CN115024994B

CN115024994B - High-safety sun-screening composition and preparation method and application thereof

Info

Publication number: CN115024994B
Application number: CN202210593580.4A
Authority: CN
Inventors: 彭海华; 李传茂; 崔英云; 张楚标; 张伟杰
Original assignee: Guangdong Danz Group Co Ltd; Guangzhou Keneng Cosmetic Research Co Ltd
Current assignee: Guangdong Danz Group Co Ltd; Guangzhou Keneng Cosmetic Research Co Ltd
Priority date: 2022-05-27
Filing date: 2022-05-27
Publication date: 2024-07-16
Anticipated expiration: 2042-05-27
Also published as: CN115024994A

Abstract

The invention belongs to the field of cosmetics, and relates to a high-safety sun-screening composition, and a preparation method and application thereof. The personal care sunscreen composition is formed by mixing one or a combination of macromolecular organic ultraviolet absorbent, inorganic ultraviolet screening agent titanium dioxide and zinc oxide and other cosmetically acceptable ingredients, is safe and nontoxic, and can perform photo-thermal conversion on the absorbed ultraviolet while scattering the ultraviolet; in addition, the macromolecular organic ultraviolet absorbent has better light stability, safety and high efficiency, so that the cosmetics are easy to spread and disperse, the sticky feeling is reduced, and the application field of the cosmetics is enlarged.

Description

High-safety sun-screening composition and preparation method and application thereof

Technical Field

The invention belongs to the field of cosmetics, and in particular relates to a high-safety type sun-screening composition and a preparation method and application thereof.

Background

Ultraviolet light is the main focus of research for current stage photoaging. Ultraviolet light is divided into three bands UVA, UVB, UVC. Wherein UVC is almost completely absorbed by the ozone layer and cannot reach the earth's surface. UVA is ultraviolet with a wavelength of 280-320nm, and most of UVA is absorbed by skin epidermis, and can denature nucleic acid or protein in skin surface cells, reddish skin, erythema (sunburn) and acute dermatitis, which is commonly called sunburn. The magnitude of the sun protection factor SPF (Sun Protection Factor) value is generally used to evaluate the resistance of sun protection cosmetics to UVB. Skin cancer is also easily caused by excessive ultraviolet radiation. UVA is ultraviolet with the wavelength of 320-400nm, has strong penetrating power, can reach the dermis layer of skin, destroy collagen and elastin of skin, cause the generation of wrinkles, the damage is cumulative, is a main cause of photoaging, and simultaneously stimulates melanin generation, so that the skin color is uneven. The sun protection cosmetic is generally evaluated for its resistance to UVA by a sun protection factor PA (Protection UVA).

Sunscreens used in cosmetics on the market at present are mainly classified into organic ultraviolet absorbers and inorganic ultraviolet screening agents. Inorganic ultraviolet screening agents, which are recognized by national security, mainly include titanium dioxide and zinc oxide, and the types and maximum addition amounts of organic ultraviolet screening agents are limited differently from country to country. Inorganic ultraviolet screening agents are considered to be non-toxic and safe to the human body. The sunscreen cosmetic has no irritation to skin and no cancer, but the sunscreen cosmetic is whitish and thick and heavy due to the addition of a large amount of titanium dioxide and zinc oxide, is difficult to disperse a coating film, and has poor experience of consumers.

Although skin is a barrier, it is not completely impermeable and molecules of sufficiently small molecular weight can penetrate the skin layer and then be absorbed, this amount typically being considered to be 500 daltons. There are no effective topical drugs with molecular weights exceeding 500 daltons and almost all known allergens are below 500 daltons. Although sunscreen products using organic UV absorbers can provide a refreshing skin feel, related studies have demonstrated that some small molecular weight organic UV absorbers (e.g., avobenzone, octocrylene, benzophenone) can penetrate the skin into the blood and present a significant safety hazard during use by humans. Safety is the biggest limiting factor in the use of sunscreens, and macromolecular sunscreens have greatly improved safety compared to small molecule sunscreens, and organic small molecule sunscreens have proven to have potential safety risks (disrupting endocrine, inducing congenital giant intestinal segments in infants, etc.). Based on this theory, only high molecular weight chemical sunscreens were selected to reduce skin irritation when developing sunscreen products.

The skin becomes dry and rough immediately after being damaged by ultraviolet irradiation, and loses elasticity and luster. Therefore, sun protection is of paramount importance. The desert muscle is the skin with rough, reddish-hot and desquamation symptoms, and the skin is dry like a desert, and is mainly caused by long-term injury accumulation, such as frequent insolation, careless maintenance, frequent exfoliating and the like. The skin is extremely sensitive, especially exposed to sunlight, and is easy to be stimulated by the outside to generate cell inflammation, so that normal physiological functions of the skin such as self-repairing and updating can be influenced, and certain destructive factors can be generated, so that the skin is damaged, the dryness is further worsened, and the aging process of the skin is accelerated.

Under the premise of ensuring the sun-screening effect, the modern sun-screening technology generally needs to add a large amount of small molecular organic sun-screening agents, and light instability, irritation and safety risks possibly exist, so that the development of macromolecular mild sun-screening cosmetics suitable for sensitive muscles and desert muscles is important. However, since the organic sunscreen agent having a large molecular weight is basically crystalline, it is easily crystallized in the formulation system, and the solubility thereof is a problem to be solved by the present invention.

Disclosure of Invention

In one aspect, the present application provides a sunscreen composition comprising, by weight:

0.1-10% of diethyl hexyl butyramide triazinone and 0.1-10% of bis-ethylhexyl oxyphenol methoxyphenyl triazine.

In some embodiments, the sunscreen composition further comprises the following materials in weight percent: polysiloxane-150.1-10%, ethylhexyl triazone 0.1-5%.

In some embodiments, the sunscreen composition further comprises a physical sunscreen agent; in some embodiments, the physical sunscreens are selected from one or both of zinc oxide or titanium dioxide; in some embodiments, the physical sunscreens are in the sunscreening composition in weight percent: 0.05-20% of zinc oxide and 0.05-20% of titanium dioxide; in some embodiments, the physical sunscreens are surface-treated physical sunscreens; in some embodiments, the surface treatment is a treatment with triethoxyoctylsilane as a surface treating agent.

In some embodiments, the sunscreen composition further comprises one or more of an emulsifier, a film former, an emollient, a thickener, a humectant, a chelating agent, a preservative, a skin conditioning agent, a fragrance, a pH adjusting agent, a solvent.

In some embodiments, the emulsifier is selected from one or more of PEG-9 dimethicone ethyl dimethicone, polyglycerol-3 dimethicone hydroxyethyl dimethicone, lauryl polyethylene glycol/polypropylene glycol-18/18-dimethicone, PEG-10 dimethicone, polyglycerol-3 polyricinoleate, polyglycerol-3 diisostearate; in some embodiments, the emulsifier is selected from the group consisting of PEG-9 polydimethylsiloxane ethyl polydimethylsiloxane and PEG-10 polydimethylsiloxane.

In some embodiments, the film former is selected from one or more of trimethylsiloxysilicate, polyurethane, hydrogenated polycyclopentadiene; in some embodiments, the film former is selected from trimethylsiloxysilicates.

In some embodiments, the emollient is selected from one or more of the group consisting of tri (ethylhexanoate), caprylic/capric triglyceride, pentaerythritol tetra (ethylhexanoate), butyl octanol salicylate, diethoxyethyl succinate, isododecane, cetyl ethylhexanoate, isopropyl myristate, isopropyl palmitate, diisopropyl sebacate, dibutyl adipate, C12-15 alcohol benzoate, dioctyl carbonate, coco-caprylate/caprate, dimethicone, octyl dimethicone, cyclopentadimethicone, phenyl trimethicone; in some embodiments, the emollient is selected from caprylic/capric triglyceride, isopropyl palmitate, C12-15 alcohol benzoate, cyclopentadimethicone; in some embodiments, the weight percent of the emollient in the sunscreen composition is: 0.5-20% of caprylic/capric triglyceride, 0.5-20% of isopropyl palmitate and 0.5-20% of C12-15 alcohol benzoate.

In some embodiments, the thickener is selected from one or more of disteardimonium hectorite, silica silylate, dextrin palmitate; in some embodiments, the thickener is selected from distearyl dimethylammonium hectorite.

In some embodiments, the pH adjuster is selected from one or more of arginine, sodium hydroxide, potassium hydroxide, triethanolamine, aminomethylpropanol.

The application also provides application of the sun-screening composition in preparing cosmetics; in some embodiments, the cosmetic is selected from any one of sun cream, sun lotion, sun cream, sun liquid, sun spray, sun gel, barrier cream, barrier lotion, BB cream.

The application also provides a preparation method of the sun-screening composition, which comprises the step of mixing the components.

The sunscreen cosmetic composition of the present invention is mainly obtained by mixing an oil phase and an aqueous phase and adding other ingredients.

The oil phase mainly comprises an emulsifier, a film forming agent, an emollient, a sun-screening agent and an oil phase thickener, but can also contain other components according to requirements.

The emulsifier is not particularly limited as long as it can form a water-in-oil (W/O) type or oil-in-water (O/W) type emulsified sunscreen cosmetic composition, and for example, PEG-9 dimethicone ethyl dimethicone, polyglycerin-3 dimethicone hydroxyethyl dimethicone, lauryl polyethylene glycol/polypropylene glycol-18/18-dimethicone, PEG-10 dimethicone, polyglycerin-3 polyricinoleate, polyglycerin-3 diisostearate, and the like can be used.

As film forming agents, for example, trimethylsiloxysilicate, polyurethane, hydrogenated polycyclopentadiene, etc. can be used.

As the emollient, an emollient commonly used in the cosmetic field can be used, and is not particularly limited.

Specifically, glycerol tri (ethylhexanoate), caprylic/capric triglyceride, pentaerythritol tetra (ethylhexanoate), butyl octanol salicylate, diethoxyethyl succinate, isododecane, cetyl ethyl hexanoate, isopropyl myristate, isopropyl palmitate, diisopropyl sebacate, dibutyl adipate, C12-15 alcohol benzoate, dioctyl carbonate, coco-caprylate/caprate, polydimethylsiloxane, octyl polymethylsiloxane, cyclopentadimethicone, phenyltrimethylpolysiloxane, and the like can be used.

As sunscreens, organic uv absorbers contain only large molecular weights and have molecular weights greater than 500 daltons, including oil-soluble ones: polysiloxane-15, ethylhexyl triazone, diethyl hexyl butyryl amino triazone, cresyl trazotrisiloxane, bis-ethylhexyl oxyphenol methoxyphenyl triazine, water soluble: disodium phenylbisbenzimidazole tetrasulfonate and organic microparticles: two or more of methylenebis-benzotriazole tetramethylbutylphenol. Inorganic uv blockers titanium dioxide and zinc oxide can be used.

As the oil phase thickener, disteardimonium hectorite, silica silylate, dextrin palmitate and the like can be mentioned.

The water phase comprises humectant, antiseptic, pH regulator, and other components as required.

The humectant is not particularly limited as long as it is a humectant commonly used in the cosmetic field, and examples thereof include glycerin, propylene glycol, seaweed extract, sodium hyaluronate, aloe extract, joba oil, polyethylene glycol/polypropylene glycol-14/7 dimethyl ether, xylitol, sorbitol, and the like.

Examples of the preservative include phenoxyethanol, ethylhexyl glycerol, hexylene glycol, and pentylene glycol.

Examples of the pH adjuster include arginine, sodium hydroxide, potassium hydroxide, triethanolamine, and aminomethylpropanol.

One or more of vitamin E, scutellariae radix extract, bisabolol, scutellariae radix extract, prinsepia utilis extract, ceramide, dextran, and vitamin B5 with damaged skin repairing effect can also be added into sunscreen cosmetic composition.

The organic ultraviolet light absorbers of the present invention are preferably polysiloxane-15, ethylhexyl triazone, diethylhexyl butyrylaminotriazone and bis-ethylhexyl oxyphenol methoxyphenyl triazine.

Wherein the polysiloxane-15, ethylhexyl triazone and ethylhexyl butyryl triazone mainly absorb ultraviolet rays in UVB wave bands, and are used for preventing skin from sun-drying; the bis-ethylhexyloxyphenol methoxyphenyl triazine is the most effective broad-spectrum UV absorber, has shielding effect on ultraviolet rays in UVA wave bands, prevents tanning and induces skin cancer, has larger absorption in the 330-350nm area with weak absorption of other three ultraviolet absorbers, is used for overcoming the defects of other three sun-screening agents, has a synergistic effect, and can obtain more stable and efficient sun-screening effect.

The preferred organic UV absorbers of the present invention are preferably used in amounts relative to sunscreen cosmetic compositions

The total weight is polysiloxane-150.1-10%, ethylhexyl triazone 0.1-5%, ethylhexyl butyramide triazone 0.1-10%, and bis-ethylhexyl oxyphenol methoxyphenyl triazone 0.1-10%.

The emollient of the present application, preferably caprylic/capric triglyceride, isopropyl palmitate, or C12-15 alcohol benzoate, is an excellent solvent for the above sunscreen agent, and can provide an effect of being more stable at low temperatures and not precipitating. Cyclopentadimethicone provides a refreshing skin feel to the compositions of the present application.

Preferred emollients of the present invention are preferably used in amounts relative to the total weight of the sunscreen cosmetic composition: 0.5-20% of caprylic/capric triglyceride, 0.5-20% of isopropyl palmitate and 0.5-20% of C12-15 alcohol benzoate.

The invention further comprises an inorganic uv blocker, preferably zinc oxide, which blocks mainly UVA, and titanium dioxide, which blocks mainly UVB.

The inorganic ultraviolet blocking agent is preferably used in an amount of 0.05 to 20% of zinc oxide and 0.05 to 20% of titanium dioxide relative to the total weight of the sunscreen cosmetic composition.

< Second aspect >

In a second aspect the present invention provides a process for the preparation of a sunscreen composition comprising the step of mixing the components of the sunscreen composition. The preparation method of the sun-proof composition is simple and easy to implement, raw materials are easy to obtain, and the sun-proof composition is suitable for mass production.

In some specific embodiments, the method of making the sunscreen composition comprises the steps of:

dissolving the oil phase and the water phase components at 70-90 ℃, preparing an oil phase and water phase mixture, and uniformly mixing by an Ika T18 homogenizer at 3000-4000 r/min; after cooling to below 45 ℃, other components are added to prepare the sunscreen composition cosmetic.

Further, the invention also provides the use of the sun protection composition according to the invention for sun protection products, such as skin care products and body products, comprising sun protection emulsions, sun protection lotions, sun protection creams, sun protection liquids, sun protection sprays, sun protection gels, barrier creams, barrier milks, barrier lotions, BB creams.

Detailed Description

The technical solution of the present invention is further illustrated by the following specific examples, which do not represent limitations on the scope of the present invention. Some insubstantial modifications and adaptations of the invention based on the inventive concept by others remain within the scope of the invention.

The sunscreen compositions of examples 1-7 were prepared according to the mass percentages of the components in table 1 below.

The preparation method of the sun-screening composition comprises the following steps:

Table 1 sunscreen compositions of examples 1-7

According to the following mass percentages of the components in Table 2, the preparation methods of examples 1 to 7 were followed to prepare sunscreen compositions of comparative examples 1 to 6.

Table 2 sunscreen compositions of comparative examples 1-6

Efficacy test

Sun Protection Factor (SPF): also known as the sun protection factor, indicates the level of sun protection efficacy that a sunscreen product can perform. The greater the SPF value, the better the sunscreen effect. It is determined based on the Minimum Erythema Dose (MED) of the skin. The minimum erythema dose of the skin increases after the sun protection product is used, and the sun protection factor SPF of the sun protection product is as follows: SPF = MED of sample protected skin/MED of unprotected skin. The SPF index is suitable for evaluating the protective effect against UVB.

Sunscreen cosmetics long wave ultraviolet protection index (Protection Factor ofUVA, PFA value): also known as UVA protection index. UVA in sunlight irradiates the skin, mainly producing a physiological effect of skin darkening, measured as the minimum sustained blackening amount (MPPD). MPPD is the minimum ultraviolet radiation dose or minimum irradiation time required to produce a slight darkening of the skin over the entire irradiated area 2-4 hours after irradiation. PFA = MPPD of sample protected skin/MPPD of unprotected skin. PFA grading refers to cosmetic label identification management standard specifications.

The evaluation scale is shown in the following Table 3:

TABLE 3 Table 3

Range of PFA values	Identification mark
		PFA＜2	UVA protection effect cannot be identified
2≤PFA≤3	Identified as PA +
		4≤PFA≤7	Identified as PA +
8≤PFA≤15	Identified as pa++ +
		PFA≥16	Identified as pa+ + with ++ +

The test samples of the test experiment are the sun-proof milk prepared in examples 1-7 and comparative examples 1-6, respectively, and the sun-proof effect of the product is tested according to the sun-proof cosmetic sun-proof index test method (human body method) of cosmetic safety technical Specification (2015 edition), and the test results are shown in the table.

Sensory evaluation

Since the sun protection milk is mostly female, 39 female volunteers are selected, with ages between 22 and 40, and all volunteers have no history of skin allergy. The volunteers can use the products according to the specifications, and complete the evaluation work according to the requirements by matching with staff, so that the volunteers have certain expression capability and can truly respond to the experience after use. The sun protection milks prepared in examples 1 to 7 and comparative examples 1 to 6 were each randomly given to volunteers, who were allowed to use the specified sun protection milk daily for 14 days continuously, and the protective milk used was subjected to sensory evaluation, for example. The evaluation items include greasy feel, heavy feel, and whiteness. The evaluation criteria used a10 minute scale, with a higher score representing a higher degree of skin feel or appearance blushing of the sample.

Crystallization precipitation: weighing crystalline ultraviolet absorber (other materials except polysiloxane-15 in oil solubility are all crystalline sunscreen agents; in addition, water solubility and particles are not crystalline) and mixing the rest materials of oil phase; heating at 80-85 deg.c for 5-15 min, dissolving to clear and transparent, and cooling to 40-45 deg.c to obtain oil phase mixture.

1. The experimental method comprises the following steps: the oil phase mixtures of examples 1 to 7 and comparative examples 1 to 6 were examined for stability by placing the prepared compositions in an environment of 5℃for 1 month, respectively, and observing the precipitation.

Table 4 evaluation results of sunscreen compositions of examples 1-7

Example 1

Example 2

Example 3

Example 4

Example 5

Example 6

Example 7

SPF

20.7

20.9

24.6

46.3

45.3

49.3

52.8

PA

++

+++

Whether or not crystallization occurs under low temperature conditions

Is that

Whether or not

Greasy feel

Not greasy

Greasiness of

Refreshing and cool

Greasiness of

Not greasy

Sense of heaviness

Light and thin

Heavy weight

Light and thin

Heavy weight

Light and thin

Pan whiteness

Transparent and transparent

No whitening

Transparent and transparent

Table 5 evaluation results of sunscreen compositions of comparative examples 1-6

Comparative example 1

Comparative example 2

Comparative example 3

Comparative example 4

Comparative example 5

Comparative example 6

SPF

20.9

11.9

26.6

20.2

32.3

29.4

PA

++

+

++

+++

Whether or not crystallization occurs under low temperature conditions

Whether or not

Is that

Greasy feel

Not greasy

Sense of heaviness

Light and thin

Heavy weight

Light and thin

Pan whiteness

Transparent and transparent

No whitening

Whitening off

No whitening

As shown in tables 4 and 5, when the comparative example 1 is compared with example 1, the sunscreen efficiency of the macromolecular sunscreen agent is higher, and the irritation and greasy feeling caused by the sunscreen agent can be reduced by using a low amount of the macromolecular sunscreen agent; the data of comparative examples 2-4 show that the pure titanium dioxide has better UVB resistance than zinc oxide, and the zinc oxide has better UVA protection than titanium dioxide, but the addition of 10% of titanium dioxide content has reduced the use feeling of partial consumers and serious whitening, the transparency of zinc oxide is better, and the skin feel is lighter and thinner. The data of example 2 and comparative examples 5-6 show that the macromolecular organic sunscreen agent can greatly improve SPF and PA values, and increases with the increase of the content; meanwhile, the sticky feeling of the cosmetics can be reduced by adding a small amount of the cosmetics, and the experience is improved; the C12-15 alcohol benzoate and caprylic/capric triglyceride have excellent solubility in crystalline chemical sunscreens. Examples 3-6 as compared to comparative example 1, it can be seen that the addition of the film former helps to form a continuous and uniform film on the skin, thereby enhancing the sun protection effect.

The data of examples 4-7 demonstrate that increasing levels of titanium dioxide, increasing SPF values in cosmetics, but excessive levels result in decreased consumer use; the content of ethylhexyl triazone and bis-ethylhexyl oxyphenol methoxyphenyl triazine is increased, the SPF value of the cosmetic is increased, but excessive content requires a large amount of grease to be dissolved, so that the sticky feel of the cosmetic is improved, and the experience of consumers is reduced. The content of titanium dioxide in the inorganic component is favorable for improving the SPF value, the content of zinc oxide is favorable for improving the PA value, and the addition of the large molecular weight organic sun-screening agent can simultaneously improve the values of the inorganic component and the zinc oxide, so that the ultraviolet UVB-UVA full-segment protection is formed.

The invention provides a macromolecular organic sun-screening composition, which is formed by mixing one or a combination of macromolecular organic ultraviolet absorbent, inorganic ultraviolet screening agent nano titanium dioxide and nano zinc oxide and other cosmetically acceptable components, is safe and nontoxic, and can carry out photothermal conversion on absorbed ultraviolet while scattering the ultraviolet; in addition, the macromolecular organic ultraviolet absorbent has better light stability, safety and high efficiency, so that the cosmetics are easy to spread and disperse, the sticky feeling is reduced, and the application field of the cosmetics is enlarged.

The above examples of the present invention are only examples for clearly illustrating the present invention, and are not limiting of the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.

Claims

1. A sunscreen composition comprising, by weight:

1% of diethyl hexyl butyramide triazinone,

2% Of bis-ethylhexyloxyphenol methoxyphenyl triazine,

Polysiloxane-15 wt%,

1.5 Percent of ethylhexyl triazone,

Zinc oxide/triethoxyoctylsilane 5%, titanium dioxide/triethoxyoctylsilane 3%,

Caprylic/capric triglyceride 5%, isopropyl palmitate 8%, C12-15 alcohol benzoate 5%, trimethylsiloxysilicate 1.5%, and the sunscreen composition as a sunscreen ingredient contains only large molecular weight and has a molecular weight greater than 500 daltons.

2. The sunscreen composition of claim 1, further comprising one or more of an emulsifier, a thickener, a humectant, a chelating agent, a preservative, a skin conditioning agent, a fragrance, a pH adjusting agent, and a solvent.

3. A sunscreen composition according to claim 2, wherein said emulsifier is selected from one or more of PEG-9 dimethicone ethyl dimethicone, polyglycerol-3 dimethicone hydroxyethyl dimethicone, lauryl polyethylene glycol/polypropylene glycol-18/18-dimethicone, PEG-10 dimethicone, polyglycerol-3 polyricinoleate, polyglycerol-3 diisostearate.

4. A sunscreen composition according to claim 2, wherein said emulsifier is selected from the group consisting of PEG-9 polydimethylsiloxane ethyl polydimethylsiloxane and PEG-10 polydimethylsiloxane.

5. A sunscreen composition according to claim 2, wherein said thickener is selected from one or more of disteardimethylammonium hectorite, silica silylate, dextrin palmitate.

6. A sunscreen composition according to claim 2, wherein said thickener is selected from the group consisting of distearyldimethylammonium hectorite.

7. A sunscreen composition according to claim 2, wherein said pH modifier is selected from one or more of arginine, sodium hydroxide, potassium hydroxide, triethanolamine, aminomethylpropanol.

8. Use of a sunscreen composition according to any of claims 1 to 7 for the preparation of a sunscreen cosmetic.

9. The use according to claim 8, wherein the sunscreen cosmetic is selected from any one of sun cream, sun lotion, sun cream, sun liquid, sun spray, sun gel, barrier cream, barrier lotion, BB cream.

10. A method of preparing a sunscreen composition according to any of claims 1 to 7, comprising the step of mixing the components.