CN115554176A - Sunscreen particle dispersion, sunscreen composition with stable sunscreen agent and preparation method of sunscreen composition - Google Patents
Sunscreen particle dispersion, sunscreen composition with stable sunscreen agent and preparation method of sunscreen composition Download PDFInfo
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- CN115554176A CN115554176A CN202211166380.7A CN202211166380A CN115554176A CN 115554176 A CN115554176 A CN 115554176A CN 202211166380 A CN202211166380 A CN 202211166380A CN 115554176 A CN115554176 A CN 115554176A
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- sunscreen
- titanium dioxide
- zinc oxide
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- 239000000516 sunscreening agent Substances 0.000 title claims abstract description 108
- 239000002245 particle Substances 0.000 title claims abstract description 105
- 230000000475 sunscreen effect Effects 0.000 title claims abstract description 104
- 239000006185 dispersion Substances 0.000 title claims abstract description 58
- 239000000203 mixture Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 167
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 112
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 83
- 239000011787 zinc oxide Substances 0.000 claims abstract description 56
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 150000002306 glutamic acid derivatives Chemical class 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000006482 condensation reaction Methods 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 31
- 238000005576 amination reaction Methods 0.000 claims description 23
- 239000012295 chemical reaction liquid Substances 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 claims description 18
- 230000004048 modification Effects 0.000 claims description 16
- 238000012986 modification Methods 0.000 claims description 16
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 16
- 125000003277 amino group Chemical group 0.000 claims description 14
- FPIRBHDGWMWJEP-UHFFFAOYSA-N 1-hydroxy-7-azabenzotriazole Chemical compound C1=CN=C2N(O)N=NC2=C1 FPIRBHDGWMWJEP-UHFFFAOYSA-N 0.000 claims description 13
- 238000009210 therapy by ultrasound Methods 0.000 claims description 13
- 150000001718 carbodiimides Chemical class 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
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- 239000007822 coupling agent Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 238000007664 blowing Methods 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000006071 cream Substances 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 7
- 239000008096 xylene Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 238000000861 blow drying Methods 0.000 claims description 4
- 235000013336 milk Nutrition 0.000 claims description 4
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- 238000004140 cleaning Methods 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 239000008267 milk Substances 0.000 claims description 3
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- 230000035484 reaction time Effects 0.000 claims description 3
- 239000006210 lotion Substances 0.000 claims description 2
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- 230000000052 comparative effect Effects 0.000 description 22
- AVBJHQDHVYGQLS-AWEZNQCLSA-N (2s)-2-(dodecanoylamino)pentanedioic acid Chemical compound CCCCCCCCCCCC(=O)N[C@H](C(O)=O)CCC(O)=O AVBJHQDHVYGQLS-AWEZNQCLSA-N 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
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- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 8
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 8
- 235000013922 glutamic acid Nutrition 0.000 description 8
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- 239000011248 coating agent Substances 0.000 description 7
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- 238000005406 washing Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
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- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 6
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- 239000002270 dispersing agent Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 3
- 150000003862 amino acid derivatives Chemical class 0.000 description 3
- 230000032798 delamination Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- GBHVZRWYYVEEFR-ZETCQYMHSA-N (2s)-2-(butylamino)pentanedioic acid Chemical compound CCCCN[C@H](C(O)=O)CCC(O)=O GBHVZRWYYVEEFR-ZETCQYMHSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
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- 125000004185 ester group Chemical group 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical class CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
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- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- BCXIBMCWAJWIAV-NSHDSACASA-N (2s)-2-(octylamino)pentanedioic acid Chemical compound CCCCCCCCN[C@H](C(O)=O)CCC(O)=O BCXIBMCWAJWIAV-NSHDSACASA-N 0.000 description 1
- BDNKZNFMNDZQMI-UHFFFAOYSA-N 1,3-diisopropylcarbodiimide Chemical compound CC(C)N=C=NC(C)C BDNKZNFMNDZQMI-UHFFFAOYSA-N 0.000 description 1
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- KMAOMYOPEIRFLB-UHFFFAOYSA-N 2-(hexadecanoylamino)pentanedioic acid Chemical compound CCCCCCCCCCCCCCCC(=O)NC(C(O)=O)CCC(O)=O KMAOMYOPEIRFLB-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 description 1
- JILBPZJGIGDIGK-UHFFFAOYSA-N 5-triethoxysilylpentan-1-amine Chemical compound CCO[Si](OCC)(OCC)CCCCCN JILBPZJGIGDIGK-UHFFFAOYSA-N 0.000 description 1
- FGGKLVJTJGWVGJ-UHFFFAOYSA-N 5-trimethoxysilylpentan-1-amine Chemical compound CO[Si](OC)(OC)CCCCCN FGGKLVJTJGWVGJ-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 1
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
- 239000004264 Petrolatum Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
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- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000008406 cosmetic ingredient Substances 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
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- 230000007547 defect Effects 0.000 description 1
- 229940008099 dimethicone Drugs 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
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- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 229960003921 octisalate Drugs 0.000 description 1
- WCJLCOAEJIHPCW-UHFFFAOYSA-N octyl 2-hydroxybenzoate Chemical compound CCCCCCCCOC(=O)C1=CC=CC=C1O WCJLCOAEJIHPCW-UHFFFAOYSA-N 0.000 description 1
- 239000002674 ointment Substances 0.000 description 1
- 244000052769 pathogen Species 0.000 description 1
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- 229920000642 polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
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- -1 silane compound Chemical class 0.000 description 1
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- 230000037072 sun protection Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- ROWWCTUMLAVVQB-UHFFFAOYSA-N triethoxysilylmethanamine Chemical compound CCO[Si](CN)(OCC)OCC ROWWCTUMLAVVQB-UHFFFAOYSA-N 0.000 description 1
- ARKBFSWVHXKMSD-UHFFFAOYSA-N trimethoxysilylmethanamine Chemical compound CO[Si](CN)(OC)OC ARKBFSWVHXKMSD-UHFFFAOYSA-N 0.000 description 1
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- 239000000230 xanthan gum Substances 0.000 description 1
Images
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—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
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
- A61K8/44—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives 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
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/58—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing atoms other than carbon, hydrogen, halogen, oxygen, nitrogen, sulfur or phosphorus
- A61K8/585—Organosilicon 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
- A61K2800/52—Stabilizers
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- 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 particle dispersion, a sunscreen composition with stable sunscreen agent and a preparation method thereof. The glutamic acid derivative is connected to the surface of the zinc oxide and/or the titanium dioxide, and the zinc oxide and/or the titanium dioxide are connected in series to form a network structure, the hydrophobic groups on the glutamic acid derivative enable the sunscreen particles to be uniformly dispersed in an organic phase, and the network structure further increases the stability of zinc oxide and/or titanium dioxide particles. The condensation reaction is mature and simple, complex processes and harsh reaction conditions are not needed, and the product can be separated by centrifugation, so that the safety of the product as a raw material of the sunscreen cosmetic is ensured. The stable sunscreen composition containing the sunscreen agent contains the sunscreen particle dispersion, can be well compatible with other raw materials of cosmetics, and has a good sunscreen effect.
Description
Technical Field
The invention belongs to the field of cosmetics, and particularly relates to a sunscreen composition with stable sunscreen particle dispersion and sunscreen agent and a preparation method thereof.
Background
Zinc oxide and titanium dioxide are a few of the cosmetic raw materials that provide UVA protection, but are themselves inorganic metal oxides that are difficult to stably exist and disperse in solution; particularly, when nano-sized particles are used as a cosmetic material, they tend to aggregate in a solution and cannot be stably dissolved and dispersed. Therefore, the nanometer zinc oxide or titanium dioxide as the cosmetic ingredients may cause the influence on the stability and the sun-screening performance of the cosmetics.
In the prior art, zinc oxide or titanium dioxide is subjected to hydrophobic modification, coating treatment is carried out, or a dispersing agent is added. When the dispersant is added, the dosage of the dispersant is often large, so that the properties and performance of the cosmetic are influenced; the coating needs to select a proper coating, otherwise, the zinc oxide or titanium dioxide can not be released to influence the protection effect. The hydrophobic modification is generally realized by a hydrophobic modifier, and commonly used treating agents comprise silicone oil, stearic acids, siloxane, amino acid derivatives and the like, and hydrophobic groups are introduced by changing groups on the surface of titanium dioxide or zinc oxide, so that the hydrophobicity is increased, and the dispersibility is changed. The hydrophobic modification is generally carried out by forming a siloxane bond or an ester group with zinc oxide or titanium dioxide through a reactive group on the treating agent, or by linking through a hydrogen bond or intermolecular force, but these links are easily broken by the influence of external conditions. The use of hydrophobically modified zinc oxide and titanium dioxide is therefore still limited.
Disclosure of Invention
In order to overcome the defects of the prior art, the first object of the present invention is to provide a sunscreen particle dispersion, wherein sunscreen particles are subjected to surface modification and then react with glutamic acid derivatives, and the sunscreen particles are connected in series through glutamic acid to form a network structure; hydrophobic groups on the glutamic acid derivative enable the sunscreen particles in the network structure to be uniformly dispersed in the organic phase.
The second purpose of the invention is to provide a preparation method of the sunscreen particle dispersion.
It is a third object of the present invention to provide a sunscreen stable sunscreen composition.
One of the purposes of the invention can be achieved by adopting the following technical scheme:
the sunscreen particles are zinc oxide and/or titanium dioxide, and the titanium dioxide is subjected to amination modification and then condensation reaction with carboxyl of a glutamic acid derivative to obtain the sunscreen particle dispersion.
Further, the method for modifying the zinc oxide and the titanium dioxide by amino comprises the following steps: zinc oxide and titanium dioxide react with amino silane in anhydrous dimethylbenzene solution at high temperature.
Further, the aminosilane has a structure represented by formula I:
wherein R is 1 Is methyl or ethyl, and m is an integer of 1 to 5.
Further, the ratio of the amount of zinc oxide and/or titanium dioxide to the amount of aminosilane is 1: (5-10); the reaction temperature is 120-140 ℃, and the reaction time is 1-5 h.
Further, the glutamic acid derivative has a structure shown in formula II:
wherein n is an integer of 5 to 15, R 1 Is H or O atom, when R 1 When it is H atom, it is a single bond; when R is 1 When it is an O atom, it is a double bond.
The second purpose of the invention can be achieved by adopting the following technical scheme:
a preparation method of the sunscreen particle dispersion comprises the following preparation steps:
s1, dispersing amination modified zinc oxide and/or titanium dioxide particles in a solvent, and heating to obtain a reaction solution A;
s2, dissolving a glutamic acid derivative, a carbodiimide coupling agent and HOAT into a solvent, and heating to obtain a reaction solution B;
and S3, dropwise adding the reaction liquid B of the S2 into the reaction liquid A prepared in the S1 for reaction, and obtaining the sunscreen particle dispersion after the reaction is finished.
Further, the molar ratio of the amination modified zinc oxide and/or titanium dioxide particles, the carbodiimide coupling agent, the HOAT and the glutamic acid derivative is 1: (2.5-5): (2.5-5): (1.2-2).
Further, the carbodiimide coupling agent is DIC; the solvent is DMF.
Further, heating in the steps S1 and S2 is carried out under the condition of 35-50 ℃ for ultrasonic treatment; the reaction condition in the step S3 is ultrasonic reaction at 35-50 ℃ for 30-90min.
Further, the method also comprises the step of preparing the amination modified zinc oxide and/or titanium dioxide particles.
Further, in step S3, a post-processing procedure is further included: and after the reaction is finished, performing centrifugal separation, respectively cleaning with water and ethanol, and blow-drying by using a nitrogen blowing instrument to obtain the sunscreen particle dispersion, wherein the centrifugal rotation speed is 10000-20000 revolutions per minute, and the centrifugal time is 15-30 minutes.
The third purpose of the invention can be achieved by adopting the following technical scheme:
a sunscreen-stable sunscreen composition comprising a dispersion of sunscreen particles as described in any of the above.
Further, the sunscreen composition is any one of cream, ointment, milk and liquid.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the sunscreen particle dispersion, amino groups are distributed on the surfaces of zinc oxide and/or titanium dioxide after amination modification is carried out on zinc oxide and/or titanium dioxide sunscreen particles, and condensation reaction is carried out on the amino groups and carboxyl groups of glutamic acid, so that glutamic acid derivatives are connected to the surfaces of zinc oxide and/or titanium dioxide, and the zinc oxide and/or titanium dioxide are further modified and modified to obtain the sunscreen particle dispersion. Hydrophobic groups on the glutamic acid derivative enable the sunscreen particles in the network structure to be uniformly dispersed in the organic phase.
2. In the sunscreen particle dispersion, an amino group of glutamic acid is connected with a fatty chain to form a hydrophobic group, and two carboxyl groups can be connected with zinc oxide and/or titanium dioxide particles subjected to different amination modifications through amide bonds in a condensation reaction to form a series network structure, so that the stability of the zinc oxide and/or titanium dioxide particles is further improved.
3. According to the preparation method of the sunscreen particle dispersion, disclosed by the invention, amination modified zinc oxide and/or titanium dioxide can be condensed with a glutamic acid derivative through a carbodiimide coupling method, the method is mature and simple, a complex synthesis process is not required, the product can be separated through centrifugation, reaction raw materials and byproducts are not introduced into the sunscreen particle dispersion, and the safety of the sunscreen cosmetic raw materials is ensured.
4. The stable sunscreen composition containing the sunscreen particle dispersion can be well compatible with other raw materials of cosmetics, and has a good sunscreen effect.
Drawings
FIG. 1 is a TEM image of the sunscreen particles of example 3;
FIG. 2 is a graph of water contact angle experiments for example 3 and comparative examples 1-2 sunscreen particles.
Detailed Description
The technical solution of the present invention will be clearly and completely described with reference to the specific embodiments. It is to be understood that the described embodiments are merely some, and not all, embodiments of the invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Titanium dioxide and zinc oxide particles, especially nanoparticles, have large specific surface area and high surface energy, and therefore, show extremely strong polarity and hydrophilic and oleophobic properties, and therefore, the titanium dioxide and zinc oxide particles are easy to agglomerate in an organic system to generate precipitates, thereby influencing the use of the titanium dioxide and zinc oxide particles. Titanium dioxide and zinc oxide are excellent UVA protective cosmetic raw materials, so that the compatibility and the dispersibility of the titanium dioxide and the zinc oxide in an organic system are improved, and the application effect is improved. It is an effective approach to modify the surface thereof to make it organic, and a common method is to form an ester group or a siloxane bond using hydroxyl groups on the surfaces of titanium dioxide and zinc oxide, but these two bonds are easily affected by the environment, and a silane compound is also introduced. The amino acid derivative itself can be used as a cosmetic raw material, and thus modification using the amino acid derivative seems to be an improvement.
The invention provides a sunscreen particle dispersion, wherein the sunscreen particles are zinc oxide and/or titanium dioxide, and the titanium dioxide is subjected to amination modification and then condensation reaction with carboxyl of a glutamic acid derivative to obtain the sunscreen particle dispersion.
After the zinc oxide and/or titanium dioxide sunscreen particles are subjected to amination modification, amino groups are distributed on the surfaces of the zinc oxide and/or titanium dioxide, and the amino groups and carboxyl groups of glutamic acid are subjected to condensation reaction, so that glutamic acid derivatives are connected to the surfaces of the zinc oxide and/or titanium dioxide, and the zinc oxide and/or titanium dioxide are further subjected to modification to obtain the sunscreen particle dispersion. The hydrophobic group on the glutamic acid derivative enables the sunscreen particles in the network structure to be uniformly dispersed in the organic phase.
As one embodiment thereof, the zinc oxide and/or titanium dioxide are nano-sized particles, preferably, the diameter of the titanium dioxide is 20 to 50nm; more preferably, the titanium dioxide has a diameter of 20 to 25nm. Preferably, the diameter of the zinc oxide is 20-100 nm; more preferably, the zinc oxide has a diameter of 20 to 50nm; more preferably, the zinc oxide has a diameter of 20 to 25nm. Firstly, nano-sized particles can be dispersed in cosmetics and are not easy to precipitate due to gravity, and secondly, the nano-sized particles have small particle size, higher specific surface area and high activity, can reflect and scatter ultraviolet rays and absorb the ultraviolet rays, thereby having stronger barrier capability to the ultraviolet rays. Preferably, the titanium dioxide is in anatase type, and the surface of the titanium dioxide is rich in hydroxyl.
As one embodiment, the method for modifying the zinc oxide and the titanium dioxide by the amino group comprises the following steps: the zinc oxide and the titanium dioxide react with the amino silane in the anhydrous dimethylbenzene solution at high temperature.
Since nitrogen has a greater nucleophilicity than alcohol, amino groups can be attached to the surfaces of zinc oxide and titanium dioxide by reacting aminosilane in a xylene solvent at high temperature to displace amino groups and hydroxyl groups. And the amino and carboxyl are condensed to form a more stable compound, so that the compound formed in the subsequent hydrophobic modification is more stable, and the difficulty of the reaction is reduced.
The solvent for the reaction is anhydrous xylene, which can be ortho-meta-para-different xylene, and is preferably selected to be anhydrous para-xylene. The reason why the solvent is anhydrous is that aminosilane is easy to hydrolyze when meeting water, and hydrolyzed hydroxyl and original hydroxyl on the surfaces of zinc oxide and titanium dioxide can be condensed to directly connect the aminosilane on the surfaces of the zinc oxide and the titanium dioxide. The anhydrous xylene can be a newly-purchased anhydrous reagent or can be xylene which is dehydrated by calcium hydride and then is redistilled.
As an embodiment thereof, the aminosilane has the structure shown in formula I:
wherein R is 1 Is methyl or ethyl, and m is an integer of 1 to 5.
In one embodiment, the aminosilane is one of (aminomethyl) triethoxysilane, (aminomethyl) trimethoxysilane, (3-aminopropyl) triethoxysilane, (5-aminopentyl) triethoxysilane, and (5-aminopentyl) trimethoxysilane. Preferably, the aminosilane is (3-aminopropyl) triethoxysilane.
As an embodiment thereof, the ratio of the amount of zinc oxide and/or titanium dioxide to the amount of aminosilane is 1: (5-10); the reaction temperature is 120-140 ℃, and the reaction time is 1-5 h. The amount of zinc oxide and/or titanium dioxide to aminosilane species affects the number of amino groups on the surface of the zinc oxide and/or titanium dioxide, and an aminosilane in an amount of 5 to 10 times the amount of zinc oxide and/or titanium dioxide species can substantially convert hydroxyl groups on the surface of the zinc oxide and/or titanium dioxide to amino groups.
As one embodiment thereof, the glutamic acid derivative has a structure represented by formula II:
wherein n is an integer of 5 to 15, R 1 Is H or O atom when R 1 In the case of an H atom, the compound is,
is a single bond; when R is 1 In the case of an O atom, the compound,
is a double bond.
The side chain connected with the amino group of the glutamic acid is a main group for realizing hydrophobicity, two carboxyl groups of the glutamic acid are main groups connected with amination modified zinc oxide and/or titanium dioxide, so the numerical value of n is limited to 5-15, the carbon atom number of the fatty chain of the side chain is 8-18, and the side chain has higher hydrophobicity, and the excessively high numerical value of n is a compound and even formed sunscreen particle dispersoid which is not favorable for being applied in subsequent cosmetics because of crosslinking or gel with excessively large molecular weight. Wherein R is 1 Which may be a H or O atom, the aliphatic chain is thus linked to glutamic acid via an imine or amide group. Preferably, the glutamic acid derivative may be lauroyl glutamic acid.
The invention also provides a preparation method of the sunscreen particle dispersion, which comprises the following preparation steps:
s1, dispersing amination modified zinc oxide and/or titanium dioxide particles in a solvent, and heating to obtain a reaction solution A;
s2, dissolving a glutamic acid derivative, a carbodiimide coupling agent and HOAT into a solvent, and heating to obtain a reaction liquid B;
and S3, dropwise adding the reaction liquid B of the S2 into the reaction liquid A prepared in the S1 for reaction, and obtaining the sunscreen particle dispersion after the reaction is finished.
The amino group of the amination modified zinc oxide and/or titanium dioxide and the carboxyl group of the glutamic acid derivative are subjected to condensation reaction, so that the reaction is carried out by a carbodiimide method, the reaction is simple, and the yield is high. Wherein step S2 is activating the carboxyl group of the glutamic acid derivative. And the glutamic acid derivative is dripped into the amination modified zinc oxide and/or titanium dioxide dispersion liquid, and the number of the amination modified zinc oxide and/or titanium dioxide can be controlled by controlling the amount of the glutamic acid derivative, so that a uniform serial form is formed, and a network structure is formed.
As an embodiment thereof, the molar ratio of the aminated modified zinc oxide and/or titanium dioxide particles, the carbodiimide-based coupling agent, HOAT and the glutamic acid derivative is 1: (2.5-5): (2.5-5): (1-2). Wherein HOAT is 1-hydroxy-7-azabenzotriazole, and can be used with carbodiimide coupling agent.
The molar ratio of zinc oxide and/or titanium dioxide particles to glutamic acid derivative is 1: (1-2) in consideration of the steric structure, the zinc oxide and/or titanium dioxide particles are condensed and extended with glutamic acid derivatives as far as possible at the distal end, and unreacted amino groups are located in the middle so that the zinc oxide and/or titanium dioxide particles maintain a steric distance.
As an embodiment thereof, the carbodiimide-based coupling agent is DIC; the solvent is DMF. DIC is N, N' -diisopropylcarbodiimide.
As one embodiment, the heating conditions in steps S1 and S2 are 35 to 50 ℃ for sonication; the reaction condition in the step S3 is ultrasonic reaction at 35-50 ℃ for 30-90min.
As one embodiment thereof, further comprising the step of preparing the aminated modified zinc oxide and/or titanium dioxide particles.
As one embodiment, step S3 further includes a post-processing step: and after the reaction is finished, performing centrifugal separation, respectively cleaning with water and ethanol, and blow-drying by using a nitrogen blowing instrument to obtain the sunscreen particle dispersion, wherein the centrifugal rotation speed is 10000-20000 revolutions per minute, and the centrifugal time is 15-30 minutes. The product can be separated by centrifugation, and no reaction raw material and by-product are introduced into the sunscreen particle dispersion, so that the safety of the sunscreen cosmetic raw material is ensured.
The invention also provides a sunscreen-stable sunscreen composition comprising a dispersion of sunscreen particles as described in any of the above. Preferably, the sunscreen particle dispersion is present in the composition in an amount of no more than 10%. According with the addition amount of zinc oxide and/or titanium dioxide as a sun-screening agent in cosmetics in China.
As one embodiment thereof, the sunscreen composition is any one of a cream, a milk, and a lotion. Since the sunscreen particle dispersion of the present invention has good hydrophobicity and is compatible and stably dispersible in an oil phase, it can be suitably used for any of creams, milks, and liquids.
Example 1:
adding 0.05mol of titanium dioxide with the particle size of about 20nm into 50ml of anhydrous p-xylene, continuing to perform ultrasonic mixing after uniform ultrasonic dispersion, adding 0.25mol of (3-aminopropyl) trimethoxysilane, continuing to perform ultrasonic mixing, then heating to 120 ℃, stirring for reaction for 5 hours, naturally cooling to room temperature, centrifuging reaction liquid at 12000 r/min, removing supernate, washing residues with ethanol and water respectively, performing centrifugal separation, and performing vacuum drying to obtain the aminated modified silicon dioxide.
Example 2:
adding 0.05mol of zinc oxide with the particle size of about 20nm into 50ml of anhydrous p-xylene, adding 0.5mol of (3-aminopropyl) triethoxysilane into the anhydrous p-xylene after uniform ultrasonic dispersion, continuing ultrasonic mixing, heating the mixture to 140 ℃, stirring the mixture for reaction for 1 hour, naturally cooling the mixture to room temperature, centrifuging the reaction solution at 12000 r/min, removing supernatant, washing residues with ethanol and water respectively, performing centrifugal separation, and performing vacuum drying to obtain the amination modified zinc oxide.
Example 3:
adding 0.05mol of amination modified titanium dioxide prepared in the embodiment 1 into 50ml of DMF, and carrying out ultrasonic treatment for 10min at the temperature of 40 ℃ in water bath to obtain reaction liquid A; adding 0.06Mol of lauroyl glutamic acid, 0.15Mol of DIC and 0.15Mol of HOAT into 100mL of DMF, and performing ultrasonic treatment for 10min at 40 ℃ in a water bath to obtain a reaction solution B; and dropwise adding the reaction liquid B into the reaction liquid A under the ultrasonic condition of 40 ℃ in a water bath, and continuing to react for 60min after completing dropwise addition. And after the reaction is finished, centrifuging at 15000 r/min for 20min, removing supernatant, respectively washing residues with water and ethanol, and drying by using a nitrogen blowing instrument to obtain the sunscreen particle dispersion.
Example 4:
adding 0.05mol of amination modified zinc oxide prepared in the embodiment 2 into 50ml of DMF, and carrying out ultrasonic treatment for 15min at 35 ℃ in a water bath to obtain a reaction solution A; adding 0.1Mol of N-octyl-glutamic acid, 0.25Mol of DIC and 0.25Mol of HOAT into 150mL of DMF, and performing ultrasonic treatment for 15min at 35 ℃ in a water bath to obtain a reaction solution B; and dropwise adding the reaction liquid B into the reaction liquid A under the ultrasonic condition of 35 ℃ in a water bath, and continuously reacting for 90min after dropwise adding is finished. And after the reaction is finished, centrifuging for 30min at 10000 r/min, removing supernatant, respectively washing residues with water and ethanol, and blow-drying by using a nitrogen blowing instrument to obtain the sunscreen particle dispersoid.
Example 5:
0.025mol of aminated zinc oxide prepared by the method of example 2 and 0.025mol of aminated silica prepared by the method of example 1 were added to 50ml of DMF, and the mixture was subjected to ultrasonic treatment in a water bath at 50 ℃ for 8min to obtain a reaction solution A; adding 0.1mol of palmitoyl glutamic acid, 0.2mol of DIC and 0.2mol of HOAT into 150mL of DMF, and performing ultrasonic treatment for 8min at 50 ℃ in a water bath to obtain a reaction solution B; and dropwise adding the reaction liquid B into the reaction liquid A under the ultrasonic condition of 50 ℃ in a water bath, and continuing to react for 30min after completing dropwise addition. And after the reaction is finished, centrifuging for 15min at 20000 rpm, removing supernatant, respectively washing residues with water and ethanol, and drying by using a nitrogen blowing instrument to obtain the sunscreen particle dispersion.
Comparative example 1:
adding 0.05mol of titanium dioxide with the particle size of about 25nm used in example 1 into 50ml of DMF, and performing ultrasonic treatment for 10min at 40 ℃ in a water bath to obtain a reaction solution A; adding 0.06Mol of lauroyl glutamic acid, 0.15Mol of DIC and 0.15Mol of HOAT into 100mL of DMF, and performing ultrasonic treatment for 10min at 40 ℃ in a water bath to obtain a reaction solution B; and dropwise adding the reaction liquid B into the reaction liquid A under the ultrasonic condition of 40 ℃ in a water bath, and continuing to react for 60min after completing dropwise addition. And after the reaction is finished, centrifuging at 15000 r/min for 20min, removing supernatant, respectively washing residues with water and ethanol, and drying by using a nitrogen blowing instrument to obtain the sunscreen particle dispersion.
Comparative example 2:
adding 0.05mol of amination modified titanium dioxide prepared in example 1 into 50ml of DMF, and carrying out ultrasonic treatment for 10min at 40 ℃ in a water bath to obtain a reaction solution A; adding 0.06Mol of N-N-butyrylglutamic acid, 0.15Mol of DIC and 0.15Mol of HOAT into 100mL of DMF, and performing ultrasonic treatment for 10min at 40 ℃ in a water bath to obtain a reaction solution B; and dropwise adding the reaction liquid B into the reaction liquid A under the ultrasonic condition of 40 ℃ in a water bath, and continuing to react for 60min after completing dropwise addition. And after the reaction is finished, centrifuging at 15000 r/min for 20min, removing supernatant, respectively washing residues with water and ethanol, and drying by using a nitrogen blowing instrument to obtain the sunscreen particle dispersion.
Test example:
1. and (3) adding the same amount of absolute ethyl alcohol into the sunscreen particle dispersion of example 3, performing ultrasonic treatment for 30min to uniformly disperse the sample, dripping 1-2 drops of the treated solution onto a copper net by using a rubber head dropper, airing, and performing TEM characterization, wherein a TEM image is shown in FIG. 1.
As can be seen from fig. 1, the sunscreen particle dispersion of example 3 formed a spherical structure with a diameter of about 450nm and a rough surface; the results show that after titanium dioxide with the diameter of 20nm is connected with lauroyl glutamic acid to form a net structure, the net structure is convoluted and interacted to finally form a similar spherical structure, wherein the lauroyl glutamic acid forms a similar polymer to enable the spherical structure to be more complete, and meanwhile, the lauroyl glutamic acid is increased in contact with a dispersing agent during dispersion to enable the dispersion stability to be higher.
2. The same mass of the sunscreen particles prepared in example 3 and comparative examples 1-2 was pressed under the same conditions to obtain a test sample with a smooth surface, and the test sample was subjected to a water contact angle test, the test results are shown in fig. 2, which are water contact angle test images of example 3, comparative example 1, and comparative example 2, respectively, from left to right.
As can be seen from fig. 2, the water contact angle of comparative example 1 is about 110 °, the water contact angle of comparative example 2 is about 100 °, and the water contact angle of example 3 is about 140 °; the lauroyl glutamic acid in the comparative example 1 has a certain coating effect on titanium dioxide, and can also improve the hydrophobicity of the surface of the titanium dioxide to a certain extent, but the modification effect is not obvious because of the common physical coating. In contrast, in comparative example 2, although N-N-butyrylglutamic acid was chemically bonded to the aminated titanium dioxide, the effect of hydrophobic modification was significantly different from that in example 3 because the hydrophobicity of the N-butyl group was weak. Example 3 lauroyl glutamic acid is bonded on the surface of the aminated modified titanium dioxide to form a network structure, wherein the hydrophobic effect of long fat chains dispersed at intervals enables the formed particle dispersion to have better hydrophobicity.
3. Dispersion stability of sunscreen particle Dispersion
The dispersion stability of the sunscreen particles of example 3 and comparative examples 1-2 was determined by the following specific methods and test results:
1) Each 2g of the sunscreen particles of example 3 and comparative examples 1 to 2 was dissolved in 20ml of edible olive oil, subjected to ultrasonic water bath at 40 ℃ for 1 hour, then naturally cooled to room temperature, placed in a refrigerator at 10 ℃ for 24 hours, taken out and placed at room temperature for 24 hours at 25 ℃, and then placed in an oven at 40 ℃ for 24 hours, and thus continuously circulated 50 times, and the presence or absence of delamination was observed.
2) And (3) centrifugal test, adding the sample treated in the step 1) into a centrifugal tube, centrifuging for 30min at 5000r/min, and observing whether layering exists.
The dispersion stability and the centrifugal test results of the sunscreen particles of example 1 and comparative examples 1 to 2 are shown in table 1:
table 1 dispersion stability test results of sunscreen particles
| Example 3 | Comparative example 1 | Comparative example 2 | |
| Stability results | Not delaminating | Slight non-lamination | Not layering |
| Centrifugal results | Not delaminating | Layering | Slight delamination |
As can be seen from the stability test and the centrifugal test results of table 1, in comparative example 1, lauroyl glutamic acid physically coats the surface of titanium dioxide, and the coating structure is attenuated by thermal changes due to dissolution and solidification of olive oil in the oil phase, thereby causing titanium dioxide particles to be more easily agglomerated, thereby having a slight layered structure, and titanium dioxide is centrifugally separated from olive oil during centrifugation. Comparative example 2 since n-butyl-glutamic acid is linked to titanium dioxide by an amide bond and can stably exist under temperature change, the dispersion stability of the example of comparative example 2 is high due to the compatibility of n-butyl-glutamic acid and olive oil, but the dispersion is affected by centrifugation and slight delamination occurs. The fatty chains in the lauroyl glutamic acid particles of example 3 have better compatibility with olive oil, so the network structure formed allows the particles of example 3 to be dispersed in olive oil, and the solubility between lauroyl glutamic acid and olive oil allows the particles of example 3 to be stably dispersed in olive oil even upon centrifugation.
4. Sunscreen index analysis of sunscreens
A sunscreen cream composition was composed of 5% weight fraction of the sunscreen particles of example 3 and comparative examples 1-2 with 3% stearic acid, 4% octyl salicylate, 4% petrolatum, 3% stearyl alcohol, 3% glyceryl stearate, 0.8% dimethicone, 2% xanthan gum, 2% preservative, 1% ph adjuster, 3% humectant 0.6% disodium edta and 68.6% water.
And (3) measuring parameters such as SPF (specific pathogen free) values, PA (Power factor) values, sun simulation irradiation intensity, critical wavelength and the like of the three groups of sunscreen creams by adopting a UV-2000S type sunscreen performance analyzer. The method comprises the following steps of accurately weighing 32mg of prepared emulsion according to the selected Collpa standard, uniformly distributing the emulsion on a clean PMMA plate, quickly and uniformly coating the whole PMMA plate with a pre-soaked latex finger cot, placing the PMMA plate in a dark room temperature environment, standing for 20min, testing the in-vitro sun protection index of the PMMA plate, then placing the PMMA plate in an Atlas illumination box for illumination for 30min, and determining the PA value of the PMMA plate. The SPF and PA values tested are shown in table 2:
TABLE 2 SPF-number, PA-number of sunscreens
| Example 3 | Comparative example 1 | Comparative example 2 | |
| SPF value | 24.56 | 17.72 | 16.23 |
| PA value | 8.35 | 6.12 | 5.45 |
As can be seen from Table 2, the SPF value of the sunscreen containing the sunscreen particles of example 3 can reach 24.56 and the PA value can also reach 8.35, which are much higher than the SPF value and PA value of the sunscreen containing the sunscreen particles of comparative examples 1-2. The reason is that the sun-screening particles of example 3 are dispersed more uniformly in the sunscreen cream, and no agglomeration occurs, and the formed spherical structure has a higher specific surface area, so that the titanium dioxide can exert the ultraviolet shielding capability of the nanoparticles to the maximum extent.
In summary, according to the sunscreen particle dispersion of the present invention, the zinc oxide and/or titanium dioxide sunscreen particles are subjected to amination modification, and then undergo condensation reaction with the carboxyl group of glutamic acid, so that glutamic acid derivatives are connected to the surfaces of zinc oxide and/or titanium dioxide, and a series network structure is formed, and the hydrophobic groups on the glutamic acid derivatives are utilized to uniformly and stably disperse the sunscreen particles in the network structure in the organic phase.
The scope of the invention should not be limited by the detailed description of the preferred embodiments, but should be construed as being encompassed by the appended claims.
Claims (10)
1. The sunscreen particle dispersion is characterized in that the sunscreen particles are zinc oxide and/or titanium dioxide, and the zinc oxide and/or titanium dioxide are subjected to amination modification and then condensation reaction with carboxyl of a glutamic acid derivative to obtain the sunscreen particle dispersion.
2. The dispersion of sunscreen particles according to claim 1, wherein said zinc oxide and/or titanium dioxide is modified with an amino group by: the zinc oxide and/or titanium dioxide are reacted with aminosilane in an anhydrous xylene solution at high temperature.
3. The dispersion of sunscreen particles according to claim 2, wherein said aminosilane has the structure of formula I:
wherein R is 1 Is methyl or ethyl, and m is an integer of 1 to 5.
4. The dispersion of sunscreen particles according to claim 2 wherein the ratio of the amount of zinc oxide and/or titanium dioxide to the amount of aminosilane is 1: (5-10); the reaction temperature is 120-140 ℃, and the reaction time is 1-5 h.
5. The dispersion of sunscreen particles according to claim 1 wherein said glutamic acid derivative has the structure of formula II:
wherein n is an integer of 5 to 15, R 1 Is H or O atom, when R 1 In the case of an H atom, the compound is,
is a single bond; when R is 1 In the case of an O atom, the compound,
is a double bond.
6. A process for the preparation of a dispersion of sunscreen particles according to any of claims 1 to 5 comprising the following preparation steps:
s1, dispersing amination modified zinc oxide and/or titanium dioxide particles in a solvent, and heating to obtain a reaction solution A;
s2, dissolving a glutamic acid derivative, a carbodiimide coupling agent and HOAT into a solvent, and heating to obtain a reaction solution B;
and S3, dropwise adding the reaction liquid B of the S2 into the reaction liquid A prepared in the S1 for reaction, and obtaining the sunscreen particle dispersion after the reaction is finished.
7. The method of claim 6, wherein the dispersion of sunscreen particles,
the mol ratio of the amination modified zinc oxide and/or titanium dioxide particles, the carbodiimide coupling agent, the HOAT and the glutamic acid derivative is 1: (2.5-5): (2.5-5): (1.2-2); the carbodiimide coupling agent is DIC; the solvent is DMF; heating in the steps S1 and S2 under the condition of 35-50 ℃ for ultrasonic treatment; the reaction condition in the step S3 is ultrasonic reaction at 35-50 ℃ for 30-90min.
8. The method of claim 6, wherein the dispersion of sunscreen particles,
also comprises the step of preparing amination modified zinc oxide and/or titanium dioxide particles; in step S3, the method further includes a post-processing procedure: and after the reaction is finished, performing centrifugal separation, respectively cleaning with water and ethanol, and blow-drying by using a nitrogen blowing instrument to obtain the sunscreen particle dispersion, wherein the centrifugal rotation speed is 10000-20000 r/min, and the centrifugal time is 15-30min.
9. A sunscreen-stabilized sunscreen composition comprising a dispersion of sunscreen particles as claimed in any one of claims 1 to 5.
10. The sunscreen composition as in claim 9 wherein the sunscreen composition is any one of a cream, a milk or a lotion.
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