WO2023109209A1 - Antibacterial microcapsule of bionic structure, preparation method therefor, and use thereof - Google Patents
Antibacterial microcapsule of bionic structure, preparation method therefor, and use thereof Download PDFInfo
- Publication number
- WO2023109209A1 WO2023109209A1 PCT/CN2022/117969 CN2022117969W WO2023109209A1 WO 2023109209 A1 WO2023109209 A1 WO 2023109209A1 CN 2022117969 W CN2022117969 W CN 2022117969W WO 2023109209 A1 WO2023109209 A1 WO 2023109209A1
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- WO
- WIPO (PCT)
- Prior art keywords
- antibacterial
- microcapsule
- microcapsules
- core material
- emulsion
- Prior art date
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- 239000003094 microcapsule Substances 0.000 title claims abstract description 142
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 130
- 239000011664 nicotinic acid Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000011162 core material Substances 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000000839 emulsion Substances 0.000 claims abstract description 29
- 239000000178 monomer Substances 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 22
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 239000002775 capsule Substances 0.000 claims abstract description 15
- 239000002131 composite material Substances 0.000 claims abstract description 14
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 11
- 239000003999 initiator Substances 0.000 claims abstract description 9
- 230000003592 biomimetic effect Effects 0.000 claims description 31
- -1 polyoxypropylene Polymers 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 10
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 10
- 239000000341 volatile oil Substances 0.000 claims description 10
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 9
- 239000000194 fatty acid Substances 0.000 claims description 9
- 229930195729 fatty acid Natural products 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 8
- 229920001214 Polysorbate 60 Polymers 0.000 claims description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 239000003945 anionic surfactant Substances 0.000 claims description 6
- 150000002191 fatty alcohols Chemical class 0.000 claims description 6
- 239000002736 nonionic surfactant Substances 0.000 claims description 6
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 235000013305 food Nutrition 0.000 claims description 5
- 239000012782 phase change material Substances 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 239000004753 textile Substances 0.000 claims description 5
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 claims description 5
- 239000011782 vitamin Substances 0.000 claims description 5
- 229930003231 vitamin Natural products 0.000 claims description 5
- 229940088594 vitamin Drugs 0.000 claims description 5
- 235000013343 vitamin Nutrition 0.000 claims description 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 4
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 claims description 4
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- 239000003814 drug Substances 0.000 claims description 4
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- 235000011069 sorbitan monooleate Nutrition 0.000 claims description 4
- 239000001593 sorbitan monooleate Substances 0.000 claims description 4
- 229940035049 sorbitan monooleate Drugs 0.000 claims description 4
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 229920001400 block copolymer Polymers 0.000 claims description 3
- 239000002537 cosmetic Substances 0.000 claims description 3
- 125000005442 diisocyanate group Chemical group 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 239000000686 essence Substances 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 3
- 238000003860 storage Methods 0.000 claims description 3
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 2
- 239000000796 flavoring agent Substances 0.000 claims description 2
- 235000019634 flavors Nutrition 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims 1
- 150000004665 fatty acids Chemical class 0.000 claims 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims 1
- 230000006870 function Effects 0.000 abstract description 8
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- 241000894006 Bacteria Species 0.000 description 10
- 241000588724 Escherichia coli Species 0.000 description 10
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- 229910052710 silicon Inorganic materials 0.000 description 10
- 239000010703 silicon Substances 0.000 description 10
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- 239000000126 substance Substances 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 6
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 5
- 241000191940 Staphylococcus Species 0.000 description 5
- 241000191967 Staphylococcus aureus Species 0.000 description 5
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 5
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- 238000003921 particle size analysis Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000010998 test method Methods 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 4
- HOWGUJZVBDQJKV-UHFFFAOYSA-N docosane Chemical compound CCCCCCCCCCCCCCCCCCCCCC HOWGUJZVBDQJKV-UHFFFAOYSA-N 0.000 description 4
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
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- 238000005516 engineering process Methods 0.000 description 3
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- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 3
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- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 2
- 229920001661 Chitosan Polymers 0.000 description 2
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- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 229950011392 sorbitan stearate Drugs 0.000 description 2
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- JLHMJWHSBYZWJJ-UHFFFAOYSA-N 1,2-thiazole 1-oxide Chemical class O=S1C=CC=N1 JLHMJWHSBYZWJJ-UHFFFAOYSA-N 0.000 description 1
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- 235000011330 Armoracia rusticana Nutrition 0.000 description 1
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- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 244000056139 Brassica cretica Species 0.000 description 1
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- 235000003343 Brassica rupestris Nutrition 0.000 description 1
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- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
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- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 1
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- QKSKPIVNLNLAAV-UHFFFAOYSA-N bis(2-chloroethyl) sulfide Chemical compound ClCCSCCCl QKSKPIVNLNLAAV-UHFFFAOYSA-N 0.000 description 1
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- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
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- 229960001927 cetylpyridinium chloride Drugs 0.000 description 1
- YMKDRGPMQRFJGP-UHFFFAOYSA-M cetylpyridinium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 YMKDRGPMQRFJGP-UHFFFAOYSA-M 0.000 description 1
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- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- CBOQJANXLMLOSS-UHFFFAOYSA-N ethyl vanillin Chemical class CCOC1=CC(C=O)=CC=C1O CBOQJANXLMLOSS-UHFFFAOYSA-N 0.000 description 1
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- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
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- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
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- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
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- 235000019362 perlite Nutrition 0.000 description 1
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- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
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- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 1
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 1
- 235000012141 vanillin Nutrition 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
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Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
Definitions
- the invention relates to the field of antibacterial products, in particular to an antibacterial microcapsule with a bionic structure and its preparation method and application.
- Antibacterial agents are generally divided into three types: inorganic antibacterial agents, organic antibacterial agents and natural antibacterial agents.
- metals such as silver, copper, and zinc
- metals such as silver, copper, and zinc (or their Ions) are fixed on the surface of porous materials such as fluorspar and silica gel to make antibacterial agents, and then added to corresponding products to obtain materials with antibacterial capabilities.
- Metals such as mercury, cadmium, and lead also have antibacterial capabilities, but they are harmful to the human body. Harmful; at the same time, copper, nickel, lead and other ions are colored, which will affect the appearance of the product.
- Zinc has certain antibacterial properties, but its antibacterial strength is only 1/1000 of silver ions;
- the prior art Chinese patent CN201910842257 proposes an antibacterial phase-change microcapsule and its formulation technology.
- This prior art uses the in-situ reduction of silver on the surface of the microcapsule to obtain a phase-change microcapsule with antibacterial function;
- another example of the prior art Chinese patent CN108686262A provides a pretreated expanded perlite as a carrier, vacuum absorbs a liquid phase change material, and then adsorbs a silver-containing chitosan layer on the surface, and then forms a sodium alginate porous gel layer to obtain a double-wall slow release
- the method of antibacterial phase-change microcapsules but the method process is more complicated; the above-mentioned method mostly uses the antibacterial ability of silver itself to carry out antibacterial.
- organic antibacterial agents vanillin or ethyl vanillin compounds, which are often used in polyethylene food packaging films to play an antibacterial role.
- organic antibacterial agents such as quaternary ammonium salts, biquats, and phenols is still under study.
- Most organic antibacterial agents have poor heat resistance, are easily hydrolyzed, and have a short validity period.
- Such as the prior art Chinese patent CN200880018078.9 proposes a polymer microcapsule containing quaternary ammonium salt and its manufacturing method, the core of the method is to use cetylpyridinium chloride as the representative antibacterial agent as the core material , and then encapsulated with polymers to form microcapsules.
- Natural antibacterial agents mainly come from the extraction of natural plants, such as chitin, mustard, castor oil, horseradish, etc., which are easy to use, but have limited antibacterial effect, poor heat resistance, low bactericidal rate, cannot be used for broad-spectrum and long-term use, and the quantity is very large few.
- the prior art Chinese patent CN201510287717.3 proposes a preparation method of essential oil microcapsules with chitosan as the wall material.
- the essential oil with antibacterial function is selected as the core material to realize the antibacterial function.
- the antibacterial rate reaches 85%.
- the present invention proposes a kind of antibacterial microcapsule of bionic structure and its preparation method and application.
- the present invention proposes a bionic structure antibacterial microcapsule and its preparation method and application.
- An antibacterial microcapsule with a bionic structure comprises a core material and a capsule wall material wrapped on the surface of the core material, the capsule wall material has a through-hole structure, and the surface of the capsule wall material is negatively charged.
- antibacterial microcapsules are spherical or spheroidal, with a D50 diameter of 0.8-10 microns.
- the inner shell surface of the core material wrapped by the capsule wall material is lipophilic
- the outer shell surface of the capsule wall material is hydrophilic
- the core material includes phase change materials, fat-soluble essences, plant essential oils, and fat-soluble vitamins. at least one.
- a preparation method of bionic structure antibacterial microcapsules comprising the steps of:
- the second mixture with the first shell is formed after 4h-8h, and then the temperature of the second mixture is raised to 60-80°C and the initiator is added to keep the temperature constant After 5h-12h, the second layer of shell is formed by polymerization to obtain antibacterial microcapsules.
- the core material includes at least one of phase change materials, fat-soluble flavors, plant essential oils, and fat-soluble vitamins;
- the silane coupling agent includes aminopropyltrimethoxysilane, aminopropyltriethoxysilane, phenyltriethoxysilane, 3-(methacryloxy)propyltrimethoxysilane, orthosilane At least two of tetraethyl orthosilicate and tetramethyl orthosilicate;
- the monomers include at least one of styrene, divinylbenzene, acrylate monomers, acrylic monomers, and diisocyanate prepolymers;
- Described composite emulsifier is the composition of anionic surfactant and nonionic surfactant.
- the complex emulsifier includes polyethylene-maleic anhydride copolymer or its hydrolyzed salt, polystyrene-maleic anhydride copolymer or its hydrolyzed salt, block copolymer of epoxy resin and polyethylene glycol, Sodium lauryl sulfate, sodium dodecylbenzene sulfonate, sorbitan monooleate polyoxyethylene ether, fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, fatty alcohol polyoxypropylene At least one of ether, glycerol monofatty acid ester, polyoxyethylene sorbitan fatty acid ester, sorbitan fatty acid ester and/or fatty acid pentaerythritol ester.
- each component includes: 25-60 parts of core material, 0.6-8 parts of silane coupling agent, 1.2-10 parts of monomer and 0.19-3 parts of composite emulsifier.
- An antibacterial product which contains the above antibacterial microcapsule with bionic structure or the antibacterial microcapsule prepared by the above preparation method.
- antibacterial microcapsules with bionic structure in transportation or storage of food, medicine, textiles or cosmetics, are the above antibacterial microcapsules with bionic structure or the antibacterial microcapsules prepared by the above preparation method.
- the antibacterial microcapsules with a bionic structure possess efficient antibacterial properties;
- the preparation process of the microcapsules of the present invention is simple, relatively universal, and the core material can be replaced conveniently. It is an excellent carrier of functional substances such as drugs, and can realize microstructure transfer, transportation or controlled release of functional substances;
- the antimicrobial microcapsules prepared by the method of the present invention can provide composite functional microcapsules with at least two functions, that is, the core material of the microcapsules provides a kind of functionality, and the core material can release the self-performance of the core material through the through holes on the surface of the microcapsules. , At the same time, the microcapsules have high antibacterial properties.
- the present invention obtains an antibacterial microcapsule with a bionic structure, and the microcapsule has a pore structure that runs through the shell.
- Staphylococcus, Candida albicans, Escherichia coli, etc. have a diameter of several microns in size, and the surface of the bacteria is negatively charged.
- the present invention itself is a beneficial and important attempt in the design and synthesis of micro-nano structural units.
- Fig. 1 is the scanning electron microscope (SEM) photo of a kind of bionic structure antibacterial microcapsule described in the embodiment of the present invention 1;
- Fig. 2 is the transmission electron microscope (TEM) photo of a kind of bionic structure antibacterial microcapsule described in embodiment 1;
- Fig. 3 is the laser particle size test curve of a kind of biomimetic structure antibacterial microcapsule of embodiment 1 gained;
- Fig. 4 is the scanning electron microscope (SEM) photograph of a kind of biomimetic structure antibacterial microcapsule of embodiment 2 gained;
- Fig. 5 is the transmission electron microscope (TEM) photograph of a kind of biomimetic structure antibacterial microcapsule of embodiment 2 gained;
- Fig. 6 is the laser particle size test curve of a kind of biomimetic structure antibacterial microcapsule of embodiment 2 gained;
- Fig. 7 is the DSC test curve of a kind of biomimetic structure antibacterial microcapsule of embodiment 2 gained;
- Fig. 8 is the scanning electron microscope (SEM) photograph of a kind of biomimetic structure antibacterial microcapsule of embodiment 3 gained;
- SEM scanning electron microscope
- the present invention adopts following technical scheme:
- a preparation method of bionic structure antibacterial microcapsules characterized in that the preparation method comprises the following steps:
- the core material includes at least one of phase change material, n-docosane, industrial paraffin, n-octadecane, pink rose essential oil, fat-soluble essence, plant essential oil, and fat-soluble vitamin;
- the core material is the core component, endowing the material with functionality, such as heat storage, temperature response, release of fragrance or functional substances, etc.;
- the core material and the continuous phase are often incompatible. At the interface between the two, a place for the formation of the microcapsule wall material is provided.
- the core material in this plan is mainly based on various staphylococcus and candida albicans during implementation. , Escherichia coli cell fluid investigation, selected materials with similar physical and chemical properties as the main component of the core material.
- silane coupling agent comprises aminopropyltrimethoxysilane coupling agent, KH550 silane coupling agent (3-aminopropyltriethoxysilane), phenyltriethoxysilane coupling agent, 3-( At least two of methacryloyloxy)propyltrimethoxysilane coupling agent, tetraethyl orthosilicate, and tetramethyl orthosilicate; the silane coupling agent is used as an inorganic silicon source, and the formed Silica is a part of the wall material.
- the silane coupling agent can effectively modify the interface through the simple and convenient sol-gel process, and the selection range of the silane coupling agent is also relatively large;
- the method introduces at least two chemical groups with different properties into the wall material by selecting at least two kinds of silane coupling agents, which can regulate the properties of the microcapsule shell to a certain extent;
- the monomers include at least one of styrene, divinylbenzene, acrylate monomers, acrylic monomers, and diisocyanate prepolymers. After the monomer initiates polymerization, it forms a composite shell with the aforementioned inorganic substances.
- the organic-inorganic composite shell formed under the method of the present invention can exhibit different properties on both sides of the shell, such as facing the core.
- the inner shell side of the material is more oleophilic, while the outer shell side facing the water phase is more hydrophilic. These two sides are actually two sides of the same shell;
- Described compound emulsifier is selected from the block copolymer of polyethylene-maleic anhydride copolymer or its hydrolyzed salt, polystyrene-maleic anhydride copolymer or its hydrolyzed salt, epoxy resin and Polyethylene Glycol, dodecane Sodium Alkyl Sulfate, Sodium Dodecyl Benzene Sulfonate, Fatty Alcohol Polyoxyethylene Ether, Tween 80 (Sorbitan Monooleate Polyoxyethylene Ether), Tween 60 (Polyoxyethylene Sorbitan Stearate ester), triton (polyethylene glycol p-isooctyl phenyl ether), alkylphenol polyoxyethylene ether, fatty alcohol polyoxypropylene ether, glycerin monofatty acid ester, polyoxyethylene sorbitan A composition of at least one anionic surfactant and at least one nonionic surfactant in fatty acid esters, sorbitan fatty acid esters,
- Surfactants provide the key guarantee for stabilizing the oil-water interface while creating sites for shell formation.
- the specific phase behavior of surfactants at the oil-water interface can be adjusted by two or more different types of surfactants to achieve different effects;
- the sum of the consumption of the core material, silane coupling agent and polymer monomer is 10.0%-59.0%wt of the final microcapsule suspension; the nonionic surfactant consumption is no more than 0.8% of the final microcapsule suspension. %wt;
- the sum of the amount of the core material, silane coupling agent, and polymer monomer is 15.0%-49.0%wt of the final microcapsule suspension, and the amount of the nonionic surfactant is the final microcapsule suspension 0.1%-0.67%wt;
- the sum of the amount of the core material, silane coupling agent, and polymer monomer is 25.0%-39.0%wt of the final microcapsule suspension, and the amount of the nonionic surfactant is the final microcapsule suspension 0.2%-0.45%wt of liquid.
- step d represents the sol-gel process
- step e represents the polymerization process of organic monomers.
- the two processes can be passed. Conditions such as temperature, pH, initiator ultraviolet light, etc. control the successive start respectively, or start at the same time;
- sol-gel process is started first, and then the organic monomer polymerization is started, which is more conducive to the formation of the biomimetic structure described in the present invention.
- the hydrophilic outer shell structure is more conducive to the formation of the through-hole structure.
- microcapsules are spherical or spheroidal, with a D50 diameter of 0.8 microns to 10 microns; the surface of the microcapsules is negatively charged; the microcapsules have a pore structure that runs through the shell;
- Staphylococcus, Candida albicans, Escherichia coli, etc. have a diameter of several microns in size, and the surface of the bacteria is negatively charged. At the same time, there are some small pore structures on the surface of the bacteria. These pore structures run through the shell, and the bacteria pass through these negatively charged membrane structures, or pores. structure for nutrition.
- the biomimetic structure microcapsule of the present invention performs very well in antibacterial aspect, and its reason includes as follows, when the microcapsule of the present invention and bacterium are in the same condition together, this type of biomimetic structure microcapsule can produce competition with some bacteria Food effect, the possibility of bacteria obtaining nutrition is greatly reduced, which hinders bacteria from obtaining nutrition and multiplying, thus achieving antibacterial effect;
- the biomimetic structure microcapsules performed poorly, because the structure biomimetic microcapsules did not contain any of the above three antibacterial agents, and could not actively kill bacteria, but in the antibacterial test Among them, it can reduce the chance of bacterial survival by competing for food.
- the above-mentioned three antibacterial agents namely inorganic antibacterial agents, organic antibacterial agents or natural antibacterial agents
- various fillers will be used during processing, such as catalysts, accelerators, covering agents, whitening agents, pigments, thinners, thickeners, curing agents, etc., and some functions will also be used sexual fillers, etc., these should be regarded as extensions or deformations that do not deviate from the technical solutions of the present invention, and fall within the scope of protection determined by the claims of the present invention.
- a biomimetic structure antibacterial microcapsule of the present invention is used in textile processing technology including at least one of finishing, coating, padding, printing or spinning, and the biomimetic structure antibacterial microcapsule can be mixed with additives In the form of finishing paste, or printing paste, padding bath, through further related processing, it is attached to the fabric or similar layered structure, thereby endowing the product with antibacterial properties, similar,
- An antibacterial product claimed in the present invention includes textiles with antibacterial function prepared in the above process;
- the antibacterial microcapsule with a bionic structure and its method described in the present invention can also be used in the fields of medical care, transportation or storage of food and medicine, cosmetics, and the like.
- biomimetic structure antibacterial silicon dioxide-polystyrene microcapsule in this example, its preparation method comprises the following steps:
- oil-in-water emulsion oil-in-water emulsion
- the temperature of the emulsion is raised to 60-80°C, the initiator AIBN (azobisisobutyronitrile) is added, and the temperature is kept for 5h-12h to make it polymerize to form the second shell.
- AIBN azobisisobutyronitrile
- Figure 2 is a TEM photo of the obtained microcapsules.
- the TEM photos show that the pores on the surface of the microcapsules penetrate the shell and form larger cavities inside the capsules.
- the hole can be used to load functional substances such as essential oils.
- the Zeta potential test showed that the Zeta potential of the microcapsules was -30.4mV, indicating that the surface of the microcapsules was negatively charged. This is because a kind of surfactant styrene-maleic anhydride hydrolyzed sodium salt used in this example is an anionic surfactant.
- Figure 3 is the laser particle size analysis curve of the obtained microcapsules, it can be seen that the D50 diameter is 0.85 microns.
- the microcapsules obtained in this example are used for the after-finishing of fabrics, and the treated fabrics are tested for antibacterial performance.
- the test method refers to FZ/T 73023-2006 antibacterial knitwear, and the results in Table 1 are obtained: the antibacterial rate of Candida albicans is 86% , The antibacterial rate of Escherichia coli is 86%, and the antibacterial rate of Staphylococcus aureus is 88%.
- n-octadecane and 8g tetraethyl silicate 0.6g aminopropyltrimethoxysilane coupling agent, 1.2g phenyltriethoxysilane coupling agent, 5g dimethacrylic acid 1,4 -butanediol ester, stirring for 20min, the process of uniformly forming an oil phase;
- the temperature of the emulsion is raised to 50-80°C, the initiator APS (ammonium persulfate) is added, and the temperature is kept for 5h-12h, so that the organic monomers are polymerized to form the second shell.
- APS ammonium persulfate
- a kind of shell layer is a biomimetic structure antibacterial microcapsule of silicon dioxide-polyacrylate
- Figure 5 is a TEM photo of the obtained microcapsules. TEM photos show that the pores on the surface of the microcapsules penetrate the shell;
- the Zeta potential test showed that the Zeta potential of the microcapsules was -16.9mV, indicating that the surface of the microcapsules was negatively charged. This is because a kind of surfactant ethylene-maleic anhydride copolymer hydrolysis salt used in this example is a kind of anionic surfactant;
- Figure 6 is the laser particle size analysis curve of the obtained microcapsules, it can be seen that the D50 diameter is 3.023 microns.
- this example has obtained a biomimetic structure microcapsule with a negatively charged surface, a D50 of 3.023 microns, and several micropores on the surface. And did not introduce any aforementioned 3 kinds of antibacterial agents in this example;
- the microcapsules obtained in this example are used for the finishing of fabrics, and the treated fabrics are tested for antibacterial properties.
- the test method refers to GB/T20944.2 Appendix B, and the results in Table 2 are obtained as follows: 99.9% antibacterial rate against Candida albicans, washed with water The antibacterial rate after 50 times is 84.9%; the antibacterial rate against Escherichia coli is 99.9%, and the antibacterial rate after washing 50 times is 92.9%; the antibacterial rate against Staphylococcus aureus is 99.9%, and the antibacterial rate after washing 50 times is 96.4%;
- each component in this example is analyzed, and each component is listed in the following table 3, and each comparative sample S2-0 etc. has expressed that only corresponding oil phase or water phase components are used, corresponding to other parts in this example 2 with etc. Measure water instead, and the operation steps are the same as in Example 2. After finishing the operation, carry out the antibacterial test respectively. The results showed that none of the formulations had antibacterial properties.
- This example provides a kind of antibacterial silicon dioxide-polystyrene-polyacrylate composite microcapsule of bionic structure, and its preparation method comprises the following steps:
- the temperature of the emulsion is raised to 60-80°C, benzoyl peroxide is added, and the temperature is kept for 5h-12h to allow it to polymerize to form a second shell.
- the described shell layer is silicon dioxide-polystyrene-polyacrylate composite microcapsules
- Accompanying drawing 8 and accompanying drawing 9 are the SEM photos of the obtained microcapsules of this example.
- Accompanying drawing 9 is the partial enlargement of capsule shell, and it can be seen that there are some tiny holes therein;
- the Zeta potential test showed that the Zeta potential of the microcapsules was -22.8mV, indicating that the surface of the microcapsules was negatively charged. This is due to the use of 2 anionic surfactants in this example;
- the differential scanning calorimetry method obtained the phase change melting point of the phase change microcapsules in this example as 43.95°C, and the corresponding phase change enthalpy value was 140.1J/g;
- the microcapsules obtained in this example are used for the finishing of fabrics, and the treated fabrics are tested for antibacterial performance.
- the test method refers to FZ/T 73023-2006 antibacterial knitwear.
- the test shows that the antibacterial rate of Candida albicans is 88%, and that of Escherichia coli The antibacterial rate is 85%, and the antibacterial rate for Staphylococcus aureus is 89%.
- microcapsules in this example have good antibacterial effect.
- This example provides a kind of biomimetic structure antibacterial silicon dioxide-polyurea composite microcapsule, and its preparation method comprises the following steps:
- the temperature of the emulsion is raised to 50-80°C, and 1,6-hexanediamine is added dropwise, and kept for 2h-8h to make it polymerize to form a second shell.
- the described shell layer is a silica-polyurea composite microcapsule
- the Zeta potential test shows that the Zeta potential of the microcapsules is -31.5mV, indicating that the surface of the microcapsules is negatively charged;
- the microcapsules obtained in this example are used for the finishing of fabrics, and the treated fabrics are tested for antibacterial properties.
- the test method refers to FZ/T 73023-2006 antibacterial knitwear.
- the test shows that the bacteriostatic rate of Candida albicans is 87%, and that of Escherichia coli The antibacterial rate is 85%, and the antibacterial rate for Staphylococcus aureus is 91%.
- microcapsules in this example have good antibacterial effect.
- the temperature of the emulsion is raised to 50-80°C, the initiator APS is added, and the temperature is kept for 5h-12h, so that the organic monomers are polymerized to form the second shell.
- a kind of shell layer is a biomimetic structure antibacterial microcapsule of silicon dioxide-polyacrylate
- the Zeta potential test shows that the Zeta potential of the microcapsules is -11.4mV, indicating that the surface of the microcapsules is negatively charged;
- the microcapsules obtained in this example are used for fabric finishing, and the treated fabric is tested for antibacterial performance.
- the test method refers to FZ/T 73023-2006 antibacterial knitwear.
- the test shows that the antibacterial rate of Candida albicans is 85%, and that of Escherichia coli The antibacterial rate is 86%, and the antibacterial rate for Staphylococcus aureus is 94%.
- microcapsules in this example have good antibacterial effect.
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Abstract
The present invention relates to the technical field of antibacterial products, and in particular to an antibacterial microcapsule of a bionic structure, a preparation method therefor and a use thereof. The solution comprises a core material and a capsule wall material wrapping the surface of the core material. The capsule wall material is provided with a through hole structure. The surface of the capsule wall material is negatively charged. The antibacterial microcapsule is spherical or sphere-like and has a diameter of 0.8 to 10 micrometers. The preparation method comprises: mixing the core material, a silane coupling agent and a monomer to form a first mixture; mixing a composite emulsifier of an aqueous phase with the first mixture to form an O/W emulsion; adjusting the pH value of the O/W emulsion to 2 to 4; and adding an initiator into the O/W emulsion, and forming the antibacterial microcapsule by means of heating and polymerization. The antibacterial microcapsule prepared from the method can provide a composite functional microcapsule having at least two functions, that is, the microcapsule core material provides a function, while the own property of the core material can be released via the through holes on the surface of the microcapsule. Meanwhile, the microcapsule has efficient antibacterial performance.
Description
本发明涉及抗菌产品领域,尤其是一种仿生结构抗菌微胶囊及其制备方法及应用。The invention relates to the field of antibacterial products, in particular to an antibacterial microcapsule with a bionic structure and its preparation method and application.
抗菌剂一般分为无机抗菌剂,有机抗菌剂和天然抗菌剂三种,利用银、铜、锌等金属的抗菌能力,通过物理吸附离子交换等方法,将银、铜、锌等金属(或其离子)固定在氟石、硅胶等多孔材料的表面制成抗菌剂,然后将其加入到相应的制品中即获得具有抗菌能力的材料,水银、镉、铅等金属也具有抗菌能力,但对人体有害;同时铜、镍、铅等离子带有颜色,将影响产品的美观,锌有一定的抗菌性,但其抗菌强度仅为银离子的1/1000;Antibacterial agents are generally divided into three types: inorganic antibacterial agents, organic antibacterial agents and natural antibacterial agents. Using the antibacterial ability of metals such as silver, copper, and zinc, metals such as silver, copper, and zinc (or their Ions) are fixed on the surface of porous materials such as fluorspar and silica gel to make antibacterial agents, and then added to corresponding products to obtain materials with antibacterial capabilities. Metals such as mercury, cadmium, and lead also have antibacterial capabilities, but they are harmful to the human body. Harmful; at the same time, copper, nickel, lead and other ions are colored, which will affect the appearance of the product. Zinc has certain antibacterial properties, but its antibacterial strength is only 1/1000 of silver ions;
如现有技术中国专利CN201910842257提出了一种抗菌相变微胶囊及其配方技术,该现有技术利用微胶囊表面原位还原银,得到了具有抗菌功能的相变微胶囊;再如现有技术中国专利CN108686262A提供了一种以预处理的膨胀珍珠岩为载体,真空吸附液态相变材料后在表面吸附含银的壳聚糖层,再形成海藻酸钠多孔凝胶层,得到双壁缓释抗菌相变微胶囊的方法,但该方法工艺较复杂;上述方法多以利用银自身的抗菌能力来进行抗菌。For example, the prior art Chinese patent CN201910842257 proposes an antibacterial phase-change microcapsule and its formulation technology. This prior art uses the in-situ reduction of silver on the surface of the microcapsule to obtain a phase-change microcapsule with antibacterial function; another example of the prior art Chinese patent CN108686262A provides a pretreated expanded perlite as a carrier, vacuum absorbs a liquid phase change material, and then adsorbs a silver-containing chitosan layer on the surface, and then forms a sodium alginate porous gel layer to obtain a double-wall slow release The method of antibacterial phase-change microcapsules, but the method process is more complicated; the above-mentioned method mostly uses the antibacterial ability of silver itself to carry out antibacterial.
有机抗菌剂的主要品种有香草醛或乙基香草醛类化合物,常用于聚乙烯类食品包装膜中,起抗菌作用,另外还有酰基苯胺类、咪唑类、 噻唑类、异噻唑酮衍生物、季铵盐类、双呱类、酚类等,有机抗菌剂的安全性尚在研究中,大多数的有机抗菌剂耐热性差些,容易水解,有效期短。如现有技术中国专利CN200880018078.9提出了一种含有季铵盐的聚合物微胶囊及其制造方法,方法的核心是将以氯化十六烷基吡啶鎓为代表的抗菌剂作为芯材物质,再将其用聚合物包封起来,形成微胶囊。The main varieties of organic antibacterial agents are vanillin or ethyl vanillin compounds, which are often used in polyethylene food packaging films to play an antibacterial role. In addition, there are anilides, imidazoles, thiazoles, isothiazolone derivatives, The safety of organic antibacterial agents such as quaternary ammonium salts, biquats, and phenols is still under study. Most organic antibacterial agents have poor heat resistance, are easily hydrolyzed, and have a short validity period. Such as the prior art Chinese patent CN200880018078.9 proposes a polymer microcapsule containing quaternary ammonium salt and its manufacturing method, the core of the method is to use cetylpyridinium chloride as the representative antibacterial agent as the core material , and then encapsulated with polymers to form microcapsules.
天然抗菌剂主要来自天然植物的提取,如甲壳素、芥末、蓖麻油、山葵等,使用简便,但抗菌作用有限,耐热性较差,杀菌率低,不能广谱长效使用,且数量很少。如现有技术中国专利CN201510287717.3提出一种壳聚糖作为壁材的精油微胶囊的制备方法,同时选用了具有抗菌功能的精油作为芯材,实现了抗菌功能,其中对葡萄球菌、大肠杆菌的抑菌率达85%。Natural antibacterial agents mainly come from the extraction of natural plants, such as chitin, mustard, castor oil, horseradish, etc., which are easy to use, but have limited antibacterial effect, poor heat resistance, low bactericidal rate, cannot be used for broad-spectrum and long-term use, and the quantity is very large few. For example, the prior art Chinese patent CN201510287717.3 proposes a preparation method of essential oil microcapsules with chitosan as the wall material. At the same time, the essential oil with antibacterial function is selected as the core material to realize the antibacterial function. The antibacterial rate reaches 85%.
然而,上述现有技术,其核心技术特征都在于,通过各种技术手段引入了抗菌剂,包括上述的无机抗菌剂,有机抗菌剂或天然抗菌剂来达到抗菌效果,而未引入抗菌剂,却能实现抗菌效果的未见现有技术报道过;Yet above-mentioned prior art, its core technical feature all is, has introduced antibacterial agent by various technical means, comprises above-mentioned inorganic antibacterial agent, organic antibacterial agent or natural antibacterial agent to reach antibacterial effect, and does not introduce antibacterial agent, but There is no prior art report that can realize the antibacterial effect;
为此,本发明提出了一种仿生结构抗菌微胶囊及其制备方法及应用。For this reason, the present invention proposes a kind of antibacterial microcapsule of bionic structure and its preparation method and application.
发明内容Contents of the invention
为解决现有技术中的问题,本发明提出了一种仿生结构抗菌微胶囊及其制备方法及应用。In order to solve the problems in the prior art, the present invention proposes a bionic structure antibacterial microcapsule and its preparation method and application.
为了实现上述目的,本发明采用了如下技术方案:In order to achieve the above object, the present invention adopts the following technical solutions:
一种仿生结构抗菌微胶囊,包括芯材和包裹在芯材表面的胶囊壁材,所述胶囊壁材上具有贯穿孔结构,所述胶囊壁材的表面带负电。An antibacterial microcapsule with a bionic structure comprises a core material and a capsule wall material wrapped on the surface of the core material, the capsule wall material has a through-hole structure, and the surface of the capsule wall material is negatively charged.
进一步地,所述抗菌微胶囊呈球形或类球形,D50直径为0.8~10微米。Further, the antibacterial microcapsules are spherical or spheroidal, with a D50 diameter of 0.8-10 microns.
进一步地,所述胶囊壁材包裹芯材的内壳面亲油,所述胶囊壁材的外壳面亲水,所述芯材包括相变材料、脂溶性香精、植物精油、脂溶性维生素中的至少一种。Further, the inner shell surface of the core material wrapped by the capsule wall material is lipophilic, the outer shell surface of the capsule wall material is hydrophilic, and the core material includes phase change materials, fat-soluble essences, plant essential oils, and fat-soluble vitamins. at least one.
一种仿生结构抗菌微胶囊的制备方法,包括如下步骤:A preparation method of bionic structure antibacterial microcapsules, comprising the steps of:
将芯材、硅烷偶联剂和单体混合形成第一混合物,将水相的复合乳化剂与第一混合物混合形成O/W乳液,调节O/W乳液的pH为2-4,在O/W乳液中加入引发剂并升温聚合形成抗菌微胶囊。Mix the core material, silane coupling agent and monomer to form the first mixture, mix the composite emulsifier of the water phase with the first mixture to form an O/W emulsion, adjust the pH of the O/W emulsion to 2-4, and adjust the pH of the O/W emulsion to 2-4. Initiator is added into the W emulsion and the temperature rises to polymerize to form antibacterial microcapsules.
进一步地,在调节O/W乳液的pH为2-4后,先经4h-8h形成具有第一层壳的第二混合物,再将第二混合物升温至60-80℃并加入引发剂,恒温5h-12h,聚合形成第二层壳,得到抗菌微胶囊。Further, after adjusting the pH of the O/W emulsion to 2-4, the second mixture with the first shell is formed after 4h-8h, and then the temperature of the second mixture is raised to 60-80°C and the initiator is added to keep the temperature constant After 5h-12h, the second layer of shell is formed by polymerization to obtain antibacterial microcapsules.
进一步地,所述芯材包括相变材料、脂溶性香精、植物精油、脂溶性维生素中的至少一种;Further, the core material includes at least one of phase change materials, fat-soluble flavors, plant essential oils, and fat-soluble vitamins;
所述硅烷偶联剂包括氨丙基三甲氧基硅烷、氨丙基三乙氧基硅烷、苯基三乙氧基硅烷、3-(甲基丙烯酰氧)丙基三甲氧基硅烷、正硅酸四乙酯、正硅酸四甲酯中的至少2种;The silane coupling agent includes aminopropyltrimethoxysilane, aminopropyltriethoxysilane, phenyltriethoxysilane, 3-(methacryloxy)propyltrimethoxysilane, orthosilane At least two of tetraethyl orthosilicate and tetramethyl orthosilicate;
所述单体包括苯乙烯、二乙烯基苯、丙烯酸酯类单体、丙烯酸类单体、二异氰酸酯类预聚物中的至少一种;The monomers include at least one of styrene, divinylbenzene, acrylate monomers, acrylic monomers, and diisocyanate prepolymers;
所述复合乳化剂为阴离子表面活性剂和非离子表面活性剂的组 合物。Described composite emulsifier is the composition of anionic surfactant and nonionic surfactant.
进一步地,所述复合乳化剂包括聚乙烯-马来酸酐共聚物或其水解盐、聚苯乙烯-马来酸酐共聚物或其水解盐、环氧树脂和聚乙二醇的嵌段共聚物、十二烷基硫酸钠、十二烷基苯磺酸钠、失水山梨醇单油酸酯聚氧乙烯醚、脂肪醇聚氧乙烯醚、烷基酚聚氧乙烯醚、脂肪醇醇聚氧丙烯醚、甘油单脂肪酸酯、聚氧乙烯失水山梨醇脂肪酸酯、失水山梨醇脂肪酸酯和/或脂肪酸季戊四醇酯中的至少一种。Further, the complex emulsifier includes polyethylene-maleic anhydride copolymer or its hydrolyzed salt, polystyrene-maleic anhydride copolymer or its hydrolyzed salt, block copolymer of epoxy resin and polyethylene glycol, Sodium lauryl sulfate, sodium dodecylbenzene sulfonate, sorbitan monooleate polyoxyethylene ether, fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, fatty alcohol polyoxypropylene At least one of ether, glycerol monofatty acid ester, polyoxyethylene sorbitan fatty acid ester, sorbitan fatty acid ester and/or fatty acid pentaerythritol ester.
进一步地,各组分的重量份包括:芯材25-60份、硅烷偶联剂0.6-8份、单体1.2-10份和复合乳化剂0.19-3份。Further, the parts by weight of each component include: 25-60 parts of core material, 0.6-8 parts of silane coupling agent, 1.2-10 parts of monomer and 0.19-3 parts of composite emulsifier.
一种抗菌产品,其上含有上述的仿生结构抗菌微胶囊或其上含有上述的制备方法制备得到的抗菌微胶囊。An antibacterial product, which contains the above antibacterial microcapsule with bionic structure or the antibacterial microcapsule prepared by the above preparation method.
仿生结构抗菌微胶囊在食品、药物的运输或储藏、纺织品或化妆品中的应用,所述抗菌微胶囊为上述的仿生结构抗菌微胶囊或为上述的制备方法制备得到的抗菌微胶囊。Application of antibacterial microcapsules with bionic structure in transportation or storage of food, medicine, textiles or cosmetics, the antibacterial microcapsules are the above antibacterial microcapsules with bionic structure or the antibacterial microcapsules prepared by the above preparation method.
本发明的有益效果:Beneficial effects of the present invention:
1、在没有引入其它抗菌剂(即无机抗菌剂,有机抗菌剂或天然抗菌剂)的情况下,本发明提供的一种仿生结构抗菌微胶囊具备高效的抗菌性能;1. Without the introduction of other antibacterial agents (i.e. inorganic antibacterial agents, organic antibacterial agents or natural antibacterial agents), the antibacterial microcapsules with a bionic structure provided by the invention possess efficient antibacterial properties;
2、本发明微胶囊制备工艺简单,较为普适,可方便的更换芯材,是药物等功能物质的优良载体,可实现功能物质的微结构传递、运输或控制释放;2. The preparation process of the microcapsules of the present invention is simple, relatively universal, and the core material can be replaced conveniently. It is an excellent carrier of functional substances such as drugs, and can realize microstructure transfer, transportation or controlled release of functional substances;
3、本发明方法制备得到的抗菌微胶囊可提供至少两种功能的复 合功能微胶囊,即微胶囊芯材提供一种功能性,芯材可以通过微胶囊表面的贯穿孔释放芯材的自身性能,同时微胶囊具备高效的抗菌性。3. The antimicrobial microcapsules prepared by the method of the present invention can provide composite functional microcapsules with at least two functions, that is, the core material of the microcapsules provides a kind of functionality, and the core material can release the self-performance of the core material through the through holes on the surface of the microcapsules. , At the same time, the microcapsules have high antibacterial properties.
4、本发明得到了一种仿生结构抗菌微胶囊,所述微胶囊有贯穿壳层的孔结构。葡萄球菌、白色念珠菌、大肠杆菌等在外形尺寸上直径几个微米,细菌表面带负电。同时细菌表面会有些细小孔结构,这些孔结构贯穿外壳。本发明本身是在微纳结构单元设计和合成方面的有益而重要的尝试。4. The present invention obtains an antibacterial microcapsule with a bionic structure, and the microcapsule has a pore structure that runs through the shell. Staphylococcus, Candida albicans, Escherichia coli, etc. have a diameter of several microns in size, and the surface of the bacteria is negatively charged. At the same time, there will be some fine pore structures on the surface of bacteria, and these pore structures run through the shell. The present invention itself is a beneficial and important attempt in the design and synthesis of micro-nano structural units.
图1为本发明实施例1所述一种仿生结构抗菌微胶囊的电子扫描显微镜(SEM)照片;Fig. 1 is the scanning electron microscope (SEM) photo of a kind of bionic structure antibacterial microcapsule described in the embodiment of the present invention 1;
图2为实施例1所述一种仿生结构抗菌微胶囊的透射电子显微镜(TEM)照片;Fig. 2 is the transmission electron microscope (TEM) photo of a kind of bionic structure antibacterial microcapsule described in embodiment 1;
图3为实施例1所得一种仿生结构抗菌微胶囊的激光粒径测试曲线;Fig. 3 is the laser particle size test curve of a kind of biomimetic structure antibacterial microcapsule of embodiment 1 gained;
图4为实施例2所得一种仿生结构抗菌微胶囊的电子扫描显微镜(SEM)照片;Fig. 4 is the scanning electron microscope (SEM) photograph of a kind of biomimetic structure antibacterial microcapsule of embodiment 2 gained;
图5为实施例2所得一种仿生结构抗菌微胶囊的透射电子显微镜(TEM)照片;Fig. 5 is the transmission electron microscope (TEM) photograph of a kind of biomimetic structure antibacterial microcapsule of embodiment 2 gained;
图6为实施例2所得一种仿生结构抗菌微胶囊的激光粒径测试曲线;Fig. 6 is the laser particle size test curve of a kind of biomimetic structure antibacterial microcapsule of embodiment 2 gained;
图7为实施例2所得一种仿生结构抗菌微胶囊的DSC测试曲线;Fig. 7 is the DSC test curve of a kind of biomimetic structure antibacterial microcapsule of embodiment 2 gained;
图8为实施例3所得一种仿生结构抗菌微胶囊的电子扫描显微镜 (SEM)照片;Fig. 8 is the scanning electron microscope (SEM) photograph of a kind of biomimetic structure antibacterial microcapsule of embodiment 3 gained;
图9为实施例3所得一种仿生结构抗菌微胶囊外壳局部放大的电子扫描显微镜(SEM)照片。9 is a scanning electron microscope (SEM) photograph of a partially enlarged shell of a bionic structure antibacterial microcapsule obtained in Example 3.
下面将结合本发明实施例中的附图,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。The following will clearly and completely describe the technical solutions in the embodiments of the present invention with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only some, not all, embodiments of the present invention.
本发明采用如下技术方案:The present invention adopts following technical scheme:
一种仿生结构抗菌微胶囊的制备方法,其特征在于,所述制备方法包括以下步骤:A preparation method of bionic structure antibacterial microcapsules, characterized in that the preparation method comprises the following steps:
a.将芯材材料和硅烷偶联剂、聚合物单体混合均匀形成油相的过程;a. The process of uniformly mixing the core material, silane coupling agent and polymer monomer to form an oil phase;
b.将复合乳化剂溶于水中,形成水相的过程;b. The process of dissolving the compound emulsifier in water to form a water phase;
c.将上述油水两相得到O/W乳液的过程;c. The process of obtaining the O/W emulsion from the above-mentioned oil-water two-phase;
d.硅烷偶联剂形成第一层壳的过程;d. The process of silane coupling agent forming the first shell;
e.单体聚合形成第二层壳的过程。e. The process of monomer polymerization to form the second shell.
所述芯材材料,包括相变材料、正二十二烷、工业石蜡、正十八烷、粉玫瑰精油、脂溶性香精、植物精油、脂溶性维生素中的至少一种;The core material includes at least one of phase change material, n-docosane, industrial paraffin, n-octadecane, pink rose essential oil, fat-soluble essence, plant essential oil, and fat-soluble vitamin;
通常的微胶囊结构中,芯材是核心组分,赋予材料功能性,如储热,温度响应,释放香味或功能物质等;In the usual microcapsule structure, the core material is the core component, endowing the material with functionality, such as heat storage, temperature response, release of fragrance or functional substances, etc.;
芯材和连续相往往会不相容,在两者接触的界面处,提供微胶囊 壁材形成的场所,本方案中的芯材,在实施中,是主要根据各类葡萄球菌、白色念珠菌、大肠杆菌细胞液的调研,选取的理化性质相近物料作为芯材主要成分。The core material and the continuous phase are often incompatible. At the interface between the two, a place for the formation of the microcapsule wall material is provided. The core material in this plan is mainly based on various staphylococcus and candida albicans during implementation. , Escherichia coli cell fluid investigation, selected materials with similar physical and chemical properties as the main component of the core material.
所述硅烷偶联剂包括氨丙基三甲氧基硅烷偶联剂、KH550硅烷偶联剂(3-氨基丙基三乙氧基硅烷)、苯基三乙氧基硅烷偶联剂、3-(甲基丙烯酰氧)丙基三甲氧基硅烷偶联剂、正硅酸四乙酯、正硅酸四甲酯中的至少2种;硅烷偶联剂是作为无机物硅源的,所形成的二氧化硅是壁材的一部分,同时,硅烷偶联剂可通过简洁方便的sol-gel过程有效的进行界面改性,并且,硅烷偶联剂的选择范围也比较大;Described silane coupling agent comprises aminopropyltrimethoxysilane coupling agent, KH550 silane coupling agent (3-aminopropyltriethoxysilane), phenyltriethoxysilane coupling agent, 3-( At least two of methacryloyloxy)propyltrimethoxysilane coupling agent, tetraethyl orthosilicate, and tetramethyl orthosilicate; the silane coupling agent is used as an inorganic silicon source, and the formed Silica is a part of the wall material. At the same time, the silane coupling agent can effectively modify the interface through the simple and convenient sol-gel process, and the selection range of the silane coupling agent is also relatively large;
本方法通过选取至少2种硅烷偶联剂,为壁材引入至少2种性质不同化学基团,可在一定程度上对微胶囊壳层的性质进行调控;The method introduces at least two chemical groups with different properties into the wall material by selecting at least two kinds of silane coupling agents, which can regulate the properties of the microcapsule shell to a certain extent;
所述单体包括苯乙烯、二乙烯基苯、丙烯酸酯类单体、丙烯酸类单体、二异氰酸酯类预聚物中的至少一种。单体在引发聚合后,与前述的无机物形成复合壳层,在本发明所述方法下形成的这种有机-无机复合壳层,在壳层两侧能表现出不同性质,如在面向芯材的内壳层一面更加亲油,而面向水相的外壳层一面更加亲水,这2个面事实上是同一个壳层的2个面;The monomers include at least one of styrene, divinylbenzene, acrylate monomers, acrylic monomers, and diisocyanate prepolymers. After the monomer initiates polymerization, it forms a composite shell with the aforementioned inorganic substances. The organic-inorganic composite shell formed under the method of the present invention can exhibit different properties on both sides of the shell, such as facing the core. The inner shell side of the material is more oleophilic, while the outer shell side facing the water phase is more hydrophilic. These two sides are actually two sides of the same shell;
所述复合乳化剂选自聚乙烯-马来酸酐共聚物或其水解盐、聚苯乙烯-马来酸酐共聚物或其水解盐、环氧树脂和聚乙二醇的嵌段共聚物、十二烷基硫酸钠、十二烷基苯磺酸钠、脂肪醇聚氧乙烯醚、Tween 80(失水山梨醇单油酸酯聚氧乙烯醚)、Tween 60(聚氧乙烯失水山梨醇硬脂酸酯)、曲拉通(聚乙二醇对异辛基苯基醚)、烷基酚聚氧 乙烯醚、脂肪醇醇聚氧丙烯醚、甘油单脂肪酸酯、聚氧乙烯失水山梨醇脂肪酸酯、失水山梨醇脂肪酸酯、脂肪酸季戊四醇酯中的至少一种阴离子表面活性剂和至少一种非离子表面活性剂的组合物;Described compound emulsifier is selected from the block copolymer of polyethylene-maleic anhydride copolymer or its hydrolyzed salt, polystyrene-maleic anhydride copolymer or its hydrolyzed salt, epoxy resin and Polyethylene Glycol, dodecane Sodium Alkyl Sulfate, Sodium Dodecyl Benzene Sulfonate, Fatty Alcohol Polyoxyethylene Ether, Tween 80 (Sorbitan Monooleate Polyoxyethylene Ether), Tween 60 (Polyoxyethylene Sorbitan Stearate ester), triton (polyethylene glycol p-isooctyl phenyl ether), alkylphenol polyoxyethylene ether, fatty alcohol polyoxypropylene ether, glycerin monofatty acid ester, polyoxyethylene sorbitan A composition of at least one anionic surfactant and at least one nonionic surfactant in fatty acid esters, sorbitan fatty acid esters, fatty acid pentaerythritol esters;
表面活性剂为稳定油水界面提供了关键的保证,同时创造了壳层生成的位点。表面活性剂在油水界面的特定相行为,可以通过2种或2种以上不同种类的表面活性剂进行调节,以达到不通的效用;Surfactants provide the key guarantee for stabilizing the oil-water interface while creating sites for shell formation. The specific phase behavior of surfactants at the oil-water interface can be adjusted by two or more different types of surfactants to achieve different effects;
这些效果包括界面稳定,两相融合或一个相在另一个相上的铺展,即诱导相分离,另一方面通过其中一种表面活性剂用量的调节,可以产生孔结构,通过种类和用量的调节,可以得到贯穿壳层的孔结构,而我们知道,葡萄球菌,大肠杆菌等细胞膜上存在可以传输能量或物质的孔结构,这一特点是本发明模仿的结构特征之一,本发明的微胶囊的贯穿孔结构可以用来释放芯材的自身的性能;These effects include interfacial stabilization, fusion of two phases or spreading of one phase on another, i.e. induction of phase separation, on the other hand through the adjustment of the amount of one of the surfactants, a pore structure can be produced, through the adjustment of the type and amount , the pore structure that runs through the shell can be obtained, and we know that there are pore structures that can transmit energy or substances on the cell membranes of Staphylococcus and Escherichia coli. This feature is one of the structural features imitated by the present invention. The microcapsules of the present invention The through-hole structure can be used to release the core material's own performance;
所述芯材材料和硅烷偶联剂、聚合物单体的用量之和为最终微胶囊悬浮液的10.0%-59.0%wt;所述非离子表面活性剂用量不超过最终微胶囊悬浮液的0.8%wt;The sum of the consumption of the core material, silane coupling agent and polymer monomer is 10.0%-59.0%wt of the final microcapsule suspension; the nonionic surfactant consumption is no more than 0.8% of the final microcapsule suspension. %wt;
优选的,所述芯材材料和硅烷偶联剂、聚合物单体的用量之和为最终微胶囊悬浮液的15.0%-49.0%wt,所述非离子表面活性剂用量为最终微胶囊悬浮液的0.1%-0.67%wt;Preferably, the sum of the amount of the core material, silane coupling agent, and polymer monomer is 15.0%-49.0%wt of the final microcapsule suspension, and the amount of the nonionic surfactant is the final microcapsule suspension 0.1%-0.67%wt;
更优选的,所述芯材材料和硅烷偶联剂、聚合物单体的用量之和为最终微胶囊悬浮液的25.0%-39.0%wt,所述非离子表面活性剂用量为最终微胶囊悬浮液的0.2%-0.45%wt。More preferably, the sum of the amount of the core material, silane coupling agent, and polymer monomer is 25.0%-39.0%wt of the final microcapsule suspension, and the amount of the nonionic surfactant is the final microcapsule suspension 0.2%-0.45%wt of liquid.
所述步骤d开始的时间早于步骤e开始的时间,本发明中,步骤 d代表了溶胶凝胶过程,而步骤e代表了有机单体聚合过程,在实际操作中,2个过程可以通过,温度,pH,引发剂紫外线等等条件控制其先后分别开始,或者同时开始;The start time of step d is earlier than the start time of step e. In the present invention, step d represents the sol-gel process, and step e represents the polymerization process of organic monomers. In actual operation, the two processes can be passed. Conditions such as temperature, pH, initiator ultraviolet light, etc. control the successive start respectively, or start at the same time;
通过实验发现先开始溶胶凝胶过程,后开始有机单体聚合,更加有利于本发明所述的仿生结构形成,更准确地说是,先进行溶胶凝胶过程,溶胶凝胶过程有利于形成更加亲水的壳层外结构,同时,更加有利于贯穿孔结构的形成。It is found through experiments that the sol-gel process is started first, and then the organic monomer polymerization is started, which is more conducive to the formation of the biomimetic structure described in the present invention. The hydrophilic outer shell structure is more conducive to the formation of the through-hole structure.
所述微胶囊为球形或类球形,D50直径为0.8微米到10微米;所述微胶囊表面带负电;所述微胶囊有贯穿壳层的孔结构;The microcapsules are spherical or spheroidal, with a D50 diameter of 0.8 microns to 10 microns; the surface of the microcapsules is negatively charged; the microcapsules have a pore structure that runs through the shell;
葡萄球菌、白色念珠菌、大肠杆菌等在外形尺寸上直径几个微米,细菌表面带负电,同时细菌表面会有些细小孔结构,这些孔结构贯穿外壳,细菌通过这些带负电的膜结构,或孔结构来获取营养。本发明的该仿生结构微胶囊,在抗菌方面表现很好,其原因包括如下,在本发明的微胶囊和细菌共同处在同样条件下时,这类仿生结构微胶囊能够跟某些细菌产生竞食效应,细菌获得营养的可能性大大降低,阻碍了细菌获取营养和繁殖,从而达到了抗菌效果;Staphylococcus, Candida albicans, Escherichia coli, etc. have a diameter of several microns in size, and the surface of the bacteria is negatively charged. At the same time, there are some small pore structures on the surface of the bacteria. These pore structures run through the shell, and the bacteria pass through these negatively charged membrane structures, or pores. structure for nutrition. The biomimetic structure microcapsule of the present invention performs very well in antibacterial aspect, and its reason includes as follows, when the microcapsule of the present invention and bacterium are in the same condition together, this type of biomimetic structure microcapsule can produce competition with some bacteria Food effect, the possibility of bacteria obtaining nutrition is greatly reduced, which hinders bacteria from obtaining nutrition and multiplying, thus achieving antibacterial effect;
同时,在进行杀菌测试时,该仿生结构微胶囊表现欠佳,这是因为,结构仿生微胶囊并不含有上述三种抗菌剂中的任何一种,并不能主动杀死细菌,但是在抗菌测试中,能够通过竞食,降低细菌存活几率。At the same time, in the bactericidal test, the biomimetic structure microcapsules performed poorly, because the structure biomimetic microcapsules did not contain any of the above three antibacterial agents, and could not actively kill bacteria, but in the antibacterial test Among them, it can reduce the chance of bacterial survival by competing for food.
本发明的上述实验论证仅对葡萄球菌,白色念珠菌,大肠杆菌的抑菌效果进行了研究,但在不脱离本发明方法和设计精神情况下的合 理外推均应视为不脱离本发明技术方案的延伸或变形,属于本发明权利要求书确定的保护范围内。The above-mentioned experimental demonstration of the present invention has only studied staphylococcus, Candida albicans, the antibacterial effect of escherichia coli, but reasonable extrapolation under the method of the present invention and design spirit situation all should be regarded as not departing from the technology of the present invention The extension or modification of the scheme belongs to the protection scope determined by the claims of the present invention.
当然为了增强杀菌效果,也可在本发明所述结构仿生微胶囊工艺中,引入上述3种抗菌剂,即无机抗菌剂,有机抗菌剂或天然抗菌剂。根据工艺实施的具体情况以及应用场景,加工中,会使用各类填料,如催化剂、促进剂、遮盖剂、增白剂、颜料、稀释剂、增稠剂、固化剂等,也会使用一些功能性填料等,这些均应视为不脱离本发明技术方案的延伸或变形,属于本发明权利要求书确定的保护范围内。Of course, in order to enhance the bactericidal effect, the above-mentioned three antibacterial agents, namely inorganic antibacterial agents, organic antibacterial agents or natural antibacterial agents, can also be introduced into the structural biomimetic microcapsule process of the present invention. According to the specific situation of process implementation and application scenarios, various fillers will be used during processing, such as catalysts, accelerators, covering agents, whitening agents, pigments, thinners, thickeners, curing agents, etc., and some functions will also be used Sexual fillers, etc., these should be regarded as extensions or deformations that do not deviate from the technical solutions of the present invention, and fall within the scope of protection determined by the claims of the present invention.
本发明的一种仿生结构抗菌微胶囊,用于纺织品加工工艺包括后整理、涂层、浸轧、印花或纺丝中的至少一种,仿生结构抗菌微胶囊,能够通过共混方式,以添加剂的形式,加入到后整理浆料中,或者印花浆料中,浸轧浴液中,通过进一步的相关加工,使其附着在面料或类似层状结构中,从而赋予产品抗菌性,类似的,在湿法纺丝中,通过向纺丝液中添加本发明所述微胶囊,也可在纺前注射,得到含有本发明所述仿生结构抗菌微胶囊的纤维材料。本发明所要求保护的一种抗菌产品包括上述过程中制备得到的具有抗菌功能的纺织品等;A biomimetic structure antibacterial microcapsule of the present invention is used in textile processing technology including at least one of finishing, coating, padding, printing or spinning, and the biomimetic structure antibacterial microcapsule can be mixed with additives In the form of finishing paste, or printing paste, padding bath, through further related processing, it is attached to the fabric or similar layered structure, thereby endowing the product with antibacterial properties, similar, In wet spinning, by adding the microcapsules of the present invention to the spinning solution, it can also be injected before spinning to obtain the fiber material containing the antibacterial microcapsules of the bionic structure of the present invention. An antibacterial product claimed in the present invention includes textiles with antibacterial function prepared in the above process;
除纺织领域外,本发明所述的一种仿生结构抗菌微胶囊及其方法,还可以用于医疗保健,食品药物的运输或储藏,美妆化妆等领域。In addition to the field of textiles, the antibacterial microcapsule with a bionic structure and its method described in the present invention can also be used in the fields of medical care, transportation or storage of food and medicine, cosmetics, and the like.
实施例1Example 1
本例中提供一种仿生结构抗菌二氧化硅-聚苯乙烯微胶囊,其制备方法包括以下步骤:Provide a kind of biomimetic structure antibacterial silicon dioxide-polystyrene microcapsule in this example, its preparation method comprises the following steps:
a.将25g粉玫瑰精油和3g硅酸四乙酯、1.2g KH550硅烷偶联 剂(3-氨基丙基三乙氧基硅烷)、5g苯乙烯、5g二乙烯苯混合,搅拌30min,均匀形成油相的过程;a. Mix 25g pink rose essential oil with 3g tetraethyl silicate, 1.2g KH550 silane coupling agent (3-aminopropyltriethoxysilane), 5g styrene, 5g divinylbenzene, stir for 30min, and form a uniform oil phase process;
b.将30g,10%wt的苯乙烯-马来酸酐水解钠盐水溶液和0.19g Tween 80(失水山梨醇单油酸酯聚氧乙烯醚)溶于100g水中,搅拌使其混合均匀;b. 30g, 10%wt styrene-maleic anhydride hydrolyzed sodium salt solution and 0.19g Tween 80 (sorbitan monooleate polyoxyethylene ether) were dissolved in 100g water, stirred to make it evenly mixed;
c.将上述油水两相经6000rpm-12000rpm,均质机处理5min,得到O/W乳液(水包油型乳液);c. The above-mentioned oil-water two-phase is subjected to 6000rpm-12000rpm, and the homogenizer is processed for 5 minutes to obtain an O/W emulsion (oil-in-water emulsion);
d.室温下,调节前述乳液pH2-4,经4h-8h形成第一层壳;d. At room temperature, adjust the pH of the aforementioned emulsion to 2-4, and form the first layer of shell after 4h-8h;
e.乳液升温到60-80℃,加入引发剂AIBN(偶氮二异丁腈),保温5h-12h,使其聚合形成第二层壳。e. The temperature of the emulsion is raised to 60-80°C, the initiator AIBN (azobisisobutyronitrile) is added, and the temperature is kept for 5h-12h to make it polymerize to form the second shell.
即得所述的一种壳层为二氧化硅-聚苯乙烯的仿生结构抗菌微胶囊。That is to obtain the antibacterial microcapsules with a biomimetic structure whose shell layer is silicon dioxide-polystyrene.
所得仿生结构微胶囊的SEM照片见附图1。从图1可看出微胶囊表面有若干孔。The SEM photo of the obtained biomimetic structure microcapsule is shown in accompanying drawing 1. It can be seen from Figure 1 that there are several holes on the surface of the microcapsules.
图2为所得微胶囊的TEM照片。TEM照片显示,微胶囊表面的孔,贯穿了壳层,并在胶囊内部形成较大的空穴。该空穴可用于负载精油等功能物质。Figure 2 is a TEM photo of the obtained microcapsules. The TEM photos show that the pores on the surface of the microcapsules penetrate the shell and form larger cavities inside the capsules. The hole can be used to load functional substances such as essential oils.
Zeta电位测试显示微胶囊的Zeta电势为-30.4mV,说明微胶囊表面带负电。这是由于本例中使用的一种表面活性剂苯乙烯-马来酸酐水解钠盐,为一种阴离子表面活性剂。The Zeta potential test showed that the Zeta potential of the microcapsules was -30.4mV, indicating that the surface of the microcapsules was negatively charged. This is because a kind of surfactant styrene-maleic anhydride hydrolyzed sodium salt used in this example is an anionic surfactant.
图3为所得微胶囊的激光粒度分析曲线,可知D50直径为0.85微米。Figure 3 is the laser particle size analysis curve of the obtained microcapsules, it can be seen that the D50 diameter is 0.85 microns.
由此可知我们得到了一种表面带负电的,D50为0.85微米,表面有若干微孔的仿生结构微胶囊。并且本例中并未引入任何前述3种抗菌剂。It can be seen that we have obtained a biomimetic structure microcapsule with a negatively charged surface, a D50 of 0.85 microns, and several micropores on the surface. And did not introduce any aforementioned 3 kinds of antibacterial agents in this example.
将本例所得微胶囊用于面料后整理,将处理过的面料进行抗菌性能测试,测试方法参考FZ/T 73023-2006抗菌针织品,得到如下表1结果:对白色念珠菌抑菌率86%,对大肠杆菌抑菌率86%,对金色葡萄球菌抑菌率88%。The microcapsules obtained in this example are used for the after-finishing of fabrics, and the treated fabrics are tested for antibacterial performance. The test method refers to FZ/T 73023-2006 antibacterial knitwear, and the results in Table 1 are obtained: the antibacterial rate of Candida albicans is 86% , The antibacterial rate of Escherichia coli is 86%, and the antibacterial rate of Staphylococcus aureus is 88%.
表1抗菌性能测试Table 1 antibacterial performance test
实施例2Example 2
本例中提供一种仿生结构抗菌二氧化硅-聚丙烯酸酯微胶囊,其制备方法包括以下步骤:Provide a kind of antibacterial silicon dioxide-polyacrylate microcapsule of biomimetic structure in this example, its preparation method comprises the following steps:
a.将50g正十八烷和8g硅酸四乙酯、0.6g氨丙基三甲氧基硅烷偶联剂、1.2g苯基三乙氧基硅烷偶联剂、5g二甲基丙烯酸1,4-丁二醇酯,搅拌20min,均匀形成油相的过程;a. 50g n-octadecane and 8g tetraethyl silicate, 0.6g aminopropyltrimethoxysilane coupling agent, 1.2g phenyltriethoxysilane coupling agent, 5g dimethacrylic acid 1,4 -butanediol ester, stirring for 20min, the process of uniformly forming an oil phase;
b.将10g,10%wt的乙烯-马来酸酐水解钠盐水溶液和0.62g Tween 60(聚氧乙烯失水山梨醇硬脂酸酯)溶于110g水中,搅拌使 其混合均匀;B. 10g, 10%wt ethylene-maleic anhydride hydrolysis sodium salt aqueous solution and 0.62g Tween 60 (polyoxyethylene sorbitan stearate) are dissolved in 110g water, stir and make it mix homogeneously;
c.将上述油水两相经6000rpm-12000rpm,均质机处理5min,得到O/W乳液;c. Process the above-mentioned oil-water two-phase through 6000rpm-12000rpm and homogenizer for 5min to obtain O/W emulsion;
d.室温下,调节前述乳液pH2-4,经4h-8h形成第一层壳;d. At room temperature, adjust the pH of the aforementioned emulsion to 2-4, and form the first layer of shell after 4h-8h;
e.乳液升温到50-80℃,加入引发剂APS(过硫酸铵),保温5h-12h,使有机单体聚合形成第二层壳。e. The temperature of the emulsion is raised to 50-80°C, the initiator APS (ammonium persulfate) is added, and the temperature is kept for 5h-12h, so that the organic monomers are polymerized to form the second shell.
即得所述的一种壳层为二氧化硅-聚丙烯酸酯的仿生结构抗菌微胶囊;That is to say, a kind of shell layer is a biomimetic structure antibacterial microcapsule of silicon dioxide-polyacrylate;
所得仿生结构微胶囊的SEM照片见附图4,可看出微胶囊表面有若干孔;The SEM photo of the obtained biomimetic structure microcapsules is shown in accompanying drawing 4, and it can be seen that there are several holes on the surface of the microcapsules;
图5为所得微胶囊的TEM照片。TEM照片显示,微胶囊表面的孔贯穿了壳层;Figure 5 is a TEM photo of the obtained microcapsules. TEM photos show that the pores on the surface of the microcapsules penetrate the shell;
Zeta电位测试显示微胶囊的Zeta电势为-16.9mV,说明微胶囊表面带负电。这是由于本例中使用的一种表面活性剂乙烯-马来酸酐共聚物水解盐,为一种阴离子表面活性剂;The Zeta potential test showed that the Zeta potential of the microcapsules was -16.9mV, indicating that the surface of the microcapsules was negatively charged. This is because a kind of surfactant ethylene-maleic anhydride copolymer hydrolysis salt used in this example is a kind of anionic surfactant;
图6为所得微胶囊的激光粒度分析曲线,可知D50直径为3.023微米。Figure 6 is the laser particle size analysis curve of the obtained microcapsules, it can be seen that the D50 diameter is 3.023 microns.
差热扫描量热法所得DSC曲线,见附图7,可知本例中相变微胶囊相变熔点为29.91℃,对应相变焓值为185.5J/g。The DSC curve obtained by differential scanning calorimetry is shown in Figure 7. It can be seen that the phase change melting point of the phase change microcapsules in this example is 29.91°C, and the corresponding phase change enthalpy is 185.5 J/g.
表2抗菌测试Table 2 Antibacterial Test
由此可知本例得到了一种表面带负电的,D50为3.023微米,表面有若干微孔的仿生结构微胶囊。并且本例中并未引入任何前述3种抗菌剂;It can be seen that this example has obtained a biomimetic structure microcapsule with a negatively charged surface, a D50 of 3.023 microns, and several micropores on the surface. And did not introduce any aforementioned 3 kinds of antibacterial agents in this example;
将本例所得微胶囊用于面料后整理,将处理过的面料进行抗菌性能测试,测试方法参考GB/T20944.2附录B,得到如下表2结果:对白色念珠菌抑菌率99.9%,水洗50次后抑菌率84.9%;对大肠杆菌抑菌率99.9%,水洗50次后抑菌率92.9%;对金色葡萄球菌抑菌率99.9%,水洗50次后抑菌率96.4%;The microcapsules obtained in this example are used for the finishing of fabrics, and the treated fabrics are tested for antibacterial properties. The test method refers to GB/T20944.2 Appendix B, and the results in Table 2 are obtained as follows: 99.9% antibacterial rate against Candida albicans, washed with water The antibacterial rate after 50 times is 84.9%; the antibacterial rate against Escherichia coli is 99.9%, and the antibacterial rate after washing 50 times is 92.9%; the antibacterial rate against Staphylococcus aureus is 99.9%, and the antibacterial rate after washing 50 times is 96.4%;
对本例中各组分进行分析,各组分列于下表3,各对比样品S2-0等表示了仅使用相应的油相或水相组分,对应于本例2中的其他部分用等量水替代,操作步骤与本例2相同。完成操作后,分别进行抗菌测试。结果显示各配方均无抗菌性能。Each component in this example is analyzed, and each component is listed in the following table 3, and each comparative sample S2-0 etc. has expressed that only corresponding oil phase or water phase components are used, corresponding to other parts in this example 2 with etc. Measure water instead, and the operation steps are the same as in Example 2. After finishing the operation, carry out the antibacterial test respectively. The results showed that none of the formulations had antibacterial properties.
表3对照组微胶囊的抗菌性测试The antibacterial property test of the control group microcapsule of table 3
该对照实验证明,本发明中各组分单独,以及若干几种组分的组合,并无明显的抗菌效果。而所得的仿生结构微胶囊,有优良的抗菌效果。This control experiment proves that each component in the present invention alone, and the combination of several components, have no obvious antibacterial effect. And the obtained microcapsule of biomimetic structure has excellent antibacterial effect.
实施例3Example 3
本例提供一种仿生结构抗菌二氧化硅-聚苯乙烯-聚丙烯酸酯复合微胶囊,其制备方法包括以下步骤:This example provides a kind of antibacterial silicon dioxide-polystyrene-polyacrylate composite microcapsule of bionic structure, and its preparation method comprises the following steps:
a.将60g 44#工业石蜡和2g硅酸四甲酯、0.8g KH570硅烷偶联剂、10g二甲基丙烯酸乙二醇酯、2g二乙烯苯混合,搅拌30min,均匀形成油相的过程;a. Mix 60g of 44# industrial paraffin with 2g of tetramethyl silicate, 0.8g of KH570 silane coupling agent, 10g of ethylene glycol dimethacrylate, and 2g of divinylbenzene, and stir for 30 minutes to form an oil phase uniformly;
b.将1g十二烷基硫酸钠,5g,10%wt的苯乙烯-马来酸酐水解钠盐水溶液和1.1g Tween 80溶于100g水中,搅拌使其混合均匀;b. 1g sodium lauryl sulfate, 5g, 10%wt styrene-maleic anhydride hydrolyzed sodium salt solution and 1.1g Tween 80 were dissolved in 100g water, stirred to make it evenly mixed;
c.将上述油水两相经5000rpm-9000rpm,均质机5min处理,得到O/W乳液;c. Process the above-mentioned oil-water two-phase at 5000rpm-9000rpm in a homogenizer for 5min to obtain an O/W emulsion;
d.室温下,调节前述乳液pH2-4,经4h-8h形成第一层壳;d. At room temperature, adjust the pH of the aforementioned emulsion to 2-4, and form the first layer of shell after 4h-8h;
e.乳液升温到60-80℃,加入过氧化苯甲酰,保温5h-12h,使其聚合形成第二层壳。e. The temperature of the emulsion is raised to 60-80°C, benzoyl peroxide is added, and the temperature is kept for 5h-12h to allow it to polymerize to form a second shell.
即得所述的一种壳层为二氧化硅-聚苯乙烯-聚丙烯酸酯复合微胶囊;That is, the described shell layer is silicon dioxide-polystyrene-polyacrylate composite microcapsules;
附图8和附图9为本例所得微胶囊的SEM照片。附图9为胶囊外壳的局部放大,可见其中有若干微小的孔;Accompanying drawing 8 and accompanying drawing 9 are the SEM photos of the obtained microcapsules of this example. Accompanying drawing 9 is the partial enlargement of capsule shell, and it can be seen that there are some tiny holes therein;
Zeta电位测试显示微胶囊的Zeta电势为-22.8mV,说明微胶囊表面带负电。这是由于本例中使用2种阴离子表面活性剂;The Zeta potential test showed that the Zeta potential of the microcapsules was -22.8mV, indicating that the surface of the microcapsules was negatively charged. This is due to the use of 2 anionic surfactants in this example;
激光粒度分析得知本例微胶囊的D50直径为7.536微米;Laser particle size analysis shows that the D50 diameter of the microcapsules in this example is 7.536 microns;
差热扫描量热法得到本例中相变微胶囊相变熔点为43.95℃,对应相变焓值为140.1J/g;The differential scanning calorimetry method obtained the phase change melting point of the phase change microcapsules in this example as 43.95°C, and the corresponding phase change enthalpy value was 140.1J/g;
由此可知我们得到了一种表面带负电的,D50为7.536微米,表面有若干微孔的仿生结构微胶囊。并且本例中并未引入任何前述3种抗菌剂;It can be seen that we have obtained a biomimetic structure microcapsule with a negatively charged surface, a D50 of 7.536 microns, and several micropores on the surface. And did not introduce any aforementioned 3 kinds of antibacterial agents in this example;
将本例所得微胶囊用于面料后整理,将处理过的面料进行抗菌性能测试,测试方法参考FZ/T 73023-2006抗菌针织品,测试可知对白色念珠菌抑菌率88%,对大肠杆菌抑菌率85%,对金色葡萄球菌抑菌率89%。The microcapsules obtained in this example are used for the finishing of fabrics, and the treated fabrics are tested for antibacterial performance. The test method refers to FZ/T 73023-2006 antibacterial knitwear. The test shows that the antibacterial rate of Candida albicans is 88%, and that of Escherichia coli The antibacterial rate is 85%, and the antibacterial rate for Staphylococcus aureus is 89%.
可见本例微胶囊有良好的抗菌效果。It can be seen that the microcapsules in this example have good antibacterial effect.
实施例4Example 4
本例提供一种仿生结构抗菌二氧化硅-聚脲复合微胶囊,其制备 方法包括以下步骤:This example provides a kind of biomimetic structure antibacterial silicon dioxide-polyurea composite microcapsule, and its preparation method comprises the following steps:
a.将45g正二十二烷和4g硅酸四乙酯、1.6g KH550硅烷偶联剂、10g异佛尔酮二异氰酸酯,搅拌30min,均匀形成油相的过程;a. Stir 45g of n-docosane, 4g of tetraethyl silicate, 1.6g of KH550 silane coupling agent, and 10g of isophorone diisocyanate for 30 minutes to form an oil phase uniformly;
b.将20g,10%wt的苯乙烯-马来酸酐水解钠盐水溶液和0.65gOP-10溶于100g水中,搅拌使其混合均匀;b. 20g, 10% wt of styrene-maleic anhydride hydrolyzed sodium salt solution and 0.65g OP-10 were dissolved in 100g of water, and stirred to make them evenly mixed;
c.将上述油水两相经5000rpm-9000rpm,均质机5min处理,得到O/W乳液;c. Process the above-mentioned oil-water two-phase at 5000rpm-9000rpm in a homogenizer for 5min to obtain an O/W emulsion;
d.室温下,调节前述乳液pH2-4,经4h-8h形成第一层壳;d. At room temperature, adjust the pH of the aforementioned emulsion to 2-4, and form the first layer of shell after 4h-8h;
e.乳液升温到50-80℃,滴加加入1,6-己二胺,保温2h-8h,使其聚合形成第二层壳。e. The temperature of the emulsion is raised to 50-80°C, and 1,6-hexanediamine is added dropwise, and kept for 2h-8h to make it polymerize to form a second shell.
即得所述的一种壳层为二氧化硅-聚脲复合微胶囊;That is, the described shell layer is a silica-polyurea composite microcapsule;
扫描电镜表明该微胶囊表面也有若干微孔;Scanning electron microscopy showed that the surface of the microcapsules also had some micropores;
Zeta电位测试显示微胶囊的Zeta电势为-31.5mV,说明微胶囊表面带负电;The Zeta potential test shows that the Zeta potential of the microcapsules is -31.5mV, indicating that the surface of the microcapsules is negatively charged;
激光粒度分析得知本例微胶囊的D50直径为4.316微米;Laser particle size analysis shows that the D50 diameter of the microcapsules in this example is 4.316 microns;
由此可知我们得到了一种表面带负电的,D50为4.316微米,表面有若干微孔的仿生结构微胶囊。并且本例中并未引入任何前述3种抗菌剂。It can be seen that we have obtained a biomimetic structure microcapsule with a negatively charged surface, a D50 of 4.316 microns, and several micropores on the surface. And did not introduce any aforementioned 3 kinds of antibacterial agents in this example.
将本例所得微胶囊用于面料后整理,将处理过的面料进行抗菌性能测试,测试方法参考FZ/T 73023-2006抗菌针织品,测试可知对白色念珠菌抑菌率87%,对大肠杆菌抑菌率85%,对金色葡萄球菌抑菌率91%。The microcapsules obtained in this example are used for the finishing of fabrics, and the treated fabrics are tested for antibacterial properties. The test method refers to FZ/T 73023-2006 antibacterial knitwear. The test shows that the bacteriostatic rate of Candida albicans is 87%, and that of Escherichia coli The antibacterial rate is 85%, and the antibacterial rate for Staphylococcus aureus is 91%.
可见本例微胶囊有良好的抗菌效果。It can be seen that the microcapsules in this example have good antibacterial effect.
实施例5Example 5
本例中提供一种仿生结构抗菌二氧化硅-聚丙烯酸酯微胶囊,其制备方法包括以下步骤:Provide a kind of antibacterial silicon dioxide-polyacrylate microcapsule of biomimetic structure in this example, its preparation method comprises the following steps:
a.将25g维生素E和8g硅酸四乙酯、0.6g氨丙基三甲氧基硅烷偶联剂、1.2g苯基三乙氧基硅烷偶联剂、5g二甲基丙烯酸1,6-己二醇酯,搅拌20min,均匀形成油相的过程;a. Combine 25g vitamin E, 8g tetraethyl silicate, 0.6g aminopropyltrimethoxysilane coupling agent, 1.2g phenyltriethoxysilane coupling agent, 5g 1,6-hexyl dimethacrylate Glycol ester, stirring for 20 minutes, the process of uniformly forming an oil phase;
b.将15g,10%wt的苯乙烯-马来酸酐水解钠盐水溶液和0.82g曲拉通(聚乙二醇对异辛基苯基醚)100溶于110g水中,搅拌使其混合均匀;b. 15g, 10%wt styrene-maleic anhydride hydrolyzed sodium salt solution and 0.82g Triton (polyethylene glycol p-isooctyl phenyl ether) 100 were dissolved in 110g water, stirred to make it evenly mixed;
c.将上述油水两相经6000rpm-12000rpm,均质机5min处理,得到O/W乳液;c. Process the above-mentioned oil-water two-phase through 6000rpm-12000rpm and homogenizer for 5min to obtain O/W emulsion;
d.室温下,调节前述乳液pH2-4,经4h-8h形成第一层壳;d. At room temperature, adjust the pH of the aforementioned emulsion to 2-4, and form the first layer of shell after 4h-8h;
e.乳液升温到50-80℃,加入引发剂APS,保温5h-12h,使有机单体聚合形成第二层壳。e. The temperature of the emulsion is raised to 50-80°C, the initiator APS is added, and the temperature is kept for 5h-12h, so that the organic monomers are polymerized to form the second shell.
即得所述的一种壳层为二氧化硅-聚丙烯酸酯的仿生结构抗菌微胶囊;That is to say, a kind of shell layer is a biomimetic structure antibacterial microcapsule of silicon dioxide-polyacrylate;
通过TEM可看出本例微胶囊表面有若干贯穿壳层的微孔;It can be seen by TEM that there are several micropores penetrating the shell on the surface of the microcapsules in this example;
Zeta电位测试显示微胶囊的Zeta电势为-11.4mV,说明微胶囊表面带负电;The Zeta potential test shows that the Zeta potential of the microcapsules is -11.4mV, indicating that the surface of the microcapsules is negatively charged;
激光粒度分析可知D50直径为1.99微米;Laser particle size analysis shows that the D50 diameter is 1.99 microns;
由此可知本例得到了一种表面带负电的,D50为1.99微米,表 面有若干微孔的仿生结构微胶囊。并且本例中并未引入任何前述3种抗菌剂。From this we can know that this example has obtained a kind of surface negatively charged, and D50 is 1.99 microns, and the biomimetic structure microcapsule of some micropores is arranged on the surface. And did not introduce any aforementioned 3 kinds of antibacterial agents in this example.
将本例所得微胶囊用于面料后整理,将处理过的面料进行抗菌性能测试,测试方法参考FZ/T 73023-2006抗菌针织品,测试可知对白色念珠菌抑菌率85%,对大肠杆菌抑菌率86%,对金色葡萄球菌抑菌率94%。The microcapsules obtained in this example are used for fabric finishing, and the treated fabric is tested for antibacterial performance. The test method refers to FZ/T 73023-2006 antibacterial knitwear. The test shows that the antibacterial rate of Candida albicans is 85%, and that of Escherichia coli The antibacterial rate is 86%, and the antibacterial rate for Staphylococcus aureus is 94%.
可见本例微胶囊有良好的抗菌效果。It can be seen that the microcapsules in this example have good antibacterial effect.
以上所述,仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,根据本发明的技术方案及其发明构思加以等同替换或改变,都应涵盖在本发明的保护范围之内。The above is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto, any person familiar with the technical field within the technical scope disclosed in the present invention, according to the technical solution of the present invention Any equivalent replacement or change of the inventive concepts thereof shall fall within the protection scope of the present invention.
Claims (10)
- 一种仿生结构抗菌微胶囊,其特征在于:包括芯材和包裹在芯材表面的胶囊壁材,所述胶囊壁材上具有贯穿孔结构,所述胶囊壁材的表面带负电。An antibacterial microcapsule with a bionic structure is characterized in that it includes a core material and a capsule wall material wrapped on the surface of the core material, the capsule wall material has a through-hole structure, and the surface of the capsule wall material is negatively charged.
- 根据权利要求1所述的一种仿生结构抗菌微胶囊,其特征在于,所述抗菌微胶囊呈球形或类球形,D50直径为0.8~10微米。The antibacterial microcapsule with bionic structure according to claim 1, characterized in that, the antibacterial microcapsule is spherical or spherical in shape, and the D50 diameter is 0.8-10 microns.
- 根据权利要求1所述的一种仿生结构抗菌微胶囊,其特征在于,所述胶囊壁材包裹芯材的内壳面亲油,所述胶囊壁材的外壳面亲水,所述芯材包括相变材料、脂溶性香精、植物精油、脂溶性维生素中的至少一种。A kind of antibacterial microcapsule of bionic structure according to claim 1, it is characterized in that, the inner shell surface of described capsule wall material wrapping core material is lipophilic, the outer shell surface of described capsule wall material is hydrophilic, and described core material comprises At least one of phase change materials, fat-soluble flavors, plant essential oils, and fat-soluble vitamins.
- 一种仿生结构抗菌微胶囊的制备方法,其特征在于,包括如下步骤:A preparation method of bionic structure antibacterial microcapsules, characterized in that it comprises the steps of:将芯材、硅烷偶联剂和单体混合形成第一混合物,将水相的复合乳化剂与第一混合物混合形成O/W乳液,调节O/W乳液的pH为2-4,在O/W乳液中加入引发剂并升温聚合形成抗菌微胶囊。Mix the core material, silane coupling agent and monomer to form the first mixture, mix the composite emulsifier of the water phase with the first mixture to form an O/W emulsion, adjust the pH of the O/W emulsion to 2-4, and adjust the pH of the O/W emulsion to 2-4. Initiator is added into the W emulsion and the temperature rises to polymerize to form antibacterial microcapsules.
- 根据权利要求4所述的一种仿生结构抗菌微胶囊的制备方法,其特征在于,在调节O/W乳液的pH为2-4后,先经4h-8h形成具有第一层壳的第二混合物,再将第二混合物升温至60-80℃并加入引发剂,恒温5h-12h,聚合形成第二层壳,得到抗菌微胶囊。The preparation method of a kind of biomimetic structure antibacterial microcapsule according to claim 4, is characterized in that, after adjusting the pH of O/W emulsion to be 2-4, first forms the second shell with first layer through 4h-8h the mixture, and then raise the temperature of the second mixture to 60-80°C, add an initiator, keep the temperature constant for 5h-12h, polymerize to form a second layer of shell, and obtain antibacterial microcapsules.
- 根据权利要求4所述的一种仿生结构抗菌微胶囊的制备方法,其特征在于,所述芯材包括相变材料、脂溶性香精、植物精油、脂溶性维生素中的至少一种;A method for preparing antibacterial microcapsules with a bionic structure according to claim 4, wherein the core material includes at least one of phase change materials, fat-soluble essences, plant essential oils, and fat-soluble vitamins;所述硅烷偶联剂包括氨丙基三甲氧基硅烷、氨丙基三乙氧基硅 烷、苯基三乙氧基硅烷、3-(甲基丙烯酰氧)丙基三甲氧基硅烷、正硅酸四乙酯、正硅酸四甲酯中的至少2种;The silane coupling agent includes aminopropyltrimethoxysilane, aminopropyltriethoxysilane, phenyltriethoxysilane, 3-(methacryloxy)propyltrimethoxysilane, orthosilane At least two of tetraethyl orthosilicate and tetramethyl orthosilicate;所述单体包括苯乙烯、二乙烯基苯、丙烯酸酯类单体、丙烯酸类单体、二异氰酸酯类预聚物中的至少一种;The monomers include at least one of styrene, divinylbenzene, acrylate monomers, acrylic monomers, and diisocyanate prepolymers;所述复合乳化剂为阴离子表面活性剂和非离子表面活性剂的组合物。The compound emulsifier is a combination of anionic surfactant and nonionic surfactant.
- 根据权利要求6所述的一种仿生结构抗菌微胶囊的制备方法,其特征在于,所述复合乳化剂包括聚乙烯-马来酸酐共聚物或其水解盐、聚苯乙烯-马来酸酐共聚物或其水解盐、环氧树脂和聚乙二醇的嵌段共聚物、十二烷基硫酸钠、十二烷基苯磺酸钠、失水山梨醇单油酸酯聚氧乙烯醚、脂肪醇聚氧乙烯醚、烷基酚聚氧乙烯醚、脂肪醇醇聚氧丙烯醚、甘油单脂肪酸酯、聚氧乙烯失水山梨醇脂肪酸酯、失水山梨醇脂肪酸酯和/或脂肪酸季戊四醇酯中的至少一种。The preparation method of a kind of bionic structure antibacterial microcapsule according to claim 6, is characterized in that, described composite emulsifier comprises polyethylene-maleic anhydride copolymer or its hydrolyzed salt, polystyrene-maleic anhydride copolymer or its hydrolyzed salt, block copolymer of epoxy resin and polyethylene glycol, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sorbitan monooleate polyoxyethylene ether, fatty alcohol Polyoxyethylene ethers, alkylphenol polyoxyethylene ethers, fatty alcohol polyoxypropylene ethers, glycerol monofatty acid esters, polyoxyethylene sorbitan fatty acid esters, sorbitan fatty acid esters and/or fatty acid pentaerythritol at least one of esters.
- 根据权利要求7所述的一种仿生结构抗菌微胶囊的制备方法,其特征在于,各组分的重量份包括:芯材25-60份、硅烷偶联剂0.6-8份、单体1.2-10份和复合乳化剂0.19-3份。The preparation method of a kind of bionic structure antibacterial microcapsule according to claim 7, is characterized in that, the weight portion of each component comprises: core material 25-60 parts, silane coupling agent 0.6-8 part, monomer 1.2- 10 parts and 0.19-3 parts of compound emulsifier.
- 一种抗菌产品,其特征在于,其上含有如权利要求1-4任一权利要求所述的仿生结构抗菌微胶囊或其上含有如权利5-9任一权利要求所述的制备方法制备得到的抗菌微胶囊。An antibacterial product, characterized in that it contains the biomimetic structure antibacterial microcapsules as described in any one of claims 1-4 or contains the preparation method as described in any one of claims 5-9. antibacterial microcapsules.
- 仿生结构抗菌微胶囊在食品、药物的运输或储藏、纺织品或化妆品中的应用,所述抗菌微胶囊为权利要求1-4任一权利要求所述的仿生结构抗菌微胶囊或为权利5-9任一权利要求所述的制备方法 制备得到的抗菌微胶囊。Application of bionic structure antibacterial microcapsules in transportation or storage of food, medicine, textiles or cosmetics, the antibacterial microcapsules are the bionic structure antibacterial microcapsules described in any one of claims 1-4 or claim 5-9 The antibacterial microcapsule prepared by the preparation method described in any claim.
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