CN116035948A

CN116035948A - Sun-proof aqueous emulsion capable of preventing water from forming film permanently and application thereof

Info

Publication number: CN116035948A
Application number: CN202211654354.9A
Authority: CN
Inventors: 肖蓉; 李成富; 李主连; 肖飞
Original assignee: Zhuhai Yatuo Biotechnology Co ltd
Current assignee: Zhuhai Yatuo Biotechnology Co ltd
Priority date: 2022-12-22
Filing date: 2022-12-22
Publication date: 2023-05-02

Abstract

The invention discloses a waterproof and durable film-forming cosmetic composition and application thereof. The cosmetic composition comprises at least one polyurethane polymer film former, at least one organic sunscreen agent, at least one inorganic sunscreen agent. The cosmetic composition can effectively stabilize the sun-screening agent and can be completely formed into a film without being influenced by the sun-screening agent by using specific polyurethane, so that the physical sun-screening agent is effectively prevented from being emulsified for the second time when meeting water after the formulation is formed into a film on the skin, the physical sun-screening agent is uniformly distributed in the film, the lasting time of the sun-screening agent is effectively prolonged, the waterproof film forming property is greatly enhanced, meanwhile, the emulsion stability of the formulation can be effectively improved, and the cosmetic composition can be widely popularized and applied.

Description

Sun-proof aqueous emulsion capable of preventing water from forming film permanently and application thereof

Technical Field

The invention relates to a sun-screening agent, in particular to a sun-screening aqueous emulsion capable of preventing water from forming a film for a long time and application thereof.

Background

It is well known that solar rays have an adverse effect on the skin because they penetrate to different depths into the skin depending on their wavelength. Shorter wavelength radiation in the UVB range (wavelength: 280-320 nm) reaches the uppermost skin layer. Rays in the UVB range cause sun burns and lead to an increased risk of skin cancer. Longer wavelength UVA radiation (wavelength: 320-400 nm) penetrates into deeper skin layers. They cause damage that is extremely important to the structure and strength of the skin. In addition, this also results in premature skin aging with ultraviolet injury which makes skin more susceptible to increased incidence of skin cancer, loss of barrier ability of the skin at the largest organs of the human body, formation of wrinkles and fine lines, irregular sagging, etc. of the skin.

Organic sunscreens and physical sunscreens have been developed in order to protect the skin from solar radiation. The organic sun-screening agent can be combined to form the sun-screening capability with more comprehensive wave bands, so that the sun-screening efficiency is effectively improved, and meanwhile, an oil film can be formed, so that the sun-screening efficiency is effectively improved. However, due to the problem of excessive energy absorption, organic sunscreens have a certain attenuation after uv irradiation, and thus, it is necessary to apply the organic sunscreens for prolonging the sun protection effect, and at the same time, the organic sunscreens have a very greasy skin feel after being used in a relatively high amount, and the uncomfortable feel causes a negative feel to the sun cream in some more desirable scenes for consumers.

While physical sunscreens have good photostability, excellent sunscreening efficacy, and better safety due to no risk of penetrating the skin, physical sunscreens are difficult to disperse after being used in high amounts, and their dispersibility directly determines the sunscreening efficacy applied to the skin. Therefore, the better differentiation appeal of the sun-screening product is achieved by effectively improving the feel of the sun-screening agent after use while the sun-screening capability is maintained.

Common systems in commercial aqueous sunscreen products are emulsifying systems and gelling systems. Sufficient amounts of emulsifier can significantly reduce the antiperspirant and water repellency of the formulation, and formulations emulsified with oil-in-water after perspiration or water exposure can make the sunscreen emulsion double-emulsified and easily wiped and wiped off. The simple gel suspension system is more convenient to use but is greasy to feel, and the sunproof effect is unstable after being smeared due to uneven distribution of the sunproof oil film. Other types of film forming agents on the market often affect the film forming capability of the sun-screening agent due to the high polarity of the sun-screening agent, so that the film forming integrity and durability of the sun-screening agent are reduced, and meanwhile, the sun-screening agent does not have emulsifying property.

Disclosure of Invention

The invention aims to overcome at least one defect of the prior art and provides a waterproof durable film-forming sun-proof aqueous emulsion.

The technical scheme adopted by the invention is as follows:

in a first aspect, the present invention provides a water-repellent, durable film-forming cosmetic composition comprising at least one polyurethane polymer film former, at least one organic sunscreen, at least one inorganic sunscreen, said polyurethane polymer film former being

And C200F, wherein the organic sun-screening agent is at least one selected from homosalate, diethylamino hydroxybenzoyl hexyl benzoate, ethylhexyl triazone, bis-ethylhexyl oxyphenol methoxyphenyl triazine or 2-phenylbenzimidazole-5-sulfonic acid.

In some examples, the polyurethane polymer film former is present in an amount of 2 to 5wt%.

In some examples, the inorganic sunscreen is selected from at least one of a sulfate of barium, an oxide of titanium, an oxide of zinc, an oxide of iron, an oxide of zirconium, an oxide of cerium, an oxide of silicon, an oxide of manganese.

In some examples, the mass ratio of the polyurethane polymer to the organic sunscreen agent is 1: (2-4).

In some examples, the organic sunscreen is homosalate.

In some examples, the sum of the mass content of the polyurethane polymer and the organic sunscreen agent is 0.5 to 10wt%.

In some examples, the cosmetic composition further comprises solvents, hydrocarbon oils, emulsifiers, sun filters, additives.

In some examples, the cosmetic composition comprises, by mass, 0.5-10wt% of the sum of the polyurethane polymer film forming agent and the organic sunscreen agent, 0.05-0.2wt% of the inorganic sunscreen agent, 64-71 wt% of the solvent, 1-1.8wt% of the hydrocarbon oil, 0.2-10wt% of the emulsifying agent, 1-20wt% of the sun-screening filter agent, and 0.5-25wt% of the additive.

In some examples, the cosmetic composition is an aqueous emulsion.

In a second aspect, the present invention provides the use of a cosmetic composition for the preparation of a sunscreen.

The beneficial effects of the invention are as follows:

the sun-proof aqueous emulsion of some examples of the invention, through using the specific polyurethane, because of its better emulsifying property in the emulsion of low viscosity, because contain IPDI group close to organic sun-proof agent at the same time on the main chain, can stabilize sun-proof agent effectively at the same time, can not influenced by sun-proof agent and complete film formation, so have better application in the sun-proof formulation of low viscosity. The film forming agent can crosslink on the skin and maintain a high-strength film after the solvent in the formula is volatilized, and the sun-screening agent is uniformly dispersed in the film forming structure. Because the film is a layer of water-resistant macromolecular polymer film, the secondary emulsification of the formula in water after the formula is formed on the skin is effectively prevented, the stability of the formula is solved, and the durable water resistance of the formula is greatly improved.

When the invention is applied to a sunscreen spray formula, a film can be formed, so that the physical sunscreen agent is uniformly distributed in the film, the lasting of the sunscreen agent is effectively prolonged, the waterproof film forming property is greatly enhanced, meanwhile, the emulsion stability of the formula can be effectively improved, and the invention can be widely popularized and applied.

Drawings

FIG. 1 is a comparison of the performance of examples 1-5 and comparative examples 1-10.

FIG. 2 is a performance evaluation of durability of examples 1 to 5 and comparative examples 1 to 10.

FIG. 3 is a performance evaluation of the emulsifiability of examples 1 to 5 and comparative examples 1 to 10.

FIG. 4 is an SPF durability evaluation of examples 1 to 5 and comparative examples 1 to 10.

Detailed Description

In the prior art, a plurality of organic sunscreens and polyurethane film forming agents exist, and the inventor discovers that the specific polyurethane polymer film forming agent is @ through a great deal of experimental data research

C200F) is combined with a specific organic sunscreen agent, and the two have groups with similar structures, can be mutually synergistic, can effectively stabilize the sunscreen agent and can form a film completely without being influenced by the sunscreen agent, so that the composition has better application in a low-viscosity sunscreen formula. The film forming agent can crosslink on the skin and maintain a high-strength film after the solvent in the formula is volatilized, and the sun-screening agent is uniformly dispersed in the film forming structure. Because the film is a layer of water-resistant macromolecular polymer film, the secondary emulsification of the formula in water after the formula is formed on the skin is effectively prevented, the stability of the formula is solved, and the durable water resistance of the formula is greatly improved. Experimental data indicate that the synergy is lost with other polyurethane polymer film formers or organic sunscreens.

A waterproof and durable film-forming cosmetic composition comprises at least one polyurethane polymer film forming agent, at least one organic sun-screening agent and at least one inorganic sun-screening agent, wherein the polyurethane polymer film forming agent is

The amount of the polyurethane polymer film forming agent can be adjusted to a certain extent as required, and generally, the higher the content of the polyurethane polymer film forming agent is, the better the film forming property is, the viscosity of the system is increased, and the uniformity of film forming is affected. In some examples, the polyurethane polymer film former is present in an amount of 2 to 5wt%. The dosage range can not only effectively form a film, but also uniformly form a film.

The inorganic sunscreens may be inorganic sunscreens commonly used in the art. In some examples, the inorganic sunscreen is selected from at least one of a sulfate of barium, an oxide of titanium, an oxide of zinc, an oxide of iron, an oxide of zirconium, an oxide of cerium, an oxide of silicon, an oxide of manganese.

The proportion of organic sunscreens is too high and may have a certain adverse effect on the film forming properties of the product. In some examples, the mass ratio of the polyurethane polymer to the organic sunscreen agent is 1: (2-4). Experimental data show that at this ratio, more organic sunscreens can be loaded, and adverse effects on film formation can be avoided.

In some examples, the organic sunscreen is homosalate. The data show homosalate

C200F has a better synergistic effect.

In some examples, the cosmetic composition is an aqueous emulsion.

All percentages in the present invention are by weight and are based on 100% by weight of the cosmetic composition of the present invention, unless otherwise indicated.

The weight referred to in the present invention is the weight of the active substance. For a substance in the form of a dispersion, the weight referred to in the present invention is the actual weight of the substance, excluding the weight of the carrier, that is, the weight of the substance referred to in the present invention in the form of a dispersion = weight of the dispersion x solid component content of the dispersion. For solid materials containing water of crystallization, the weight of the material referred to in the present invention is the weight of the removed water of crystallization.

The composition used in the examples or comparative examples of the present invention is shown in the following table, wherein wt% means the weight percentage of the solid component in the composition based on the total weight of the formulation sample.

TABLE 1 raw materials and reagent model Meter

Both the examples and the comparative examples in the present invention can be prepared as follows: the aqueous phase is added as a combination according to the invention with stirring at a stirring speed of 500-600rpm to participate in the emulsion addition of the formulation.

Table 2 comparative examples and examples composition table

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The skin used in the following experiments was asian skin. All the skins were healthy and undamaged.

Experiment of Water-resistance film Forming Property

30 male/female subjects, ranging in age from 20 to 50 years, were selected for health, no skin disease, bright and clean front of arm without affecting scoring scars, pigmentation, etc. Before the test, the front end of the arm of the subject is scored for makeup removal after 20 minutes after loading and 20 minutes after washing.

On the test day 1H-3H of the test, the test subjects were unable to contact water, the test subjects were rubbed with dry facial tissues on the inner sides of the forearms of the hands, the test areas of 2cmx2cm were marked on the inner sides of the forearms of the test subjects by the experimenters, 4 areas were marked on the same arm, and each test area was spaced at least 1cm apart.

The graph of the performance analysis for the overall evaluation is shown in fig. 1. As shown in fig. 1, C200F had the most significant performance improvement in the durability of water resistance and film forming properties of the prepared example 1.

Durability test

The method comprises the steps of cleaning the face of a subject with a facial cleaning product, wiping the skin with dry facial tissues, sitting for 10min, applying makeup (full face makeup), and then applying a make-up product to the half face; subject self-assessment questionnaire at T12.

Detailed analysis of durability data as shown in fig. 2, example 1 prepared with C200F had the best durability performance and still achieved good results even with up to 12 hours of evaluation.

Emulsifying property test

The sample is put into a centrifuge tube to a height of 2/3, the rotating speed is adjusted to 3000r/min and 5min, and the instant, T0.5, T1, T4 and T6 conditions are observed for scoring.

The differences in the emulsifying properties of the formulations by the addition of different polymers are shown in fig. 3, and it can be seen from fig. 3 that the addition of polymers can effectively enhance the stability of the formulations.

Finally, the water-resistant film forming property experiment, the durability experiment and the grading result of the durability experiment are shown in the following table 3.

TABLE 3 evaluation results of comparative and example Components

SPF evaluation experiment

8mg of the smear sample was applied in a 2x2cm area, and the "SPF persistence" test was performed in a special climatic laboratory with >60% relative humidity. The temperature of the chamber was 25 ℃. SPF was evaluated at test conditions of 1h,2h,4 h.

Table 4 comparative and example SPF evaluation tables

Time	0h	1h	2h	4h
					Comparative example 1	15.6	12.1	9.3	7.4
Comparative example 2	16.6	14.3	12.8	11.4
					Comparative example 3	17.2	14.8	13.2	11.9
Comparative example 4	17.8	15.4	13.7	12.4
					Comparative example 5	19	17.3	15.5	13.7
Comparative example 6	19.7	18.2	16.6	14.5
					Comparative example 7	20.4	18.9	17.2	15.1
Comparative example 8	16.1	13.5	11.3	9.4
					Comparative example 9	16.6	14.2	12.2	10.2
Comparative example 10	17.1	14.9	12.7	11.4
					Example 1	19.9	18.3	17.1	15.9
Example 2	21.8	20	18.9	18.1
					Example 3	23.6	22.3	20.7	19.8
Example 4	22.7	20.8	19.9	18.9
					Example 5	20.4	18.5	17.4	16.4

From fig. 4 and table 4, C200F can be seen: the homosalate has the optimal SPF lasting effect with the weight ratio of 1:2-1:3. Excellent SPF persistence effect can be exhibited even at 4 hours. The use of polymers increases the efficiency of the SPF.

Stability test:

the examples and comparative examples were each subjected to the following 4 environments for observation, and the product thereof was tested for bulk stability.

The normal temperature sample is kept stand at 25 ℃ and 60% RH for comparison test.

Cold resistance test: the freezer compartment of the refrigerator was left for 10 days.

Cold and hot circulation: -10 ℃,25% rh;25 ℃,60% rh;38 ℃,75% rh, 24h per temperature, 6 cycles total.

High temperature acceleration: the test conditions were 50 ℃ + -1deg.C, 25% RH+ -5% RH for 1 month.

As shown in the following table, each of example 1 and comparative examples 2 to 4 passed the stability test under each condition.

Among them, comparative example 1 failed the cold and hot cycle and high temperature stability test because it contained less polyurethane film former than example 1.

Table 5 stability evaluation table

Test conditions	Normal temperature appearance	Cold-resistant	Cold and hot circulation	High temperature	Stability of
						Example 1	Qualified product	By passing through	By passing through	By passing through	Is that
Example 2	Qualified product	By passing through	By passing through	By passing through	Is that
						Example 3	Qualified product	By passing through	By passing through	By passing through	Is that
Example 4	Qualified product	By passing through	By passing through	By passing through	Is that
						Example 5	Qualified product	By passing through	By passing through	By passing through	Is that
Comparative example 1	Qualified product	By passing through	Thinning of	Thinning of	Whether or not
						Comparative example 2	Qualified product	By passing through	By passing through	By passing through	Is that
Comparative example 3	Qualified product	By passing through	By passing through	By passing through	Is that
						Comparative example 4	Qualified product	By passing through	By passing through	By passing through	Is that
Comparative example 5	Qualified product	By passing through	By passing through	By passing through	Is that
						Comparative example 6	Qualified product	By passing through	By passing through	By passing through	Is that
Comparative example 7	Qualified product	By passing through	By passing through	By passing through	Is that
						Comparative example 8	Qualified product	By passing through	By passing through	By passing through	Is that
Comparative example 9	Qualified product	By passing through	By passing through	By passing through	Is that
						Comparative example 10	Qualified product	By passing through	By passing through	By passing through	Is that

The experiment again proves that the polyurethane C200F can effectively improve the film forming property, the waterproof property and the lasting property of the formula.

The above description of the present invention is further illustrated in detail and should not be taken as limiting the practice of the present invention. It is within the scope of the present invention for those skilled in the art to make simple deductions or substitutions without departing from the concept of the present invention.

Claims

1. A waterproof permanent film-forming cosmetic composition, characterized in that it comprises at least one polyurethane polymer film-forming agent, at least one organic sunscreen agent, at least one inorganic sunscreen agent, said polyurethane polymer film-forming agent being Pra-Membtech C200F, said organic sunscreen agent being at least one selected from homosalate, diethylamino hydroxybenzoyl hexyl benzoate, ethylhexyl triazone, bis-ethylhexyloxyphenol methoxyphenyl triazine or 2-phenylbenzimidazole-5-sulphonic acid.

2. The cosmetic composition according to claim 1, wherein the polyurethane polymer film former is present in an amount of 2 to 5% by weight.

3. The cosmetic composition of claim 1, wherein the inorganic sunscreen is selected from at least one of a sulfate of barium, an oxide of titanium, an oxide of zinc, an oxide of iron, an oxide of zirconium, an oxide of cerium, an oxide of silicon, and an oxide of manganese.

4. The cosmetic composition according to claim 1, characterized in that the mass ratio of the polyurethane polymer and the organic sunscreen agent is 1: (2-4).

5. The cosmetic composition of claim 4, wherein the organic sunscreen is homosalate.

6. Cosmetic composition according to any one of claims 1 to 5, characterized in that the sum of the mass contents of the polyurethane polymer and of the organic sunscreen agent is between 0.5 and 10% by weight.

7. The cosmetic composition according to any one of claims 1 to 5, characterized in that it further comprises solvents, hydrocarbon oils, emulsifiers, sun filters, additives.

8. The cosmetic composition according to any one of claims 1 to 5, wherein the cosmetic composition comprises, by mass, 0.5 to 10% of the sum of the polyurethane polymer film forming agent and the organic sunscreen agent, 0.05 to 0.2% of the inorganic sunscreen agent, 64 to 71% of the solvent, 1 to 1.8% of the hydrocarbon oil, 0.2 to 10% of the emulsifier, 1 to 20% of the sunscreen filter, and 0.5 to 25% of the additive.

9. The cosmetic composition according to any one of claims 1 to 5, characterized in that it is an aqueous emulsion.

10. Use of a cosmetic composition according to any one of claims 1 to 9 for the preparation of a sunscreen.