WO2020051934A1

WO2020051934A1 - Lightwave barrier agent having high safety, preparation method, and sunscreen spray containing lightwave barrier agent

Info

Publication number: WO2020051934A1
Application number: PCT/CN2018/106282
Authority: WO
Inventors: 朱国君; 张永胜; 王菁; 罗晓丹
Original assignee: 上海铭美生物科技有限公司
Priority date: 2018-09-14
Filing date: 2018-09-18
Publication date: 2020-03-19
Also published as: CN109091400B; CN109091400A

Abstract

The present invention relates to the technical field of sunscreen spray cosmetics, and aiming at a problem of acceleration of skin ageing caused by using titanium dioxide as a lightwave barrier agent in the current sunscreen spray, disclosed are a lightwave barrier agent having high safety, a preparation method, and a sunscreen spray containing the lightwave barrier agent. The lightwave barrier agent is prepared by coating a reactant on the surface of a cerium oxide aqueous dispersion after performing reaction on chloroplatinic acid and sodium hydroxide, and comprises the aqueous dispersion of which an inner core is cerium oxide and a composite particle structure of which an outer shell is a platinum layer; and the sunscreen spray uses water as a solvent and further contains amphipathic molecule ectoin. The lightwave barrier agent of the present invention has no ultraviolet light catalytic activity, and has barrier performance on full wavelength bands of ultraviolet light; cerium oxide particles are uniformly dispersed and difficult to agglomerate; moreover, the sunscreen spray obtained from the lightwave barrier agent can use water as the solvent, and the lightwave barrier agent and the ectoin take a synergistic effect, so that compared with a sunscreen spray containing titanium dioxide, the sunscreen spray obtained from the lightwave barrier agent is safer and has a good ultraviolet-proof effect.

Description

Lightwave blocking agent with high safety, preparation method and sunscreen spray containing the same

Technical field

The invention belongs to the technical field of sunscreen spray cosmetics, and particularly relates to a light wave blocking agent with high safety, a preparation method thereof, and a sunscreen spray containing the light wave blocking agent.

Background technique

Ultraviolet rays are electromagnetic waves with a wavelength of 10 to 400 nm. They can be divided into UVC segments of 200 to 280 nm, UVB segments of 280 to 320 nm, and UVA segments of 320 to 400 nm according to the wavelength. Among them, the UVC segment and the shorter wavelength ultraviolet rays are basically absorbed by the ozone layer. The UVB band has medium penetration, less than 2% can reach the earth's surface, can be absorbed by the skin epidermis, can cause strong light damage to the skin, dermal blood vessels in the irradiated area expand, and the skin appears redness, swelling, blisters and other symptoms , Long-term exposure to the skin will cause erythema, inflammation, and skin aging. The UVA segment of UV penetrates clothing and human skin far more strongly than the UVB segment. It can reach deep in the dermis and can act on melanin in the epidermis, causing skin melanin deposits, darkening the skin, and long-term accumulation. Skin aging and severe damage. Therefore, to prevent skin damage caused by ultraviolet radiation to the human body, it is necessary to prevent both UVB ultraviolet radiation and UVA ultraviolet radiation.

At the same time, the widespread use of LED lights and electronic products such as mobile phones has increased the exposure time of human skin to high-energy blue light with a wavelength of 400 to 480 nm, and it will also cause human skin damage after long-term contact, but the current sunscreen spray for this band Blu-ray protection involves less.

Sunscreen sprays are new sunscreen products that can make up for the problem of being unable to reapply sunscreen for a long time outdoors. At present, the sunscreen sprays on the market mainly use water-soluble titanium dioxide as a photoblocker, and cooperate with chemical sunscreen agents, and add a large amount of alcohol to dissolve chemical sunscreen agents. On the one hand, the water-soluble titanium dioxide particles have uneven distribution, serious light leakage, and excessive use. It can cause pore blockage, and only has a blocking effect on the narrow band of UVB. The sun protection effect is not good. It also accelerates skin aging due to its UV photocatalytic activity. Long-term use will damage skin health. On the other hand, ethanol will irritate the skin and cause damage.

Chinese patent CN201810112078.0, the application date is February 5, 2018, the patent name is consistent sunscreen spray and its preparation method, which discloses ethylhexyl methoxycinnamate, orkolin, bis-ethylhexyloxyphenol Methoxyphenyltriazine, butylmethoxydibenzoylmethane, natural phospholipids, absolute ethanol, titanium dioxide, zinc oxide, polydimethylsiloxane, glycerol, emulsifier, 1,2-pentanediol, phosphoric acid Sunscreen spray made of disodium hydrogen, sodium alginate, mannitol, sodium hyaluronate, water, etc., uses anhydrous ethanol as dissolution, and uses titanium dioxide and chemical ultraviolet absorber as light wave blocking or absorbing agent, which is highly irritating. And ethylhexyl methoxycinnamate has been banned in the United States. Soon the European Union will have regulations to restrict its use. Long-term use will affect skin health.

Summary of the Invention

Aiming at the problem that long-term use of titanium dioxide as a light wave blocker in sunscreen sprays is detrimental to skin health, the purpose of the present invention is to provide a high-security light wave blocker, which is more safe than titanium dioxide and has a long-term effect on the skin. Little impact.

Another object of the present invention is to provide a method for preparing the light wave blocking agent with high safety.

The invention also provides a sunscreen spray containing the light wave blocking agent.

The technical solution provided by the present invention is as follows:

A light wave blocking agent with high safety. The light wave blocking agent is a composite particle composed of a core and a shell covering the core. The core is an aqueous dispersion of cerium oxide and the shell is a platinum layer.

As a preference of the present invention, the composite particles are made by coating cerium oxide aqueous dispersion liquid after reacting chloroplatinic acid with sodium hydroxide.

A method for preparing the above-mentioned light wave blocking agent includes the following steps:

(1) During the stirring process, a sodium hydroxide solution is added dropwise to the cerium oxide particles, and then the ultrasonic vibration is sealed to obtain a mixed system;

(2) The temperature of the mixed system is increased to 90 to 100 ° C, and the chloroplatinic acid solution is added dropwise under ultrasonic-assisted stirring to form precipitate particles;

(3) during the formation of precipitated particles, the supernatant is continuously removed until the conductivity of the mixed system is lower than 150 uS / cm;

(4) dispersing the obtained precipitate particles into water with stirring to form an aqueous dispersion, and then adding citric acid to mix;

(5) The composite particles are obtained by drying the water dispersion liquid after adding the citric acid solution in step (4), which is a light wave blocking agent.

As a preference of the method of the present invention, the molar ratio of chloroplatinic acid to cerium oxide in step (2) is 1:46 to 52, and the chloroplatinic acid solution is added dropwise to a mixed system containing 100 g of cerium oxide within 60 to 90 minutes.

As a preference of the method of the present invention, the temperature of the mixed system in step (2) is 100 ° C.

As a preference of the method of the present invention, the concentration of sodium hydroxide in step (1) is 1 to 1.6 mol / L, and it is added dropwise to 100 g of cerium oxide particles at a rate of 1 to 3 drops / s within 40 to 80 minutes.

As a preference of the method of the present invention, in the step (1), the stirring rate is 4000 to 6000 rpm, the ultrasonic frequency is 60 to 400 KHz, the ultrasonic time is 60 to 120 min, and the temperature of the mixed system is 25 to 35 ° C.

As a preferred method of the present invention, the mass concentration of the precipitated particles in the aqueous dispersion obtained in step (4) is 8 to 15% by weight, and the citric acid concentration is 1 to 5 ppmm.

A sunscreen spray containing the above-mentioned light wave blocking agent.

As a preferred sunscreen spray of the present invention, a 100% by weight sunscreen spray is composed of the following mass percentage components: light wave blocking agent 3 to 23 wt%, glycerol 2 to 5 wt%, trehalose 1 to 3 wt%, and 1,3-propanediol 1.5 5% by weight, 1-3% by weight of tetrahydromethylpyrimidinecarboxylic acid, 5% by weight of panthenol, 1-3% by weight of natural plant preservatives, and the balance of water.

The light wave blocker of the present invention is a platinum-modified cerium oxide dispersion, in which chloroplatinic acid reacts with sodium hydroxide to form platinum particles, and the dispersed cerium oxide particles are inlaid and adhered to the surface under the synergistic effect of stirring and ultrasound. Or it is trapped and fixed into the surface structure of platinum particles to form composite particles in which the outer shell is platinum and the inner core is cerium oxide dispersion. Compared with titanium dioxide, cerium oxide dispersion does not have ultraviolet catalytic activity, so it does not harm the skin through ultraviolet catalysis. In addition, the inventors found through research and accumulation that the cerium oxide dispersion has a full blocking effect on light waves with a wavelength of 190nm to 440nm, and also has a certain blocking effect on visible light in the wavelength range of 440nm to 690nm. The smaller the wavelength, the more blocking effect It is strong, so the light wave blocking of cerium oxide covers UVC, UVB and UVC, and it also has a blocking effect on the blue light region of 400 ～ 480nm. Compared with the blocking range of titanium dioxide, the blocking range of light wave is wider, which can effectively block the ultraviolet rays of UVA segment. , It is more effective for ultraviolet protection, good light wave blocking effect and higher safety.

However, existing studies have also shown that cerium oxide particles are prone to agglomeration. The inventors found through transmission electron microscopy that cerium oxide particles with a particle diameter of about 20 nm prepared by the sol-gel method are extremely easy to form agglomerated particles with a particle diameter of 150 nm in an aqueous dispersion, which greatly limits the application of cerium oxide in light wave blocking . Therefore, the inventor, through groping and detailed experimental control, coated the cerium oxide dispersion inside the platinum particles to form a composite particle structure of the core shell. The particle size of the composite particles obtained by the inventor using a dynamic light scattering particle size distribution tester is about 40 nanometers. Therefore, the agglomeration of cerium oxide particles is effectively prevented by the coating of the platinum layer, and the electron transfer is prevented from occurring under the illumination of cerium oxide. The stability of the cerium oxide aqueous dispersion was improved.

Therefore, the sunscreen spray containing the light wave blocking agent of the present invention not only has the light blocking effect of the entire ultraviolet band, but also has certain blocking protection for the blue light region. The inventor has found through research that when the content of the light wave blocking agent is above 3% by weight, the sunscreen Spray can achieve 100% blue light blocking. And because there is no ultraviolet photocatalytic activity, long-term use will not cause skin loss and cause skin aging. At the same time, the tetrahydromethylpyrimidinecarboxylic acid contained in the sunscreen spray of the present invention is an amphoteric molecule, which can reduce the oxidative stress response of the skin caused by blue light, synergize and strengthen the lightwave blocking effect of the lightwave blocker, and the sunscreen of the present invention The spray uses water as a solvent, which is less irritating to human skin than ethanol, and is more gentle to use.

The beneficial effects of the present invention are as follows:

The light wave blocking agent of the present invention is made of a core cerium oxide dispersion liquid and a shell platinum particle. The cerium oxide particles are uniformly dispersed, it is not easy to generate agglomeration, and it has no ultraviolet photocatalytic activity, and has the blocking performance of the entire wavelength range of ultraviolet light. The sunscreen spray can use water as a solvent, and the light wave blocker works synergistically with tetrahydromethylpyrimidinecarboxylic acid. Compared with the sunscreen spray containing titanium dioxide, it is more safe and has better UV and blue light protection effects.

detailed description

The following further describes the implementation manner of the present invention through specific examples.

The cerium oxide particles used in the present invention are prepared by a sol-coagulation method and have a particle diameter of 20 nm. The natural plant preservative in the examples is grapefruit extract.

Example 1

A light wave blocking agent with high safety. The light wave blocking agent is a composite particle composed of a core and a shell covering the core, wherein the core is an aqueous dispersion of cerium oxide and the shell is a platinum layer; It is made by coating the surface of cerium oxide aqueous dispersion after reacting with sodium hydroxide.

(1) 1.3 mol / L sodium hydroxide solution was added dropwise to 100 g of cerium oxide particles at a rate of 1 drop / s in 25 min at 25 ° C, with a stirring rate of 4000 rpm, and then sealed with ultrasonic vibration for 60 min to obtain a mixed system. Frequency 60KHz;

(2) The temperature of the mixed system was raised to 90 ° C, and the chloroplatinic acid solution was added dropwise to the mixed system within 80 minutes under ultrasonic-assisted stirring at 60KHz to form precipitate particles. The molar ratio of chloroplatinic acid to cerium oxide was 1:46. Stirring rate is 4000rpm;

(4) dispersing the obtained precipitated particles into water to form an aqueous dispersion with stirring, the mass concentration of the precipitated particles is 8 wt%, and then citric acid is added and mixed, and the concentration of citric acid is 3 ppmm;

A sunscreen spray containing the above-mentioned light wave blocking agent, wherein 100% by weight of the sunscreen spray is composed of the following mass percentage components: light wave blocking agent 3% by weight, glycerin 4% by weight, trehalose 2% by weight, 1,3-propanediol 3% by weight, four Hydromethylpyrimidinecarboxylic acid 2 wt%, panthenol 2 wt%, natural plant preservative 2 wt%, and the balance of water. The sunscreen spray has a full blocking effect on the UVA segment and the UVB segment, and has a 100% blocking effect on the blue light segment.

Example 2

(1) Add 1 mol / L sodium hydroxide solution to 100 g of cerium oxide particles at a rate of 2 drops / s at 30 ° C within 60 min, with a stirring rate of 5000 rpm, and then seal the ultrasonic vibration for 120 min to obtain a mixed system. Ultrasonic frequency 200KHz;

(2) The temperature of the mixed system was raised to 100 ° C, and the chloroplatinic acid solution was added dropwise to the mixed system within 60 minutes under ultrasonic-assisted stirring at a frequency of 200KHz to form precipitate particles. The molar ratio of chloroplatinic acid to cerium oxide was 1: 49, stirring speed is 5000rpm;

(4) dispersing the obtained precipitate particles into water with stirring to form an aqueous dispersion, the mass concentration of the precipitate particles is 10% by weight, and then adding citric acid for mixing, the concentration of citric acid is 1 ppmm;

A sunscreen spray containing the above-mentioned light wave blocking agent, wherein 100% by weight of the sunscreen spray is composed of the following mass percentage components: light wave blocking agent 20% by weight, glycerin 2% by weight, trehalose 1% by weight, 1,3-propanediol 1.5% by weight, 1% by weight of tetrahydromethylpyrimidinecarboxylic acid, 1% by weight of panthenol, 1% by weight of natural plant preservatives, and the balance of water.

The sunscreen spray has a full blocking effect on the UVA segment and the UVB segment, and has a 100% blocking effect on the blue light segment.

Example 3

(1) 1.6 mol / L sodium hydroxide solution was added dropwise to 100 g of cerium oxide particles at a rate of 3 drops / s at 35 ° C within 80 min, with a stirring rate of 6000 rpm, and then sealed with ultrasonic vibration for 100 min to obtain a mixed system. Frequency 400KHz;

(2) The temperature of the mixed system was raised to 95 ° C, and the chloroplatinic acid solution was added dropwise to the mixed system within 90 minutes under ultrasonic-assisted stirring at a power of 400KHz to form precipitate particles. The molar ratio of chloroplatinic acid to cerium oxide was 1:52. , Stirring speed is 6000rpm;

(4) dispersing the obtained precipitated particles into water to form an aqueous dispersion with stirring, the mass concentration of the precipitated particles is 15 wt%, and then citric acid is added and mixed, and the concentration of citric acid is 5 ppmm;

A sunscreen spray containing the above-mentioned light wave blocking agent, wherein 100% by weight of the sunscreen spray is composed of the following mass percentage components: light wave blocking agent 23% by weight, glycerin 5% by weight, trehalose 3% by weight, 1,3-propanediol 5% by weight, four Hydromethylpyrimidinecarboxylic acid 3 wt%, panthenol 5 wt%, natural plant preservative 3 wt% and the balance of water.

Claims

A light wave blocking agent with high safety, characterized in that the light wave blocking agent is a composite particle composed of a core and a shell covering the core, wherein the core is an aqueous dispersion of cerium oxide and the shell is a platinum layer.
The light wave blocking agent according to claim 1, wherein the composite particles are made by coating a surface of an aqueous cerium oxide dispersion after reacting chloroplatinic acid with sodium hydroxide.
The method for preparing a light wave blocking agent according to claim 1 or 2, further comprising the following steps:

(1) During the stirring process, a sodium hydroxide solution is added dropwise to the cerium oxide particles, and then the ultrasonic vibration is sealed to obtain a mixed system;

(2) The temperature of the mixed system is increased to 90 to 100 ° C, and the chloroplatinic acid solution is added dropwise under ultrasonic-assisted stirring to form precipitate particles;

(3) during the formation of precipitated particles, the supernatant is continuously removed until the conductivity of the mixed system is lower than 150 uS / cm;

(4) dispersing the obtained precipitate particles into water with stirring to form an aqueous dispersion, and then adding citric acid to mix;

(5) The composite particles are obtained by drying the water dispersion liquid after adding the citric acid solution in step (4), which is a light wave blocking agent.
The method for preparing a light wave blocking agent according to claim 3, wherein the molar ratio of chloroplatinic acid to cerium oxide in step (2) is 1: 46-52, and the chloroplatinic acid solution is dropped within 60 to 90 minutes. It was added to a mixed system containing 100 g of cerium oxide.
The method for preparing a light wave blocking agent according to claim 4, wherein the temperature of the mixed system in step (2) is 100 ° C.
The method for preparing a light wave blocking agent according to claim 3 or 4 or 5, characterized in that the concentration of sodium hydroxide in step (1) is 1 to 1.6 mol / L, and 1 to 3 drops per 40 to 80 min / The s rate was added dropwise to 100 g of cerium oxide particles.
The method for preparing a light wave blocking agent according to claim 3 or 4 or 5, characterized in that in the step (1), the stirring rate is 4000 to 6000 rpm, the ultrasonic frequency is 60 to 400 KHz, the ultrasonic time is 60 to 120 min, and the temperature of the mixed system is 25 to 35 ° C.
The method for preparing a light wave blocking agent according to claim 3, wherein the mass concentration of the precipitated particles in the aqueous dispersion obtained in step (4) is 8 to 15 wt%, and the citric acid concentration is 1 to 5 ppmm.
A sunscreen spray comprising a light wave blocking agent according to claim 1 or 2.
The sunscreen spray according to claim 9, characterized in that 100% by weight of the sunscreen spray is composed of the following mass percentage components: light wave blocker 3 to 23 wt%, glycerol 2 to 5 wt%, trehalose 1 to 3 wt%, 1 1,3-propanediol 1.5 to 5 wt%, tetrahydromethylpyrimidine carboxylic acid 1 to 3 wt%, ubiquinol 1 to 5 wt%, natural plant preservative 1 to 3 wt%, and the balance of water.