CN103169625B - Wrap up the microcapsule of solid sunscreen, preparation method and application thereof - Google Patents
Wrap up the microcapsule of solid sunscreen, preparation method and application thereof Download PDFInfo
- Publication number
- CN103169625B CN103169625B CN201310098635.5A CN201310098635A CN103169625B CN 103169625 B CN103169625 B CN 103169625B CN 201310098635 A CN201310098635 A CN 201310098635A CN 103169625 B CN103169625 B CN 103169625B
- Authority
- CN
- China
- Prior art keywords
- microcapsule
- sunscreen
- solid
- combination
- natural 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
Links
Abstract
The invention discloses a kind of wrap up solid sunscreen microcapsule, preparation method and application thereof.Described microcapsule comprises solid sunscreen and natural polymer, and described solid sunscreen is wrapped in the microcapsule of described natural polymer formation, and wherein, described solid sunscreen is inorganic UV screener, organic uv absorbers or its mixture; Described natural polymer is agar, agarose, cellulose, chitosan or derivatives thereof.Microcapsule of the present invention can be used in cosmetics, effectively avoid the decomposition of solid sunscreen, and solid sunscreen and skin are separated, reduce the stimulation to skin, hydrophilic natural polymer can hide color, improve feel, strengthen its conformability in cosmetics.
Description
Technical field
The present invention relates to microcapsule, be specifically related to a kind of wrap up solid sunscreen microcapsule, preparation method and application thereof.
Background technology
The mankind recognize for a long time and are exposed to for a long time in ultraviolet (wavelength 280-400nm) radiation and can cause damage to skin, even burn as the UV-B of wavelength between 280-320nm makes skin produce erythema, the UV-A of wavelength between 320-400nm can accelerate skin elasticity and run off, cause premature skin ageingly occurring wrinkle, even promote the startup of erythematous response or expand erythematous response.
Ultraviolet absorber and ultraviolet light screener two kinds can be divided into according to sun-proof mechanism at present for sun-proof chemicals, ultraviolet absorber is generally lipophilic liquid or solid, hydroxyl hydrogen in molecule on phenyl ring can form intramolecular hydrogen bond and form chelate ring between adjacent ketonic oxygen, when molecule generation thermal vibration after absorption ultraviolet light, the hydrogen bond chelate ring that breaks opens formation ionic compound.Ultraviolet light screener is the solids such as titanium dioxide, zinc oxide mainly, and when being subject to high energy ultraviolet and irradiating, the electronics Absorbable rod ultraviolet in valence band is excited on conduction band and produces electron-hole pair.In addition, because particle diameter is less than ultraviolet wavelength, the electronics in particle is forced to vibration becomes secondary wave source to all directions emitting electromagnetic wave scatters ultraviolet.
Ultraviolet absorber has the high feature of sun-proof efficiency, but poor stability, directly use Diazolidinyl Urea, in cosmetics, usually have content to limit; Ultraviolet light screener has safety, stable advantage, in cosmetics, content does not limit, if but directly use content Tai Gaoyi to be deposited as white layer at skin surface, affect the secretion of visual effect and sebaceous gland, sweat gland, microparticle compositions also has the dry and astringent shortcoming of feel.Usually simultaneously containing ultraviolet absorber and ultraviolet light screener in current sun care preparations.
No matter be solid ultraviolet absorber, or solid ultraviolet light screener, usually be directly distributed in oil phase in particulate form and form emulsion for cosmetics, the shortcoming of its poor stability, chafe (ultraviolet absorber) or sense of touch dry and astringent (ultraviolet light screener) cannot be avoided.
Therefore, in order to play anti-sunlight function better, reducing the stimulation to skin, needing to improve existing sun-proof chemicals.
Summary of the invention
The object of the present invention is to provide a kind of microcapsule, adopt natural polymer parcel solid sunscreen, make sunscreen play anti-sunlight function better, improve sunscreen stability.And the problem alleviated to the stimulation of skin and sense of touch difference in direct use procedure.
A first aspect of the present invention provides one a kind of microcapsule, and described microcapsule comprises solid sunscreen and natural polymer, and described solid sunscreen is wrapped in the microcapsule of described natural polymer formation, wherein,
Described solid sunscreen is inorganic UV screener, organic uv absorbers or its mixture;
Described natural polymer is agar, agarose, cellulose, chitosan, or derivatives thereof.
In another preference, with the total weight of described microcapsule, the content of described solid sunscreen is 0.1-80%.
In another preference, with the total weight of described microcapsule, the content of described natural polymer is 0.1-50%.
In another preference, the mean diameter of described microcapsule is 200 nanometer-20 microns.
In another preference, the mean diameter of described microcapsule is 1 micron-10 microns.
In another preference, described inorganic UV screener is selected from: Zinc oxide particles, titanium dioxide granule and combination thereof.
In another preference, described organic uv absorbers is selected from: dibenzoyl methane class, benzophenone, cinnamate derivative, hydroxy phenyl s-triazine, benzotriazole and combination thereof.
In another preference, described microcapsule is also containing water, organic solvent, surfactant, stabilizing agent or its combination.
In another preference, described microcapsule also comprises liquid sunscreen, and described liquid sunscreen and described solid sunscreen are all wrapped in the microcapsule that described natural polymer formed.
Second aspect present invention provides the preparation method of the microcapsule described in a kind of first aspect present invention, comprises the following steps:
A natural polymer is dissolved in water or aqueous solution and forms solution by ();
B solid sunscreen is dispersed in the solution that step (a) obtains and forms S/W dispersion liquid by (), or be liquid by solid sunscreen heating and melting, is dispersed in the solution that step (a) obtains and forms O/W emulsion;
C S/W dispersion liquid that step (b) obtains by () or O/W emulsion dispersion form S/W/O emulsion or O/W/O emulsion in containing the oil phase of lipophilic surfactant;
D described S/W/O emulsion that step (c) obtains by () or the solidification of O/W/O emulsion obtain described microcapsule,
Wherein, described natural polymer, solid sunscreen are as described in the first aspect of the invention;
Described lipophilic surfactant is sorbitan sesquioleate, polyoxyethylene ether, polyoxyethylene hydrogenated Oleum Ricini, sorbitan trioleate, sorbitan monooleate, anhydrous sorbitol tristearate, alkylglycoside, cithrol or its combination;
Described oil phase is silicone oil, liquid paraffin, olive oil, Oleum Cocois, Oleum Ricini, hardened soybean oil or its combination.
In another preference, the mass concentration of the solution that described step (a) obtains is 0.1-50%.
In another preference, the mass ratio of described solid dispersion and described natural polymer is 800-0.002.
In another preference, in step (c), in described oil phase, lipophilic surfactant consumption is the 0.5-20wt% of oil phase, preferably, is 0.5-10wt%.
In another preference, in step (c), S/W dispersion liquid or O/W emulsion are 10:1-1:10 with the mass ratio of the oil phase containing lipophilic surfactant.
In another preference, in described step (d), by following, S/W/O emulsion or O/W/O emulsion can well known to a person skilled in the art that mode is cured: for the polymer of high-temperature digestion low-temperature setting, solidification that the S/W/O emulsion formed as embedded material as agar, agarose or O/W/O emulsion (can be less than 40 DEG C of even ice baths) at a lower temperature; The S/W/O emulsion that the cellulose dissolved for low temperature, highly basic, Strong shear power condition is formed as embedded material or O/W/O emulsion can be solidified under the condition of room temperature, acid adding; The S/W/O emulsion formed as embedded material as chitosan for the material solidified under cross-linking agent existence condition or O/W/O emulsion, can add aldehydes, as hexandial, glutaraldehyde etc., or phosphoric acid salt, the solidifications such as tripolyphosphate, four Quadrafos.
In another preference, in described step (b), in the solution that described step (a) obtains, be also added with liquid sunscreen.
In another preference, in described step (b), in the solution that described step (a) obtains, also add organic solvent, surfactant, stabilizing agent or its combination;
Described organic solvent is selected from: ethanol, isopropyl alcohol, methanol, acetone, silicone oil, liquid paraffin, olive oil, Oleum Cocois, Oleum Ricini, hardened soybean oil and combination thereof;
Described surfactant is selected from: Tween, Triton, SDS (sodium lauryl sulphate), CTAB (cetyl trimethyl ammonium bromide), SDBS (dodecylbenzene sodium sulfonate), sodium alkyl sulfate, polyoxyethylene ether, alkylglycoside, cithrol, sorbitan sesquioleate, polyoxyethylene hydrogenated Oleum Ricini, sorbitan trioleate, sorbitan monooleate, anhydrous sorbitol tristearate and combination thereof;
Described stabilizing agent is selected from: polyvinyl alcohol, Polyethylene Glycol, polyvinylpyrrolidone, gelatin, xanthan gum, hydroxypropyl cellulose, phosphate, polyphosphate and combination thereof.
In another preference, described organic solvent, surfactant, stabilizing agent or its consumption combined are the 0-50wt% of S/W dispersion liquid or O/W emulsion gross weight; Be preferably 0.5-40wt%; Be more preferably 5-35wt%.
Third aspect present invention provides a kind of sun care preparations, containing the microcapsule described in first aspect present invention.
In another preference, the microcapsule also containing parcel liquid sunscreen in described sun care preparations, liquid sunscreen and solid sunscreen are all wrapped in the microcapsule of natural polymer stroke.
Should be understood that within the scope of the present invention, above-mentioned each technical characteristic of the present invention and can combining mutually between specifically described each technical characteristic in below (eg embodiment), thus form new or preferred technical scheme.As space is limited, tiredly no longer one by one to state at this.
Accompanying drawing explanation
Fig. 1 is the optical microscope photograph of chitosan imbedded 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole.
Fig. 2 is the grain size distribution of chitosan imbedded 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole.
Fig. 3 is the optical microscope photograph of agar embedding butyl methoxydibenzoylmethise.
Fig. 4 is the grain size distribution of agar embedding butyl methoxydibenzoylmethise.
Fig. 5 is the optical microscope photograph of Agarose embedding titanium dioxide.
Fig. 6 is the grain size distribution of Agarose embedding titanium dioxide.
Fig. 7 is the optical microscope photograph of cellulose embedding zinc oxide.
Fig. 8 is the grain size distribution of cellulose embedding zinc oxide.
Fig. 9 is the optical microscope photograph of Agarose embedding zinc oxide and ethylhexyl methoxy cinnamate.
Figure 10 is the optical microscope photograph of chitosan imbedded 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole.
Figure 11 is the grain size distribution of chitosan imbedded 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole.
Figure 12 is the uv absorption property being used alone two kinds of solid-state UV absorbent microcapsules.
Figure 13 compares with the uv absorption property of liquid ultraviolet absorber microcapsule (OMC) used in combination and solid ultraviolet absorber microcapsule (UV360) for being used alone a kind of liquid ultraviolet absorber microcapsule (OMC).
Figure 14 compares with the uv absorption property of liquid ultraviolet absorber microcapsule (OMC) used in combination and solid ultraviolet absorber microcapsule (Parsol1789) for being used alone a kind of liquid ultraviolet absorber microcapsule (OMC).
Detailed description of the invention
Present inventor is through extensively and in depth studying, unexpected discovery adopts natural polymer parcel solid sunscreen, effectively can avoid the decomposition of sunscreen, and solid sunscreen and skin can be separated, reduce the stimulation to skin, in addition, the effect that hydrophilic natural polymer also can play and hide color, improve feel, strengthen its conformability in cosmetics.On this basis, the present invention is completed.
Solid sunscreen
Solid sunscreen of the present invention refers to inorganic UV screener, organic uv absorbers or its mixture.
Inorganic UV screener is selected from Zinc oxide particles, titanium dioxide granule and combination thereof.
Organic uv absorbers is selected from dibenzoyl methane class, benzophenone, cinnamate derivative, hydroxy phenyl s-triazine, benzotriazole and combination thereof, as butyl methoxydibenzoylmethise, 2,4-diethoxy-6-(2 ', 4 '-dihydroxy phenyl)-1,3,5-triazine, 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole, di-2-ethylhexylphosphine oxide [6-BTA-4-tert-octylphenol].
Natural polymer
Natural polymer is that occurring in nature exists, the polymer of unartificial synthesis, can derive from animal body, as chitosan, also can derive from plant, as cellulose, can also derive from algae, as agar, agarose.
The natural polymer that the present invention is used, includes but not limited to agar, agarose, cellulose, Chitosan-phospholipid complex.
As known in the art, in order to obtain the good polymeric material of quality, physical or chemical treatment may be carried out to the polymer of these natural origins, as purification, chemical modification.As carried out deacetylatedly making it more easily dissolve to chitosan, filtration is carried out to agar and removes insoluble matter and make that it is more stable, carry out ethyoxyl to agarose modifies and can dissolve at a lower temperature.
Microcapsule
Microcapsule of the present invention, comprises natural polymer and solid sunscreen, and described solid sunscreen is wrapped in the microcapsule of described natural polymer formation.
Microcapsule of the present invention, mean diameter is 200 nanometer-20 microns, is preferably 1 micron-10 microns.
Solid sunscreen is coated by natural polymer, can effectively avoid the decomposition of sunscreen and itself and skin are separated reducing its stimulation to skin, hydrophilic natural polymer also can play and hide color, improve feel, strengthen its conformability in cosmetics.
In addition, natural polymer solidify to form in the process of gel particle under certain condition, can store large quantity of moisture in its macromolecular network structure.Therefore, microcapsule also can be moisture.
In order to promote the dispersion of solid sunscreen in macromolecular material, organic solvent can be added, as ethanol, isopropyl alcohol, methanol, acetone, silicone oil, liquid paraffin, olive oil, Oleum Cocois, Oleum Ricini, hardened soybean oil or its combination etc.; Surfactant can be added, as Tween, Triton (as TX-100), SDS, CTAB, SDBS, sodium alkyl sulfate, polyoxyethylene ether (as PO-500, PO-310), alkylglycoside, cithrol, sorbitan sesquioleate (as Arlacel83), polyoxyethylene hydrogenated Oleum Ricini, sorbitan trioleate (as Span85), sorbitan monooleate (as Span80), anhydrous sorbitol tristearate (as Span65) or its combination; Stabilizing agent can be added, as polyvinyl alcohol, Polyethylene Glycol, polyvinylpyrrolidone, gelatin, xanthan gum, hydroxypropyl cellulose, phosphate, polyphosphate or its combination etc.Therefore, microcapsule also can contain organic solvent, surfactant, stabilizing agent or its combination.
Usually, in order to improve sun-proof result, can by used in combination to a kind of solid sunscreen (as solid sunscreen ZnO nano granule) and other liquid sunscreen (as ethylhexyl methoxy cinnamate).Microcapsule of the present invention can also comprise liquid sunscreen, and described liquid sunscreen and described solid sunscreen are all wrapped in the microcapsule that described natural polymer formed, and liquid sunscreen and solid sunscreen are embedded in microcapsule simultaneously.In addition, also the microcapsule of the microcapsule of parcel solid sunscreen of the present invention with parcel liquid sunscreen can be mixed, in sun care preparations.
Preparation method
Microcapsule preparation method of the present invention, comprises the following steps:
A natural polymer is dissolved in water or aqueous solution and forms solution by ();
B solid sunscreen is dispersed in the solution that step (a) obtains and forms S/W dispersion liquid by (), or be liquid by solid sunscreen heating and melting, is dispersed in the solution that step (a) obtains and forms O/W emulsion;
C S/W dispersion liquid that step (b) obtains by () or O/W emulsion dispersion form S/W/O emulsion or O/W/O emulsion in containing the oil phase of lipophilic surfactant;
D described S/W/O emulsion that step (c) obtains by () or the solidification of O/W/O emulsion obtain described microcapsule.
Solid sunscreen described in natural polymer described in step (a), step (b) as previously mentioned.
In step (a), described aqueous solution refers to the solution that acid is formed with water, alkali and water, salt and water or polymer and water, and wherein the quality of water accounts for the 50%-99.9% of aqueous solution quality, is preferably 75-99.5%, is more preferably 85-99%.Described acid is mineral acid or its mixture such as the organic acid such as acetic acid, citric acid or phosphoric acid, hydrochloric acid, sulphuric acid, and described alkali is sodium hydroxide, potassium hydroxide, ammonia or its mixture.Described salt is for containing Na
+, K
+, Mg
2+, Ca
2+, Zn
2+, NH
4 +deng and water-soluble salt under normal temperature and pressure state, as sodium chloride, potassium chloride, sodium sulfate, calcium chloride etc.
As is known to the person skilled in the art, according to natural polymer dissolubility and concentration, suitable temperature can be chosen, add acid or alkali, shearing force, make it be dissolved in the water.Such as deacetylated chitosan can be dissolved in the water under pH is less than the normal temperature condition of 4, needs to add acetic acid when dissolving; Low solubility agarose can be dissolved in water at about 80 DEG C; Agar dissolves under needing the temperature more than 100 DEG C; Cellulose needs just can be dissolved in water under low temperature, highly basic, Strong shear power condition, also needs to add highly basic in course of dissolution, and as sodium hydroxide solution, after certain hour is freezing, high speed machine stirs again; During dissolution of high-concentration cellulose solution, required shearing force is larger than low concentration solution, and dissolution of high-concentration agarose solution is temperature required higher than low concentration agarose solution.
The solid sunscreen be wrapped by can be liquid in preparation process, if butyl methoxydibenzoylmethise melting when high temperature (more than 95 DEG C) is liquid, also can be solid particle state, as zinc oxide, titania nanoparticles.
In preparation process, also can liquid sunscreen together be joined in the solution that step (a) obtains with solid sunscreen (preferably after melting), obtain the microcapsule simultaneously wrapping up solid sunscreen and liquid sunscreen.Liquid sunscreen is various liquid sunscreen known in the art, as ethylhexyl methoxy cinnamate (OMC), 2-cyano group-3,3-diphenyl 2-Propenoic acid-2-ethylhexyl ester etc.
In described step (b), organic solvent can be added, as ethanol, isopropyl alcohol, methanol, acetone, silicone oil, liquid paraffin, olive oil, Oleum Cocois, Oleum Ricini, hardened soybean oil or its combination etc. in the solution that described step (a) obtains.Surfactant can be added if Tween is (as Tween20 in the solution that described step (a) obtains, Tween40, Tween60, Tween80 etc.), Triton (as TX-100), SDS, CTAB, SDBS, sodium alkyl sulfate, polyoxyethylene ether is (as PO-500, PO-310), alkylglycoside, cithrol, sorbitan sesquioleate (as Arlacel83), polyoxyethylene hydrogenated Oleum Ricini, sorbitan trioleate (as Span85), sorbitan monooleate (as Span80), anhydrous sorbitol tristearate (as Span65), or its combination, promote sunscreen dispersion.Also can add stabilizing agent in the solution that described step (a) obtains as polyvinyl alcohol, Polyethylene Glycol, polyvinylpyrrolidone, gelatin, xanthan gum, hydroxypropyl cellulose, phosphate, polyphosphate or its combination, promote sunscreen dispersion.Such as, when sunscreen is butyl methoxydibenzoylmethise, surfactant Tween20, Tween80 and TX-100 can be added, be distributed under the condition of high speed shear in agarose solution and form O/W emulsion; For solid-state sunscreen, as titania nanoparticles, surfactant can be added as polyoxyethylene ether, cithrol etc., under the condition of high speed shear, first be distributed to cellulose aqueous solution be mixed to form S (solid)/W (water) dispersion liquid.Sunscreen be liquid and solid mixture time, surfactant and stabilizing agent can be added simultaneously and dispersible in chitosan-acetic acid solution form S/O/W dispersion liquid as ethylhexyl methoxy cinnamate and Zinc oxide nanoparticle mixture add Tween20 and PEG-10000.The dispersion effect that also can reach in conjunction with dispersing modes such as ultrasonic, grindings.Organic solvent, surfactant, stabilizing agent or its consumption combined are the 0-50wt% of S/W dispersion liquid or O/W emulsion gross weight, and preferably, being 0.5-40wt%, is more preferably 5-35wt%.
Oil phase described in step (c) be in preparation process for liquid, be insoluble to solution that step (a) formed and adding the solution formed with step (a) under lipophilic surfactant condition and can be formed the compound of emulsion, can be silicone oil, liquid paraffin, olive oil, Oleum Cocois, Oleum Ricini, hardened soy bean wet goods country allow to use in cosmetics and be grease or its combination of liquid at the operational.In oil phase consumption and step (b), S/W dispersion liquid or O/W emulsion consumption mass ratio are 1:10-10:1, if mass ratio is too little, microcapsule diameter is difficult to control; If mass ratio is too large, microcapsule productive rate is too low.
Lipophilic surfactant described in step (c) is dissolved in used oil phase, can be selected from sorbitan sesquioleate (as Arlacel83), polyoxyethylene ether (as PO-500, PO-310), polyoxyethylene hydrogenated Oleum Ricini, sorbitan trioleate (as Span85), sorbitan monooleate (as Span80), anhydrous sorbitol tristearate (as Span65), alkylglycoside, cithrol etc.In oil phase, lipophilic surfactant consumption is the 0.5-10wt% of oil phase, if consumption, is difficult to control microcapsule diameter very little; If consumption is too many, the control of particle diameter is not improved.
According to the stability of polymer solution, the temperature of corresponding set-up procedure (c).As when polymer be agar and agarose time, the temperature of step (c) is 40 DEG C-100 DEG C; When polymer is cellulose, the temperature of step (c) is-10 DEG C-40 DEG C.In addition, step (c) is prepared in S/W/O emulsion or O/W/O emulsion process except adding aqueous phase, oil phase, surfactant, the compound making emulsion-stabilizing can also be added, as stabilizing agents such as polyvinyl alcohol, Polyethylene Glycol, polyvinylpyrrolidone, gelatin, xanthan gum, hydroxypropyl cellulose, phosphate, polyphosphates.Wherein, aqueous phase refers to the described S/W dispersion liquid that step (b) obtains or O/W emulsion.
In step (d), S/W/O emulsion or O/W/O emulsion solidify to form the condition of granule can depending on natural polymer dissolution properties.For the polymer of high-temperature digestion low-temperature setting, as agar, agarose, solidification that the S/W/O emulsion formed as embedded material or O/W/O emulsion (can be less than 40 DEG C of even ice baths) at a lower temperature.The S/W/O emulsion that the cellulose dissolved for low temperature, highly basic, Strong shear power condition is formed as embedded material or O/W/O emulsion can be solidified under the condition of room temperature, acid adding.In addition, cross-linking agent can be added in step (d), microencapsulated material is solidified under the process conditions of suitable control, as microencapsulated material be chitosan time, aldehydes, hexandial, glutaraldehyde etc. can be added, or phosphoric acid salt, tripolyphosphate, four Quadrafos etc. shorten the hardening time of chitosan.
Sun care preparations
The present invention also provides a kind of sun care preparations, and it contains microcapsule of the present invention.
In order to improve the sun-proof result of cosmetics, also can containing liquid sunscreen or the microcapsule wrapping up liquid sunscreen in cosmetics of the present invention.
The above-mentioned feature that the present invention mentions, or the feature that embodiment is mentioned can combination in any.All features that this case description discloses can with any composition forms and use, each feature disclosed in description, anyly can provide identical, alternative characteristics that is impartial or similar object replaces.Therefore apart from special instruction, the feature disclosed is only general example that is impartial or similar features.
Beneficial effect of the present invention is:
(1) a kind of microcapsule of novel parcel solid sunscreen is provided, there is preferably uv absorption property, improve sun protection;
(2) the solid sunscreen in microcapsule is wrapped up by natural polymer, effectively can avoid the decomposition of solid sunscreen;
(3) solid sunscreen and skin are separated by natural polymer, reduce its stimulation to skin;
(4) effect that hydrophilic natural polymer also can play and hide color, improve feel, strengthen its conformability in cosmetics.
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example, the usually conveniently conditioned disjunction condition of advising according to manufacturer.
Unless otherwise defined, all specialties used in literary composition and scientific words and one skilled in the art the same meaning be familiar with.In addition, any method similar or impartial to described content and material all can be applicable in the inventive method.The use that better implementation method described in literary composition and material only present a demonstration.
Embodiment 1
It is in 1wt% aqueous acetic acid that deacetylated for 0.3g chitosan (deacetylation 89%) is joined 20g concentration, and stirring 30min at 200 rpm, to make it fully dissolve for subsequent use.
5g2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole (UV360), 0.017g PVAC polyvinylalcohol (degree of polymerization 1750) are joined in above-mentioned dissolving deacetylated chitosan solution for subsequent use, under room temperature, 1000RPM, stirs 10min afterwards obtain S/W dispersion liquid.
Using for subsequent use as the oil phase containing lipophilic surfactant for the mixing material 50g (Span80 accounts for the 4wt% of olive oil weight) of olive oil and Span80.
Above-mentioned S/W dispersion liquid is joined in the oil phase olive oil containing lipophilic surfactant Span80, under room temperature, 1000RPM, stirs 60min obtain S/W/O emulsion.3.75 × 10 are dripped afterwards under room temperature, 200RPM stir
-3the glutaraldehyde water solution of g (amino is 1:1 with the mol ratio of aldehyde radical) 1wt%, cross-linking reaction 1h at 300 rpm, makes S/W/O emulsion solidify, sucking filtration afterwards, with distilled water wash product.
Obtained microcapsule optical microscope photograph is shown in accompanying drawing 1, and particle size distribution is shown in accompanying drawing 2, and the particle diameter (MalvernZetasizerNanoZS test) of product is distributed in 2-7 μm, and mean diameter is 3.73 μm, and particle diameter is very even.
Embodiment 2
0.8g agar is joined in 20g water, under 110 DEG C of oil baths, heat 30min make it fully dissolve, for subsequent use at 95 DEG C afterwards.
5g organic uv absorbers butyl methoxydibenzoylmethise (Parsol1789) is mixed at 95 DEG C with 0.3gTween80, join in above-mentioned dissolving agar solution for subsequent use, afterwards 95 DEG C, stir 10min under 1000RPM and obtain O/W emulsion.
Liquid paraffin and PO-500 mixing material 50g (PO-500 accounts for the 0.5wt% of liquid paraffin weight) are preheating to 95 DEG C for subsequent use as the oil phase containing lipophilic surfactant.
Above-mentioned O/W emulsion is joined in the oil phase containing lipophilic surfactant, 95 DEG C, stir 60min under 1000RPM and obtain O/W/O emulsion.
O/W/O emulsion slowly stirs 60min cooling at 200 rpm and is down to cold curing, and sucking filtration is with distilled water wash product afterwards.
Obtained microcapsule optical microscope photograph is shown in accompanying drawing 3, and particle size distribution is shown in accompanying drawing 4, and the particle size distribution of product is between 3-8 micron, and mean diameter is 5.1 microns, and particle diameter is very even.
Embodiment 3
0.8g agarose is joined in 20g water, under 110 DEG C of oil baths, heat 30min make it fully dissolve, for subsequent use at 80 DEG C afterwards.
3g titanium dioxide, 0.01g polyvinylpyrrolidone PVP-K90,15g dehydrated alcohol are joined in above-mentioned dissolving agarose solution for subsequent use, afterwards 80 DEG C, stir 10min under 1000RPM and obtain S/W dispersion liquid.
Liquid paraffin and Span80 mixing material 25g (Span80 accounts for the 10wt% of liquid paraffin weight) are preheating to 80 DEG C for subsequent use as the oil phase containing lipophilic surfactant.
S/W dispersion liquid is joined in the oil phase containing lipophilic surfactant 80 DEG C, stir 60min under 1000RPM and obtain S/W/O emulsion.
S/W/O emulsion slowly stirs 60min cooling at 200 rpm and is down to cold curing, and sucking filtration is with distilled water wash product afterwards.
Obtained microcapsule optical microscope photograph is shown in accompanying drawing 5, and particle size distribution is shown in accompanying drawing 6, and the particle size distribution of product is at 2-7 μm, and mean diameter is 3.62 μm, and particle diameter is very even.
Embodiment 4
1.8g cellulose, 1.4g sodium hydroxide and 2.4g carbamide are joined in 16g water, at-12 DEG C, cools 30min, take out and stir 30min at 1,000 rpm to make it fully dissolve for subsequent use.
5g zinc oxide and liquid organic uv absorbers ethylhexyl methoxy cinnamate (OMC) of 5g, 0.05gPEG-10000,0.3gTween80 are mixed to join in above-mentioned dissolving cellulose solution for subsequent use, under room temperature, 1000RPM, stir 10min afterwards obtain S/O/W dispersion liquid.
Using liquid paraffin and Span80 mixing material 300g (Span80 accounts for the 6wt% of liquid paraffin weight) for subsequent use as the oil phase containing lipophilic surfactant.
S/O/W dispersion liquid is joined in the oil phase containing lipophilic surfactant and under room temperature, 1000RPM, stir 60min obtain S/W/O emulsion.Under room temperature, 200RPM, stir 60min afterwards make the precuring of S/W/O emulsion, drip 12g1mol/L hydrochloric acid solution to neutrality afterwards and make after it fully solidifies, sucking filtration is with distilled water wash product.
Obtained microcapsule optical microscope photograph is shown in accompanying drawing 7, and particle size distribution is shown in accompanying drawing 8, and the particle size distribution of product is at 3-7 μm, and mean diameter is 5.1 μm, and particle diameter is very even.
Embodiment 5
2g agarose is joined in 20g water, under 110 DEG C of oil baths, heat 30min make it fully dissolve, for subsequent use at 80 DEG C afterwards.
2g zinc oxide and liquid organic uv absorbers ethylhexyl methoxy cinnamate (OMC) of 5g, 0.05gPEG-10000,0.3gTween80 are mixed to join in above-mentioned dissolving cellulose solution for subsequent use, under room temperature, 1000RPM, stir 10min afterwards obtain S/O/W dispersion liquid.
Using liquid paraffin and Span80 mixing material 50g (Span80 accounts for the 6wt% of liquid paraffin weight) for subsequent use as the oil phase containing lipophilic surfactant.
S/O/W dispersion liquid is joined in the oil phase containing lipophilic surfactant 80 DEG C, stir 60min under 1000RPM and obtain S/O/W/O emulsion.
S/O/W/O emulsion slowly stirs 60min cooling at 200 rpm and is down to cold curing, and sucking filtration obtains with distilled water wash product the microcapsule embedding zinc oxide solid particle and ethylhexyl methoxy cinnamate (OMC) liquid afterwards.Obtained microcapsule optical microscope photograph is shown in accompanying drawing 9.
Embodiment 6
It is in 1wt% aqueous acetic acid that deacetylated for 0.1g chitosan (deacetylation 89%) is joined 20g concentration, and stirring 30min at 200 rpm, to make it fully dissolve for subsequent use.
10g2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole, 0.017g PVAC polyvinylalcohol (degree of polymerization 1750) are joined in above-mentioned dissolving deacetylated chitosan solution for subsequent use, under room temperature, 1000RPM, stirs 10min afterwards obtain S/W dispersion liquid.
Using for subsequent use as the oil phase containing lipophilic surfactant for the mixing material 50g (Span80 accounts for the 4wt% of olive oil weight) of olive oil and Span80.
Above-mentioned S/W dispersion liquid is joined in the oil phase olive oil containing lipophilic surfactant Span80, under room temperature, 1000RPM, stirs 60min obtain S/W/O emulsion.3.75 × 10 are dripped afterwards under room temperature, 200RPM stir
-3the glutaraldehyde water solution of g (amino is 1:1 with the mol ratio of aldehyde radical) 1wt%, cross-linking reaction 1h at 300 rpm, S/W/O emulsion is solidified, sucking filtration afterwards, obtains embedding the microcapsule of solid sunscreen 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole with distilled water wash product.Obtained microcapsule optical microscope photograph is shown in accompanying drawing 10, and particle size distribution is shown in accompanying drawing 11, and the particle size distribution of product is at 3-7 μm, and mean diameter is 5.1 μm, and particle diameter is very even.
Comparative example 1
0.8g agar is joined in 20g water, under 110 DEG C of oil baths, heat 30min make it fully dissolve, for subsequent use at 80 DEG C afterwards.
After liquid for 5g organic uv absorbers ethylhexyl methoxy cinnamate (OMC) is mixed with 0.3gTween80, join in above-mentioned dissolving agar solution for subsequent use, afterwards 80 DEG C, stir 10min under 1000RPM and obtain O/W emulsion.
50g soybean oil and Arlacal83 mixing material (Arlacal83 accounts for the 6wt% of soybean oil weight) are preheating to 95 DEG C for subsequent use as the oil phase containing lipophilic surfactant.
Above-mentioned O/W emulsion is joined in the oil phase containing lipophilic surfactant, 95 DEG C, stir 60min under 1000RPM and obtain O/W/O emulsion.
O/W/O emulsion slowly stirs 60min cooling at 200 rpm and is down to cold curing, and sucking filtration is with distilled water wash product afterwards.
Sun-proof performance test 1
Microcapsule prepared by 1.1 embodiments 1
The 3M that the embedding 2-that embodiment 1 method prepared (2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole (UV360) uniform microcapsule is applied in area 7cm*7cm imitates on skin adhesive tape, uv absorption is surveyed, rate of absorbing UV > 95% in 250-350nm.See Figure 12.
Microcapsule prepared by 1.2 embodiments 2
Embedding butyl methoxydibenzoylmethise (Parsol1789) microcapsule embodiment 2 method prepared is got 0.1g uniform application and is imitated on skin adhesive tape in the 3M that area is 7cm*7cm, uv absorption is surveyed, rate of absorbing UV > 95% in 250-350nm.See Figure 12.
Visible, be used alone embedding solid-state UV absorbent microcapsule, at 250-350nm Inner, there is excellent sun-proof performance.
Sun-proof performance test 2
Microcapsule prepared by 2.1 comparative examples 1
Getting embedding liquid organic uv absorbers ethylhexyl methoxy cinnamate uniform microcapsule that 0.1g prepared according to comparative example 1 method, to be applied in area be that the 3M of 7cm*7cm imitates on skin adhesive tape, uv absorption is surveyed in 250-380nm, see OMC in Figure 13, embed liquid organic uv absorbers ethylhexyl methoxy cinnamate microcapsule rate of absorbing UV within the scope of 250-330nm to be greater than within the scope of 96%, 330-380nm without obvious uv absorption.
Microcapsule prepared by 2.2 comparative examples 1 and embodiment 1
After the embedding ethylhexyl methoxy cinnamate microcapsule prepared according to comparative example 1 method and the embedding 2-prepared according to embodiment 1 method (2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole (UV360) microcapsule is mixed according to 1:1 mass ratio, getting 0.1g uniform application imitates on skin adhesive tape in the 3M that area is 7cm*7cm, uv absorption is surveyed in 250-380nm, see OMC+UV360 in Figure 13, embedding liquid state and solid-state organic uv absorbers microcapsule mixture rate of absorbing UV within the scope of 330-380nm obviously increase.
Microcapsule prepared by 2.3 comparative examples 1 and embodiment 2
After the embedding ethylhexyl methoxy cinnamate microcapsule prepared according to comparative example 1 method and the embedding butyl methoxydibenzoylmethise microcapsule prepared according to embodiment 2 method are mixed according to 1:1 mass ratio, getting 0.1g uniform application imitates on skin adhesive tape in the 3M that area is 7cm*7cm, uv absorption is surveyed in 250-380nm, see OMC+Parsol1789 in Figure 14, embedding liquid state and solid-state organic uv absorbers microcapsule mixture rate of absorbing UV within the scope of 320-380nm obviously increase.
Visible, after adding embedding solid-state UV absorbent microcapsule, sun-proof performance obviously strengthens.
The all documents mentioned in the present invention are quoted as a reference all in this application, are just quoted separately as a reference as each section of document.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read above-mentioned teachings of the present invention, these equivalent form of values fall within the application's appended claims limited range equally.
Claims (8)
1. a microcapsule, is characterized in that, described microcapsule comprises solid sunscreen and natural polymer, and described solid sunscreen is wrapped in the microcapsule of described natural polymer formation, wherein,
Described solid sunscreen is inorganic UV screener, SOLID ORGANIC ultraviolet absorber or its mixture;
Described natural polymer is agar, agarose, cellulose or chitosan,
The mean diameter of described microcapsule is 200 nanometer-20 microns,
And described microcapsule also comprises liquid sunscreen, described liquid sunscreen and described solid sunscreen are all wrapped in the microcapsule that described natural polymer formed,
Wherein, described SOLID ORGANIC ultraviolet absorber is selected from: dibenzoyl methane class, benzophenone, hydroxy phenyl s-triazine, benzotriazole and combination thereof.
2. microcapsule as claimed in claim 1, it is characterized in that, the mean diameter of described microcapsule is 1 micron-10 microns.
3. microcapsule as claimed in claim 1, it is characterized in that, described inorganic UV screener is selected from: Zinc oxide particles, titanium dioxide granule and combination thereof.
4. microcapsule as claimed in claim 1, it is characterized in that, described SOLID ORGANIC ultraviolet absorber is butyl methoxydibenzoylmethise, 2,4-diethoxy-6-(2 ', 4 '-dihydroxy phenyl)-1,3,5-triazine, 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole, di-2-ethylhexylphosphine oxide [6-BTA-4-tert-octylphenol].
5. microcapsule as claimed in claim 1, is characterized in that, described microcapsule is also containing water, organic solvent, surfactant, stabilizing agent or its combination.
6. a preparation method for microcapsule according to claim 1, is characterized in that, comprises the following steps:
A natural polymer is dissolved in water or aqueous solution and forms solution by ();
B solid sunscreen is dispersed in the solution that step (a) obtains and forms S/W dispersion liquid by ();
C S/W dispersion liquid that step (b) obtains by () is dispersed in the oil phase containing lipophilic surfactant and forms S/W/O emulsion;
D described S/W/O emulsion solidification that step (c) obtains by () obtains described microcapsule,
Wherein, described natural polymer, solid sunscreen are as claimed in claim 1;
Described lipophilic surfactant is sorbitan sesquioleate, polyoxyethylene ether, polyoxyethylene hydrogenated Oleum Ricini, sorbitan trioleate, sorbitan monooleate, anhydrous sorbitol tristearate, alkylglycoside, cithrol or its combination;
Described oil phase is silicone oil, liquid paraffin, olive oil, Oleum Cocois, Oleum Ricini, hardened soybean oil or its combination;
And in described step (b), in the solution that described step (a) obtains, be also added with liquid sunscreen.
7. preparation method as claimed in claim 6, is characterized in that, in described step (b), also adds organic solvent, surfactant, stabilizing agent or its combination in the solution that described step (a) obtains;
Described organic solvent is selected from: ethanol, isopropyl alcohol, methanol, acetone, silicone oil, liquid paraffin, olive oil, Oleum Cocois, Oleum Ricini, hardened soybean oil and combination thereof;
Described surfactant is selected from: Tween, Triton, SDS (sodium lauryl sulphate), CTAB (cetyl trimethyl ammonium bromide), SDBS (dodecylbenzene sodium sulfonate), sodium alkyl sulfate, polyoxyethylene ether, alkylglycoside, cithrol, sorbitan sesquioleate, polyoxyethylene hydrogenated Oleum Ricini, sorbitan trioleate, sorbitan monooleate, anhydrous sorbitol tristearate and combination thereof;
Described stabilizing agent is selected from: polyvinyl alcohol, Polyethylene Glycol, polyvinylpyrrolidone, gelatin, xanthan gum, hydroxypropyl cellulose, phosphate, polyphosphate and combination thereof.
8. a sun care preparations, is characterized in that, containing the microcapsule described in any one of claim 1 to 5.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310098635.5A CN103169625B (en) | 2013-03-25 | 2013-03-25 | Wrap up the microcapsule of solid sunscreen, preparation method and application thereof |
| TW102139690A TWI601538B (en) | 2013-03-25 | 2013-11-01 | Microcapsule encapsulating a solid sunscreen, and preparation and use thereof |
| JP2014055886A JP2014185152A (en) | 2013-03-25 | 2014-03-19 | Microcapsule for enclosing solid sunscreen agent, production method thereof, and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310098635.5A CN103169625B (en) | 2013-03-25 | 2013-03-25 | Wrap up the microcapsule of solid sunscreen, preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103169625A CN103169625A (en) | 2013-06-26 |
| CN103169625B true CN103169625B (en) | 2016-04-13 |
Family
ID=48630120
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310098635.5A Active CN103169625B (en) | 2013-03-25 | 2013-03-25 | Wrap up the microcapsule of solid sunscreen, preparation method and application thereof |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP2014185152A (en) |
| CN (1) | CN103169625B (en) |
| TW (1) | TWI601538B (en) |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104336013B (en) * | 2013-08-02 | 2016-05-25 | 浙江农林大学 | The preparation method of Tebuconazole Nano capsule |
| CN103610600A (en) * | 2013-11-15 | 2014-03-05 | 上海应用技术学院 | Ethyl cellulose particle loaded with oil-soluble sun screener benzophenone-3 and preparation method thereof |
| CN104434548B (en) * | 2014-12-16 | 2018-01-05 | 重庆小丸科贸有限公司 | A kind of hydrogel microcapsule with sun-proof function |
| CN104873411B (en) * | 2015-05-04 | 2017-08-25 | 上海应用技术学院 | A kind of styrene cross-linked polymer particle for loading fat-soluble sun-screening agent and preparation method thereof |
| CN104873412B (en) * | 2015-05-04 | 2017-08-25 | 上海应用技术学院 | A kind of methyl methacrylate cross-linked polymer particle and preparation method for loading fat-soluble sun-screening agent |
| JP6797139B2 (en) * | 2015-06-05 | 2020-12-09 | フイルメニツヒ ソシエテ アノニムＦｉｒｍｅｎｉｃｈ Ｓａ | Microcapsules with a high degree of deposition on the surface |
| CN105232353B (en) * | 2015-11-04 | 2018-03-27 | 南京华狮新材料有限公司 | A kind of cold-type yellow (clear) suncream or skin cream and preparation method thereof |
| KR101833612B1 (en) * | 2016-03-30 | 2018-02-28 | 선진뷰티사이언스(주) | Polymer composite particles containing much of organic sunscreen agents and the method for preparing thereof |
| CN108852863A (en) * | 2017-05-10 | 2018-11-23 | 滕州市悟通香料有限责任公司 | A kind of handguard capsule |
| CN107519025A (en) * | 2017-08-23 | 2017-12-29 | 中山大学惠州研究院 | A kind of hydrophobic sun-proof microcapsules and preparation method thereof |
| CN111358711B (en) * | 2018-12-25 | 2023-08-11 | 万华化学集团股份有限公司 | Photosensitive material/calcium alginate core-shell nanocapsule dispersoid and preparation method thereof |
| CN109771306B (en) * | 2019-01-02 | 2021-11-30 | 江南大学 | Inorganic-organic sunscreen agent composite microsphere and preparation method thereof |
| CN109999737A (en) * | 2019-03-20 | 2019-07-12 | 华南理工大学 | A kind of antifouling microcapsules of Degradable environment protection and the preparation method and application thereof |
| CN110387748A (en) * | 2019-06-21 | 2019-10-29 | 李新根 | A kind of preparation method of antiultraviolet microcapsule dressing agent |
| CN110484042B (en) * | 2019-07-05 | 2022-03-08 | 中山大学 | Self-repairing super-hydrophobic nano anticorrosive coating and preparation method thereof |
| CN112169716A (en) * | 2020-09-09 | 2021-01-05 | 中国科学院山西煤炭化学研究所 | Preparation method of microcapsule coated with solid microparticles |
| CN112402291A (en) * | 2020-11-26 | 2021-02-26 | 上海应用技术大学 | Composite wall material particle coated with fat-soluble sunscreen agent, preparation method and application |
| CN114931515A (en) * | 2022-06-23 | 2022-08-23 | 上海臻臣化妆品有限公司 | Process for preparing microencapsulated sunscreen agents, microencapsulated sunscreen agents and sunscreen products comprising same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1287877A (en) * | 1999-07-27 | 2001-03-21 | 株式会社资生堂 | Micro-capsule and its prepn. method |
| CN1422609A (en) * | 2002-12-11 | 2003-06-11 | 曾仲韬 | Microcapsul water-aqua type cosmetic, personal care article and external-use medicine |
| CN101293191A (en) * | 2007-04-25 | 2008-10-29 | 中国科学院过程工程研究所 | Gelose gel rubber microsphere and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5632604B2 (en) * | 2008-11-28 | 2014-11-26 | 花王株式会社 | Hydrogel particles |
| JP4840829B2 (en) * | 2009-09-01 | 2011-12-21 | 株式会社 資生堂 | Sunscreen cosmetics |
-
2013
- 2013-03-25 CN CN201310098635.5A patent/CN103169625B/en active Active
- 2013-11-01 TW TW102139690A patent/TWI601538B/en active
-
2014
- 2014-03-19 JP JP2014055886A patent/JP2014185152A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1287877A (en) * | 1999-07-27 | 2001-03-21 | 株式会社资生堂 | Micro-capsule and its prepn. method |
| CN1422609A (en) * | 2002-12-11 | 2003-06-11 | 曾仲韬 | Microcapsul water-aqua type cosmetic, personal care article and external-use medicine |
| CN101293191A (en) * | 2007-04-25 | 2008-10-29 | 中国科学院过程工程研究所 | Gelose gel rubber microsphere and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103169625A (en) | 2013-06-26 |
| TWI601538B (en) | 2017-10-11 |
| JP2014185152A (en) | 2014-10-02 |
| TW201436808A (en) | 2014-10-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103169625B (en) | Wrap up the microcapsule of solid sunscreen, preparation method and application thereof | |
| US10729624B2 (en) | High-ultraviolet absorption lignin/chemical sun-screening agent microcapsule and preparation method therefor | |
| Awan et al. | Cellulose nanocrystal–ZnO nanohybrids for controlling photocatalytic activity and UV protection in cosmetic formulation | |
| CN102029400B (en) | A kind of method of preparing silver nanometer wire with controllable wire diameter by cation control microwave | |
| CN1323579A (en) | Micro-capsule contg. water soluble beauty-care activity component water nuclear, and composition contg. same | |
| CN108837779B (en) | Ion-crosslinked lignin microcapsule and preparation method thereof | |
| CN108699427A (en) | Include the synthesis and its application of the inorganic silicon dioxide microcapsules of phase-change material | |
| WO2008088586A3 (en) | New phototherapeutic materials prepared through nanoparticle assembly | |
| CN101392461A (en) | Phase change energy storage low temperature face mask substrate material and preparation method thereof | |
| CN103665393A (en) | Electrostatic interaction induced micelle preparation method | |
| CN102274192A (en) | Carboxymethyl chitosan medicament-carrying microspheres and preparation method thereof | |
| CN103688928B (en) | A kind of slow-release pesticide and preparation method thereof | |
| US20170143597A1 (en) | Compositions for cosmetic raw material and methods for making the same | |
| CN104607119A (en) | Acetic acid styracin nanometer capsule and preparation method thereof | |
| BR112015010226B1 (en) | drive composition for two-stage controlled release of functional chemical actives, and absorbent article | |
| CN102179219B (en) | Method of preparing microcapsule emulsion with high-concentration and high core/wall ratio by adopting complex coacervation method | |
| KR20140080467A (en) | Polymer Nano Particle Containing UV Blocking Material and Method of Preparing the Same | |
| CN102373507A (en) | Method for hydrothermally synthesizing Bi2WO6 material under assistance of imidazole ionic liquids | |
| CN114081869B (en) | Microcapsule-embedded chitosan solid fragrance and preparation method and application thereof | |
| CN105030554A (en) | Solid lipid sunscreen particles coated with high-concentration sun screener and preparation method of solid lipid sunscreen particles | |
| CN108850007A (en) | A kind of bird repellent of electric system and preparation method thereof | |
| CN103610600A (en) | Ethyl cellulose particle loaded with oil-soluble sun screener benzophenone-3 and preparation method thereof | |
| Zhang et al. | Preparation of enzymolysis porous corn starch composite microcapsules embedding organic sunscreen agents and its UV protection performance and stability | |
| CN100528956C (en) | Nano particle of enwrapping water-soluble active ingredient, and preparation method | |
| WO2021174188A1 (en) | A personal care product and a method for making a personal care product by an additive process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20160316 Address after: 200233 No. 1397, Xuhui District, Shanghai, Yishan Road Applicant after: Changxin (China) Investment Co., Ltd. Address before: 519050 Guangdong province Zhuhai Gaolan Port Industrial Zone Petrochemical Zone Bi Yang Road Applicant before: Eternal Chemical Material (Zhuhai) Co., Ltd. |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |