discloses an application of a composition of flat almond oil and rutin in a sun-screening agent, wherein the flat almond oil and the rutin are oil-soluble, are difficult to be applied to an aqueous system, need solubilization, are easy to precipitate and are opaque.

Disclosure of Invention

The invention aims to provide safe and effective transparent aqueous sunscreen spray and a preparation method thereof aiming at the defects of the prior art.

The invention is realized by the following technical scheme:

a transparent aqueous sunscreen spray comprises the following components in percentage by mass:

the cress is a callus culture filtrate of the cress.

The thickening agent is selected from one or more of hydroxyethyl cellulose, carbomer, acrylic acid (ester)/C10-30 alkanol acrylate cross-linked polymer, xanthan gum and sodium acrylate/sodium acryloyldimethyl taurate copolymer.

The humectant is selected from one or more of glycerol, butanediol, betaine, erythritol, methyl propylene glycol, sodium hyaluronate, panthenol and trehalose.

The skin conditioner is selected from one or more of bisabolol, tocopherol acetate, herba Portulacae extract, Aloe Barbadensis (Aloe Barbadensis) leaf juice, dipotassium glycyrrhizinate, and flos Chrysanthemi Indici (Anthemis NOBILIS) flower water.

The pH regulator is selected from one or more of triethanolamine, potassium hydroxide, arginine and sodium hydroxide.

Preferably, the transparent aqueous agent sunscreen spray comprises the following components in percentage by mass: 0.1-5% of troxerutin, 10-40% of cerium oxide, 0.01-0.05% of a celery coastal callus culture filtrate, 0.01-0.1% of acrylic acid (ester)/C10-30 alkanol acrylate cross-linked polymer, 1-6% of butanediol, 1-4% of betaine, 0.01-0.1% of dipotassium glycyrrhizinate, 1-5% of chamomile flower water, 0.01-0.1% of arginine, 0.01-0.1% of chlorphenesin, 0.01-0.8% of phenoxyethanol and the balance of water.

The invention also provides a preparation method of the transparent aqueous agent sunscreen spray, which comprises the following steps:

s1: adding water, a humectant and a thickening agent into a vacuum emulsifying pot, stirring and heating to 80-85 ℃, fully and uniformly stirring, and keeping the temperature for later use;

s2: cooling to below 40 deg.C, adding skin conditioner, pH regulator, troxerutin, cerium oxide, and Cress, stirring, discharging, and standing; and after the inspection is qualified, filling and packaging to obtain the transparent aqueous agent sunscreen spray.

The preparation method of the transparent aqueous sunscreen spray further comprises a step of adding a preservative, wherein the preservative is added in step S1 or S2.

The Troxerutin is a product of Guangzhou Clinton Biotech, Inc., with the trade name of TeeCare Troxerutin and the name of INCI Troxerutin.

The cerium oxide is commercially available as Aqua Ceria, and the INCI is cerium oxide, colloidal platinum, and water, and is a product of GSI Corcishi.

The described Bin maritima is sold under the trade name CELTOSME Eryngium MARITIMUM, and INCI is called Bin maritima (ERYNGIUM MARITIMUM) callus culture filtrate, and is a product of France Biotech Marine.

Troxerutin can absorb ultraviolet rays with the wavelength of 240-400 nm, can effectively shield the ultraviolet rays, can also inhibit UVB-induced apoptosis of HaCaT cells (human immortalized keratinocytes), and inhibit MAPK signal pathway transduction and transcription factor AP-1, thereby playing a role in resisting photodamage. The cerium oxide can absorb ultraviolet rays with the wavelength of 190-440 nm, inhibit active oxygen products and effectively inhibit photoaging. The Cress maritima is rich in flavonoids and amino acids, and has effects of resisting inflammatory aging, stimulating epidermal regeneration, reconstructing skin and dermis binding layer, and reducing irritation and inflammation caused by illumination.

In the composition, troxerutin, cerium oxide and coastal cress play a remarkable synergistic role, have good ultraviolet absorption capacity, can effectively resist deterioration or damage to objects/human bodies caused by ultraviolet rays, and have an obvious sun-proof effect. And the system compounded by the three components has stable property, can form a transparent and uniform aqueous solution system, and has no obvious character difference and good stability compared with the solution system before the test through the test of heat resistance (40 +/-1) DEG C and cold resistance (5 +/-1) DEG C.

Compared with the prior art, the invention has the following beneficial effects:

(1) the invention discovers for the first time that the coastal cress without the sun-screening effect is combined with troxerutin and cerium oxide, the sun-screening effect of the troxerutin and the cerium oxide can be improved, the SPF value and the PA value are increased, the sun-screening effect of the combination of the troxerutin and the cerium oxide is optimal, the SPF value is 53, the PA value is + + + +, the synergistic effect is obvious, and the sun-screening effect is excellent.

(2) According to the invention, troxerutin, cerium oxide and coastal cress are used in a combined manner as active ingredients, so that the sunscreen lotion has excellent sunscreen performance and stable compounding performance, can form a transparent and uniform aqueous solution system, has no obvious character change through a heat-resistant and cold-resistant test system, and is good in stability.

(3) The transparent aqueous sunscreen spray disclosed by the invention is mild and stable in property, safe and effective, free of skin irritation, simple in preparation method, controllable in conditions and stable in process.

Detailed Description

The following examples are further illustrative of the present invention and are not intended to be limiting thereof. The components of the formulations in the following examples are, unless otherwise specified, conventional commercial products.

Examples 1-3 and comparative examples 1-7 preparation of clear aqueous sunscreen spray

Examples 1-3 and comparative examples 1-7 clear aqueous sunscreen spray comprised of the following components in the mass percent indicated in table 1:

TABLE 1 formulation composition

Preparation procedure for examples 1-3:

s1: adding phase A raw materials (water, butanediol, betaine, chlorphenesin and acrylic acid (ester)/C10-30 alkanol acrylate cross-linked polymer) into a vacuum emulsifying pot, stirring and heating to 80-85 ℃, fully and uniformly stirring, and keeping the temperature for later use;

s2: cooling to below 40 deg.C, adding phase B materials (dipotassium glycyrrhizinate, flos Chrysanthemi Indici (Anthemis NOBILIS) flower water, arginine, phenoxyethanol) and phase C materials (troxerutin, cerium oxide, and Cress maritima callus culture filtrate), stirring, discharging, and standing; and after the inspection is qualified, filling and packaging to obtain the transparent aqueous sunscreen spray.

Comparative examples 1-7 preparation procedure reference examples 1-3.

Test example I, physical and chemical index detection

Physical and chemical indexes of the transparent aqueous sunscreen sprays prepared in examples 1-3 and comparative examples 1-7 of the invention are detected according to QB/T2660, and the results are shown in Table 2.

TABLE 2 results of physical and chemical index measurements

Remarking: the temperature is required to be kept at 40 +/-1 ℃ for 24h, and no obvious character difference exists between the temperature after the temperature is restored to the room temperature and before the test;

the cold resistance requirement is kept at (-5 +/-1) DEG C for 24h, and no obvious character difference exists between the cold resistance and the cold resistance before the test after the cold resistance is restored to the room temperature.

As can be seen from Table 2, the transparent aqueous sunscreen spray prepared in examples 1-3 of the present invention has good physical and chemical properties, stable system, no obvious property difference in the system through heat resistance and cold resistance tests, and good stability. As can be seen from comparative example 7, when zinc oxide was used instead of cerium oxide, the sunscreen spray system was unstable and the solution was layered, and the above results indicate that cerium oxide was well compounded with other components of the sunscreen spray, and the system was promoted to form a transparent and uniform aqueous solution system.

Test example two, application Performance test

Firstly, product safety test:

the transparent aqueous sunscreen spray prepared in examples 1-3 was tested for body patches according to the method described in cosmetic safety specifications 2015.

1. The experimental population is as follows: total 36, 30 women, 6 men, age 21-59, 12 per group, composite subject volunteer enrollment criteria;

2. the test method comprises the following steps: the selection area is not more than 50mm^2，A suitable patch tester having a depth of about 1mm is prepared by applying about 0.020 to 0.025mL of a test substance to a patch tester in a closed patch test format.The patch tester is applied to the curved side of the forearm of the subject, the subject is removed 24 hours later, the skin reaction is observed 0.5 hour, 24 hours and 48 hours after the removal, and the result is recorded according to the skin reaction grading standard in the technical Specification for cosmetic safety 2015.

3. And (3) test results: the 36 subjects scored 0 at 3 observation time points 0.5h, 24h, 48h after removal of the patch (negative response).

Secondly, detecting sun-screening performance:

the experimental method comprises the following steps: the in vitro SPF value measurement adopts an optical principle, namely measuring the ultraviolet absorbance or transmittance of the sunscreen cosmetic to evaluate the sunscreen effect of the sunscreen cosmetic. Can be divided into two types: first, a common ultraviolet spectrophotometer is used to prepare a sunscreen cosmetic into an extremely thin liquid film (thin film method), or to coat or sandwich a quartz plate, and the absorption spectrum or ultraviolet absorption value of the sunscreen cosmetic in the ultraviolet region is measured. Another method is to measure the uv absorbance of a thin layer of sunscreen cosmetic coated on medical breathable tape using an SPF instrument (approved by FDA in the united states) made according to the principle of uv spectrophotometer, which automatically converts to SPF value output. For example, the SPF-290 sun protection factor analyzer is a widely used instrument at home and abroad, and stores early-stage testing data of the human body in europe and america in a computer, and samples of sun protection cosmetics are automatically converted into SPF values to be output after spectral measurement.

1. Measurement of SPF (Sun protection factor):

defining: the ratio of the minimum amount of erythema (MED) required to cause erythema on skin protected by a sunscreen cosmetic to the MED required to cause erythema on unprotected skin is the SPF of the sunscreen cosmetic.

The method comprises the following steps: the sample was measured at 2mg/cm²The amount of (c) was coated on a clear venting tape, followed by drying for 15 minutes and measurement using an SPF290 measuring instrument. SPF values are the average of 3 tests.

2. Determination of PFA (Protection factor of UVA, PFA):

defining: the ratio of the MPPD required to cause darkening of the skin protected by the sunscreen cosmetic to the MPPD required to cause darkening of the unprotected skin is the PFA value of the sunscreen cosmetic.

PA (protection of UVA) reflects the UVA protection rating of the sunscreen product, the PA value being indicated by "+", according to the method described in technical Specification for cosmetic safety 2015.

The results of the experiment are shown in table 3 below:

TABLE 3 sunscreen Performance test results

Group of	SPF	PA	Sunscreen properties	Remarks for note
					Example 1	53	++++	Good taste	Transparent body
Example 2	42	+++	Good taste	Transparent body
					Example 3	43	++++	Good taste	Transparent body
Comparative example 1	1.8	/	Is free of	Transparent body
					Comparative example 2	8.7	/	Difference (D)	Transparent body
Comparative example 3	28.3	++	In general	Transparent body
					Comparative example 4	12.5	+	Difference (D)	Transparent body
Comparative example 5	33.4	++	In general	Transparent body
					Comparative example 6	40.1	+++	Good taste	Transparent body
Comparative example 7	20.8	++	In general	Stratification of a body

Examples 1-3 were made with addition of troxerutin, cerium oxide and cress. The method comprises the following steps of adding the coastal cress independently in a comparative example 1, adding troxerutin independently in a comparative example 2, adding cerium oxide independently in a comparative example 3, adding troxerutin and coastal cress in a comparative example 4, adding cerium oxide and coastal cress in a comparative example 5, adding troxerutin and cerium oxide in a comparative example 6, adding troxerutin, coastal cress and zinc oxide in a comparative example 7, wherein the zinc oxide cannot be uniformly and stably dispersed in a system and precipitates to cause the material body to be layered. As shown in table 3, from the test results, it can be seen that: the sunscreen effect of the coastal cress cannot be tested when the coastal cress is used alone, but the sunscreen effect is better when the coastal cress is compounded with troxerutin or cerium oxide. The SPF and PA test values of the example 1 are obviously superior to those of the comparative examples 1-7, and the sun-screening performance of the example 1 is obviously superior to that of the comparative examples 1-6 in the case of compounding troxerutin, cerium oxide and coastal dropwort, and any one or two of the troxerutin, the cerium oxide and the coastal dropwort are added independently. According to the proportion of the troxerutin and the cerium oxide, the troxerutin and the cerium oxide can fully play a sun-screening role, have a synergistic effect with the coastal cress, have good ultraviolet absorption capacity, and the obtained spray product is a transparent aqueous solution, does not contain a chemical sun-screening agent and has a good sun-screening effect. Comparative example 7 shows that the sunscreen spray prepared by replacing cerium oxide with zinc oxide has poor stability, layered material body and obviously weaker sunscreen effect than the sunscreen spray prepared in example 1 of the invention, and the sunscreen spray has reasonable formula, scientific proportion and unexpected technical effect.

Example 4 preparation of clear aqueous sunscreen spray

Example 4 a clear aqueous sunscreen spray comprising the following components in mass percent: troxerutin 0.3%, cerium oxide 30%, cress maritima callus culture filtrate 0.02%, sodium acrylate/sodium acryloyldimethyl taurate copolymer 0.5%, glycerol 10%, betaine 5%, tocopherol acetate 2%, triethanolamine 0.2%, ethylhexyl glycerol 1%, and the balance of water.

The preparation procedure is as in example 1.

Example 5 preparation of clear aqueous sunscreen spray

Example 5 a clear aqueous sunscreen spray comprising the following components in mass percent: troxerutin 4%, cerium oxide 25%, cress maritima callus culture filtrate 0.05%, hydroxyethyl cellulose 1%, sodium hyaluronate 2%, trehalose 3%, purslane extract 1%, arginine 0.8%, methylparaben 0.1%, phenoxyethanol 0.2%, and the balance of water.

Preparation procedure reference example 1 was made.

The above is only a preferred embodiment of the present invention, and it should be noted that the above preferred embodiment should not be considered as limiting the present invention, and the protection scope of the present invention should be subject to the scope defined by the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and these modifications and adaptations should be considered within the scope of the invention.

Claims (7)

1. The transparent aqueous sunscreen spray is characterized by comprising the following components in percentage by mass:

the name of the cerium oxide INCI is cerium oxide, colloidal platinum and water;

the cress is a callus culture filtrate of the cress.

2. A clear aqueous sunscreen spray as claimed in claim 1 wherein said thickener is selected from one or more of hydroxyethyl cellulose, carbomer, acrylic acid/C10-30 alkanol acrylate crosspolymer, xanthan gum, sodium acrylate/sodium acryloyldimethyl taurate copolymer.

3. The transparent aqueous sunscreen spray of claim 1, wherein the humectant is selected from one or more of glycerin, butylene glycol, betaine, erythritol, methyl propylene glycol, sodium hyaluronate, panthenol, and trehalose.

4. The clear aqueous sunscreen spray of claim 1 wherein the skin conditioning agent is selected from one or more of bisabolol, tocopheryl acetate, purslane extract, aloe barbadensis leaf juice, dipotassium glycyrrhizinate, chamomile water.

5. The transparent aqueous sunscreen spray of claim 1, wherein the pH modifier is selected from one or more of triethanolamine, potassium hydroxide, arginine, and sodium hydroxide.

6. A transparent aqueous sunscreen spray according to any of claims 1 to 5, comprising the following components in percentage by mass: 0.1-5% of troxerutin, 10-40% of cerium oxide, 0.01-0.05% of a celery coastal callus culture filtrate, 0.01-0.1% of acrylic acid (ester)/C10-30 alkanol acrylate cross-linked polymer, 1-6% of butanediol, 1-4% of betaine, 0.01-0.1% of dipotassium glycyrrhizinate, 1-5% of chamomile flower water, 0.01-0.1% of arginine, 0.01-0.1% of chlorphenesin, 0.01-0.8% of phenoxyethanol and the balance of water.

7. A process for preparing a clear aqueous sunscreen spray according to any of claims 1 to 5 comprising the steps of:

s1: adding water, a humectant and a thickening agent into a vacuum emulsifying pot, stirring and heating to 80-85 ℃, fully and uniformly stirring, and keeping the temperature for later use;

s2: cooling to below 40 deg.C, adding skin conditioner, pH regulator, troxerutin, cerium oxide, and Cress, stirring, discharging, and standing; after the inspection is qualified, filling and packaging are carried out, and the transparent aqueous sunscreen spray is obtained; the preservative is added in step S1 or S2.