CN113662861A - Antibacterial material and preparation method and application thereof - Google Patents
Antibacterial material and preparation method and application thereof Download PDFInfo
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- CN113662861A CN113662861A CN202110852591.5A CN202110852591A CN113662861A CN 113662861 A CN113662861 A CN 113662861A CN 202110852591 A CN202110852591 A CN 202110852591A CN 113662861 A CN113662861 A CN 113662861A
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- antibacterial agent
- antibacterial material
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- 239000000463 material Substances 0.000 title claims abstract description 60
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000010146 3D printing Methods 0.000 claims abstract description 13
- 239000003242 anti bacterial agent Substances 0.000 claims description 30
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 27
- 239000002994 raw material Substances 0.000 claims description 18
- 238000001723 curing Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 239000000178 monomer Substances 0.000 claims description 11
- 239000011521 glass Substances 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 9
- 238000000465 moulding Methods 0.000 claims description 9
- 239000002270 dispersing agent Substances 0.000 claims description 5
- 239000000945 filler Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000009736 wetting Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 239000000049 pigment Substances 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 239000005388 borosilicate glass Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 239000005365 phosphate glass Substances 0.000 claims description 2
- 239000005360 phosphosilicate glass Substances 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 230000000845 anti-microbial effect Effects 0.000 claims 5
- 238000005516 engineering process Methods 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 210000000214 mouth Anatomy 0.000 abstract description 4
- 230000036541 health Effects 0.000 abstract description 3
- 241000894006 Bacteria Species 0.000 description 18
- 239000011347 resin Substances 0.000 description 13
- 229920005989 resin Polymers 0.000 description 13
- 239000004599 antimicrobial Substances 0.000 description 9
- 229910052709 silver Inorganic materials 0.000 description 6
- 239000004332 silver Substances 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 5
- 238000007639 printing Methods 0.000 description 5
- 230000001954 sterilising effect Effects 0.000 description 5
- 238000004659 sterilization and disinfection Methods 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- -1 Silver ions Chemical class 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- 238000000016 photochemical curing Methods 0.000 description 3
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-UHFFFAOYSA-N 0.000 description 2
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000010718 Oxidation Activity Effects 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 210000002421 cell wall Anatomy 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 210000003296 saliva Anatomy 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- MUTNCGKQJGXKEM-UHFFFAOYSA-N tamibarotene Chemical compound C=1C=C2C(C)(C)CCC(C)(C)C2=CC=1NC(=O)C1=CC=C(C(O)=O)C=C1 MUTNCGKQJGXKEM-UHFFFAOYSA-N 0.000 description 2
- 239000003440 toxic substance Substances 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- YDIYEOMDOWUDTJ-UHFFFAOYSA-N 4-(dimethylamino)benzoic acid Chemical compound CN(C)C1=CC=C(C(O)=O)C=C1 YDIYEOMDOWUDTJ-UHFFFAOYSA-N 0.000 description 1
- XVZXOLOFWKSDSR-UHFFFAOYSA-N Cc1cc(C)c([C]=O)c(C)c1 Chemical group Cc1cc(C)c([C]=O)c(C)c1 XVZXOLOFWKSDSR-UHFFFAOYSA-N 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- NQSMEZJWJJVYOI-UHFFFAOYSA-N Methyl 2-benzoylbenzoate Chemical compound COC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 NQSMEZJWJJVYOI-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002567 autonomic effect Effects 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical compound [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000005548 dental material Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000002147 killing effect Effects 0.000 description 1
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- RZFODFPMOHAYIR-UHFFFAOYSA-N oxepan-2-one;prop-2-enoic acid Chemical compound OC(=O)C=C.O=C1CCCCCO1 RZFODFPMOHAYIR-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
- A61K6/887—Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/70—Preparations for dentistry comprising inorganic additives
- A61K6/71—Fillers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/70—Preparations for dentistry comprising inorganic additives
- A61K6/71—Fillers
- A61K6/77—Glass
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
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- Health & Medical Sciences (AREA)
- Oral & Maxillofacial Surgery (AREA)
- General Health & Medical Sciences (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Plastic & Reconstructive Surgery (AREA)
- Dental Preparations (AREA)
- Dental Prosthetics (AREA)
Abstract
The invention discloses an antibacterial material and a preparation method and application thereof. The temporary crown made of the antibacterial material through a 3D printing technology has the advantages of low labor cost, short manufacturing period, high precision and the like, and meanwhile, the temporary crown has the autonomous antibacterial performance, maintains the health in the oral cavity and is stable in color.
Description
Technical Field
The invention relates to the technical field of dental materials and 3D printing and forming, in particular to an antibacterial material and a preparation method and application thereof.
Background
3D printing is a rapid prototyping additive manufacturing technology, and constructs an object by increasing printing materials layer by layer based on a three-dimensional digital model. The 3D printing technology can be combined with personalized design to manufacture various complex morphological structures, and personalized requirements are met. The basic principle of photocuring molding printing is that a light source is controlled through a digital signal, so that photosensitive resin materials are printed and molded point by point or layer by layer in a superposed mode according to a preset shape, and the photocuring molding printing method has the characteristics of easiness in operation, low cost, high precision, high efficiency and the like. The raw materials of the light-cured material mainly comprise a reactive diluent or a monomer, a light-cured resin, a cross-linking agent, a photoinitiator and the like.
In the dental field, a temporary crown, also called a temporary crown, is a temporary full crown that is temporarily bonded in a patient's mouth after preparation of a tooth body for crown restoration and before final crown restoration is completed, and the patient cannot freely take and wear the temporary crown. Since saliva in the oral cavity contains various bacteria, when the temporary crown is worn in the oral cavity, the surface of the temporary crown is not tightly bonded, so that a gap is formed, saliva is retained, and bacteria are easy to grow in the gap. The growth of bacteria not only affects the performance of the temporary crown worn, but also affects the oral health.
The existing temporary crown preparation raw materials mainly comprise various plastic resins, a large amount of manual molding is needed, and the defects of high early-stage input cost, long manufacturing period, high labor cost, low efficiency, general precision and the like exist. At present, the 3D printing photocuring material which is applied to the temporary dental crown and has the antibacterial effect and the application process thereof are rarely reported. Most of the existing 3D printing material systems are used for non-human body contact scenes such as model making and the like, and the sterilization requirements of the dental temporary crown are difficult to meet. The sterilization performance of the 3D printing material in contact with the human body can be achieved by adding an inorganic antibacterial agent. Common inorganic antimicrobial agents include various noble metal inorganic antimicrobial agents, such as silver-based antimicrobial agents. However, silver-based antibacterial agents have disadvantages of being easily discolored, difficult to manufacture, and complicated in material use process. Silver ions dissociated from the material have no photocatalytic activity, can not degrade bacterial metabolites, can be easily reduced into simple substance silver to be gray or brown under the irradiation of sunlight or after being heated to a certain temperature, influence the appearance effect of the temporary crown, and simultaneously, the cost of the silver antibacterial agent is always high due to the rare and noble silver raw materials.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides an antibacterial material which has good antibacterial performance and is stable to resin color.
Meanwhile, the invention also provides a preparation method and application of the antibacterial material.
Specifically, the invention adopts the following technical scheme:
the invention provides an antibacterial material, which is prepared from raw materials including an antibacterial agent, a prepolymer, an active monomer and an initiator, wherein the antibacterial agent comprises a transparent glass carrier and zinc ions loaded in the glass carrier.
The antibacterial material according to the first aspect of the present invention has at least the following advantageous effects:
the material of the glass carrier loaded with zinc ions is used as the antibacterial agent, the transparency is good, the antibacterial agent can slowly release the zinc ions, free active zinc ions have no influence on the color of resin formed by the reaction of the prepolymer, the active monomer and the initiator, and the color stability of the resin is not influenced. Meanwhile, zinc ions are easily adsorbed on the surface of bacteria, so that the electrolyte balance of the bacteria is destroyed, and the bacteria die due to cell wall damage; simultaneously enter the interior of the bacteria to inhibit the activity of cell enzyme and the reproduction and regeneration of the bacteria; in addition, under the illumination condition, zinc ions and-OH and H adsorbed on the surface of the material2O and O2Iso-reaction to produce O2-、H2O2And OH-The groups with strong oxidation activity can not only decompose the components of the microorganism to achieve the purpose of sterilization, but also can degrade toxic substances generated by the bacteria. Therefore, the material with the glass carrier loaded with zinc ions is used as the antibacterial agent, so that the antibacterial resin has a good antibacterial effect and cannot influence the color stability of the resin.
In some embodiments of the invention, the glass comprises phosphosilicate glass, borosilicate glass, phosphate glass, and the like. The preparation method of the antibacterial agent comprises the steps of fully mixing oxides (zinc oxide, silicon oxide, aluminum oxide and the like), phosphates (sodium phosphate, potassium phosphate, calcium phosphate and the like), or borates (sodium borate, potassium borate and the like), silicates (sodium silicate, potassium silicate and the like) and hydroxides (sodium hydroxide, potassium hydroxide and the like), then melting at the high temperature of 900-1300 ℃, quenching to obtain sheet-shaped or block-shaped glass, and finally physically crushing to obtain powder with required particle size, thus obtaining the antibacterial agent.
In some embodiments of the invention, the antimicrobial agent has a zinc mass loading of 0.1% to 0.5%.
In some embodiments of the invention, the antimicrobial agent is a commercial zinc ion antimicrobial agent, including CBM type zinc ion antimicrobial agents of HOLPOSON, iHeir-IP (001) zinc ion antimicrobial agents, iHeir-ZPT zinc ion antimicrobial agents.
In some embodiments of the present invention, the antibacterial material comprises the following preparation raw materials in parts by mass:
0.1 to 0.5 portion of antibacterial agent
20-50 parts of prepolymer
20-80 parts of active monomer
1-5 parts of an initiator.
In some embodiments of the present invention, the raw materials for preparing the antibacterial material further include pigments, fillers, auxiliaries, and the like, wherein the auxiliaries include wetting dispersants, stabilizers, impact resistance agents, and the like, and preferably include wetting dispersants.
In some embodiments of the present invention, the antibacterial material comprises the following preparation raw materials in parts by mass:
0.1 to 0.5 portion of antibacterial agent
20-50 parts of prepolymer
20-80 parts of active monomer
1-5 parts of initiator
1-10 parts of pigment and filler
0.05-0.1 part of an auxiliary agent.
In some embodiments of the present invention, the prepolymer is a macromolecular prepolymer having a molecular weight of 10000 to 100000.
In some embodiments of the invention, the prepolymer comprises one or more of newebecryl 8412, yokol FSP8054, sabomoma Ebecry8311, EBLEO10801, sabomoma CN307, CNUVE151 NS, SB 400.
In some embodiments of the invention, the reactive monomer is a photocurable reactive monomer comprising one or more of 9-ethoxylated trimethylolpropane triacrylate (EO9-TMPTA), 2- (propoxylated) neopentyl glycol diacrylate (npg (PO)2DA), ethoxylated trimethylolpropane triacrylate (EO3-TMPTA), propoxylated trimethylolpropane triacrylate (PO3-TMPTA), tetrahydrofurfuryl acrylate (THFA), ethylene glycol isooctyl ether monoacrylate, hydroxyl terminated caprolactone acrylate.
In some embodiments of the invention, the initiator comprises a photoinitiator comprising one or more of the photoinitiator poly (ethylene glycol) bis (p-dimethylaminobenzoate) (ASA), the photoinitiator Isopropyl Thioxanthone (ITX), the photoinitiator methyl benzoylbenzoate (OMBP), the photoinitiator 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone (369), the photoinitiator phenylbis (2,4, 6-trimethylbenzoyl) oxidation (819).
In some embodiments of the invention, the color filler comprises one or more of titanium white, chrome yellow, iron blue, cadmium red, cadmium yellow, lithopone, carbon black, iron oxide red, iron oxide yellow, and the like.
In some embodiments of the invention, the wetting and dispersing agent comprises a polyether phosphate such as digaTEGO Dispers 655.
The second aspect of the present invention provides a method for preparing the above antibacterial material, comprising the following steps: and mixing the prepared raw materials, and stirring to obtain the antibacterial material.
In some embodiments of the invention, the stirring temperature is 25-50 ℃ and the stirring time is 30-45 ℃.
The third aspect of the invention is to provide the application of the antibacterial material in the preparation of temporary crowns.
The invention also provides a preparation method of the temporary crown, which comprises the following steps: the antibacterial material is used as a raw material, and is subjected to primary curing molding and secondary curing to obtain the temporary crown.
Generally, the mechanical property of the antibacterial material after primary curing can not meet the requirement, and the mechanical property of the temporary crown is improved by carrying out deep curing through secondary curing.
In some embodiments of the present invention, the one-shot curing molding method is 3D printing, and the 3D printing includes, but is not limited to, SLA stereolithography, DLP data optical processing technology, LCD liquid crystal display molding technology, and the like.
In some embodiments of the present invention, the wavelength of the light source used in the secondary curing process is 385-405 nm, and the time of the secondary curing is 10 min.
Further, after printing is completed, before secondary curing is performed, it is necessary to remove residual resin attached to the surface of the temporary crown print, which includes, but is not limited to, spin-drying, washing, and the like. The cleaning operation may be selected according to the type of the material, and isopropyl alcohol, alcohol or water may be used.
Compared with the prior art, the invention has the following beneficial effects:
the material of the glass carrier loaded with zinc ions is used as the antibacterial agent, the transparency is good, the antibacterial agent can slowly release the zinc ions, free active zinc ions have no influence on the color of resin formed by the reaction of the prepolymer, the active monomer and the initiator, and the color stability of the resin is not influenced; and the antibacterial component is stable, and the antibacterial effect is long in duration. The addition rate is low, a good antibacterial effect can be achieved generally when the mass addition rate is more than 0.1%, and the antibacterial detection requirement can be achieved only by one to five thousandths of the addition amount. The detection shows that the antibacterial material of the invention has no harm to human body and environment.
The temporary crown material is added with a zinc ion antibacterial agent to play roles in killing bacteria and inhibiting the growth of the bacteria. The zinc ion antibacterial agent is a broad-spectrum antibacterial agent with inorganic zinc ion compound as an active component. The method is mainly used for protecting resin system products from being corroded by microorganisms such as bacteria and the like and providing antibacterial effect on the surfaces of the products. The zinc ion antibacterial agent can slowly release zinc ions, and the zinc ions are adsorbed on the surface of bacteria to destroy the electrolyte balance of the bacteria, so that the bacteria die due to the damaged cell walls. The zinc ions enter the bacteria simultaneously, inhibit the activity of cell enzyme and the reproduction and regeneration of the bacteria, and simultaneously, the zinc ions and-OH and H adsorbed on the surface of the material under the illumination condition2O and O2Iso-reaction to produce O2-、H2O2And OH-The groups with strong oxidation activity can not only decompose the components of the microorganism to achieve the purpose of sterilization, but also can degrade toxic substances generated by the bacteria. Compared with other precious metal antibacterial agents, the zinc ions have lower cost and do not influence the color stability of the resin.
Make antibiotic material into interim hat through 3D printing technique, have that the cost of labor is low, the preparation cycle is short, advantages such as precision height, interim hat has autonomic antibiotic performance simultaneously, maintains the oral health, and the colour is stable.
Drawings
Fig. 1 is a real object diagram of a temporary crown product printed with the antibacterial material of example 1.
Detailed Description
The technical solution of the present invention is further described below with reference to specific examples. The starting materials used in the following examples, unless otherwise specified, are available from conventional commercial sources; the processes used, unless otherwise specified, are conventional in the art.
An antibacterial material is prepared from the following raw materials in the following table 1:
TABLE 1 preparation raw material ratio (mass fraction) of antibacterial material
Mixing the raw material components according to the mass fraction ratio, and then stirring for 45min at 30 ℃ to obtain the required antibacterial material. Printing and molding the antibacterial material by adopting a DLP data light processing technology, and then performing post-curing in a curing box with a band light source of 385-405 nm to obtain a temporary crown finished product which is milky yellow as shown in figure 1.
The antibacterial materials of the embodiments 1-3 are printed into standard sample strips by a DLP printer, the prepared sample strips are subjected to mechanical property test by referring to ASTM D638, ASTM D790 and ASTM D2240 respectively, and the antibacterial property test of Escherichia coli is performed by referring to GB/B31402-. The results are shown in table 2 below.
TABLE 2 test results of mechanical and antibacterial properties
| Item | Example 1 | Example 2 | Example 3 |
| Tensile Strength (MPa) | 38.33 | 35.25 | 34.44 |
| Flexural strength (Mpa) | 66.84 | 65.2 | 62.51 |
| Notched impact resistance (J/m)2) | 29.3 | 27.3 | 26 |
| Hardness (shore D) | 82 | 84 | 83 |
| Rate of sterilization | 95.6％ | 96.6％ | 97.2％ |
In addition, the antibacterial materials of examples 1-3 were printed into A, B, C color squares using a DLP printer, and color stability was tested according to the formulation of metrology JJJG 595-2002.
TABLE 3 color stability test results
According to the test results in table 2, the finished products of the antibacterial materials of examples 1-3 after 3D printing have good mechanical properties and antibacterial effects. Generally, when the color difference value Δ E is 1 or less, the human eye does not feel a significant color difference. Table 3 shows that the difference in color Δ E after a long-term standing of the antibacterial materials of examples 1 to 3 was 0.6 or less, which was not noticeable to the human eye, reflecting that the antibacterial materials of examples 1 to 3 had excellent color stability. Meanwhile, the color difference values in table 3 also reflect that the color difference values change greatly just after the curing is finished, which is mainly that yellowing occurs just after the curing is finished; as the standing time is increased, the yellowing and fading are realized, the color difference value is reduced, and the color is gradually stabilized.
Comparative example 1
This comparative example differs from example 1 in that the zinc ion antibacterial agent was replaced with a commercial silver ion antibacterial agent. As a result, the obtained antibacterial material became black after being left for 1 month after 3D printing.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. An antibacterial material, characterized in that: the antibacterial material is prepared from raw materials including an antibacterial agent, a prepolymer, an active monomer and an initiator, wherein the antibacterial agent comprises a transparent glass carrier and zinc ions loaded in the glass carrier.
2. The antimicrobial material of claim 1, wherein: the glass comprises at least one of phosphosilicate glass, borosilicate glass, and phosphate glass.
3. The antimicrobial material of claim 2, wherein: in the antibacterial agent, the mass loading of zinc is 0.1-0.5%.
4. The antimicrobial material of claim 3, wherein: the antibacterial agent comprises at least one of CBM type zinc ion antibacterial agent, iHeir-IP (001) zinc ion antibacterial agent and iHeir-ZPT zinc ion antibacterial agent.
5. The antibacterial material according to any one of claims 1 to 4, wherein: the antibacterial material comprises the following preparation raw materials in parts by mass:
0.1 to 0.5 portion of antibacterial agent
20-50 parts of prepolymer
20-80 parts of active monomer
1-5 parts of an initiator.
6. The antimicrobial material of claim 5, wherein: the raw materials for preparing the antibacterial material also comprise pigments, fillers and auxiliaries; preferably, the auxiliary agent comprises at least one of wetting dispersant, stabilizer and impact resistant agent, and preferably comprises wetting dispersant.
7. The antimicrobial material of claim 6, wherein: the antibacterial material comprises the following preparation raw materials in parts by mass:
0.1 to 0.5 portion of antibacterial agent
20-50 parts of prepolymer
20-80 parts of active monomer
1-5 parts of initiator
1-10 parts of pigment and filler
0.05-0.1 part of an auxiliary agent.
8. A method for preparing the antibacterial material according to any one of claims 1 to 7, characterized in that: the method comprises the following steps: and mixing the prepared raw materials, and stirring to obtain the antibacterial material.
9. Use of the antibacterial material according to any one of claims 1 to 7 for the preparation of temporary crowns.
10. A method for preparing a temporary crown is characterized by comprising the following steps: the method comprises the following steps: taking the antibacterial material as claimed in any one of claims 1 to 7 as a raw material, carrying out primary curing molding, and then carrying out secondary curing to obtain a temporary crown; preferably, the one-time curing molding method is 3D printing.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105246929A (en) * | 2014-01-13 | 2016-01-13 | 顶科股份有限公司 | Photo-curable resin compositions and method of using the same in three-dimensional printing for manufacturing artificial teeth and denture base |
| CN108329437A (en) * | 2017-10-23 | 2018-07-27 | 同济大学 | A kind of 3D printing UV curing antibiotic material and preparation method thereof |
| CN110787066A (en) * | 2019-10-24 | 2020-02-14 | 深圳永昌和科技有限公司 | Dental 3D printing antibacterial material and preparation method thereof |
| WO2020042669A1 (en) * | 2018-08-31 | 2020-03-05 | 深圳市绎立锐光科技开发有限公司 | Antimicrobial photocuring 3d printing material and preparation method therefor and 3d printing device |
| CN112043608A (en) * | 2020-09-11 | 2020-12-08 | 无锡市腰果新材料有限公司 | DLP type 3D printing photocuring material for clinical dentistry |
| CN112353694A (en) * | 2020-11-06 | 2021-02-12 | 无锡市腰果新材料有限公司 | Dlp type 3d printing photocureable material for clinical dental temporary crown |
-
2021
- 2021-07-27 CN CN202110852591.5A patent/CN113662861B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105246929A (en) * | 2014-01-13 | 2016-01-13 | 顶科股份有限公司 | Photo-curable resin compositions and method of using the same in three-dimensional printing for manufacturing artificial teeth and denture base |
| CN108329437A (en) * | 2017-10-23 | 2018-07-27 | 同济大学 | A kind of 3D printing UV curing antibiotic material and preparation method thereof |
| WO2020042669A1 (en) * | 2018-08-31 | 2020-03-05 | 深圳市绎立锐光科技开发有限公司 | Antimicrobial photocuring 3d printing material and preparation method therefor and 3d printing device |
| CN110787066A (en) * | 2019-10-24 | 2020-02-14 | 深圳永昌和科技有限公司 | Dental 3D printing antibacterial material and preparation method thereof |
| CN112043608A (en) * | 2020-09-11 | 2020-12-08 | 无锡市腰果新材料有限公司 | DLP type 3D printing photocuring material for clinical dentistry |
| CN112353694A (en) * | 2020-11-06 | 2021-02-12 | 无锡市腰果新材料有限公司 | Dlp type 3d printing photocureable material for clinical dental temporary crown |
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Application publication date: 20211119 Assignee: WUXI YAOGUO NEW MATERIAL CO.,LTD. Assignor: GUANGZHOU HEYGEARS IMC. Inc. Contract record no.: X2024980003915 Denomination of invention: An antibacterial material and its preparation method and application Granted publication date: 20230519 License type: Common License Record date: 20240403 |
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