阅读说明：本技术 一种舒适型皮肤防晒涂布液及其制备方法 (Comfortable skin sunscreen coating liquid and preparation method thereof ) 是由 周树学 李萍 王棽 来旭春 陈磊 吴梁 李青峰 于 2020-04-22 设计创作，主要内容包括：本发明属于精细化工技术领域,具体涉及一种舒适型皮肤防晒涂布液及其制备方法。本发明舒适型皮肤防晒涂布液组成包括乙烯基硅油乳液55-80 wt%,含氢硅油乳液5-20 wt%,Karstedt催化剂胶囊乳液2-15 wt%,紫外线屏蔽剂2-15 wt%,助剂1-10wt%；其中紫外线屏蔽剂为无机紫外吸收剂、有机紫外吸收剂或无机/有机复配紫外吸收剂,助剂包括润湿剂、消光剂、防腐剂、增稠剂和香精。该涂布液可采用涂抹或喷涂方式使用,在室温下通过硅氢加成反应形成弹性膜,具有安全无毒、防水、透气、透湿、紫外屏蔽效果佳等优点,使用后人体舒适感佳,持久性好,可满足不同场合的皮肤防晒保护需求。(The invention belongs to the technical field of fine chemical engineering, and particularly relates to a comfortable skin sunscreen coating liquid and a preparation method thereof. The comfortable skin sunscreen coating liquid comprises 55-80 wt% of vinyl silicone oil emulsion, 5-20 wt% of hydrogen-containing silicone oil emulsion, 2-15 wt% of Karstedt catalyst capsule emulsion, 2-15 wt% of ultraviolet screening agent and 1-10wt% of auxiliary agent; the ultraviolet screening agent is inorganic ultraviolet absorbent, organic ultraviolet absorbent or inorganic/organic compound ultraviolet absorbent, and the auxiliary agent comprises wetting agent, delustering agent, preservative, thickener and essence. The coating liquid can be used by smearing or spraying, forms an elastic film through hydrosilylation reaction at room temperature, has the advantages of safety, no toxicity, water resistance, air permeability, moisture permeability, good ultraviolet shielding effect and the like, has good comfort and durability for a human body after use, and can meet the requirements of skin sunscreen protection on different occasions.)

1. A comfortable skin sunscreen coating liquid is characterized in that the components comprise vinyl silicone oil emulsion, hydrogen-containing silicone oil emulsion, Karstedt catalyst capsule emulsion, ultraviolet screening agent and auxiliary agent; the weight ratio of each component is as follows:

vinyl silicone oil emulsion: 55-80 wt%;

hydrogen-containing silicone oil emulsion: 5-20 wt%;

karstedt catalyst capsule emulsion: 2-15 wt%;

ultraviolet screening agent: 2-15 wt%;

auxiliary agent: 1-10 wt%;

the total amount of the components is 100 percent.

2. A comfortable skin sunscreen coating fluid according to claim 1 wherein the oil phase of the vinyl silicone emulsion is vinyl silicone oil, or a mixture of vinyl silicone oil and solvent silicone oil; the viscosity range of the vinyl silicone oil is 500-20000 mPa.s, and the viscosity range of the solvent silicone oil is 2-50 mPa.s.

3. The coating solution for comfortable skin sunscreen according to claim 1, wherein the hydrogen-containing silicone oil emulsion has a hydrogen content of 0.1-2.0%.

4. A comfortable skin sunscreen coating fluid according to claim 1 wherein the vinyl silicone oil emulsion and the hydrogen-containing silicone oil emulsion have a solids content of 30-50 wt%.

5. A comfortable skin sunscreen coating solution as claimed in claim 1, wherein the Karstedt catalyst capsule emulsion has capsule wall material selected from one of polystyrene, polyacrylate, styrene-acrylate copolymer, polyvinyl acetate and its copolymer, polyester, polylactic acid, polyurethane resin, ethyl cellulose and hydroxypropyl methyl cellulose, vinyl silicone oil, methyl silicone oil, and hydroxy silicone oil.

6. The comfortable skin sunscreen coating solution according to claim 1, wherein the Karstedt catalyst capsule emulsion is prepared by a solvent evaporation method or a direct emulsification method; the solid content of the emulsion is 20-40 wt%.

7. A comfortable skin sunscreen coating fluid as claimed in claim 1, wherein the uv screening agent comprises three types of inorganic, organic, inorganic and organic compounds;

the inorganic ultraviolet screening agent is selected from nano silicon oxide, nano titanium oxide, nano zinc oxide, nano cerium oxide, nano iron oxide, nano magnesium oxide and nano layered double metal oxide;

the organic ultraviolet screening agent is selected from avobenzone, octocrylene, isooctyl methoxycinnamate, ethylhexyl methoxycinnamate, octyl salicylate, hydroxybenzophenone, phenylbenzimidazole sulfonic acid, octocrylene, methylbenzylidene camphor, and menthyl anthranilate.

8. A comfortable skin sunscreen coating fluid according to claim 1 wherein the adjuvant is one or more of a humectant, a matting agent, a preservative, a thickener and a perfume.

9. A process for preparing a comfortable skin sunscreen coating solution as claimed in any of claims 1 to 8, comprising the steps of:

(1) preparing vinyl silicone oil emulsion: dissolving a surfactant in deionized water to obtain an aqueous solution; dropwise adding a surfactant solution into vinyl silicone oil or a vinyl silicone oil/solvent silicone oil mixture, and shearing and stirring at a high speed while dropwise adding; after the dropwise adding is finished, further shearing and dispersing at high speed for 0.5-2 h; the solid content of the emulsion is 30-50 wt%;

preparing hydrogen-containing silicone oil emulsion: dissolving a surfactant in deionized water to obtain an aqueous solution, and dropwise adding the aqueous solution into hydrogen-containing silicone oil under high-speed shearing dispersion; after the dropwise adding is finished, further shearing and dispersing at high speed for 0.5-2 h; the hydrogen content in the hydrogen-containing silicone oil emulsion is 0.1 to 2.0 percent; the solid content of the emulsion is 30-50 wt%;

preparing Karstedt catalyst capsule emulsion by a solvent evaporation method or a direct emulsification method;

(2) and sequentially stirring and mixing the prepared vinyl silicone oil emulsion, hydrogen-containing silicone oil emulsion, Karstedt catalyst capsule emulsion and ultraviolet screening agent at a low speed, then adding the auxiliary agent E, and stirring and mixing uniformly.

10. The preparation method of the comfortable skin sunscreen coating liquid is characterized by comprising the following steps:

for the ultraviolet shielding agent is a pure inorganic ultraviolet shielding agent, firstly dispersing the inorganic ultraviolet shielding agent in deionized water, uniformly dispersing by ultrasonic to prepare an aqueous dispersion, and then adding the aqueous dispersion into the coating liquid;

the ultraviolet screening agent is a pure organic ultraviolet screening agent, the organic ultraviolet screening agent is added into an oil phase during preparation of the vinyl silicone oil emulsion, and then the emulsion is emulsified together to prepare the vinyl silicone oil emulsion containing the organic ultraviolet screening agent, and then the emulsion is added into the coating liquid;

and for the ultraviolet screening agent which is an inorganic/inorganic compound ultraviolet screening agent, the inorganic and organic ultraviolet screening agents are respectively introduced into the coating liquid according to the adding method.

Technical Field

The invention belongs to the technical field of fine chemical engineering, and particularly relates to a comfortable skin sunscreen coating liquid and a preparation method thereof.

Background

With the increasing activity of the human industry, the environmental pollution is more and more serious, so that the ozone layer is damaged to different degrees, and the radiation dose and the intensity of ultraviolet rays are increasingly enhanced; meanwhile, the development of science and technology promotes the continuous emergence and application of novel artificial ultraviolet radiation sources, so that the influence of ultraviolet rays on human skin is becoming serious day by day. According to the band division, the ultraviolet light covers a long-wave band UVA (320-400 nm), a middle-wave band UVB (280-320 nm) and a short-wave band UVC (200-280 nm), wherein the UVA and the UVB can penetrate through the atmospheric layer to reach the earth surface, and the UVC is almost completely absorbed by the ozone layer. In daily life, sunlight is a main source of ultraviolet rays, and human skin is easily subjected to long-term exposure to sunlight and ultraviolet rays (UVR, including natural ultraviolet rays and artificial ultraviolet rays) to cause photoaging, damage to DNA (deoxyribonucleic acid) and cause immunity reduction, and even malignant skin cancer can be induced. In particular, UVA acts slowly on the dermis layer of the skin, causing browning of the skin, phototoxic or photosensitive reactions, a decrease in elasticity and the generation of wrinkles, resulting in "darker and darker" skin; UVB acts on the top layer of the skin and acts rapidly, causing skin pigmentation and brown spots, resulting in "getting more sunburned and redder" skin. Therefore, ultraviolet rays have become the biggest threat to human health, causing wrinkles, aging, laxity, black spots and even carcinogenic greatest violence of human skin. Therefore, it is very important to effectively defend all ultraviolet rays in the whole ultraviolet region, protect the human body from being damaged and delay aging. Also because of the urgent application requirements, the development of sunscreen products capable of effectively shielding ultraviolet rays has become an important direction of attention and research.

The existing sunscreen products on the market are various, and include forms of face cream, lotion, BB cream, spray, aerosol, film-forming sunscreen emulsion and the like, relatively well-known brands comprise Coppertone, ANESSA, SHISEIDO, DECORTE, Mistine, BANANA BOAT, Biore and the like, the sunscreen products have better sunscreen spectrum, but have the defects of heavy weight, whitening, greasiness, mud rubbing, strong sensitization, low light stability, poor biodegradability, insufficient skin protection effect and the like, and some products also have some safety problems, such as endocrine interference, skin permeation and potential biological toxicity. In order to overcome the above problems, new sunscreen products are continuously reported. For example, chinese patent CN110051617A reports that a sunscreen lotion with a high sun protection index, which is composed of water, ethylhexyl methoxycinnamate, bis-ethylhexyloxyphenol methoxyphenyl triazine, dioctyl carbonate, coco-caprylate/caprate, octocrylene, propylene glycol, hexyl diethylamino hydroxybenzoyl benzoate, glycerin, polydimethylsiloxane, microcrystalline cellulose, etc., can stay on the surface of skin for a long time, has improved sun protection and durability, is natural and pollution-free, has high affinity to human body, but its higher sun protection index is not good for skin health, has poor skin feel after long-term use, is greasy and heavy, is easy to cause skin allergy, and has strong irritation. Chinese invention patent CN107496276A reports an oil-in-water sunscreen cream composed of glycerin, magnesium aluminum silicate, EDTA disodium, water-dispersible titanium dioxide, ethylhexyl methoxycinnamate, homosalate, ethylhexyl salicylate, hydrogenated polyisobutene, glyceryl stearate, sodium stearoyl lactylate, and the like, because a hydrophobic film is formed on the surface of the skin, the oil-soluble sunscreen agent is uniformly attached to the skin, the water resistance is good, but the oil-in-water sunscreen cream can cause the skin to feel thick and sticky, and causes the discomfort phenomena of skin impermeability, allergy and the like, and the uniformity of the formed film is not enough. Chinese invention patent CN108366916A reports a water-in-oil emulsified spray type sunscreen cosmetic comprising 40 wt% of an ultraviolet absorber, an organically modified clay mineral, an oil phase thickener, a silicone surfactant, a spherical resin powder and a volatile silicone oil, which is particularly suitable for spraying through a sprayer, is convenient and flexible, has a good ultraviolet protection effect, but is not easy to be smeared after being sprayed on the skin, has insufficient sunscreen capability for a long time, needs to be sprayed for many times to improve the durability, and has greater skin irritation due to a higher amount of the ultraviolet absorber. Chinese patent CN103402488A discloses an oil-in-water sunscreen cosmetic composition comprising an aqueous dispersion of an oil-soluble ultraviolet absorber, a cross-linked polyether-modified silicone, a cross-linked alkyl-polyether-modified silicone, a low viscosity silicone oil, and water, which can form a coating film having a high ultraviolet protection effect when applied, can effectively protect against ultraviolet rays in UVB and UVA bands, has a water-moist cool feeling during use, and is excellent in stability, but has poor stability due to easy precipitation of the ultraviolet absorber, insufficient sunscreen durability, and poor long-term skin feel. Chinese invention patent CN109820786A reports a skin damage repairable sunscreen cream composed of 1-30 parts by mass of industrial hemp flower and leaf extract, 60-90 parts by mass of solvent, 20-35 parts by mass of additive, 0-10 parts by mass of physical sunscreen agent, 3-25 parts by mass of UVA chemical sunscreen agent, 3-20 parts by mass of UVB chemical sunscreen agent and the like, can effectively protect ultraviolet rays in UVB and UVA bands, has no stimulation to skin, can be simultaneously suitable for mild exposure of indoor ultraviolet rays and strong exposure of outdoor ultraviolet rays, can timely repair photochemical damage of ultraviolet rays to skin and slow down skin aging, but the needed industrial hemp flower and leaf extract has limited cannabidiol content, causes high product price, has high sunscreen agent component content and contains a large amount of solvent, and causes greasy, heavy and poor skin feeling. The Chinese invention patent CN109833257A reports an oil-control sun-proof BB cream which is composed of titanium dioxide, polyglycerol-2 dipolyhydroxystearate, glycerol, cyclopentadimethylsiloxane, trimethylsiloxy silicate, capric triglyceride, a sun-screening agent, spherical silicon dioxide, a methyl methacrylate cross-linked polymer, toner, a thickening agent, a humectant, phenoxyethanol, essential oil and deionized water, and has good sun-screening and oil-control functions, but the embarrassing phenomena of drying, powder removal, whitening, mud rubbing, pilling and the like are easily caused by high content of titanium dioxide, silicon dioxide and the like contained in the BB cream, so that skin pores are easily blocked, the air permeability is poor, and the damage to the skin is large.

Although the novel sunscreen cream has a certain multifunctional effect, the defects of the existing sunscreen products are partially overcome, the novel sunscreen cream still has the defects of greasiness, water intolerance, easiness in erasing and the like, the sunscreen capability and the concealment are contradictory when the novel sunscreen cream is used, the comfort is weak, and the high-end requirements of people on sunscreen products cannot be met. Therefore, the development of sunscreen products with high comfort, strong sunscreen ability and good concealment is still urgent.

Disclosure of Invention

The invention aims to provide a skin sunscreen coating liquid with good ultraviolet protection effect, good air and moisture permeability and good human body comfort and a preparation method thereof.

The comfortable skin sunscreen coating liquid provided by the invention comprises the components of vinyl silicone oil emulsion A, hydrogen-containing silicone oil emulsion B, Karstedt catalyst capsule emulsion C, ultraviolet screening agent D and auxiliary agent E; the weight ratio of each component is as follows:

vinyl silicone oil emulsion a: 55-80 wt%;

hydrogen-containing silicone oil emulsion B: 5-20 wt%;

karstedt catalyst capsule emulsion C: 2-15 wt%;

ultraviolet-shielding agent D: 2-15 wt%;

and (3) auxiliary agent E: 1-10 wt%;

the total amount of the components is 100 percent.

In the invention, the oil phase of the vinyl silicone oil emulsion A is vinyl silicone oil or a mixture of the vinyl silicone oil and solvent silicone oil. Wherein the viscosity range of the vinyl silicone oil is 500-20000 mPa.s, and the viscosity range of the solvent silicone oil is 2-50 mPa.s.

Further, the vinyl silicon oil emulsion A can be prepared by the following preparation method: dissolving a surfactant in deionized water to obtain an aqueous solution; dropwise adding a surfactant solution into vinyl silicone oil or a vinyl silicone oil/solvent silicone oil mixture, and shearing and stirring at a high speed while dropwise adding; after the dropwise addition is finished, the mixture is further sheared and dispersed at high speed for 0.5 to 2 hours.

In the invention, the hydrogen content of the hydrogen-containing silicone oil emulsion B is 0.1-2.0%.

Further, the hydrogen-containing silicone oil emulsion B can be prepared by the following preparation method: dissolving a surfactant in deionized water to obtain an aqueous solution, and dropwise adding the aqueous solution into hydrogen-containing silicone oil under high-speed shearing dispersion; after the dropwise addition is finished, the mixture is further sheared and dispersed at high speed for 0.5 to 2 hours.

Further, the solid content of the silicone oil emulsion A and the silicone oil emulsion B is 30-50 wt%.

In the Karstedt catalyst capsule emulsion C, the capsule wall material is one of polystyrene, polyacrylate, styrene-acrylate copolymer, polyvinyl acetate and a copolymer thereof, polyester, polylactic acid, polyurethane resin, ethyl cellulose, hydroxypropyl methyl cellulose, vinyl silicone oil, methyl silicone oil and hydroxyl silicone oil.

Further, the Karstedt catalyst capsule emulsion C is prepared by a solvent evaporation method or a direct emulsification method. The solid content of the emulsion is 20-40 wt%.

In the invention, the ultraviolet screening agent D comprises three types of inorganic, organic, inorganic and organic compounding.

Further, the inorganic ultraviolet shielding agent D is selected from nano silicon oxide, nano titanium oxide, nano zinc oxide, nano cerium oxide, nano iron oxide, nano magnesium oxide and nano layered double metal oxide.

Further, the organic ultraviolet screening agent D is selected from avobenzone, octocrylene, isooctyl methoxycinnamate, ethylhexyl methoxycinnamate, octyl salicylate, hydroxybenzophenone, phenylbenzimidazole sulfonic acid, octocrylene, methylbenzylidene camphor, menthyl anthranilate.

In the invention, the auxiliary agent E is one or more of a wetting agent, a delustering agent, a preservative, a thickening agent and a essence which are commonly used.

The preparation method of the comfortable skin sunscreen coating liquid comprises the following steps: and sequentially stirring and mixing the prepared vinyl silicone oil emulsion A, the prepared hydrogen-containing silicone oil emulsion B, Karstedt catalyst capsule emulsion C and the prepared ultraviolet screening agent D at a low speed, then adding the auxiliary agent E, and stirring and mixing uniformly.

Preferably, in the preparation method of the comfortable skin sunscreen coating liquid, if the ultraviolet screening agent is a pure inorganic ultraviolet screening agent, the inorganic ultraviolet screening agent is firstly dispersed in deionized water, and is uniformly dispersed by ultrasound to prepare an aqueous dispersion, and then the aqueous dispersion is added into the coating liquid; if the ultraviolet screening agent is a pure organic ultraviolet screening agent, firstly adding the organic ultraviolet screening agent into an oil phase during preparation of the vinyl silicone oil emulsion A, then emulsifying together to prepare the vinyl silicone oil emulsion A containing the organic ultraviolet screening agent, and then adding the vinyl silicone oil emulsion A into the coating liquid; if the ultraviolet screening agent is an inorganic/inorganic compound ultraviolet screening agent, the inorganic and organic ultraviolet screening agents are respectively introduced into the coating liquid according to the adding method.

The comfortable skin sunscreen coating liquid can be attached to the skin by smearing or spraying, and can be crosslinked and cured at room temperature to form a protective coating film similar to skin elasticity.

The action mechanism of the comfortable skin sunscreen coating liquid is as follows: when the coating is coated on the surface of a human body, the vinyl silicon silicone oil and the hydrogen-containing silicone oil are melted together with the volatilization of water, and are subjected to hydrosilylation crosslinking under the action of a catalyst to finally form an elastic coating film, and the mechanical property of the elastic coating film is similar to that of the skin of the human body. The ultraviolet screening agent has the function of blocking ultraviolet rays by absorbing the ultraviolet rays, and protects the skin from being damaged by the ultraviolet rays. If the ultraviolet shielding agent is an inorganic ultraviolet shielding agent, the ultraviolet shielding agent can also play a role in mechanical enhancement, and simultaneously can improve the mechanical strength of the ultraviolet shielding coating and improve the use durability of the coating on the skin surface.

The existing sunscreen products on the market are more, and the relatively well-known brands include Coppertone, ANESSA, SHISEIDO, DECORTE, Mistine, BANANA BOAT, Biore and the like, but the products cannot form an elastic coating after being coated, are easy to run off or be erased by clothes, and have short existence time on the skin surface; the coating layer has small thickness and weak ultraviolet shielding effect. In order to increase the ultraviolet shielding effect of the product, a large amount of organic ultraviolet absorbent is usually added in the product, so that the product has strong greasy feeling and poor comfort after being coated on human skin. And the existence of a large amount of organic ultraviolet screening agents brings safety hidden troubles to human bodies, and skin allergy and the like are easy to occur. The comfortable skin sunscreen coating liquid can overcome the problems of the existing sunscreen products, and has the following advantages:

(1) the coating can be applied in various ways such as coating or spraying, and can be thick-coated;

(2) the protective coating can be firmly attached to the surface of human skin and is not easy to fall off;

(3) a coating film with the similar skin mechanical strength can be formed, the surface has no stickiness, the comfort of a human body is good, and the lasting protection performance is good;

(4) the coating liquid has low content of organic ultraviolet screening agent, high safety and no skin irritation;

(5) can shield all ultraviolet rays with the wavelength of 200-400 nm ultraviolet region, namely comprises three wave bands of UVC, UVB and UVA, and can keep better transparency in a visible light region, and the harmony of the concealment and the high sun-proof capability is good;

(6) good waterproof, air and moisture permeability.

The comfortable skin sunscreen coating liquid is particularly suitable for occasions with high sunscreen requirements, such as plateau areas, tropical areas, field sports occasions and the like.

The main performance test method of the comfortable skin sunscreen coating liquid provided by the invention comprises the following steps:

(1) ultraviolet shielding performance test: coating the coating liquid on a film containing rhodamine B, placing the film in an accelerated aging instrument, and respectively testing the ultraviolet-visible absorption spectrum of the rhodamine film at different time intervals;

(2) sun protection durability test: and (3) placing the coating formed after the coating liquid is dried in an accelerated aging instrument, and testing the ultraviolet-visible transmission spectrum of the coating after aging for different time. Aging the instrument: artificial accelerated aging apparatus (model: QUV/se, Q-Lab), apparatus parameters: wavelength of 310 nm and ultraviolet intensity of 0.71W/m². And (3) circulating program: ultraviolet irradiating at 60 deg.C for 4 hr, condensing at 50 deg.C for 4 hr, and repeating above steps.

Drawings

FIG. 1 is an ultraviolet-visible transmission spectrum (film thickness: 80 μm) of the coating film containing an inorganic ultraviolet-screening agent prepared in example 1.

FIG. 2 is an ultraviolet-visible transmission spectrum (film thickness: 80 μm) of the coating film containing the organic ultraviolet-screening agent prepared in example 2.

FIG. 3 is an ultraviolet-visible transmission spectrum (film thickness: 80 μm) of the coating film containing the inorganic-organic composite ultraviolet-screening agent prepared in example 3.

FIG. 4 is a UV-visible transmission spectrum (film thickness: 80 μm) of a polysiloxane coating film containing no UV-shielding base prepared in comparative example 1.

Detailed Description

The present invention will be further described with reference to the following examples. The examples are given solely for the purpose of illustration and are not intended to be limiting.