CN105708713A - Pit and fissure sealing agent for dentistry and preparation method thereof - Google Patents
Pit and fissure sealing agent for dentistry and preparation method thereof Download PDFInfo
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- CN105708713A CN105708713A CN201610141807.6A CN201610141807A CN105708713A CN 105708713 A CN105708713 A CN 105708713A CN 201610141807 A CN201610141807 A CN 201610141807A CN 105708713 A CN105708713 A CN 105708713A
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- fissure sealant
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- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 238000007789 sealing Methods 0.000 title abstract 4
- 239000011347 resin Substances 0.000 claims abstract description 72
- 229920005989 resin Polymers 0.000 claims abstract description 72
- 239000000945 filler Substances 0.000 claims abstract description 43
- 238000002156 mixing Methods 0.000 claims abstract description 21
- 239000003085 diluting agent Substances 0.000 claims abstract description 18
- 230000001476 alcoholic effect Effects 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 239000000068 pit and fissure sealant Substances 0.000 claims description 73
- 239000011230 binding agent Substances 0.000 claims description 49
- 239000000203 mixture Substances 0.000 claims description 23
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 22
- 238000011049 filling Methods 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 16
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 claims description 11
- -1 PEG400 modified urethane Chemical class 0.000 claims description 11
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 11
- 238000012856 packing Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 8
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 7
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052788 barium Inorganic materials 0.000 claims description 6
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 6
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical group COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 claims description 6
- 238000002444 silanisation Methods 0.000 claims description 5
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 claims description 4
- QLIBJPGWWSHWBF-UHFFFAOYSA-N 2-aminoethyl methacrylate Chemical compound CC(=C)C(=O)OCCN QLIBJPGWWSHWBF-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 229930006711 bornane-2,3-dione Natural products 0.000 claims description 4
- 235000011837 pasties Nutrition 0.000 claims description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- SKDGWNHUETZZCS-UHFFFAOYSA-N 2,3-ditert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(O)=C1C(C)(C)C SKDGWNHUETZZCS-UHFFFAOYSA-N 0.000 claims 1
- 239000000178 monomer Substances 0.000 abstract description 26
- 238000000034 method Methods 0.000 abstract description 19
- 238000006116 polymerization reaction Methods 0.000 abstract description 14
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 239000012620 biological material Substances 0.000 abstract description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract 2
- 238000012360 testing method Methods 0.000 description 16
- 239000000243 solution Substances 0.000 description 11
- 239000000805 composite resin Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- AMFGWXWBFGVCKG-UHFFFAOYSA-N Panavia opaque Chemical compound C1=CC(OCC(O)COC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OCC(O)COC(=O)C(C)=C)C=C1 AMFGWXWBFGVCKG-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 230000008901 benefit Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000011256 inorganic filler Substances 0.000 description 6
- 229910003475 inorganic filler Inorganic materials 0.000 description 6
- 238000007711 solidification Methods 0.000 description 6
- 230000008023 solidification Effects 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- 208000002925 dental caries Diseases 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 229940106691 bisphenol a Drugs 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 230000001976 improved effect Effects 0.000 description 2
- 239000010954 inorganic particle Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 210000000214 mouth Anatomy 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 238000013268 sustained release Methods 0.000 description 2
- 239000012730 sustained-release form Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000000675 anti-caries Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001013 cariogenic effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 230000003670 easy-to-clean Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000320 mechanical mixture Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 230000036314 physical performance Effects 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 210000003296 saliva Anatomy 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/15—Compositions characterised by their physical properties
- A61K6/19—Self-expanding, e.g. for filling teeth
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/60—Preparations for dentistry comprising organic or organo-metallic additives
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/60—Preparations for dentistry comprising organic or organo-metallic additives
- A61K6/62—Photochemical radical initiators
-
- 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
- A61K6/76—Fillers comprising silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
Landscapes
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Epidemiology (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Biophysics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dental Preparations (AREA)
Abstract
The invention relates to a pit and fissure sealing agent for dentistry and a preparation method thereof, and belongs to the field of medical biological materials. The pit and fissure sealing agent for dentistry is prepared from 5-50wt% of filler and 50-95wt% of base resin, wherein the average grain diameter of the filler is 0.010-0.120 micrometer, the content of filter with the grain diameter larger than 0.120 micrometer is smaller than 50wt%, and the base resin is composed of PEGUDMA, DIAUDMA, diluent and photoinitiator. The pit and fissure sealing agent is prepared by mixing a nanometer zirconia alcoholic solution and the resin monomer through a solvent removal method; by means of the method, the nanometer filler can be more evenly dispersed in the resin monomer, and the content of the nanometer filler can be greatly increased without affecting product flowability, so that the mechanical strength of the product is enhanced (the compressive strength is at least 200 MPa), and the polymerization shrinkage rate is reduced to be smaller than 5%.
Description
Technical field
The present invention relates to a kind of dental pit and fissure sealant and preparation method thereof, belong to biomaterial for medical purpose field.
Background technology
The principle of fissure blockade prevention pit and fissure caries is with macromolecular material, the nest ditch of tooth to be filled and led up, and makes facing become smooth easy to clean, on the one hand, after fissure blockade, in nest ditch, original antibacterial has broken off the source of nutrition, dead gradually；The cariogenic antibacterial of outside can not enter back on the other hand, thus reaching the purpose of prevention pit and fissure caries.The closed material that fissure blockade uses is called pit and fissure sealant, with furrow bank close adhesion after its solidification, and has certain anti-masticatory pressure, feed is not hindered, and nontoxic after pit and fissure sealant solidification, harmless.Sealer generally can retain for a long time.
The pit and fissure sealant being widely used at present mainly has two types, namely self-solidifying curing type is (after coating, in 1-2 minute, the effect of catalyzed dose, material polymerizing curable) and visible light curable (being irradiated 30 seconds by the light of certain wavelength, namely curable), both anti-caries effect difference are little, from Clinical practice angle contrast, it is seen that light-cured type clinician's more convenient operation, it it is pit and fissure sealant conventional at present.
Current pit and fissure sealant major problem is that, in order to ensure that it has good mobility, generally makes the inorganic filler amount in pit and fissure sealant reduce, but the minimizing of amount of filler causes again, and pit and fissure sealant shrinkage factor when solidifying increases, mechanical strength reduces.How to make mobility that pit and fissure sealant not only had but also there is low cure shrinkage and higher mechanical strength is always up a study hotspot simultaneously.
Fissure blockade agent material is a kind of is the macromolecule composite resin mainly comprised by inorganic fillers and resinous substrates.Wherein, resinous substrates is the main part in composite resin, is generally made up of the bigger monomer (viscosity monomer) of viscosity and oligomer (including performed polymer, cross-linking monomer) and diluent (diluting monomer) etc..It is as the continuous phase of inorganic filler, under the effect of initiator, it is possible to curing molding in the at room temperature shorter time, and gives the certain physical and mechanical properties of material and clinical manipulation performance.Wherein performed polymer is most important ingredient, is not only related to the color and luster of resin, and affects processing characteristics, physical and chemical performance.
Although on domestic and international market, general gear division pit and fissure sealant substrate mostly uses Bis-GMA at present, but the adhesion strength of tooth is not as big by it, and viscosity is high, polymerisation conversion is low, and service life is not long, and resistance to water is poor simultaneously, under the long term of saliva of buccal cavity, dissolving is easily occurred to come off.And it contains bisphenol-A, its bio-safety performance need to be further characterized by.
Owing to Bis-GMA viscosity is relatively big, not easily operate, it is therefore desirable to add diluting monomer and play its operating characteristics of diluent improved effect.Diluting monomer not only plays diluent effect, can also participate in reaction simultaneously and use as a kind of cross-linking agent.But it is short all to there is storage period in current used diluent, easy to change, the shortcomings such as polymerisation conversion is low, polymerization shrinkage is big.And TEGDMA widely used at present or a kind of combination property are better, for a kind of diluent that producer is widely used.But its storage period is still short than the storage period of Bis-GMA resinoid monomer, polymerisation conversion is low, and its adhesion strength is not high yet simultaneously.
Although the basic components of pit and fissure sealant is grasped by people, but dispersed very difficult in high viscosity monomer of ultra micro inorganic filler, cause that pit and fissure sealant shrinkage factor when solidifying increases, mechanical strength reduces.
Summary of the invention
For the deficiencies in the prior art, it is an object of the invention to provide a kind of dental pit and fissure sealant, this material is a kind of tooth fissure blockade compositions, wherein being mixed with homodisperse ultra-fine enhancing granule, this granule shows high intensity, sustained release fluorion, good wearability, low polymerization shrinkage in Clinical practice.
The preparation method that it is a further object of the present invention to provide above-mentioned dental pit and fissure sealant, blended with nano zircite alcoholic solution and resin monomer, the method that removal of solvents and filler combine with resin monomer mechanical mixture prepares pit and fissure sealant, compared to only preparing pit and fissure sealant by inorganic filler and this conventional method of resin monomer mechanical blending, the method can make Nano filling in resin monomer scattered evenly, the content of Nano filling can be greatly increased when not affecting product mobility, thus strengthening the mechanical strength of pit and fissure sealant, reduce the polymerization shrinkage of pit and fissure sealant.
For achieving the above object, the present invention is by the following technical solutions:
A kind of dental pit and fissure sealant, it includes following two material by weight percentage:
Filler, content is 5-50wt%, mean diameter is 0.010-0.120 μm (0.02 μm, 0.05 μm, 0.08 μm, 0.10 μm)；In described filler, the particle diameter filer content more than 0.120 μm is less than 50wt%；
Binder resin, content is 50-95wt%, described binder resin is composed of the following components: PEG400 modified urethane double methyl methacrylate (PEG400ExtendedUrethaneDimethacrylate, be called for short PEGUDMA), dimeric dibasic acid carbamate double methyl methacrylate (DimerAcidUrethaneDimethacrylate, be called for short DIAUDMA), diluent and light trigger.
Above-mentioned dental pit and fissure sealant, as a kind of preferred implementation, in described binder resin, with PEG400 modified urethane double methyl methacrylate (PEG400ExtendedUrethaneDimethacrylate, it is called for short PEGUDMA), dimeric dibasic acid carbamate double methyl methacrylate (DimerAcidUrethaneDimethacrylate, it is called for short DIAUDMA), diluent and light trigger are 100wt% meter, the content of PEG400 modified urethane double methyl methacrylate and dimeric dibasic acid carbamate double methyl methacrylate is 84-99wt%；The content of diluent is 0-15wt%；The content of light trigger is 1.0-2.5wt%.It is highly preferred that the mass ratio of described PEG400 modified urethane double methyl methacrylate (PEGUDMA) and described dimeric dibasic acid carbamate double methyl methacrylate (DIAUDMA) is 0.4-2.5:1 (such as 0.5:1,0.7:1,1:1,1.5:1,2:1,2.2:1,2.4:1).The advantage of PEGUDMA is that intensity is high, and the advantage of DIAUDMA is that polymerization shrinkage is little, and the two mass ratio is maintained at above-mentioned scope and can realize both and preferably coordinate advantage.
Above-mentioned dental pit and fissure sealant, as a kind of preferred implementation, described diluent is hydroxyethyl methylacrylate (HEMA).
The present invention absorbs the experience that inventor is obtained in the R&D process of light-cured composite, adopt international state-of-the art resin modified monomer to replace the tackifying resin monomer in present pit and fissure sealant product, improve mobility and the intensity of resin monomer in pit and fissure sealant, reduce the polymerization shrinkage of resin monomer.The resinous substrates that specifically present invention adopts is PEGUDMA and DIAUDMA, because PEGUDMA has the polymerisation conversion of the mechanical strength higher than Bis-GMA, better biocompatibility and Geng Gao；DIAUDMA has more better biocompatibility than Bis-GMA, higher polymerisation conversion and less polymerization shrinkage；Additionally due to the viscosity of PEGUDMA and DIAUDMA is far below Bis-GMA, thus it is remarkably improved the amount of filler of pit and fissure sealant and does not affect its mobility.The present invention adopts hydroxyethyl methylacrylate (HEMA) as diluent, has storage period long, and dilution effect is good, adhesion strength advantages of higher, it is possible to improve the adhesive property of pit and fissure sealant.
Above-mentioned dental pit and fissure sealant, as a kind of preferred implementation, described light trigger is by N, N dimethylamine amino ethyl methacrylate, 2,6-toluene di-tert-butyl phenols and camphorquinone composition.
Above-mentioned dental pit and fissure sealant, as a kind of preferred implementation, in described filler, the percentage ratio of the filler weight that particle diameter > is 0.120 μm and filler gross weight is not higher than 10%.Because the more many anti-wear performances of bulky grain are more poor, oarse-grained content to be controlled.
Above-mentioned dental pit and fissure sealant, as a kind of preferred implementation, in described filler, the percentage ratio of particle diameter≤0.01 μm filler weight and filler gross weight is 1.0-10.0%.Because while the wearability of little granular filler is good, if but small particle content is too high, and the rupture strength of pit and fissure sealant can be very poor；In order to realize the equilibrium of pit and fissure sealant wearability and rupture strength, the filler mean diameter of the present invention to control 0.010-0.120 μm.
Above-mentioned dental pit and fissure sealant, described filler can be the inorganic particle such as Fluoridizing or untreated silicon oxide, aluminium oxide, aluminosilicate, titanium oxide, silanization barium aluminosilicate, as a kind of preferred implementation, described filler is the silanization barium aluminosilicate of Fluoridizing.
Above-mentioned dental pit and fissure sealant, as a kind of preferred implementation, possibly together with nano zircite in described dental pit and fissure sealant.Add nano zircite and can strengthen the abrasion resistance of pit and fissure sealant, such that it is able to increase pit and fissure sealant retention time in the oral cavity.It is highly preferred that in described dental pit and fissure sealant, the content of described filler is 5-50wt%；The content of described binder resin is 35-75wt%；The content of described nano zircite is 10-22wt%.Further, the mean diameter of described nano zircite is 5-10nm (such as 6nm, 7nm, 8nm, 9nm).
The preparation method of a kind of above-mentioned dental pit and fissure sealant, specifically includes following steps:
The preparation process of binder resin, is first according to said ratio and each component forming described binder resin is carried out mixed processing and obtain uniform binder resin；
Filling step, according to said ratio by described filling packing to described uniform binder resin, finally gives described dental pit and fissure sealant.
In above-mentioned preparation method, as a kind of preferred implementation, when in described dental pit and fissure sealant possibly together with nano zircite, the mixture preparation process of nano zircite and binder resin is also included between preparation process and the described filling step of described binder resin, in described binder resin, nano zircite alcoholic solution is added according to said ratio, mixing certain time, under light protected environment, finally it is dried removal alcohol solvent, thus obtaining the mixture of nano zircite and binder resin.More preferably, in the described nano zircite mixture preparation process with binder resin, the time of described mixing is 0.5-1.5h (such as 0.8h, 1.2h), the temperature of described mixing is 20-30 DEG C (such as 22 DEG C, 25 DEG C, 28 DEG C), described dries as 0.5-1.5h (such as 0.8h, 1.2h) dry under-0.1MPa in Rotary Evaporators.Further, the concentration of described nano zircite alcoholic solution is 15-25wt% (such as 16%, 18%, 21%, 23%, 24%).
In above-mentioned preparation method, as a kind of preferred implementation, in the preparation process of described binder resin, the time of described mixed processing is 20-40min (such as 25min, 28min, 32min, 35min, 38min), and the temperature of described mixed processing is 20-30 DEG C (such as 22 DEG C, 24 DEG C, 26 DEG C, 28 DEG C).
In above-mentioned preparation method, as a kind of preferred implementation, described filling step comprises the following specific steps that: described uniform binder resin or described nano zircite is joined in blender with the mixture of binder resin and mixes, constant temperature is to 40-60 DEG C (such as 42 DEG C, 45 DEG C, 48 DEG C, 52 DEG C, 55 DEG C, 58 DEG C), then according to described filler is slowly added to by above-mentioned corresponding proportioning on 2-4h (such as 2.5h, 3h, 3.5h) inner edge mixing limit；It is further continued for mixing 1-1.5h (such as 1.2h, 1.4h) and by gained resin pasty state material vent under certain vacuum degree, finally gives described dental pit and fissure sealant.
Compared with prior art, the invention has the beneficial effects as follows:
(1) existing pit and fissure sealant has been cooked substantial amounts of improvement by the present invention, including, the application of novel monomeric, special formulation design without Bis-GMA or its modified monomer etc. with bisphenol-A, the performance making material improves a lot, the present invention provides the comprcssive strength of dental pit and fissure sealant to be at least 200MPa, and polymerization shrinkage is less than 5%.
(2) traditional mechanical agitation methods is to make nano-particle be dispersed in resin monomer, and nanoparticle agglomerates phenomenon is very serious, and the reunion of nano-particle can be effectively avoided in solution mixing, so that it is dispersed in resin.Present invention nano zircite alcoholic solution and resin monomer method blended, removal of solvents prepare pit and fissure sealant, pit and fissure sealant is prepared compared to by inorganic filler and this conventional method of resin monomer mechanical blending, the method can make Nano filling in resin monomer scattered evenly, the content of Nano filling can be greatly increased, thus strengthening the mechanical strength of pit and fissure sealant, reducing the polymerization shrinkage of pit and fissure sealant when not affecting product mobility.
(3) preparation method that the present invention proposes is using acrylate as the dental pit and fissure sealant of photo polymerization monomer, in whole solidification process, heat release is few, it is little to shrink, the degree of cross linking is high, intensity is high, after solidification, material is high with the adhesive strength of tooth, and do not contain any unconverted monomer after solidifying, thus avoid these harmful monomers tissue is produced infringement.
(4) preparation method that the present invention proposes is using the inorganic particle through Fluoridizing as the dental pit and fissure sealant of filler, after solidification material can sustained release fluorion, such that it is able to preventing decayed tooth or stop the effect that dental caries destroy further.In the preparation method that the present invention proposes, the curing mechanism of polymer is photocuring, is therefore exposed under light and can accelerate polymerization and solidification process.
(5) this technology solves domestic pit and fissure sealant product quality and does not reach the technical barrier of clinical requirement, also can solve existing pit and fissure sealant after operation and be completely dependent on the situation of import, its cheap price generally must accept for vast oral cavity patient, provides fissure blockade agent material safe, cheap, high-quality for patient；Its social benefit, economic benefit are huge.
Detailed description of the invention
Below by specific embodiment, technical scheme is described in detail.In embodiment, PEG400 modified urethane double methyl methacrylate (PEG400ExtendedUrethaneDimethacrylate, it is called for short PEGUDMA) purchased from American ESSTECH company, dimeric dibasic acid carbamate double methyl methacrylate (DimerAcidUrethaneDimethacrylate, it is called for short DIAUDMA) purchased from American ESSTECH company, diluent and light trigger equal purchased from American SIGMA company；Nano zircite alcoholic solution is purchased from NYACPLNANOTECHNOLOGLE, INC., the U.S.；The silanization barium aluminosilicate (GM39923Rawglass (25% barium content)) of Fluoridizing is purchased from SchottGlasswerke, Lan Cihute, Germany.
Embodiment 1
The concrete preparation method of the dental pit and fissure sealant that embodiment 1 provides is as follows:
(1) each for 100g binder resin component (in binder resin, the content of each component is as described in table 1) is added to a planetary-type mixer and constant temperature is to 25 DEG C, planetary-type mixer is started 30 minutes with hybrid resin phase；Being added thereto to the nano zircite alcoholic solution that 150g concentration is 20wt% and continue mixing 1 hour, wherein zirconic particle diameter is 5-10nm；Then, mixed solution is removed alcohol solvent in dry 1 hour under-0.1MPa with Rotary Evaporators in light protected environment, obtain the mixture of nano zircite that nano oxidized zirconium content is 23% and binder resin.
(2) by preparation test sample in the mixture of 20wt% filling packing to nano zircite and binder resin 1 (namely filler is 20:80 with the mass ratio of nano zircite and the mixture of binder resin), prepare test sample 2 (namely filler is 30:70 with the mass ratio of nano zircite and the mixture of binder resin) with 30wt% filling packing nano zircite composite resin, prepare test sample 3 (namely filler is 40:60 with the mass ratio of nano zircite and the mixture of binder resin) with 40wt% filling packing nano zircite composite resin；Test sample 3 (namely filler is 50:50 with the mass ratio of nano zircite and the mixture of binder resin) is prepared with 50wt% filling packing nano zircite composite resin；With 3M company CONSICE pit and fissure sealant as comparative sample.Concrete fill method is as follows: added to planetary-type mixer by the mixture of the nano zircite prepared in step (1) with binder resin and constant temperature is to 50 DEG C, be then slowly added within the time of about 3 hours by the filler containing physical parameter listed in table 2 and component；It is further continued for mixing 1 hour and by the resin pasty state material vent of gained under vacuum degree condition, finally gives described dental pit and fissure sealant.
All of test all uses the ISO method of standard to implement, and is listed in bracket by standard deviation.Wherein, the method for testing of rockwell's hardness is: is 10mm at diameter and is highly the meansigma methods of 3 measured values on cylindrical sample surface of 4mm；Described sample light is solidified 40 seconds, and places 24 hours in the water of 37 DEG C before measuring.Table 2 details the physical property of the test sample pastes obtained by the present embodiment and comparative sample, as can be seen from Table 2: the present invention effectively increases the addition of Nano filling by the method for solution blending under the premise not affecting product mobility；Compared to comparative sample, pit and fissure sealant prepared by the present embodiment all greatly improves in mechanical properties or in polymerization shrinkage.
Binder resin composition in table 1 embodiment of the present invention 1
| PEG400 modified urethane double methyl methacrylate | 50.2wt% |
| Dimeric dibasic acid carbamate double methyl methacrylate | 35.5wt% |
| Hydroxyethyl methylacrylate | 13.0wt% |
| N, N dimethylamine amino ethyl methacrylate | 1.0wt% |
| 2,6-toluene di-tert-butyl phenols | 0.05wt% |
| Camphorquinone | 0.25wt% |
| Amount to | 100 |
The pit and fissure sealant of table 2 embodiment of the present invention 1 preparation and the physical property of comparative sample
Embodiment 2
The concrete preparation method of the dental pit and fissure sealant that embodiment 2 provides is as follows:
(1) by each for 100g binder resin component (in the embodiment of the present invention 2, binder resin forms as described in table 3), add to a planetary-type mixer and constant temperature is to 25 DEG C, planetary-type mixer is started 30 minutes with hybrid resin phase；It is added thereto to the nano zircite alcoholic solution that 150g concentration is 20% and continues mixing 1 hour, wherein zirconic particle diameter is 5-10nm, mixed solution is removed alcohol solvent in dry 1 hour under-0.1MPa with Rotary Evaporators in light protected environment, obtains the nano zircite composite resin that nano oxidized zirconium content is 23%.
(2) by preparation test sample in the mixture of 25wt% filling packing to nano zircite and binder resin 5 (namely filler is 25:75 with the mass ratio of nano zircite and the mixture of binder resin), prepare test sample 6 (namely filler is 35:65 with the mass ratio of nano zircite and the mixture of binder resin) with 35wt% filling packing nano zircite composite resin, prepare test sample 7 (namely filler is 45:55 with the mass ratio of nano zircite and the mixture of binder resin) with 45wt% filling packing nano zircite composite resin；Comparative sample is prepared with 3M company CONSICE pit and fissure sealant.Nano zircite composite resin is added to planetary-type mixer and constant temperature is to 50 DEG C, then the filler containing physics blending component listed in table 4 is slowly added within the time of about 3 hours；It is further continued for mixing 1 hour and by the resin pasty state material vent of gained under certain vacuum, finally gives described dental pit and fissure sealant.All of test all uses the ISO method of standard to implement, and is listed in bracket by standard deviation.Wherein, the method for testing of rockwell's hardness is: is 10mm at diameter and is highly the meansigma methods of 3 measured values on cylindrical sample surface of 4mm；Described sample light is solidified 40 seconds, and places 24 hours in the water of 37 DEG C before measuring.Table 4 detail the test sample pastes obtained by the present embodiment and comparative sample physical property and performance, as can be seen from Table 4: preparation method provided by the invention can also be added without diluent resin, under the premise not affecting product mobility, the addition of Nano filling is effectively increased by the method for solution blending；Compared to comparative sample, pit and fissure sealant prepared by the present embodiment all greatly improves in mechanical properties or in polymerization shrinkage；Compared to the test sample (the test sample 1-test sample 4 in embodiment 1) adding diluent, this experimental sample is substantially free of change in mechanical properties, but reduce further the polymerization shrinkage of product, thus further increase the Clinical practice effect of product.
Binder resin composition in table 3 embodiment of the present invention 2
| PEG400 modified urethane double methyl methacrylate | 60% |
| Dimeric dibasic acid carbamate double methyl methacrylate | 38.7% |
| N, N dimethylamine amino ethyl methacrylate | 1.0wt% |
| 2,6-toluene di-tert-butyl phenols | 0.05wt% |
| Camphorquinone | 0.25wt% |
| Amount to | 100 |
The pit and fissure sealant of table 4 embodiment of the present invention 2 preparation and the physical property of comparative sample
Obviously, above-described embodiment is only for clearly demonstrating example, and is not the restriction to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here without also cannot all of embodiment be given exhaustive.And the apparent change thus extended out or variation are still among the protection domain of the invention.
Claims (10)
1. a dental pit and fissure sealant, it is characterised in that include following two material by weight percentage:
Filler, content is that 5-50wt%, mean diameter are 0.010-0.120 μm；In described filler, the particle diameter filer content more than 0.120 μm is less than 50wt%；
Binder resin, content is 50-95wt%, and described binder resin is composed of the following components: PEG400 modified urethane double methyl methacrylate, dimeric dibasic acid carbamate double methyl methacrylate, diluent and light trigger.
2. dental pit and fissure sealant according to claim 1, it is characterized in that, in described binder resin, counting with PEG400 modified urethane double methyl methacrylate, dimeric dibasic acid carbamate double methyl methacrylate, diluent and light trigger for 100wt%, the content of PEG400 modified urethane double methyl methacrylate and dimeric dibasic acid carbamate double methyl methacrylate is 84-99wt%；The content of diluent is 0-15wt%；The content of light trigger is 1.0-2.5wt%；It is highly preferred that the mass ratio of described PEG400 modified urethane double methyl methacrylate and described dimeric dibasic acid carbamate double methyl methacrylate is 0.4-2.5:1.
3. dental pit and fissure sealant according to claim 1, it is characterised in that described diluent is hydroxyethyl methylacrylate；Described light trigger is by N, N dimethylamine amino ethyl methacrylate, 2,6-toluene di-tert-butyl phenol and camphorquinone composition；Described filler is Fluoridizing or untreated silicon oxide, aluminium oxide, aluminosilicate, titanium oxide or silanization barium aluminosilicate；Being preferably, described filler is the silanization barium aluminosilicate of Fluoridizing.
4. dental pit and fissure sealant according to claim 1, it is characterised in that in described filler, the percentage ratio of the filler weight that particle diameter > is 0.120 μm and filler gross weight is not higher than 10%.
5. dental pit and fissure sealant according to claim 1, it is characterised in that in described filler, the percentage ratio of particle diameter≤0.01 μm filler weight and filler gross weight is 1.0-10.0%.
6. dental pit and fissure sealant according to claim 1, it is characterised in that possibly together with nano zircite in described dental pit and fissure sealant；Preferably, in described dental pit and fissure sealant, the content of described filler is 5-50wt%, and the content of described binder resin is 35-75wt%, and the content of described nano zircite is 10-22wt%；Further, the mean diameter of described nano zircite is 5-10nm.
7. the preparation method of dental pit and fissure sealant according to any one of claim 1-5, it is characterised in that specifically include following steps:
The preparation process of binder resin, is first according to the arbitrary described proportioning of claim 1-5 and each component forming described binder resin is carried out mixed processing obtains uniform binder resin；
Filling step, the proportioning according to any one of claim 1-5, by described filling packing to described uniform binder resin, finally gives described dental pit and fissure sealant.
8. preparation method according to claim 7, it is characterized in that, when in described dental pit and fissure sealant possibly together with nano zircite, the mixture preparation process of nano zircite and binder resin is also included between preparation process and the described filling step of described binder resin, proportioning described in claim 6 adds nano zircite alcoholic solution in described binder resin, mixing certain time, finally under light protected environment, it is dried removal alcohol solvent, thus obtaining the mixture of nano zircite and binder resin；Preferably, in the mixture preparation process of described nano zircite and binder resin, the time of described mixing is 0.5-1.5h, and the temperature of described mixing is 20-30 DEG C, described dries as 0.5-1.5h dry under-0.1MPa in Rotary Evaporators；Further, the concentration of described nano zircite alcoholic solution is 15-25wt%.
9. the preparation method according to claim 7 or 8, it is characterised in that in the preparation process of described binder resin, the time of described mixed processing is 20-40min, and the temperature of described mixed processing is 20-30 DEG C.
10. the preparation method according to claim 7 or 8, it is characterized in that, described filling step comprises the following specific steps that: described uniform binder resin or described nano zircite is joined in blender with the mixture of binder resin and mixes, constant temperature is to 40-60 DEG C, then according to described filler is slowly added to by the arbitrary described proportioning of claim 1-6 on 2-4h inner edge mixing limit；It is further continued for mixing 1-1.5h and by gained resin pasty state material vent under certain vacuum degree, finally gives described dental pit and fissure sealant.
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| CN107670112A (en) * | 2017-08-30 | 2018-02-09 | 浙江美加华医疗技术有限公司 | A kind of organic-inorganic nanocomposite corona and its 3D subtraction preparation method |
| CN108158827A (en) * | 2017-12-22 | 2018-06-15 | 黄小艳 | A kind of composite material for dental prosthetic |
| JP2020090459A (en) * | 2018-12-06 | 2020-06-11 | Ｙａｍａｋｉｎ株式会社 | Dental adhesive composition |
| CN115212117A (en) * | 2022-07-13 | 2022-10-21 | 北京安泰生物医用材料有限公司 | Flowable dental filling resin and preparation method thereof |
| CN115381722A (en) * | 2022-09-28 | 2022-11-25 | 桂林凯文彼德科技有限公司 | Dental color-changing pit and fissure sealant, its preparation method and application |
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| CN103876944A (en) * | 2014-03-28 | 2014-06-25 | 北京固琦健康科技有限公司 | Pit and fissure sealant for dental department |
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| CN101347386A (en) * | 2008-08-28 | 2009-01-21 | 成都军区昆明总医院 | Dentistry compound resin ceramic whisker stuffing surface modification and method of preparing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107670112A (en) * | 2017-08-30 | 2018-02-09 | 浙江美加华医疗技术有限公司 | A kind of organic-inorganic nanocomposite corona and its 3D subtraction preparation method |
| CN108158827A (en) * | 2017-12-22 | 2018-06-15 | 黄小艳 | A kind of composite material for dental prosthetic |
| JP2020090459A (en) * | 2018-12-06 | 2020-06-11 | Ｙａｍａｋｉｎ株式会社 | Dental adhesive composition |
| CN115212117A (en) * | 2022-07-13 | 2022-10-21 | 北京安泰生物医用材料有限公司 | Flowable dental filling resin and preparation method thereof |
| CN115381722A (en) * | 2022-09-28 | 2022-11-25 | 桂林凯文彼德科技有限公司 | Dental color-changing pit and fissure sealant, its preparation method and application |
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|---|---|
| CN105708713B (en) | 2018-08-24 |
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