CN113069381B - High-efficiency sunscreen liquid - Google Patents

High-efficiency sunscreen liquid Download PDF

Info

Publication number
CN113069381B
CN113069381B CN202110364141.1A CN202110364141A CN113069381B CN 113069381 B CN113069381 B CN 113069381B CN 202110364141 A CN202110364141 A CN 202110364141A CN 113069381 B CN113069381 B CN 113069381B
Authority
CN
China
Prior art keywords
zno
core
acrylamide
methyl methacrylate
polymer
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
Application number
CN202110364141.1A
Other languages
Chinese (zh)
Other versions
CN113069381A (en
Inventor
郑小青
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Budweiser Shanghai Cosmetics Co ltd
Original Assignee
Budweiser Shanghai Cosmetics Co ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Budweiser Shanghai Cosmetics Co ltd filed Critical Budweiser Shanghai Cosmetics Co ltd
Priority to CN202110364141.1A priority Critical patent/CN113069381B/en
Publication of CN113069381A publication Critical patent/CN113069381A/en
Application granted granted Critical
Publication of CN113069381B publication Critical patent/CN113069381B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/37Esters of carboxylic acids
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0241Containing particulates characterized by their shape and/or structure
    • A61K8/025Explicitly spheroidal or spherical shape
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/27Zinc; Compounds thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/35Ketones, e.g. benzophenone
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141Compositions 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
    • A61K8/8152Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00Barrier 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
    • A61Q17/04Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • A61Q19/02Preparations for care of the skin for chemically bleaching or whitening the skin
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/41Particular ingredients further characterized by their size
    • A61K2800/412Microsized, i.e. having sizes between 0.1 and 100 microns
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/60Particulates further characterized by their structure or composition
    • A61K2800/61Surface treated
    • A61K2800/62Coated
    • A61K2800/621Coated by inorganic compounds
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/60Particulates further characterized by their structure or composition
    • A61K2800/65Characterized by the composition of the particulate/core
    • A61K2800/654The particulate/core comprising macromolecular material

Landscapes

  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Epidemiology (AREA)
  • Birds (AREA)
  • Emergency Medicine (AREA)
  • Dermatology (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Cosmetics (AREA)

Abstract

The invention provides a high-efficiency sunscreen lotion, which is characterized in that PMMA polymer microspheres containing-CH 2-NH2 and-CO-NH 2 groups are prepared, 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 obviously improved by the inorganic core-shell structure.

Description

High-efficiency sunscreen liquid
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 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 (the particle size is less than 100 nm) is not 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 formula principle; 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. Sun Protection Factor (SPF) and UVA protection index (PFA) are commonly measured attributes of sunscreen compositions that indicate the 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 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 is oversized, resulting in too low sunscreen properties; (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 octocrylene;
50mg/g octyl salicylate;
butyl methoxy dibenzoylmethane 30mg/g;
25mg/g of 4-methylbenzylidene camphor;
PMMA @ ZnO core-shell particles 50-60 mg/g.
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 50-200nm.
Further, 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, 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 10-15min; 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.
Furthermore, the molar ratio of the zinc acetate to the sodium hydroxide is not less than 1:2.
Further, the program temperature of the drying treatment is 1-2 at normal temperature o Cmin is increased to 70-80 o C, performing constant temperature treatment for 1-2h, stopping heating for 30-40min, and then increasing the temperature by 3-5 ℃ to 90-95 DEG o And 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-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 with-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 with-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 higher content than that of the zinc acetate added at one time, adding a splint, continuously and 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 the hydroxide through-CH 2-NH2 and-CO-NH 2N on the surface of PMMA, and forming a Zn hydroxide shell 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, then 3-5 deg.C heating to 90-95 deg.C 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) According to the invention, by controlling a heat treatment means, a heat dissipation space is formed between PMMA and ZnO, and the sun protection comfort 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 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
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 50mg/g.
The preparation method of PMMA @ ZnO is as follows:
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 performing 80 percent reaction 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 absolute ethyl alcohol 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, adding 0.1M sodium hydroxide absolute ethyl alcohol solution into the solution in the step 3) by needle titration, wherein the titration time is 2h, and standing 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, carrying out constant temperature treatment for 1h, stopping heating for 30min, and then increasing at 3 DEGIs arranged at 90 o And C, keeping for 2min, 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.
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 55mg/g.
The preparation method of PMMA @ ZnO is as follows:
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 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 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
The efficient sunscreen liquid is characterized by comprising
80mg/g of trimethyl cyclohexyl salicylate;
60mg/g of octocrylene;
50mg/g octyl salicylate;
butyl methoxy dibenzoylmethane 30mg/g;
25mg/g of 4-methylbenzylidene camphor;
PMMA @ ZnO core-shell particles 60mg/g.
The preparation method of PMMA @ ZnO is as follows:
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 performing 80 percent reaction 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, 110ml of a 0.075M ethanol solution of zinc acetate was added thereto, and the stirring was continued.
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 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 C, holdingContinuing 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 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 25mg/g.
Figure DEST_PATH_IMAGE001
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 (1)

1. The sunscreen lotion 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;
poly (methyl methacrylate-acrylamide) polymer @ ZnO core-shell particles 50-60 mg/g;
the poly (methyl methacrylate-acrylamide) polymer in the poly (methyl methacrylate-acrylamide) polymer @ ZnO is taken as a core, znO is taken as a shell, the diameter of the poly (methyl methacrylate-acrylamide) polymer core is 9-13 mu m, the ZnO shell is 50-200nm,
the preparation method of the poly (methyl methacrylate-acrylamide) polymer @ ZnO core-shell particle 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 3-5g of white solid in 150ml of absolute ethanol, slowly adding 75-90ml of 0.025-0.05M zinc acetate ethanol solution, and standing for 10-15min; then adding 100-110ml of 0.05-0.075M zinc acetate ethanol solution, and continuously stirring;
4) Stirring at 50-75rpm, titrating the needle in the solution obtained in the step 3) with 0.1-0.15M sodium hydroxide anhydrous ethanol solution for 2-3h, and standing for 30-40min;
5) Filtering, drying to obtain poly (methyl methacrylate-acrylamide) polymer @ ZnO core-shell particles, wherein the temperature of the drying process is increased to 70-80 ℃ at normal temperature at 1-2 ℃/min, treating at constant temperature for 1-2h, stopping heating for 30-40min, increasing to 90-95 ℃ at 3-5 ℃/min, continuing for 2-3min, naturally cooling,
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.
CN202110364141.1A 2021-04-03 2021-04-03 High-efficiency sunscreen liquid Active CN113069381B (en)

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 CN113069381A (en) 2021-07-06
CN113069381B true 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)

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN101475726B (en) * 2009-01-12 2010-08-18 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
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
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
CN110080011B (en) * 2019-04-04 2021-11-09 东华大学 Functional structural color dye and preparation and application thereof

Also Published As

Publication number Publication date
CN113069381A (en) 2021-07-06

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
JP4528776B2 (en) Zinc oxide powder produced by thermal decomposition and surface-modified
JP4030133B2 (en) Ultraviolet shielding zinc oxide excellent in transparency and composition containing the same
CN1231543C (en) Particulate metal oxide
KR101769170B1 (en) Oil-in-water-type emulsion cosmetic
JPH11193354A (en) Silica-coated zinc oxide particle, its preparation, and composition containing it
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
JP3330610B2 (en) Photochromic composite oxide and cosmetic containing the photochromic composite oxide
JP2687640B2 (en) Ultrafine zinc oxide powder having excellent ultraviolet absorption capacity and method for producing the same
KR20150113469A (en) Coreshell inorganic material having the structure
CN113069381B (en) High-efficiency sunscreen liquid
CN113057896B (en) Preparation method of sunscreen lotion
US20100291166A1 (en) Use of nitrogen-doped titanium oxide nanoparticles as agents for protecting against ultraviolet radiation
AU2005226840B2 (en) UV-protective cosmetic preparation and use of decorative pigments comprising a protective layer
KR20120033593A (en) Composite dispersion for sun screnn and manufacturing method thereof
JP2008050242A (en) Light multiply-scattering titanium oxide and composite body of the same
KR101578466B1 (en) Porous sphere type zinc oxide powder of nanosize, manufacturing method thereof and color cosmetic composition using the same
KR102494433B1 (en) Development of core-shell microparticle
JP4100898B2 (en) Method for producing titanium dioxide cerium oxide composite
JP3644563B2 (en) How to evaluate makeup cosmetics
KR100602731B1 (en) Cosmetic Raw Materials With Improved Feeling of Use, Their Preparation Method and Cosmetics Comprising Them
TWI496586B (en) Modified composite microparticle, manufacturing method therepf and sunblock formulation thereof
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: 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

GR01 Patent grant
GR01 Patent grant