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CN108743411A - A kind of method that LBL self-assembly prepares sun-proof Nano capsule - Google Patents

A kind of method that LBL self-assembly prepares sun-proof Nano capsule Download PDF

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Publication number
CN108743411A
CN108743411A CN201810696441.8A CN201810696441A CN108743411A CN 108743411 A CN108743411 A CN 108743411A CN 201810696441 A CN201810696441 A CN 201810696441A CN 108743411 A CN108743411 A CN 108743411A
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Prior art keywords
solution
added
sun
nano capsule
proof
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CN201810696441.8A
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Inventor
纪红兵
李有梅
曾雪敏
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Huizhou Research Institute of Sun Yat Sen University
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Huizhou Research Institute of Sun Yat Sen University
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Priority to CN201810696441.8A priority Critical patent/CN108743411A/en
Publication of CN108743411A publication Critical patent/CN108743411A/en
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    • 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
    • A61K8/04Dispersions; Emulsions
    • A61K8/06Emulsions
    • A61K8/068Microemulsions
    • 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
    • A61K8/20Halogens; 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
    • A61K8/36Carboxylic acids; Salts or anhydrides thereof
    • A61K8/361Carboxylic acids having more than seven carbon atoms in an unbroken chain; Salts or anhydrides 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
    • A61K8/40Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/44Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives 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
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73Polysaccharides
    • A61K8/733Alginic acid; Salts 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
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73Polysaccharides
    • A61K8/736Chitin; Chitosan; Derivatives 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
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/86Polyethers
    • 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
    • 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
    • A61K2800/413Nanosized, i.e. having sizes below 100 nm

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  • 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)
  • Chemical & Material Sciences (AREA)
  • Emergency Medicine (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Dermatology (AREA)
  • Cosmetics (AREA)

Abstract

The invention discloses a kind of methods that LBL self-assembly prepares sun-proof Nano capsule, include the following steps:(1) core material, composite emulsifier are placed in beaker;Deionized water is added, in 25-40 DEG C of water-bath;(2) chitosan solution is prepared, acetic acid/sodium acetate buffer dissolving is added, pH is in 3-4.5;(3) step (1) solution, volume ratio 1 is added:1;In 25-40 DEG C of water-bath;(4) sodium alginate aqueous solution is prepared, pH is in 6-8 for control;(5) two level solution is added;(6) curing agent solution is prepared;(7) it is added in curing agent solution, obtains sun-proof Nano capsule.Stable charged drop is prepared as template by compounding nonionic emulsifier and ionic emulsifying agent, and complicated operation such as removing template is gone in release, and wall material thickness is controlled by LBL self-assembly, forms fine and close capsule wall, content is avoided to leak.Average grain diameter is between 200-400nm, and PDI range 0.1-0.3 adapt to ultra light sun block lotion, and cream prepares environment;Gained Nano capsule has the comparable sun-proof result of sun-screening agent.

Description

A kind of method that LBL self-assembly prepares sun-proof Nano capsule
Technical field
The invention belongs to field of fine chemical, and in particular to a kind of technology of preparing of sun-proof Nano capsule.
Background technology
It is generally known that the ultraviolet light in daylight is divided into three types:Ultraviolet C (200~290 nm), Ultraviolet B (290 ~320 nm) and ultraviolet light,long wave (320~400 nm), short wave ultraviolet C pathogenic effects are most strong, but the shortwave contained in daylight is purple Outside line is almost fully absorbed by ozone layer, and the ultraviolet light for reaching ground is largely long wave ultraviolet, and only a few is that medium wave is ultraviolet Line.Ultraviolet B radiation B has erythema effect to human body, and long-term or excessive exposure can cause the chronic disease of skin, for example induce With exacerbation idiopathic illumination skin disease, causes scytitis to react, lead to red and swollen decortication;Long wave ultraviolet A can be attacked through epidermis Skin corium is hit, enables ossein and elastin laminin in skin be inflicted heavy losses on, and dermal cell self-protection ability is poor, minimal amount Long wave ultraviolet A just can cause great damage.
With the promotion of people's quality of life, more and more people keep out ultraviolet light using sun-proof chemical product, commonly Sun-proof chemical product is divided into physical sunscreen and chemical sunscreen, and physical sunscreen is mainly that titanium dioxide and Zinc oxide particles reflection are ultraviolet Line, due to the characteristic of itself, smearing has sense of discomfort on the skin, and content height can also influence colour of skin beauty etc.;On the contrary, chemistry is anti- Solarization ultraviolet absorption effect is notable, and chemical compatibility is good, and skin sense is suitble to.Although chemical sun can effectively inhibit ultraviolet in daylight Beta radiation, but also bring some harm during use:(1) sunscreen products intersect allergic phenomena and photosensitization caused by compounding Disease.(2) there is penetrability to skin, chemical sun molecular weight is smaller, has very strong skin penetration characteristics, security performance Receive the concern of people.(3) photo-labile, most sun-screening agents shine degrade under light illumination, are generated in degradation process high Living radical, damages organism macromolecular and cell, and unsaturated fatty acid in oxysome causes human body blood circulation to be deteriorated, Influence itself spf value simultaneously.
Chemical sun is used for greater safety, sun-proof Nano capsule is now prepared using LBL self-assembly method, by changing The thickness for becoming assembling number of plies regulation and control Nano capsule cyst wall, realizes the Controlled release of sun-screening agent.The sun-proof nanometre glue formed after package Capsule can provide the ultraviolet absorption effect for being equal to sun-screening agent, and promote sun-screening agent more stable, long-acting, mild, and it is green to cater to safety The demand in the sun-proof market of color.Sun-proof Nano capsule at present on the market is fewer, and sun-proof Nano capsule prepared by the present invention is with steady It is template to determine charged drop, and the wall material for adding oppositely charged carries out layer assembly, and tight can not only effectively inhibit anti- The release of agent is shone, also there is good dispersibility and stability, it is good with sun-proof articles compatibility.
Invention content
It is an object of the invention to overcome the shortcomings of at present sunscreen capsule on the market, it is anti-to provide a kind of LBL self-assembly preparation The method for shining Nano capsule, to solve the problems such as sun-proof Nano capsule preparation process is complicated, template remains, stability is poor.
To achieve the goals above, the present invention adopts the following technical scheme that:
A kind of method that LBL self-assembly prepares sun-proof Nano capsule, includes the following steps:
(1) core material, composite emulsifier are placed in beaker, the core material and composite emulsifier 1:1-1:2;
Control mixing speed is 250-1250 rpm;
Deionized water is added in beaker, the deionized water is 68%-98% by weight;
In 25-40 DEG C of water-bath 10-30min, obtain stablizing negatively charged drop primary emulsion (NEI);
(2) chitosan solution is prepared, acetic acid/sodium acetate buffer dissolving is added, control pH value of solution is in 3-4.5;
(3) in the solution in step (2), step (1) solution is added, the two volume ratio is 1:1;
Control mixing speed is 250-1250 rpm;
In 25-40 DEG C of water-bath 10-30min, positively charged drop two level lotion (NEII) is obtained;
(4) sodium alginate aqueous solution is prepared, pH is in 6-8 for control;
(5) in the solution in step (4), step (3) two level solution is added, repeats step (3), obtains negatively charged drop three-level Lotion (NEIII);
(6) curing agent solution is prepared, curing agent is 2%-10% by weight;
(7) the three-level lotion in step (5) is added in step (6) curing agent solution, repeats step (3), obtains sun-proof nanometre glue Capsule.
In the method that above-mentioned LBL self-assembly prepares sun-proof Nano capsule, the core material is that p-(dimethylamino)-benzoic acid is different Monooctyl ester (EHA);The wall material is chitosan or sodium alginate;The curing agent is calcium chloride.It is electro-hydraulic that stabilized zone is prepared with core material Drop is template, wall material sequential deposition, crosslinking in drop template.
In the method that above-mentioned LBL self-assembly prepares sun-proof Nano capsule, the core material is by composite emulsifier (Tween-80 With lauryl both sexes sodium acetate) emulsification formed stablize charged drop, the wall material chitosan, sodium alginate amount fall in a range Interior, the range is selected from by weight, chitosan 0.025% to 0.25%, sodium alginate 0.05% to 0.1%.
In the method that above-mentioned LBL self-assembly prepares sun-proof Nano capsule, the composite emulsifier is Tween-80 and the moon Osmanthus base both sexes sodium acetate, weight ratio are Tween-80:Lauryl both sexes sodium acetate=9:1.
Compared with prior art, the present invention has the advantages that:The present invention by compound nonionic emulsifier and from It is template that sub- emulsifier, which prepares stable charged drop, and release goes complicated operation such as removing template, wall is controlled by LBL self-assembly Material thickness forms fine and close capsule wall, content is avoided to leak.The capsule is stabilized in aqueous solution, and average grain diameter exists Between 200-400nm, PDI range 0.1-0.3 adapt to ultra light sun block lotion, and cream prepares environment;Gained Nano capsule has anti- Shine the comparable sun-proof result of agent.
Description of the drawings
Fig. 1 is sun-proof agent emulsion transmission electron microscope picture obtained by embodiment;
Fig. 2 is sun-proof Nano capsule transmission electron microscope picture obtained by embodiment;
Fig. 3 is Nano capsule grain size distribution obtained by embodiment;
Fig. 4 is sun-proof Nano capsule UV absorption figure obtained by embodiment;
Fig. 5 is sun-proof Nano capsule change of size figure obtained by embodiment;
Fig. 6 is sun-proof Nano capsule potential change figure obtained by embodiment;
Fig. 7 is sun-proof Nano capsule tablets in vitro figure obtained by embodiment.
Specific implementation mode
The invention will be further described in conjunction with the embodiments.
Embodiment 1:
Lauryl both sexes sodium acetate 0.05g is weighed in 50mL beakers, 0.45g Tween-80s are added, stirs evenly, adds 0.5g isooctyl p-dimethylaminobenzoate, stirs evenly, and is placed in 25 DEG C of water-baths, controls rotating speed r=750rpm, and 49mL is added Deionized water reacts 15min.It obtains stablizing negatively charged drop primary emulsion (NEI).Accurately weighing 0.01g chitosans is placed in burning In cup, acetic acid/acetate buffer solution 40mL of pH=4.5, magnetic agitation dissolving is added.40mL primary emulsions are taken, at 25 DEG C, stirring Speed r=750, are added dropwise in chitosan solution, react 15min, obtain positively charged two level lotion (NEII).Accurately weigh 0.01g sodium alginates are placed in beaker, and 20mL deionized waters are added, and 20mL two level lotions are added, 25 in magnetic agitation dissolving DEG C, mixing speed r=750 react 15min, obtain electronegative three-level lotion (NEIII).Really weighing 1.6g calcium chloride is placed in burning In cup, 20mL deionized waters are added, are eventually adding 20mL three-level lotions, at 25 DEG C, mixing speed r=750, reaction 15min is obtained Nano capsule.
Embodiment 2:
Lauryl both sexes sodium acetate 0.2g is weighed in 50mL beakers, 1.8g Tween-80s are added, stirs evenly, adds 1g pairs The different monooctyl ester of dimethylaminobenzoic acid, stirs evenly, and is placed in 25 DEG C of water-baths, controls rotating speed r=1250rpm, and 47mL deionizations are added Water reacts 15min.It obtains stablizing negatively charged drop primary emulsion (NEI).It accurately weighs 0.01g chitosans to be placed in beaker, add Enter acetic acid/acetate buffer solution 40mL of pH=4.5, magnetic agitation dissolving.40mL primary emulsions are taken, at 25 DEG C, mixing speed r= 1250, it is added dropwise in chitosan solution, reacts 15min, obtain positively charged two level lotion (NEII).It is accurate to weigh the seas 0.01g Mosanom is placed in beaker, and 20mL deionized waters are added, and 20mL two level lotions are added in magnetic agitation dissolving, at 25 DEG C, stirring speed R=1250 are spent, 15min is reacted, obtains electronegative three-level lotion (NEIII).It really weighs 1.2g calcium chloride to be placed in beaker, add Enter 20mL deionized waters, be eventually adding 20mL three-level lotions, at 25 DEG C, mixing speed r=1250, reaction 15min obtains nanometre glue Capsule.
Embodiment 3:
Lauryl both sexes sodium acetate 0.6g is weighed in 50mL beakers, 5.4g Tween-80s are added, stirs evenly, adds 4g pairs The different monooctyl ester of dimethylaminobenzoic acid, stirs evenly, and is placed in 25 DEG C of water-baths, controls rotating speed r=1000rpm, and 40mL deionizations are added Water reacts 15min, obtains stablizing negatively charged drop primary emulsion (NEI).It accurately weighs 0.04g chitosans to be placed in beaker, add Enter acetic acid/acetate buffer solution 40mL of pH=3.5, magnetic agitation dissolving.40mL primary emulsions are taken, at 25 DEG C, mixing speed r= 1000, it is added dropwise in chitosan solution, reacts 15min, obtain positively charged two level lotion (NEII).It is accurate to weigh the seas 0.08g Mosanom is placed in beaker, and 40mL deionized waters are added, and 40mL two level lotions are added in magnetic agitation dissolving, at 25 DEG C, stirring speed R=1000 are spent, 15min is reacted, obtains electronegative three-level lotion (NEIII).It really weighs 1.0g calcium chloride to be placed in beaker, add Enter 20mL deionized waters, be eventually adding 20mL three-level lotions, at 25 DEG C, mixing speed r=1000, reaction 15min obtains nanometre glue Capsule.
Embodiment 4:
Lauryl both sexes sodium acetate 0.4g is weighed in 50mL beakers, 3.6g Tween-80s are added, stirs evenly, adds 4g pairs The different monooctyl ester of dimethylaminobenzoic acid, stirs evenly, and is placed in 25 DEG C of water-baths, controls rotating speed r=500rpm, and 42mL deionizations are added Water reacts 10min.It obtains stablizing negatively charged drop primary emulsion (NEI).It accurately weighs 0.1g chitosans to be placed in beaker, add Enter acetic acid/acetate buffer solution 40mL of pH=4, magnetic agitation dissolving.40mL primary emulsions are taken, at 25 DEG C, mixing speed r=500, It is added dropwise in chitosan solution, reacts 10min, obtain positively charged two level lotion (NEII).Accurately weigh 0.2g sodium alginates It being placed in beaker, 40mL deionized waters is added, 40mL two level lotions are added in magnetic agitation dissolving, at 25 DEG C, mixing speed r= 500,10min is reacted, electronegative three-level lotion (NEIII) must be obtained.It really weighs 0.4g calcium chloride to be placed in beaker, be added 20mL deionized waters are eventually adding 20mL three-level lotions, and at 25 DEG C, mixing speed r=500, reaction 10min obtains Nano capsule.
Embodiment 5:
Lauryl both sexes sodium acetate 0.4g is weighed in 50mL beakers, 3.6g Tween-80s are added, stirs evenly, adds 2g pairs The different monooctyl ester of dimethylaminobenzoic acid, stirs evenly, and is placed in 40 DEG C of water-baths, controls rotating speed r=250rpm, and 44mL deionizations are added Water reacts 30min.It obtains stablizing negatively charged drop primary emulsion (NEI).It accurately weighs 0.1g chitosans to be placed in beaker, add Enter acetic acid/acetate buffer solution 40mL of pH=3, magnetic agitation dissolving.40mL primary emulsions are taken, at 25 DEG C, mixing speed r=250, It is added dropwise in chitosan solution, reacts 30min, obtain positively charged two level lotion (NEII).Accurately weigh 0.2g sodium alginates It being placed in beaker, 40mL deionized waters is added, 40mL two level lotions are added in magnetic agitation dissolving, at 25 DEG C, mixing speed r= 250,30min is reacted, electronegative three-level lotion (NEIII) must be obtained.It really weighs g calcium chloride to be placed in beaker, 20mL is added Deionized water is eventually adding 20mL three-level lotions, and at 25 DEG C, mixing speed r=250, reaction 30min obtains Nano capsule.

Claims (4)

1. a kind of method that LBL self-assembly prepares sun-proof Nano capsule, it is characterised in that include the following steps:
(1) core material, composite emulsifier are placed in beaker, the core material and composite emulsifier 1:1-1:2;
Control mixing speed is 250-1250 rpm;
Deionized water is added in beaker, the deionized water is 68%-98% by weight;
In 25-40 DEG C of water-bath 10-30min, obtain stablizing negatively charged drop primary emulsion;
(2) chitosan solution is prepared, acetic acid/sodium acetate buffer dissolving is added, control pH value of solution is in 3-4.5;
(3) in the solution in step (2), step (1) solution is added, the two volume ratio is 1:1;
Control mixing speed is 250-1250 rpm;
In 25-40 DEG C of water-bath 10-30min, positively charged drop two level lotion is obtained;
(4) sodium alginate aqueous solution is prepared, pH is in 6-8 for control;
(5) in the solution in step (4), step (3) two level solution is added, repeats step (3), obtains negatively charged drop three-level Lotion;
(6) curing agent solution is prepared, curing agent is 2%-10% by weight;
(7) the three-level lotion in step (5) is added in step (6) curing agent solution, repeats step (3), obtains sun-proof nanometre glue Capsule.
2. the method that LBL self-assembly as described in claim 1 prepares sun-proof Nano capsule, which is characterized in that the core material is pair The different monooctyl ester of dimethylaminobenzoic acid;The wall material is chitosan or sodium alginate;The curing agent is calcium chloride.
3. the method that LBL self-assembly as described in claim 1 prepares sun-proof Nano capsule, which is characterized in that
The addition weight of the chitosan is 0.025%-0.25%, and the addition weight of sodium alginate is 0.05%-0.1%.
4. the method that LBL self-assembly as described in claim 1 prepares sun-proof Nano capsule, which is characterized in that the compound emulsion Agent is that Tween-80 and lauryl both sexes sodium acetate mix, and weight ratio is Tween-80:Lauryl both sexes sodium acetate=9:1.
CN201810696441.8A 2018-06-29 2018-06-29 A kind of method that LBL self-assembly prepares sun-proof Nano capsule Pending CN108743411A (en)

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Cited By (4)

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Publication number Priority date Publication date Assignee Title
CN111643377A (en) * 2020-07-23 2020-09-11 中国热带农业科学院南亚热带作物研究所 Hemp oil nano microcapsule and preparation method and application thereof
CN113101375A (en) * 2021-05-08 2021-07-13 惠州市绿亚生物材料有限公司 Chitosan grafted salicylic acid microcapsule and preparation method thereof
CN113499282A (en) * 2021-07-15 2021-10-15 厦门大学 Sunscreen agent based on gold nanoparticle load and preparation method thereof
CN115463052A (en) * 2022-09-22 2022-12-13 武汉纺织大学 Preparation method and sunscreen agent of polymer microsphere sunscreen composition embedded with organic ultraviolet absorber

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111643377A (en) * 2020-07-23 2020-09-11 中国热带农业科学院南亚热带作物研究所 Hemp oil nano microcapsule and preparation method and application thereof
CN111643377B (en) * 2020-07-23 2023-08-11 中国热带农业科学院南亚热带作物研究所 A kind of hemp oil nano microcapsule and its preparation method and application
CN113101375A (en) * 2021-05-08 2021-07-13 惠州市绿亚生物材料有限公司 Chitosan grafted salicylic acid microcapsule and preparation method thereof
CN113499282A (en) * 2021-07-15 2021-10-15 厦门大学 Sunscreen agent based on gold nanoparticle load and preparation method thereof
CN113499282B (en) * 2021-07-15 2022-11-08 厦门大学 A kind of sunscreen agent based on gold nanoparticle loading and preparation method thereof
CN115463052A (en) * 2022-09-22 2022-12-13 武汉纺织大学 Preparation method and sunscreen agent of polymer microsphere sunscreen composition embedded with organic ultraviolet absorber

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Application publication date: 20181106