CN113057896B - Preparation method of sunscreen lotion - Google Patents
Preparation method of sunscreen lotion Download PDFInfo
- Publication number
- CN113057896B CN113057896B CN202110364142.6A CN202110364142A CN113057896B CN 113057896 B CN113057896 B CN 113057896B CN 202110364142 A CN202110364142 A CN 202110364142A CN 113057896 B CN113057896 B CN 113057896B
- Authority
- CN
- China
- Prior art keywords
- solution
- sunscreen
- zno
- pmma
- core
- 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.)
- Active
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
- A61K8/02—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
- A61K8/72—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
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Abstract
The invention provides a preparation method of a sunscreen lotion microsphere, which is characterized in that the PMMA polymer microsphere containing-CH 2-NH2 and-CO-NH 2 groups is prepared, so that excellent adsorption sites are provided for subsequent zinc oxide deposition, a PMMA polymer microsphere core and a zinc oxide shell are convenient to form, and the inorganic core-shell structure can obviously improve the SPF value and the PA value of sunscreen cosmetics.
Description
Technical Field
The invention belongs to the field of cosmetics, and particularly relates to a preparation method of a sunscreen lotion microsphere, belonging to additives of sunscreen lotions.
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 invention discloses a sunscreen agent, which is divided into physical anti-blocking and chemical methods, and mainly focuses on researching a physical sunscreen agent, wherein the physical sunscreen agent refers to nano zinc oxide and nano titanium dioxide, and the sunscreen performance of the physical 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-Sup>A and UV-B radiation. The Sun Protection Factor (SPF) and UVA protection index (PFA) are commonly measured attributes of sunscreen compositions that indicate Sup>A corresponding protection of skin from exposure to UV-B and UV-Sup>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 pigmentation; however, znO provides only 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. Therefore, in order 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 is oversized, which results in excessively low sun protection performance; (2) The small size of the ZnO particles, although good in sunscreen performance, may cause the body to hair follicle blockade in physical sunscreens where 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 preparation method of sunscreen lotion microspheres comprises the following steps:
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 temperature to 85 ℃, continuously reacting for 4 hours, ending the experiment, pouring out the product, filtering in vacuum, cleaning with tetrahydrofuran, and 80 percent o C, washing with deionized water to obtain a white solid;
3) Ultrasonically dispersing the 3-5g white solid in 150ml of absolute ethyl alcohol, slowly adding the obtained solution into 75-90ml of 0.025-0.05M zinc acetate ethanol solution, and standing; then adding 100-110ml of 0.05-0.075M zinc acetate ethanol solution, and continuously stirring;
4) Stirring at 50-75rpm, titrating the solution obtained in step 3) with a needle, adding 0.1-0.15M sodium hydroxide absolute ethanol solution for 2-3h, and standing for 30-40min;
5) Filtering and drying to obtain PMMA @ ZnO core-shell particles;
6) Adding PMMA @ ZnO core-shell particles obtained after drying treatment serving as an additive into the sunscreen base solution to obtain the sunscreen solution.
Further, the molar ratio of the zinc acetate to the sodium hydroxide is more than or equal to 1.
Further, the program temperature of the drying treatment is 1-2 at normal temperature o Raising Cmin to 70-80 ℃, carrying out constant temperature treatment for 1-2h, stopping heating for 30-40min, then raising at 3-5 ℃ and placing at 90-95 DEG o And C, continuing for 2-3min, and naturally cooling.
Further, PMMA is taken as a core and ZnO is taken as a shell in the PMMA @ ZnO, the diameter of the PMMA core is 9-13 microns, and the ZnO shell is 50-200nm.
Furthermore, PMMA is used as a core in the PMMA @ ZnO, znO is used as a shell, the diameter of the PMMA core is 9-13 microns, and the ZnO shell is 50-200nm.
Furthermore, the PMMA @ ZnO core-shell particles are used as additives, and the proportion of the PMMA @ ZnO core-shell particles in the sunscreen base liquid is 50-60mg/g.
Further, the sunscreen cream, the sunscreen lotion and the sunscreen water.
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-CH 2-NH2 and-CO-NH 2 groups, and the-CH 2-NH2 and-CO-NH 2 are easier to enrich and adsorb Zn 2+ 。
Secondly, dispersing a PMMA polymer containing-CH 2-NH2 and-CO-NH 2 on the surface into ethanol, adding zinc acetate, wherein the weakly acidic zinc acetate can perform adsorption reaction with PMMA containing-NH 2 on the weakly alkaline surface, namely depositing zinc hydroxide seed crystals on the surface of the PMMA polymer, standing for 10-15min for full reaction, then adding 100-110ml of 0.05-0.075M zinc acetate with the content higher than that of the zinc acetate added once, adding a splint, continuously and slowly titrating by a needle, adding 0.1-0.15M sodium hydroxide absolute 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 the hydroxide seed crystals by-CH 2-NH2 and-CO-NH 2 on the surface of PMMA, and forming Zn hydroxide shells on the surface of PMMA through subsequent deposition reaction.
By simple drying treatment at 70-80 deg.C o C heat treatment, dewatering to obtain ZnO, and 3-5 oC The volume of the solution is increased to 90-95 min o And 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) The inorganic sunscreen particles have good stability, do not cause inflammation, and are strong in skin friendliness.
(4) 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.
(5) 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 present invention.
FIG. 3 TEM image of PMMA @ ZnO obtained by the preparation of the present invention.
FIG. 4 TEM image of PMMA @ ZnO obtained by the present invention.
FIG. 5 TEM-Mapping pattern 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
A preparation method of sunscreen lotion microspheres 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 temperature to 85 ℃, continuously reacting for 4 hours, ending the experiment, pouring out the product, filtering in vacuum, cleaning with tetrahydrofuran, and 80 percent o And 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 10min; then, the mixture was added to 100ml of a 0.05M ethanol solution of zinc acetate, and the stirring was continued.
4) Stirring speed is 50rpm, 0.1M sodium hydroxide absolute ethyl alcohol solution is titrated into the solution in the step 3) by a needle, the titration time is 2h, and standing is carried out for 30min.
5) Filtering, drying to obtain PMMA @ ZnO core-shell particles, wherein the program temperature of the drying treatment is 1 at normal temperature o Cmin is raised to 70 o C, performing constant temperature treatment for 1h, stopping heating for 30min, and then placing at 90 ℃ in a 3-degree-rising manner o And C, keeping for 2min, and naturally cooling.
6) Adding PMMA @ ZnO core-shell particles obtained after drying treatment serving as an additive into the sunscreen base solution to obtain the sunscreen solution.
Example 2
A preparation method of sunscreen lotion microspheres 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, and thenHeating to 85 deg.C, reacting for 4 hr, pouring out the product, vacuum filtering, cleaning with tetrahydrofuran, and 80% o And 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 12.5min; then adding the mixture into 105ml of 0.06M zinc acetate ethanol solution, and continuously stirring;
4) Stirring at 70rpm, adding 0.13M sodium hydroxide absolute ethanol solution into the solution obtained in step 3) by needle titration for 2.5h, and standing for 35min.
5) Filtering, drying to obtain PMMA @ ZnO core-shell particles, wherein the program temperature of the drying treatment is 1.5 at normal temperature o Cmin is increased to 75 o C, performing constant temperature treatment for 1.5h, stopping heating for 35min, and then placing at 92 ℃ in a 4-degree-rise mode o And C, keeping for 2.5min, and naturally cooling.
6) Adding PMMA @ ZnO core-shell particles obtained after drying treatment serving as an additive into the sunscreen base solution to obtain the sunscreen solution.
Example 3
A preparation method of sunscreen lotion microspheres 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 temperature to 85 ℃, continuously reacting for 4 hours, ending the experiment, pouring out the product, filtering in vacuum, cleaning with tetrahydrofuran, and 80 percent o And C, washing with deionized water to obtain a white solid.
3) Ultrasonically dispersing the 5g of white solid in 150ml of absolute ethyl alcohol, slowly adding the obtained solution into 90ml of 0.05M zinc acetate ethanol solution, and standing for 15min; then added to 110ml of a 0.075M solution of zinc acetate in ethanol, and stirred continuously.
4) Stirring speed is 75rpm, 0.15M sodium hydroxide absolute ethyl alcohol solution is added into the solution in the step 3) through needle titration, titration time is 3h, and standing is carried out for 40min.
5) Filtering, drying to obtain PMMA @ ZnO core-shell particles, wherein the program temperature of the drying treatment is 2 at normal temperature o Cmin is increased to 80 o C, performing constant temperature treatment for 2 hours, stopping heating for 40min, and then placing at 95 ℃ in a 5-degree liter manner o And C, keeping for 3min, and naturally cooling.
6) Adding PMMA @ ZnO core-shell particles obtained after drying treatment serving as an additive into the sunscreen base solution to obtain the sunscreen solution.
The PMMA @ ZnO prepared by the above examples 1-3 can well obtain a core-shell structure, as shown in the attached drawing 1, the surface of the obtained PMMA microsphere is clean and smooth, the sphere has uniform size, the diameter is 9-13 micrometers, and the ZnO shell is obtained on the upper surface of the PMMA through subsequent zinc hydroxide deposition and drying treatment, as shown in the attached drawing 2, the clean and smooth PMMA surface becomes rough, znO is proved to be uniformly attached to the ZnO surface, and the ZnO surrounds the PMMA sphere like a black ring from the attached drawings 3 and 4, so that the dispersity of the sphere is better, and no obvious free zinc oxide is found. As shown in attached figure 5, when the Mapping treatment is carried out on the PMMA @ ZnO edge, obvious Zn and O elements are shown at the shell, no Zn exists at the core, and obvious C and O elements exist at the inner core, namely the core-shell structure of PMMA @ ZnO is proved, wherein the ZnO shell is 50-200nm.
Comparative example 1
A preparation method of sunscreen lotion microspheres 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 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 the product, performing vacuum filtration, washing with tetrahydrofuran, and performing 80 percent reaction o And C, washing with deionized water to obtain a white solid.
3) Ultrasonically dispersing the 4g of white solid in 150ml of absolute ethyl alcohol; then 105ml of 0.06M ethanol solution of zinc acetate was added with continuous stirring.
4) Stirring at 70rpm, adding 0.13M sodium hydroxide absolute ethanol solution into the solution obtained in step 3) by needle titration for 2.5h, and standing for 35min.
5) Filtering, drying to obtain PMMA @ ZnO core-shell particles, wherein the program temperature of the drying treatment is 1.5 at normal temperature o Cmin is increased to 75 o C, performing constant temperature treatment for 1.5h, stopping heating for 35min, and then placing at 92 ℃ in a 4-degree-rise mode o And C, keeping for 2.5min, and naturally cooling.
6) Adding PMMA @ ZnO core-shell particles obtained after drying treatment as an additive into the sunscreen base solution to obtain the sunscreen solution.
ZnO prepared by the method is completely isolated from PMMA, and hydroxide of Zn is dissociated outside the PMMA, so that the nuclear shell structure cannot exist.
Example 4
A 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;
PMMA @ ZnO core-shell particles are 55mg/g;
the preparation method of the PMMA @ ZnO core-shell particles comprises the following steps:
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 performing 80 percent reaction o C deionized Water washingWashing to obtain a white solid;
3) Ultrasonically dispersing the 4g of white solid in 150ml of absolute ethyl alcohol, slowly adding the absolute ethyl alcohol into 82.5ml of 0.03M zinc acetate ethanol solution, and standing for 12.5min; then adding the mixture into 105ml of 0.06M zinc acetate ethanol solution, and continuously stirring;
4) Stirring at 70rpm, titrating the solution obtained in the step 3) with a needle, adding 0.13M sodium hydroxide absolute ethyl alcohol solution for 2.5h, and standing for 35min;
5) Filtering, drying to obtain PMMA @ ZnO core-shell particles, wherein the program temperature of the drying treatment is 1.5 at normal temperature o Cmin is increased to 75 o C, performing constant temperature treatment for 1.5h, stopping heating for 35min, and then placing at 92 ℃ in a 4-degree-rise mode o And C, keeping for 2.5min, and naturally cooling.
6) Adding PMMA @ ZnO core-shell particles obtained after drying treatment as an additive into the sunscreen base solution to obtain the sunscreen solution.
Comparative example 2
A sunscreen liquid comprises
80mg/g of trimethyl cyclohexyl salicylate;
60mg/g of octocrylene;
50mg/g of octyl salicylate;
butyl methoxy dibenzoylmethane 30mg/g;
4-methylbenzylidene camphor 25mg/g.
By comparing the SPF and PA experiments of example 4 and comparative example 2, 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 can be implemented in other ways without departing from the spirit of the present invention.
Claims (1)
1. A preparation method of a sun-screening liquid is characterized in that the sun-screening liquid comprises
80mg/g of trimethyl cyclohexyl salicylate;
60mg/g of octocrilin;
50mg/g of octyl salicylate;
butyl methoxy dibenzoylmethane 30mg/g;
25mg/g of 4-methylbenzylidene camphor;
55mg/g of poly (methyl methacrylate-acrylamide) polymer @ ZnO core-shell particles;
the preparation method of the poly (methyl methacrylate-acrylamide) polymer @ ZnO core-shell particles comprises the following steps:
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) To the solution obtained in step 1) were added 3g of methyl methacrylate and 1.5g of acrylamide, and N was slowly passed through 2 Protecting for 30min, heating to 85 deg.C, reacting for 4 hr, pouring out, vacuum filtering, washing with tetrahydrofuran, and washing with 80 deg.C deionized water to obtain white solid;
3) Ultrasonically dispersing 4g of white solid in 150ml of absolute ethanol, slowly adding the white solid into 82.5ml of 0.03M zinc acetate ethanol solution, and standing for 12.5min; then adding the mixture into 105ml of 0.06M zinc acetate ethanol solution, and continuously stirring;
4) Stirring at 70rpm, titrating the solution obtained in the step 3) with a needle, adding 0.13M sodium hydroxide absolute ethyl alcohol solution for 2.5h, and standing for 35min;
5) Filtering, drying to obtain poly (methyl methacrylate-acrylamide) polymer @ ZnO core-shell particles, wherein the temperature of the drying process is increased to 75 ℃ at normal temperature at 1.5 ℃/min, treating for 1.5h at constant temperature, stopping heating for 35min, increasing to 92 ℃ at 4 ℃/min, keeping for 2.5min, and naturally cooling.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110364142.6A CN113057896B (en) | 2021-04-03 | 2021-04-03 | Preparation method of sunscreen lotion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110364142.6A CN113057896B (en) | 2021-04-03 | 2021-04-03 | Preparation method of sunscreen lotion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113057896A CN113057896A (en) | 2021-07-02 |
| CN113057896B true CN113057896B (en) | 2022-12-16 |
Family
ID=76565550
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110364142.6A Active CN113057896B (en) | 2021-04-03 | 2021-04-03 | Preparation method of sunscreen lotion |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113057896B (en) |
Citations (2)
| 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 |
| 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 |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100890428B1 (en) * | 2007-08-20 | 2009-03-26 | 주식회사 선진화학 | Polymer composite particles containing sunscreen agents for cosmetic composition and the method for preparing thereof |
| JP5392697B2 (en) * | 2008-02-07 | 2014-01-22 | 独立行政法人産業技術総合研究所 | Core-shell type zinc oxide fine particles or dispersion containing the same, their production method and use |
| 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 |
| CN104072678B (en) * | 2013-03-29 | 2017-02-08 | 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 |
| CN110080011B (en) * | 2019-04-04 | 2021-11-09 | 东华大学 | Functional structural color dye and preparation and application thereof |
-
2021
- 2021-04-03 CN CN202110364142.6A patent/CN113057896B/en active Active
Patent Citations (2)
| 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 |
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| 功能化聚甲基丙烯酸甲酯复合微球制备与性能研究;陈碧云;《中国优秀硕士学位论文全文数据库 （电子期刊）》;20141231;第29页倒数第2段，第48页第3段 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113057896A (en) | 2021-07-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101094141B1 (en) | Organic-inorganic Complex with UV-Blocking Effect, a Preparation method thereof, and a Use of the Same | |
| JP4849586B2 (en) | Cosmetics | |
| JP3520785B2 (en) | Zinc oxide particle composition with suppressed surface activity, method for producing the same, and cosmetic containing the composition | |
| CA2534389C (en) | Surface-modified zinc oxides | |
| JPH11193354A (en) | Silica-coated zinc oxide particle, its preparation, and composition containing it | |
| WO2004085315A1 (en) | Porous titanium oxide powder and method for production thereof | |
| JP3330610B2 (en) | Photochromic composite oxide and cosmetic containing the photochromic composite oxide | |
| JP3894597B2 (en) | Ultrafine titanium oxide and method for producing the same | |
| JP4890251B2 (en) | Metal oxide dispersion method | |
| JP2006514115A (en) | Sunscreen | |
| KR102414297B1 (en) | Silicon oxide-coated zinc oxide and method for preparing same, and composition and cosmetic material containing silicon oxide-coated zinc oxide | |
| KR20110062501A (en) | Organic-inorganic composite powder, a preparation method thereof, and a use of the same | |
| JP7084986B2 (en) | Hydroxycinnamic acid ester and silanol adduct film Inorganic UV protection agent | |
| JP3267508B2 (en) | Silica / cerium oxide composite particles, method for producing the same, resin composition containing the same, and cosmetics | |
| CN113057896B (en) | Preparation method of sunscreen lotion | |
| CN113069381B (en) | High-efficiency sunscreen liquid | |
| AU2005226840B2 (en) | UV-protective cosmetic preparation and use of decorative pigments comprising a protective layer | |
| KR101578466B1 (en) | Porous sphere type zinc oxide powder of nanosize, manufacturing method thereof and color cosmetic composition using the same | |
| KR20120033593A (en) | Composite dispersion for sun screnn and manufacturing method thereof | |
| JP2008050242A (en) | Light multiply-scattering titanium oxide and composite body of the same | |
| JP4100898B2 (en) | Method for producing titanium dioxide cerium oxide composite | |
| KR101236770B1 (en) | Complex powder of Zinc oxide / titanium dioxide and preparation method of the same | |
| JP3644563B2 (en) | How to evaluate makeup cosmetics | |
| KR100602731B1 (en) | Cosmetic Raw Materials With Improved Feeling of Use, Their Preparation Method and Cosmetics Comprising Them | |
| CN111346022A (en) | Light-sensitive sun-proof pressed powder |
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 | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20221111 Address after: 342800 Industrial Park, Ningdu County, Ganzhou City, Jiangxi Province Applicant after: JIANGXI YONGTONG TECHNOLOGY 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 |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |