CN113069372A - Sunscreen composition based on melanin coated particles and preparation method thereof - Google Patents
Sunscreen composition based on melanin coated particles and preparation method thereof Download PDFInfo
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- CN113069372A CN113069372A CN202110369699.9A CN202110369699A CN113069372A CN 113069372 A CN113069372 A CN 113069372A CN 202110369699 A CN202110369699 A CN 202110369699A CN 113069372 A CN113069372 A CN 113069372A
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- melanin
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- XUMBMVFBXHLACL-UHFFFAOYSA-N Melanin Chemical compound O=C1C(=O)C(C2=CNC3=C(C(C(=O)C4=C32)=O)C)=C2C4=CNC2=C1C XUMBMVFBXHLACL-UHFFFAOYSA-N 0.000 title claims abstract description 170
- 239000002245 particle Substances 0.000 title claims abstract description 83
- 239000000516 sunscreening agent Substances 0.000 title claims abstract description 56
- 230000000475 sunscreen effect Effects 0.000 title claims abstract description 53
- 239000000203 mixture Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 125
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 98
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 60
- 239000011787 zinc oxide Substances 0.000 claims abstract description 49
- 239000010954 inorganic particle Substances 0.000 claims abstract description 26
- 239000006185 dispersion Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 239000002105 nanoparticle Substances 0.000 abstract description 24
- 230000000694 effects Effects 0.000 abstract description 11
- 230000000149 penetrating effect Effects 0.000 abstract description 4
- 230000004224 protection Effects 0.000 abstract description 4
- 231100000957 no side effect Toxicity 0.000 abstract description 2
- 230000009982 effect on human Effects 0.000 abstract 1
- 239000002537 cosmetic Substances 0.000 description 35
- 210000003491 skin Anatomy 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 238000010521 absorption reaction Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000000576 coating method Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 231100000252 nontoxic Toxicity 0.000 description 4
- 230000003000 nontoxic effect Effects 0.000 description 4
- 239000002250 absorbent Substances 0.000 description 3
- 230000002745 absorbent Effects 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- 150000003384 small molecules Chemical class 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 description 2
- 241000544912 Melanoides Species 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 208000000453 Skin Neoplasms Diseases 0.000 description 2
- 206010042496 Sunburn Diseases 0.000 description 2
- 230000006750 UV protection Effects 0.000 description 2
- HEAHZSUCFKFERC-LRVMPXQBSA-N [(2e)-2-[[4-[(z)-[7,7-dimethyl-3-oxo-4-(sulfomethyl)-2-bicyclo[2.2.1]heptanylidene]methyl]phenyl]methylidene]-7,7-dimethyl-3-oxo-4-bicyclo[2.2.1]heptanyl]methanesulfonic acid Chemical compound CC1(C)C2CCC1(CS(O)(=O)=O)C(=O)\C2=C/C(C=C1)=CC=C1\C=C/1C(=O)C2(CS(O)(=O)=O)CCC\1C2(C)C HEAHZSUCFKFERC-LRVMPXQBSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- XNEFYCZVKIDDMS-UHFFFAOYSA-N avobenzone Chemical compound C1=CC(OC)=CC=C1C(=O)CC(=O)C1=CC=C(C(C)(C)C)C=C1 XNEFYCZVKIDDMS-UHFFFAOYSA-N 0.000 description 2
- 229960005193 avobenzone Drugs 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000008280 blood Substances 0.000 description 2
- 210000004369 blood Anatomy 0.000 description 2
- 230000000711 cancerogenic effect Effects 0.000 description 2
- 231100000315 carcinogenic Toxicity 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 229960001149 dopamine hydrochloride Drugs 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229960003747 ecamsule Drugs 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 210000002615 epidermis Anatomy 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000007760 free radical scavenging Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- FMJSMJQBSVNSBF-UHFFFAOYSA-N octocrylene Chemical group C=1C=CC=CC=1C(=C(C#N)C(=O)OCC(CC)CCCC)C1=CC=CC=C1 FMJSMJQBSVNSBF-UHFFFAOYSA-N 0.000 description 2
- 229960000601 octocrylene Drugs 0.000 description 2
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 description 2
- 229960001173 oxybenzone Drugs 0.000 description 2
- 201000000849 skin cancer Diseases 0.000 description 2
- 230000005808 skin problem Effects 0.000 description 2
- 210000000434 stratum corneum Anatomy 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 206010002198 Anaphylactic reaction Diseases 0.000 description 1
- 201000004624 Dermatitis Diseases 0.000 description 1
- 206010014970 Ephelides Diseases 0.000 description 1
- 206010015150 Erythema Diseases 0.000 description 1
- GHASVSINZRGABV-UHFFFAOYSA-N Fluorouracil Chemical compound FC1=CNC(=O)NC1=O GHASVSINZRGABV-UHFFFAOYSA-N 0.000 description 1
- WTDRDQBEARUVNC-UHFFFAOYSA-N L-Dopa Natural products OC(=O)C(N)CC1=CC=C(O)C(O)=C1 WTDRDQBEARUVNC-UHFFFAOYSA-N 0.000 description 1
- 208000003351 Melanosis Diseases 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 108091005461 Nucleic proteins Proteins 0.000 description 1
- 241000238371 Sepiidae Species 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 208000003455 anaphylaxis Diseases 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000017531 blood circulation Effects 0.000 description 1
- 210000004204 blood vessel Anatomy 0.000 description 1
- 230000019522 cellular metabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229940098363 cuttle fish ink Drugs 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 210000004207 dermis Anatomy 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- MHUWZNTUIIFHAS-CLFAGFIQSA-N dioleoyl phosphatidic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(COP(O)(O)=O)OC(=O)CCCCCCC\C=C/CCCCCCCC MHUWZNTUIIFHAS-CLFAGFIQSA-N 0.000 description 1
- 210000004177 elastic tissue Anatomy 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 210000005175 epidermal keratinocyte Anatomy 0.000 description 1
- 231100000321 erythema Toxicity 0.000 description 1
- 229960002949 fluorouracil Drugs 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 229960004502 levodopa Drugs 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 210000002780 melanosome Anatomy 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 210000003205 muscle Anatomy 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000036470 plasma concentration Effects 0.000 description 1
- 229920001690 polydopamine Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000036559 skin health Effects 0.000 description 1
- 231100000245 skin permeability Toxicity 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000036561 sun exposure Effects 0.000 description 1
- 230000037072 sun protection Effects 0.000 description 1
- 239000012801 ultraviolet ray absorbent Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/29—Titanium; Compounds thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/27—Zinc; Compounds thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
- A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/41—Particular ingredients further characterized by their size
- A61K2800/413—Nanosized, i.e. having sizes below 100 nm
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/56—Compounds, absorbed onto or entrapped into a solid carrier, e.g. encapsulated perfumes, inclusion compounds, sustained release forms
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/59—Mixtures
- A61K2800/592—Mixtures of compounds complementing their respective functions
- A61K2800/5922—At least two compounds being classified in the same subclass of A61K8/18
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/60—Particulates further characterized by their structure or composition
- A61K2800/61—Surface treated
- A61K2800/62—Coated
- A61K2800/624—Coated by macromolecular compounds
Landscapes
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Dermatology (AREA)
- Cosmetics (AREA)
Abstract
The invention discloses a sunscreen composition based on melanin coated particles and a preparation method thereof. The sunscreen composition comprises: inorganic particles and melanin coated particles; the inorganic particles comprise the following components in parts by weight: 100 parts by weight; melanin-coated particles: 1-1000 parts by weight; the inorganic particles are titanium dioxide or titanium dioxide and zinc oxide; the melanin-coated particles are melanin-coated titanium dioxide and/or melanin-coated zinc oxide. The invention can effectively improve the SPF value and the PA value, obtain the sunscreen composition with excellent full ultraviolet wave band protection effect, is safe and effective, can greatly reduce the possibility of the inorganic nano particles penetrating the skin, and has no side effect on human bodies.
Description
Technical Field
The invention relates to the technical field of sunscreen agents, and further relates to a sunscreen composition based on melanin coated particles and a preparation method thereof.
Background
As the environmental problem becomes more serious, the atmospheric ozone layer becomes thinner and thinner, ozone holes appear, and the irradiation intensity of ultraviolet A region (UVA, wavelength 320-400nm) and ultraviolet B region (UVB, wavelength 280-320nm) is increased, so that the oxygen free radicals are increased. The damage of sunlight to human skin mainly comes from UVA and UVB: UVA has strong penetrating power to skin, can penetrate epidermis and dermis, gradually destroys elastic fibers, causes muscle to lose elasticity, further causes skin relaxation, and has wrinkles, freckles and age spots, and skin cancer is easily caused if excessive irradiation is carried out; UVB denatures nucleic acids or proteins in cells on the skin surface, the skin turns red, produces erythema (sunburn), forms melanin on the skin, and produces acute dermatitis, often referred to as sunburn. There are nearly 50 million new skin cancer patients in the united states each year, and the results of the study demonstrate that over 98% of these patients are carcinogenic by sun exposure. Ultraviolet light can be said to be a large enemy of skin health.
The sunscreen agents used in the cosmetics on the market are mainly classified into organic small molecule ultraviolet absorbers and inorganic ultraviolet screening agents. The inorganic ultraviolet screening agent which is determined by the national safety of each country mainly comprises titanium dioxide and zinc oxide, and the limitation of each country to the type and the maximum addition amount of the organic micromolecular ultraviolet absorbent is different. For organic small molecule sunscreens, The U.S. Food and Drug Administration (FDA) published studies at 2019, 5 months earlier, comparing The total exposure of 4 common organic Active Ingredients in different commercially available sunscreens Under maximum Use Conditions, and The results are published in JAMA (Effect of sunlight Application underlying maximum Use Conditions on Plasma concentrations of sunlight Active Ingredients, The Journal of The American Medical Association, 321). Although the types and the addition amounts of the sunscreen ingredients of the sunscreen products on the market are within the regulation, the research result shows that 4 chemical ingredient levels of avobenzone (avobenzone), oxybenzone (oxybenzone), octocrylene (octocrylene) and ecamsule (ecamsule) in the blood of the volunteers using the sunscreen products for one day exceed the level of 0.5 nanogram per milliliter, which is regulated by the authorities; and the concentration of these chemicals in the blood continues to increase with repeated use of the sunscreen product. Therefore, the organic micromolecule ultraviolet absorbent still has great potential safety hazard in the use process of the human body.
According to previous researches, the inorganic ultraviolet screening agent is considered to be basically nontoxic and safe to human bodies, has no irritation to skin and is not carcinogenic; however, the sunscreen agent has no significant effect on the absorption and shielding of ultraviolet rays, needs to be added in a large amount and needs to be compounded with an organic small-molecular ultraviolet ray absorbent for use, and the sunscreen cosmetic has an extremely low Sun Protection Factor (SPF) when the content is small; titanium dioxide absorbs UVB better than zinc oxide, but absorbs UVA less strongly than zinc oxide. According to the regulations in the technical safety standards for cosmetics (IECIC 2015) of China, the maximum addition amounts of titanium dioxide and zinc oxide are 25%, but the addition of a large amount of titanium dioxide and zinc oxide can make the sunscreen cosmetic whitish and thick, the sunscreen cosmetic is not easy to coat and disperse, and the experience of consumers is poor.
The latest research results show that when inorganic nanoparticles such as titanium dioxide are applied to the surface of the skin, part of the nanoparticles can penetrate into the deep layer of the skin through the epidermis of the human body, and are more likely to enter blood circulation, and are enriched in the heart and lung center or the tail end of a blood vessel, so that various potential hazards are generated to the human body.
Therefore, the development of safe, non-toxic, impermeable and sunscreen compositions with good sunscreen effect is highly urgent.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a sunscreen composition based on melanin-coated particles and a preparation method thereof. According to the invention, the titanium dioxide particles and/or the zinc oxide particles coated with the melanin are compounded with the titanium dioxide or the titanium dioxide and the zinc oxide particles, so that the SPF value and the PA value can be effectively increased, the sunscreen composition with excellent full-ultraviolet band protection effect can be obtained, and the sunscreen composition is safe and effective, can greatly reduce the possibility of the inorganic nanoparticles penetrating the skin, and has no side effect on a human body.
One of the objects of the present invention is to provide a sunscreen composition based on melanin-coated particles.
The sunscreen composition comprises:
inorganic particles and melanin coated particles;
the components are calculated according to the parts by weight,
inorganic particles: 100 parts by weight;
melanin-coated particles: 1-1000 parts by weight;
the inorganic particles are titanium dioxide or titanium dioxide and zinc oxide;
the melanin-coated particles are melanin-coated titanium dioxide and/or melanin-coated zinc oxide.
In a preferred embodiment of the present invention,
the components are calculated according to the parts by weight,
inorganic particles: 100 parts by weight;
melanin-coated particles: 5-500 parts by weight.
In a preferred embodiment of the present invention,
the particle size range of the inorganic particles is 20-300 nm;
the particle size range of the melanin-coated particles is 50-250nm, and more preferably 50-150 nm;
in a preferred embodiment of the present invention,
the crystal form of the titanium dioxide is rutile;
the particle size range of the titanium dioxide is 20-200 nm.
In a more preferred embodiment of the present invention,
the particle size range of the titanium dioxide is 30-100 nm.
In a preferred embodiment of the present invention,
the particle size range of the zinc oxide is 30-300 nm.
In a more preferred embodiment of the present invention,
the particle size range of the zinc oxide is 50-100 nm.
In a preferred embodiment of the present invention,
the inorganic particles are titanium dioxide and zinc oxide;
the inorganic particle component is added to the aqueous dispersion in an amount of 100 parts by weight,
1-95 parts by weight of titanium dioxide;
5-99 parts of zinc oxide.
In a more preferred embodiment of the present invention,
the inorganic particle component is added to the aqueous dispersion in an amount of 100 parts by weight,
50-90 parts of titanium dioxide;
10-50 parts of zinc oxide.
The method for coating zinc oxide or titanium dioxide with melanin in the invention can adopt the coating method disclosed in the prior art.
In the present invention, the coating is preferably performed by the following method:
dispersing inorganic particles in deionized water, dissolving melanin precursor in the dispersion, stirring, adjusting temperature, adding a certain amount of alkaline substance to adjust the pH of the solution, reacting after 12 hours, and centrifuging to obtain melanin-coated inorganic particles.
The invention also provides a preparation method of the sunscreen composition.
The method comprises the following steps:
the components are uniformly mixed according to the dosage to prepare the sunscreen composition.
The main sunscreen principle of the sunscreen composition based on melanin-coated particles of the present invention is to absorb and scatter ultraviolet rays.
The invention coats melanin on titanium dioxide or zinc oxide mixed nano particles with proper particle size, and then compounds the nano particles with titanium dioxide or titanium dioxide and zinc oxide particles. When ultraviolet light is applied to particles in a medium, electrons in the particles are forcibly vibrated (the vibration frequency is the same as the frequency of incident light) by the size of the nanoparticles being smaller than or equal to the wavelength of the ultraviolet light, and become secondary wave sources, and electromagnetic waves are emitted in all directions to scatter the ultraviolet light.
In the invention, the synergistic effect is achieved between the melanin-coated particles and the inorganic particles and between the melanin and the inorganic titanium dioxide or zinc oxide when absorbing ultraviolet rays, so that the final sunscreen composition based on the melanin-coated particles has an ultraviolet absorption effect superior to that of any one of the original components. This is because titanium dioxide and zinc oxide, which are inorganic substances, are both N-type semiconductors, and when irradiated with ultraviolet light, electrons in the valence band absorb the ultraviolet light and are excited to the conduction band, and at the same time, hole-electron pairs are generated, and therefore titanium dioxide and zinc oxide have a function of absorbing ultraviolet light. However, titanium dioxide and zinc oxide can only absorb limited ultraviolet rays because the ultraviolet rays absorbing capacity of the hole-electron pair is limited, and the titanium dioxide and zinc oxide cannot convert the absorbed ultraviolet rays into heat or electric energy, so that the hole-electron pair cannot be vacated to absorb ultraviolet rays. Melanin can convert 99% of the proton absorption energy into heat energy in a non-radiative form in a very short time (50ps) (wavelet-dependent photo cosmetic study of skin. photo. biol,1998,68(3):296-298), but the use of melanin in large amounts leads to a darker color and a reduced consumer acceptance of the cosmetic. Therefore, the invention coats a proper amount of melanin on the surface of inorganic titanium dioxide or zinc oxide, and ultraviolet rays can consume a part of the melanin layer firstly; ultraviolet rays enter the melanin layer, and then a part of the ultraviolet rays are scattered by the inorganic particles and return to the melanin for multiple consumption; the residual ultraviolet rays enter the particles and are absorbed by titanium dioxide or zinc oxide, electrons on a valence band are excited to a conduction band, and hole-electron pairs are generated at the same time and are transferred through a large pi conjugated system of melanin, so that the ultraviolet rays can be consumed through the photothermal conversion of the melanin continuously, and the ultraviolet absorption capacity is greatly improved; and the coated particles are compounded with the inorganic particles of titanium dioxide and zinc oxide, so that the possibility that the nano particles penetrate through the skin of a human body can be greatly reduced, and the apparent color of the system can be regulated and controlled.
The melanin and the melanoid used when the particles are coated are biomacromolecules, and have multiple functions of oxidation resistance, ultraviolet absorption, transdermal resistance and the like; different from other organic micromolecule ultraviolet absorbers, the melanin is a human metabolic product, is safe and nontoxic, does not cause skin anaphylactic reaction and has multiple effects. Melanin is a peculiar biological macromolecule, widely exists in animals and plants, and has excellent performances such as ultraviolet light absorption, heat dissipation, metal ion chelation, temperature regulation, antibacterial property, free radical scavenging and the like (Journal of Physics.D: Applied Physics 2009,42(3): 035502). The ultraviolet absorption area of melanin completely covers UVA and UVB, and the melanin can capture and remove free radicals generated by a human body, and has obvious antioxidant effect. The synthesized biological melanin can be endocytosed by a human body like melanin generated by the human body, and forms a cell protective layer on human epidermal keratinocytes to reduce ultraviolet injury; meanwhile, melanoid can also undergo cellular metabolism and be excreted out of the body (Mimicking Melanosomes: Polydopamine Nanoparticles as Art microparticles, ACS Cent. Sci.2017,3, 564-.
As for inorganic nanoparticles, titanium dioxide has stronger capability of absorbing ultraviolet rays with the wavelength of 290-355nm, zinc oxide has stronger effect of absorbing ultraviolet rays with the wavelength of 355-385nm than titanium dioxide, and melanin has absorption in the ultraviolet band; meanwhile, the coated melanin can generate good synergistic effect with the inorganic nano particles. Therefore, the personal care sunscreen composition with excellent full ultraviolet band protection effect can be obtained by compounding the inorganic nanoparticles and the melanin-coated particles. The sunscreen composition is formed by compounding the melanin coated particles with one or a combination of inorganic nano-particle titanium dioxide and zinc oxide, and is doped into cosmetic components, so that the SPF value, the PA value and the free radical scavenging capacity are greatly improved while no organic small-molecule ultraviolet absorbent is added, the oxidation resistance and the ultraviolet resistance of the cosmetic are effectively improved, the ultraviolet rays are prevented from damaging human bodies, various skin problems caused by ultraviolet irradiation are avoided, and the application field of the cosmetic is expanded; while the SPF value is ensured, the addition of the melanin-coated particles can reduce the use amount of titanium dioxide and zinc oxide, regulate and control the color of the product, and solve the problems that the experience of consumers is affected by whitening, heavy skin feel, difficult smearing, and the like of the product caused by using a large amount of inorganic sun-screening agents.
The sunscreen compositions of the present application are not only suitable for use in cosmetics, but also in other fields, such as: can be used in some transparent polymers for shielding ultraviolet rays.
The beneficial technical effects of the invention are as follows:
1. after the melanin coated particles with proper thickness are compounded with the inorganic nanoparticles, when ultraviolet rays act on the particles in a medium, the ultraviolet rays can be scattered because the size of the nanoparticles is smaller than the wavelength of the ultraviolet rays.
2. After the melanin coated particles and the inorganic nanoparticles are compounded, the titanium dioxide and the zinc oxide can continuously carry out photo-thermal conversion on the absorbed ultraviolet rays through the melanin, and the ultraviolet absorption capacity is greatly improved.
3. The melanin coating layer can play multiple roles of eliminating free radicals, absorbing and scattering ultraviolet rays, stably dispersing, preventing inorganic nanoparticles from penetrating into skin and the like in cosmetics; meanwhile, the color of the cosmetic can be improved, the cosmetic is easy to apply and disperse, and the sticky feeling is reduced.
4. After the melanin coated particles and the inorganic nanoparticles are compounded, the SPF value and the PA value can be effectively improved, and the sunscreen composition with excellent full ultraviolet band protection effect is obtained.
Detailed Description
While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.
All materials are commercially available in the examples.
Preparation of melanin-coated nanoparticles
The particle size of the titanium dioxide 1 is 30nm, rutile type;
the particle size of the titanium dioxide 2 is 60nm, rutile type;
the particle size of the titanium dioxide 3 is 100nm, rutile type;
the particle size of the zinc oxide 1 is 50 nm;
the particle size of the zinc oxide 2 is 100 nm;
(1) preparation of melanin-coated particles 1-2: dispersing titanium dioxide 1 in deionized water, dissolving dopamine hydrochloride (specification: AR) in the dispersion, stirring, adjusting temperature, adding a certain amount of alkaline substance to adjust pH, reacting after 4 hours, and centrifuging to obtain melanin-coated particles 1 with particle size of 50 nm; preparing melanin-coated particles 2 with the particle size of 150nm by using titanium dioxide 3;
(2) preparation of melanin-coated particles 3: dispersing titanium dioxide 2 in deionized water, dissolving DOPA (provided by Shanghai Aladdin Biotechnology and technology Co., Ltd.; specification: AR) and 5-fluorouracil (provided by national drug group chemical reagent Co., Ltd.; specification: BR) in the dispersion, stirring, adjusting temperature, adding a certain amount of alkaline substance to adjust pH of the solution, after 12 hours, finishing the reaction, and centrifuging to obtain melanin 3 with particle size of 75 nm;
(3) preparation of melanin-coated particles 4: buying cuttlefish (tin-free Nanchan Temple vegetable market) from the market, taking cuttlefish ink, centrifuging, adding deionized water to obtain a natural melanin dispersion, adding titanium dioxide 3, uniformly dispersing, stirring, adding a certain amount of alkaline substance to adjust pH, reacting after 4 hours, centrifuging to obtain melanin-coated particles 4 with the particle size of 250 nm;
(4) preparation of melanin-coated particles 5-6: dispersing zinc oxide 1 in deionized water, dissolving dopamine hydrochloride (specification: AR) in the dispersion, stirring, adjusting temperature, adding a certain amount of alkaline substance to adjust pH, reacting after 4 hours, and centrifuging to obtain melanin-coated particles 5 with particle size of 80 nm; zinc oxide 2 is used to prepare melanin coated particles 6 with the particle size of 150 nm.
Examples 1 to 12
The formula is shown in table 1, and the sun-proof composition (calculated by weight parts) is prepared by uniformly mixing the components
TABLE 1
And (3) testing:
the basic formula of the cosmetic is shown in Table 2
TABLE 2
The method comprises the following steps:
respectively dissolving oil phase and water phase components at a certain temperature to prepare a lipophilic and hydrophilic mixture, and uniformly mixing by a homogenizer; after cooling, a suitable amount of a pH stabilizer is added thereto to prepare a sunscreen composition cosmetic.
Comparative example 1
Adding 40 parts by weight of titanium dioxide 1 and 300 parts by weight of water based on 100 parts by weight of the basic formula of the cosmetic;
comparative example 2
Adding 1 part by weight of zinc oxide 40 parts by weight and 300 parts by weight of water based on 100 parts by weight of the basic formula of the cosmetic;
comparative example 3
Adding 20 parts by weight of titanium dioxide 1, 20 parts by weight of zinc oxide 1 and 300 parts by weight of water based on 100 parts by weight of the basic formula of the cosmetic;
example 13
Adding 40 parts by weight of the sunscreen composition prepared in the example 1 based on 100 parts by weight of the cosmetic basic formula; 300 parts by weight of water;
example 14
Adding 40 parts by weight of the sunscreen composition prepared in the example 2 based on 100 parts by weight of the cosmetic basic formula; 300 parts by weight of water;
example 15
Adding 40 parts by weight of the sunscreen composition prepared in the example 3 based on 100 parts by weight of the cosmetic basic formula; 300 parts by weight of water;
example 16
Adding 40 parts by weight of the sunscreen composition prepared in example 7 based on 100 parts by weight of the cosmetic basic formula; 300 parts by weight of water;
example 17
Adding 40 parts by weight of the sunscreen composition prepared in the example 8 based on 100 parts by weight of the cosmetic basic formula; 300 parts by weight of water;
example 18
Adding 40 parts by weight of the sunscreen composition prepared in example 11 based on 100 parts by weight of the cosmetic basic formula; 300 parts by weight of water;
example 19
Adding 40 parts by weight of the sunscreen composition prepared in example 12 based on 100 parts by weight of the cosmetic basic formula; 300 parts by weight of water;
evaluation item
1. SPF test
Uniformly coating each sample of 2mg/cm on a special plate for SPF test2And naturally drying for 15 minutes in dark. After that, ultraviolet irradiation was performed at a distance of 10mm above the glass plate. An ultraviolet transmittance analyzer (Labsphere Inc., USA) detects 5 random positions on a quartz glass plate in the range of 280-400nm to obtain the SPF value, and the average value of five times is taken to be recorded as the SPF.
2. PA test
Uniformly coating 2mg/cm of each sample on a special PA test plate2And naturally drying for 15 minutes in dark. After that, ultraviolet irradiation was performed at a distance of 10mm above the glass plate. The UV transmittance analyzer (Labsphere Inc., USA) detects at random 5 on the quartz glass plate in the range of 280-400nm to obtain PFA value, PFA is marked as PA + at 2-3, PFA is marked as PA + + +, and PFA is larger than or equal to 16.
3. Emulsion stability
The appearance of the test specimens after storage for one month at 25 ℃ was examined by visual observation and evaluated according to the following criteria.
Very good: the sample is uniform and stable;
o: emulsion separation was observed in the sample;
and (delta): oil slick was observed in the sample;
x: the sample was completely separated.
4. Feeling of use
10 volunteers were selected, each sample was applied to the face, and the stickiness at the time of absorption was investigated and evaluated according to the following criteria.
Very good: 9-10 people answer no greasy;
o: 6-8 people answer no greasy;
and (delta): 3-5 people answer no greasy;
x: 0-2 people do not feel sticky.
5. Skin permeability test
The permeability of the skin of the nanoparticles is tested by selecting fresh pigskin to replace the skin of a human body, and the evaluation is carried out according to the following standard.
O: the nano particles in the sample diffuse and do not penetrate the stratum corneum of the skin;
and (delta): the nanoparticles in the sample diffuse through the stratum corneum of the skin.
The test results are shown in Table 3
TABLE 3
As can be seen from the data of comparative examples 1-3 listed in table 3, titanium dioxide alone is better at protecting UVB than zinc oxide, while zinc oxide is better at protecting UVA than titanium dioxide, but the addition of 10% level has reduced the consumer appeal in part. Examples 13-15 compare to comparative example 1, which shows that the addition of melanin coated particles can effectively increase the SPF and PA values, and increase with the increase of the ratio of melanin coated particles; meanwhile, the addition of the melanin-coated particles can reduce the sticky feeling of the cosmetics and improve the experience feeling. The data of examples 16-19 demonstrate that the compounded addition of titanium dioxide and zinc oxide nanoparticles after addition of melanin-coated particles can also affect the SPF of the cosmetic; the smaller the particle size of the melanin coated particles is, the higher the SPF value is; in the mixing of inorganic particles, the titanium dioxide is more beneficial to the improvement of SPF value, and the zinc oxide is added to adjust the color. In summary, when the melanin-coated particles are not added or the addition amount is small, the whole color of the cosmetic appears white; with the increase of the proportion of the melanin coated particles, the color of the cosmetic tends to change in light brown, the apparent performance of the cosmetic can be regulated, and the cosmetic is suitable for different skin colors.
The invention provides a sunscreen composition based on melanin-coated particles and a preparation method thereof, wherein melanin is directly coated on the surface of inorganic particles, and then the melanin is mixed with one or a combination of inorganic titanium dioxide and zinc oxide to form the sunscreen composition, so that a synergistic effect can be achieved during scattering and ultraviolet absorption, and the final sunscreen composition based on the melanin-coated particles has an ultraviolet protection effect superior to that of any one of the original components. Meanwhile, the melanin coated particles can better stably disperse cosmetics, effectively resist oxidation, are safe and non-toxic, adjust the color of the cosmetics, avoid the penetration of inorganic nanoparticles into skin, avoid various skin problems caused by ultraviolet irradiation, and expand the application field of the cosmetics.
Those of ordinary skill in the art will understand that: the invention is not to be considered as limited to the specific embodiments thereof, but is to be understood as being modified in all respects, all changes and equivalents that come within the spirit and scope of the invention.
Claims (10)
1. A sunscreen composition based on melanin coated particles, characterized in that it comprises:
inorganic particles and melanin coated particles;
the components are calculated according to the parts by weight,
inorganic particles: 100 parts by weight;
melanin-coated particles: 1-1000 parts by weight;
the inorganic particles are titanium dioxide or titanium dioxide and zinc oxide;
the melanin-coated particles are melanin-coated titanium dioxide and/or melanin-coated zinc oxide.
2. The sunscreen composition of claim 1 wherein:
the components are calculated according to the parts by weight,
inorganic particles: 100 parts by weight;
melanin-coated particles: 5-500 parts by weight.
3. The sunscreen composition of claim 1 wherein:
the particle size range of the inorganic particles is 20-300 nm;
the particle size of the melanin-coated particles is in the range of 50 to 250nm, preferably 50 to 150 nm.
4. The sunscreen composition of claim 1 wherein:
the crystal form of the titanium dioxide is rutile;
the particle size range of the titanium dioxide is 20-200 nm.
5. The sunscreen composition of claim 4 wherein:
the particle size range of the titanium dioxide is 30-100 nm.
6. The sunscreen composition of claim 1 wherein:
the particle size range of the zinc oxide is 30-300 nm.
7. The sunscreen composition of claim 6 wherein:
the particle size range of the zinc oxide is 50-100 nm.
8. The sunscreen composition of claim 1 wherein:
the inorganic particles titanium dioxide and zinc oxide;
the inorganic particle component is added to the aqueous dispersion in an amount of 100 parts by weight,
1-95 parts by weight of titanium dioxide;
5-99 parts of zinc oxide.
9. The sunscreen composition of claim 8 wherein:
the inorganic particle component is added to the aqueous dispersion in an amount of 100 parts by weight,
50-90 parts of titanium dioxide;
10-50 parts of zinc oxide.
10. A process for the preparation of a sunscreen composition according to any of claims 1 to 9, characterized in that it comprises:
the components are uniformly mixed according to the dosage to prepare the sunscreen composition.
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CN115040424A (en) * | 2022-06-17 | 2022-09-13 | 江南大学 | Zinc oxide quantum dot coating, coating strategy, product and application |
FR3143982A1 (en) * | 2022-12-22 | 2024-06-28 | Dic Corporation | SUN PROTECTION AGENT |
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