CN113069381A - High-efficiency sunscreen liquid - Google Patents
High-efficiency sunscreen liquid Download PDFInfo
- Publication number
- CN113069381A CN113069381A CN202110364141.1A CN202110364141A CN113069381A CN 113069381 A CN113069381 A CN 113069381A CN 202110364141 A CN202110364141 A CN 202110364141A CN 113069381 A CN113069381 A CN 113069381A
- Authority
- CN
- China
- Prior art keywords
- pmma
- zno
- core
- sunscreen
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/37—Esters of carboxylic acids
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/0241—Containing particulates characterized by their shape and/or structure
- A61K8/025—Explicitly spheroidal or spherical shape
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/27—Zinc; Compounds thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/35—Ketones, e.g. benzophenone
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- A61K8/8152—Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
- A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
- A61Q19/02—Preparations for care of the skin for chemically bleaching or whitening the skin
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/41—Particular ingredients further characterized by their size
- A61K2800/412—Microsized, i.e. having sizes between 0.1 and 100 microns
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/60—Particulates further characterized by their structure or composition
- A61K2800/61—Surface treated
- A61K2800/62—Coated
- A61K2800/621—Coated by inorganic compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/60—Particulates further characterized by their structure or composition
- A61K2800/65—Characterized by the composition of the particulate/core
- A61K2800/654—The particulate/core comprising macromolecular material
Abstract
The invention provides high-efficiency sunscreen liquid, which is prepared from PMMA polymer microspheres containing-CH 2-NH2 and-CO-NH 2 groups, so that excellent adsorption sites are provided for subsequent zinc oxide deposition, a PMMA polymer microsphere core and a zinc oxide shell are conveniently formed, and the SPF value and the PA value of a sunscreen cosmetic can be remarkably improved by the inorganic core-shell structure.
Description
Technical Field
The invention belongs to the field of cosmetics, and particularly relates to a high-efficiency sunscreen lotion.
Background
With the environmental pollution and the global atmospheric destruction, more ultraviolet rays, high-energy blue light and infrared rays are irradiated on the earth surface, various harmful lights cause certain damage to human bodies, and people pay more attention to sun protection. In addition to traditional hard sunscreens: sunshades, sun protection clothing, sun protection hats, sun protection glasses, and the like; there is also an increasing demand for sunscreen skin care products having broad spectrum and high sunscreen properties. At present, most of the sunscreens used in sunscreen products on the market are pure chemical sunscreens, pure physical sunscreens or chemical sunscreens and physical sunscreens.
The traditional chemical sun-screening agent not only has potential harm to human bodies, but also has great negative influence on the environment; physical sunscreens also present potential safety hazards such as problems of oral nasal inhalation and photocatalytic activity. In recent years, more and more people like traveling near the sea, and the sun-screening agent smeared on the bodies of the people has serious influence on the marine environment and marine organisms, particularly coral reefs. Therefore, the search for safe, renewable natural substances with sunscreen properties would be an important concern in the field of sunscreen technology.
The sunscreen agent is divided into physical anti-blocking and chemical methods, the physical sunscreen agent is mainly researched intensively, the physical sunscreen agent refers to nano zinc oxide and nano titanium dioxide, and the sunscreen performance of the sunscreen agent mainly depends on the crystal form, the particle size distribution, the shape, the surface treatment technology, the wrapping technology and the collocation of the physical sunscreen agent. However, the addition of a large amount of physical sunscreen in the formula can cause the problem of poor use performance of the sunscreen product (for example, whitening after being applied to skin), especially the combination of the sunscreen product and the polymer can easily cause the product to be mud in the application process, and the zinc oxide is an amphoteric oxide and can react with other acid and alkaline substances in the formula.
Because the potential harm to human body caused by nano-scale physical sun-screening agent (particle size less than 100 nm) is not yet determined, the national food and drug administration publishes the guidelines for the declaration and evaluation of cosmetics for children, and the raw materials prepared by nano-technology are not encouraged by the regulations in the principle of formulation; the european union consumer safety science commission (SCCS) has specified nano-physical sunscreens.
Although many UV-B sunscreens are known and approved for protection against UV radiation, the search for new methods of protection against UVA radiation has become an important task in the art, with the goal of developing broad spectrum sunscreen products that can protect against UV-a and UV-B radiation. Sun Protection Factor (SPF) and UVA protection index (PFA) are commonly measured attributes of sunscreen compositions, which indicate the corresponding protection of skin from exposure to UV-B and UV-a radiation.
Zinc oxide is a globally recognized sunscreen active and has been widely used in sunscreen formulations because it is inert and does not cause irritation or irritation to consumers of sensitive skin. Zinc oxide has been approved as a UVA sunscreen ingredient primarily because of its UVA absorption. Studies have shown that micron ZnO can provide satisfactory UVA protection as indicated by PFA values determined by in vivo persistent pigment darkening; however, ZnO only provides weak UVB protection. In particular, as the fundamental dimensions of ZnO become larger, for example in the non-nanometer range, their protective effect in the UVA and UVB regions is not as effective as the nano ZnO counterparts. Thus, to meet the performance requirements of SPF 30 or higher and broad spectrum protection, ZnO is often used with other organic sunscreens and/or titanium dioxide.
Namely, the zinc oxide used as the main raw material for physical sun protection in the prior art faces the following technical problems: (1) the ZnO has too large size, so that the sun-screening performance of the ZnO is too low; (2) the small sized ZnO particles, while good in sunscreen performance, may cause human hair follicle blockage for physical sunscreens, i.e. too large ZnO particles are safe, but too low and too small ZnO particles are high, but the safety is questionable.
Disclosure of Invention
Based on the problems in the prior art, the core-shell physical sunscreen particles prepared by the invention have the advantages that the size of zinc oxide is ensured to be nanoscale, meanwhile, larger size particles are endowed, namely, the particles have sunscreen performance and safety performance, the core-shell structure takes a micron-level high polymer as a core and nanoscale zinc oxide as a shell, and the core-shell structure can be directly mixed with a sunscreen emulsion matrix in the prior art.
A high-efficiency sunscreen liquid comprises
80mg/g of trimethyl cyclohexyl salicylate;
60mg/g of octocrilin;
50mg/g octyl salicylate;
butyl methoxy dibenzoylmethane 30mg/g;
25mg/g of 4-methylbenzylidene camphor;
50-60 mg/g of PMMA @ ZnO core-shell particles.
Furthermore, in the PMMA @ ZnO core-shell particles PMMA @ ZnO, PMMA is used as a core, ZnO is used as a shell, the diameter of the PMMA core is 9-13 microns, and the ZnO shell is 50-200 nm.
Further, the preparation method of the PMMA @ ZnO core-shell particles is as follows:
1) adding 72mg of initiator azobisisobutyronitrile, 2.5g of dispersant polyvinylpyrrolidone and 0.79ml of cross-linking agent ethylene glycol dimethacrylate into a solvent of 95vol.% acetonitrile/5 vol.% toluene, and fully dispersing to obtain a solution;
2) adding 3g of methyl methacrylate and 1.5g of acrylamide into the solution obtained in the step 1), slowly introducing N2 for protection for 30min, raising the reaction temperature to 85 ℃, continuously reacting for 4 hours, ending the experiment, pouring out a product, filtering in vacuum, cleaning with tetrahydrofuran, and washing with 80 percent of wateroC, washing with deionized water to obtain a white solid;
3) ultrasonically dispersing the white solid 3-5g in 150ml of absolute ethanol, slowly adding into 75-90ml of 0.025-0.05M zinc acetate ethanol solution, and standing for 10-15 min; then adding 100-110ml of 0.05-0.075M zinc acetate ethanol solution, and continuously stirring;
4) stirring at 50-75rpm, adding 0.1-0.15M sodium hydroxide absolute ethanol solution into the solution obtained in step 3) by needle titration for 2-3h, and standing for 30-40 min;
5) filtering and drying to obtain PMMA @ ZnO core-shell particles;
6) and adding PMMA @ ZnO core-shell particles obtained after drying treatment serving as an additive into the sun-screening base solution to obtain the sun-screening solution.
Furthermore, the molar ratio of the zinc acetate to the sodium hydroxide is more than or equal to 1: 2.
Further, the program temperature of the drying treatment is 1-2 at normal temperatureoCmin is increased to 70-80oC, performing constant temperature treatment for 1-2h, stopping heating for 30-40min, and then increasing the temperature by 3-5 ℃ to 90-95 DEGoAnd C, continuing for 2-3min, and naturally cooling.
Furthermore, the SPF value of the sun-screening liquid is more than or equal to 50, and the PA value is more than or equal to 25.
The PMMA core and the nano ZnO shell are prepared by the following mechanism:
firstly, regarding the PMMA core, partial high molecular microsphere particles are usually added into the whitening cosmetic, the high molecular microspheres have excellent glossiness, good light scattering performance and whitening effect, and meanwhile, the high molecular microspheres have small density and are easy to mix with other components in the cosmetic, so that the comfort, the touch and the extensibility of the cosmetic on the skin are improved.
The invention takes methyl methacrylate and acrylamide as monomers, azodiisobutyronitrile as an initiator, polyvinylpyrrolidone as a dispersant and ethylene glycol dimethacrylate as a cross-linking agent to prepare the PMMA polymer with the surface containing two groups of-CH 2-NH2 and-CO-NH 2, -CH2-NH2 and-CO-NH 2 which are easier to enrich and adsorb Zn2+。
Secondly, dispersing a PMMA polymer with the surface containing-CH 2-NH2 and-CO-NH 2 into ethanol, adding zinc acetate, wherein the weakly acidic zinc acetate can perform adsorption reaction with PMMA with the weakly alkaline surface containing-NH 2, namely depositing zinc hydroxide seed crystals on the surface of the PMMA polymer, standing for 10-15min for full reaction, then adding 100ml of 0.05-0.075M zinc acetate with higher content than that of the zinc acetate added at one time, adding a splint, continuously slowly titrating by a needle, adding 0.1-0.15M sodium hydroxide anhydrous ethanol solution, titrating for 2-3h, standing for 30-40min, preferentially depositing large-particle hydroxide on the zinc hydroxide seed crystals deposited on the surface of the PMMA polymer, namely preferentially adsorbing and depositing seed crystals by-CH 2-NH2 and-CO-NH 2 on the surface of PMMA, and forming a Zn hydroxide shell on the surface of the PMMA by subsequent deposition reaction.
By simple drying treatment at 70-80 deg.CoC, heat treatment, dewatering to obtain ZnO, then 3-5 deg.C heating to 90-95 deg.CoAnd C, lasting for 2-3min, wherein the process mainly softens PMMA, and PMMA and ZnO are subjected to small-range mass-wall separation, and the mass-wall separation can be used as a heat absorption space to relieve the burning sensation caused by sun protection.
Advantageous technical effects
(1) According to the preparation method, the PMMA polymer microsphere containing the-CH 2-NH2 and-CO-NH 2 groups is prepared, so that excellent adsorption sites are provided for subsequent zinc oxide deposition, and the PMMA polymer microsphere core and the zinc oxide shell are conveniently formed.
(2) According to the invention, hydroxide crystal seeds are formed on the surface of PMMA in advance, so that the subsequent formation of the hydroxide shell is facilitated.
(3) According to the invention, by controlling the heat treatment means, a heat dissipation space is formed between PMMA and ZnO, so that the sun protection comfort level is improved.
(4) The sunscreen lotion microsphere prepared by the method has the advantages that the SPF value and the PA value of sunscreen cosmetics can be obviously improved.
Drawings
FIG. 1 is an SEM image of PMMA microspheres prepared by the invention.
FIG. 2 is an SEM image of PMMA @ ZnO obtained by the preparation of the present invention.
FIG. 3 TEM image of PMMA @ ZnO obtained by the inventive preparation.
FIG. 4 TEM image of PMMA @ ZnO obtained by the inventive preparation.
FIG. 5 TEM-Mapping of PMMA @ ZnO obtained by the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention.
Example 1
The efficient sunscreen liquid is characterized by comprising
80mg/g of trimethyl cyclohexyl salicylate;
60mg/g of octocrilin;
50mg/g octyl salicylate;
butyl methoxy dibenzoylmethane 30mg/g;
25mg/g of 4-methylbenzylidene camphor;
PMMA @ ZnO core-shell particles are 50 mg/g.
The preparation method of PMMA @ ZnO comprises the following steps:
1) 72mg of azobisisobutyronitrile as an initiator, 2.5g of polyvinylpyrrolidone as a dispersant, and 0.79ml of ethylene glycol dimethacrylate as a crosslinking agent were added to a solvent of 95vol.% acetonitrile/5 vol.% toluene, and sufficiently dispersed to obtain a solution.
2）Adding 3g of methyl methacrylate and 1.5g of acrylamide into the solution obtained in the step 1), slowly introducing N2 for protection for 30min, raising the reaction temperature to 85 ℃, continuously reacting for 4 hours, ending the experiment, pouring out a product, filtering in vacuum, cleaning with tetrahydrofuran, and washing with 80 percent of wateroAnd C, washing with deionized water to obtain a white solid.
3) Ultrasonically dispersing the 3g of white solid in 150ml of absolute ethyl alcohol, slowly adding the obtained solution into 75ml of 0.025M zinc acetate ethanol solution, and standing for 10 min; then added to 100ml of 0.05M ethanol solution of zinc acetate with continuous stirring.
4) Stirring speed is 50rpm, adding 0.1M sodium hydroxide absolute ethyl alcohol solution into the solution of the step 3) by needle titration, wherein the titration time is 2h, and standing for 30 min.
5) Filtering and drying to obtain PMMA @ ZnO core-shell particles, wherein the program temperature of the drying treatment is 1 at normal temperatureoCmin is raised to 70oC, performing constant temperature treatment for 1h, stopping heating for 30min, and then placing at 90 ℃ in a 3-degree-rising manneroAnd C, keeping for 2min, and naturally cooling.
6) Adding PMMA @ ZnO core-shell particles obtained after drying treatment serving as an additive into sun-screening base liquid to obtain sun-screening liquid.
Example 2
The efficient sunscreen liquid is characterized by comprising
80mg/g of trimethyl cyclohexyl salicylate;
60mg/g of octocrilin;
50mg/g octyl salicylate;
butyl methoxy dibenzoylmethane 30mg/g;
25mg/g of 4-methylbenzylidene camphor;
PMMA @ ZnO core-shell particles are 55 mg/g.
The preparation method of PMMA @ ZnO comprises the following steps:
1) 72mg of azobisisobutyronitrile as an initiator, 2.5g of polyvinylpyrrolidone as a dispersant, and 0.79ml of ethylene glycol dimethacrylate as a crosslinking agent were added to a solvent of 95vol.% acetonitrile/5 vol.% toluene, and sufficiently dispersed to obtain a solution.
2) Adding 3g of methyl methacrylate into the solution obtained in step 1)Ester and 1.5g acrylamide are slowly introduced into N2 for protection for 30min, then the temperature is raised to 85 ℃, the experiment is finished after 4 hours of continuous reaction, the product is poured out, vacuum filtration, tetrahydrofuran cleaning and 80 percentoAnd C, washing with deionized water to obtain a white solid.
3) Ultrasonically dispersing the 4g of white solid in 150ml of absolute ethanol, slowly adding the obtained solution into 82.5ml of 0.03M zinc acetate ethanol solution, and standing for 12.5 min; then adding the mixture into 105ml of 0.06M zinc acetate ethanol solution, and continuously stirring;
4) stirring speed is 70rpm, 0.13M sodium hydroxide absolute ethyl alcohol solution is added into the solution of the step 3) in a needle titration manner, the titration time is 2.5h, and standing is carried out for 35 min.
5) Filtering and drying to obtain PMMA @ ZnO core-shell particles, wherein the program temperature of the drying treatment is 1.5 at normal temperatureoCmin is increased to 75oC, performing constant temperature treatment for 1.5h, stopping heating for 35min, and then placing at 92 ℃ in a 4-degree-rise modeoAnd C, keeping for 2.5min, and naturally cooling.
6) Adding PMMA @ ZnO core-shell particles obtained after drying treatment serving as an additive into sun-screening base liquid to obtain sun-screening liquid.
Example 3
The efficient sunscreen liquid is characterized by comprising
80mg/g of trimethyl cyclohexyl salicylate;
60mg/g of octocrilin;
50mg/g octyl salicylate;
butyl methoxy dibenzoylmethane 30mg/g;
25mg/g of 4-methylbenzylidene camphor;
PMMA @ ZnO core-shell particles are 60 mg/g.
The preparation method of PMMA @ ZnO comprises the following steps:
1) 72mg of azobisisobutyronitrile as an initiator, 2.5g of polyvinylpyrrolidone as a dispersant, and 0.79ml of ethylene glycol dimethacrylate as a crosslinking agent were added to a solvent of 95vol.% acetonitrile/5 vol.% toluene, and sufficiently dispersed to obtain a solution.
2) 3g of methyl methacrylate and 1.5g of acrylamide are added to the solution obtained in step 1), and protection is slowly introduced with N230min, heating to 85 deg.C, reacting for 4 hr, pouring out, vacuum filtering, washing with tetrahydrofuran, and 80%oAnd C, washing with deionized water to obtain a white solid.
3) Ultrasonically dispersing 5g of the white solid in 150ml of absolute ethanol, slowly adding the obtained solution into 90ml of 0.05M zinc acetate ethanol solution, and standing for 15 min; then added to 110ml of 0.075M zinc acetate in ethanol with constant stirring.
4) Stirring at 75rpm, adding 0.15M sodium hydroxide absolute ethanol solution into the solution obtained in step 3) by needle titration for 3h, and standing for 40 min.
5) Filtering and drying to obtain PMMA @ ZnO core-shell particles, wherein the program temperature of the drying treatment is 2 at normal temperatureoCmin is increased to 80oC, carrying out constant temperature treatment for 2h, stopping heating for 40min, and then placing at 95 ℃ in a 5-degree liter manneroAnd C, lasting for 3min, and naturally cooling.
6) Adding PMMA @ ZnO core-shell particles obtained after drying treatment serving as an additive into sun-screening base liquid to obtain sun-screening liquid.
The PMMA @ ZnO prepared by the above examples 1-3 can well obtain a core-shell structure, as shown in figure 1, the surface of the obtained PMMA microsphere is clean and smooth, the size of the sphere is uniform, the diameter is 9-13 micrometers, ZnO as a shell is obtained on the upper surface of PMMA through subsequent zinc hydroxide deposition and drying treatment, as shown in figure 2, the clean and smooth PMMA surface becomes rough, ZnO is proved to be uniformly attached to the surface of ZnO, and the dispersibility of the sphere is better and no obvious free zinc oxide is found when the ZnO surrounds the PMMA sphere like black ring from figures 3 and 4. As shown in figure 5, by Mapping treatment on the edge of PMMA @ ZnO, it can be seen that obvious Zn and O elements are displayed at the shell, no Zn is displayed at the core, and obvious C and O elements are displayed at the inner core, thus proving the core-shell structure of PMMA @ ZnO, wherein the ZnO shell is 50-200 nm.
Comparative example 1
A sunscreen liquid comprises
80mg/g of trimethyl cyclohexyl salicylate;
60mg/g of octocrilin;
50mg/g octyl salicylate;
butyl methoxy dibenzoylmethane 30mg/g;
4-methylbenzylidene camphor 25 mg/g.
By comparing the SPF and PA experiments of the example 2 and the comparative example 1, the PMMA @ ZnO prepared by the invention has extremely high sun-screening effect, the SPF value is as high as 52.3, and the PA value is as high as 27.9.
The above-described embodiments are preferred implementations of the present invention, and the present invention may be implemented in other ways without departing from the spirit of the present invention.
Claims (6)
1. The efficient sunscreen liquid is characterized by comprising
80mg/g of trimethyl cyclohexyl salicylate;
60mg/g of octocrilin;
50mg/g octyl salicylate;
butyl methoxy dibenzoylmethane 30mg/g;
25mg/g of 4-methylbenzylidene camphor;
50-60 mg/g of PMMA @ ZnO core-shell particles.
2. The efficient sunscreen lotion according to claim 1, wherein the PMMA @ ZnO core-shell particles PMMA @ ZnO are characterized in that PMMA is used as a core, ZnO is used as a shell, the PMMA core diameter is 9-13 microns, and the ZnO shell is 50-200 nm.
3. The efficient sunscreen lotion according to claim 1, wherein the preparation method of the PMMA @ ZnO core-shell particles is as follows:
1) adding 72mg of initiator azobisisobutyronitrile, 2.5g of dispersant polyvinylpyrrolidone and 0.79ml of cross-linking agent ethylene glycol dimethacrylate into a solvent of 95vol.% acetonitrile/5 vol.% toluene, and fully dispersing to obtain a solution;
2) adding 3g of methyl methacrylate and 1.5g of acrylamide into the solution obtained in the step 1), slowly introducing N2 for protection for 30min, raising the reaction temperature to 85 ℃, continuously reacting for 4 hours, ending the experiment, pouring out a product, filtering in vacuum, cleaning with tetrahydrofuran, and washing with 80 percent of wateroC, washing with deionized water to obtain a white solid;
3) ultrasonically dispersing the white solid 3-5g in 150ml of absolute ethanol, slowly adding into 75-90ml of 0.025-0.05M zinc acetate ethanol solution, and standing for 10-15 min; then adding 100-110ml of 0.05-0.075M zinc acetate ethanol solution, and continuously stirring;
4) stirring at 50-75rpm, adding 0.1-0.15M sodium hydroxide absolute ethanol solution into the solution obtained in step 3) by needle titration for 2-3h, and standing for 30-40 min;
5) filtering and drying to obtain PMMA @ ZnO core-shell particles;
6) and adding PMMA @ ZnO core-shell particles obtained after drying treatment serving as an additive into the sun-screening base solution to obtain the sun-screening solution.
4. The efficient sunscreen liquid as claimed in claim 3, wherein the molar ratio of the zinc acetate to the sodium hydroxide is greater than or equal to 1: 2.
5. The highly effective sunscreen liquid according to claim 3, wherein the drying process is carried out at a temperature of 1-2 deg.CoCmin is increased to 70-80oC, performing constant temperature treatment for 1-2h, stopping heating for 30-40min, and then increasing the temperature by 3-5 ℃ to 90-95 DEGoAnd C, continuing for 2-3min, and naturally cooling.
6. The highly effective sunscreen lotion according to claim 1 wherein said sunscreen lotion has an SPF value of 50 or more and a PA value of 25 or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110364141.1A CN113069381B (en) | 2021-04-03 | 2021-04-03 | High-efficiency sunscreen liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110364141.1A CN113069381B (en) | 2021-04-03 | 2021-04-03 | High-efficiency sunscreen liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113069381A true CN113069381A (en) | 2021-07-06 |
| CN113069381B CN113069381B (en) | 2022-12-27 |
Family
ID=76615056
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110364141.1A Active CN113069381B (en) | 2021-04-03 | 2021-04-03 | High-efficiency sunscreen liquid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113069381B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101475726A (en) * | 2009-01-12 | 2009-07-08 | 浙江理工大学 | Polymethyl methacryate microsphere coating zinc oxide composite material and preparation thereof |
| JP2009184885A (en) * | 2008-02-07 | 2009-08-20 | National Institute Of Advanced Industrial & Technology | Core-shell type zinc oxide fine particles or dispersion containing the same, method for producing them, and their application |
| US20130177616A1 (en) * | 2010-03-19 | 2013-07-11 | Instituto De Pesquisas Tecnologicas Do Estado De Sao Paulo S.A.-Ipt | Nanostructured sun protection agent and process |
| CN104072678A (en) * | 2013-03-29 | 2014-10-01 | 中国科学院大连化学物理研究所 | Polymer microsphere, preparation and applications thereof |
| KR20150113469A (en) * | 2014-03-30 | 2015-10-08 | 주식회사 착한생각 | Coreshell inorganic material having the structure |
| CN108852875A (en) * | 2018-08-23 | 2018-11-23 | 无限极（中国）有限公司 | A kind of sunscreen composition and its cosmetics of preparation |
| CN110080011A (en) * | 2019-04-04 | 2019-08-02 | 东华大学 | A kind of functionalization schemochrome dyestuff and its preparation and application |
-
2021
- 2021-04-03 CN CN202110364141.1A patent/CN113069381B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009184885A (en) * | 2008-02-07 | 2009-08-20 | National Institute Of Advanced Industrial & Technology | Core-shell type zinc oxide fine particles or dispersion containing the same, method for producing them, and their application |
| CN101475726A (en) * | 2009-01-12 | 2009-07-08 | 浙江理工大学 | Polymethyl methacryate microsphere coating zinc oxide composite material and preparation thereof |
| US20130177616A1 (en) * | 2010-03-19 | 2013-07-11 | Instituto De Pesquisas Tecnologicas Do Estado De Sao Paulo S.A.-Ipt | Nanostructured sun protection agent and process |
| CN104072678A (en) * | 2013-03-29 | 2014-10-01 | 中国科学院大连化学物理研究所 | Polymer microsphere, preparation and applications thereof |
| KR20150113469A (en) * | 2014-03-30 | 2015-10-08 | 주식회사 착한생각 | Coreshell inorganic material having the structure |
| CN108852875A (en) * | 2018-08-23 | 2018-11-23 | 无限极（中国）有限公司 | A kind of sunscreen composition and its cosmetics of preparation |
| CN110080011A (en) * | 2019-04-04 | 2019-08-02 | 东华大学 | A kind of functionalization schemochrome dyestuff and its preparation and application |
Non-Patent Citations (3)
| Title |
|---|
| FENG BAI: "Narrow-Disperse or Monodisperse Crosslinked and Functional Core–Shell Polymer Particles Prepared by Two-Stage Precipitation Polymerization", 《JOURNAL OF APPLIED POLYMER SCIENCE》 * |
| REIKO SAITO: "Synthesis of Core–Shell Type Microsphere with Reactive Seed Microspheres", 《JOURNAL OF APPLIED POLYMER SCIENCE》 * |
| 陈碧云: "功能化聚甲基丙烯酸甲酯复合微球制备与性能研究", 《中国优秀硕士学位论文全文数据库 （电子期刊）》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113069381B (en) | 2022-12-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4030133B2 (en) | Ultraviolet shielding zinc oxide excellent in transparency and composition containing the same | |
| JP4849586B2 (en) | Cosmetics | |
| CN1231543C (en) | Particulate metal oxide | |
| KR101094141B1 (en) | Organic-inorganic Complex with UV-Blocking Effect, a Preparation method thereof, and a Use of the Same | |
| US9789037B2 (en) | Zinc oxide particle, method for producing the same, ultraviolet shielding agent, and cosmetic | |
| JP3330610B2 (en) | Photochromic composite oxide and cosmetic containing the photochromic composite oxide | |
| JP2004292266A (en) | Porous titanium oxide powder and its manufacturing method | |
| US20160347624A1 (en) | Hexagonal plate-shaped zinc oxide particles, method for production of the same, and cosmetic, filler, resin composition, infrared reflective material, and coating composition containing the same | |
| JP5075385B2 (en) | Porous titanium oxide and method for producing the same | |
| KR20110062501A (en) | Organic-inorganic composite powder, a preparation method thereof, and a use of the same | |
| JP2002154915A (en) | Cosmetic | |
| JP2004115541A (en) | Cosmetic, silica coated metallic oxide powder and method for producing the powder | |
| JP3267508B2 (en) | Silica / cerium oxide composite particles, method for producing the same, resin composition containing the same, and cosmetics | |
| CN113069381B (en) | High-efficiency sunscreen liquid | |
| CN113057896B (en) | Preparation method of sunscreen lotion | |
| AU2005226840B2 (en) | UV-protective cosmetic preparation and use of decorative pigments comprising a protective layer | |
| JP4740458B2 (en) | Cosmetics, surface-hydrophobized silica-coated metal oxide particles, silica-coated metal oxide sol, and production methods thereof | |
| JP2003192349A (en) | Close-cropped titanium oxide powder and its production method | |
| KR101578466B1 (en) | Porous sphere type zinc oxide powder of nanosize, manufacturing method thereof and color cosmetic composition using the same | |
| JP2008050242A (en) | Light multiply-scattering titanium oxide and composite body of the same | |
| KR20120033593A (en) | Composite dispersion for sun screnn and manufacturing method thereof | |
| JP4100898B2 (en) | Method for producing titanium dioxide cerium oxide composite | |
| JP2017036221A (en) | Particles for cosmetic and method for producing the same, and cosmetic composition using particles for cosmetic | |
| JP3644563B2 (en) | How to evaluate makeup cosmetics | |
| KR100602731B1 (en) | Cosmetic Raw Materials With Improved Feeling of Use, Their Preparation Method and Cosmetics Comprising Them |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20221206 Address after: March 2014, Floor 6, Building 2, No. 50, Maoyuan Road, Fengxian District, Shanghai Applicant after: Budweiser (Shanghai) Cosmetics Co.,Ltd. Address before: 010021 School of chemistry and chemical engineering, Inner Mongolia University, qiaokao West Street, Saihan District, Hohhot City, Inner Mongolia Autonomous Region Applicant before: Zheng Xiaoqing |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |