CN101569593B - Preparation method of multicomponent composite materials used for single paste type cavity filling - Google Patents
Preparation method of multicomponent composite materials used for single paste type cavity filling Download PDFInfo
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- CN101569593B CN101569593B CN2009101118902A CN200910111890A CN101569593B CN 101569593 B CN101569593 B CN 101569593B CN 2009101118902 A CN2009101118902 A CN 2009101118902A CN 200910111890 A CN200910111890 A CN 200910111890A CN 101569593 B CN101569593 B CN 101569593B
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- 238000011049 filling Methods 0.000 title claims abstract description 22
- 239000002131 composite material Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 55
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims abstract description 46
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims abstract description 46
- 230000004048 modification Effects 0.000 claims abstract description 29
- 238000012986 modification Methods 0.000 claims abstract description 29
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- 239000000203 mixture Substances 0.000 claims description 85
- 239000000843 powder Substances 0.000 claims description 76
- 241000186216 Corynebacterium Species 0.000 claims description 55
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- 229920005989 resin Polymers 0.000 claims description 41
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 36
- 230000000694 effects Effects 0.000 claims description 33
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 20
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- 239000002114 nanocomposite Substances 0.000 claims description 18
- 238000009826 distribution Methods 0.000 claims description 13
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- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 11
- 239000000945 filler Substances 0.000 claims description 9
- -1 methyl methacrylate triethylene glycol ester Chemical class 0.000 claims description 8
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 7
- 239000007822 coupling agent Substances 0.000 claims description 6
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 claims description 4
- 230000004044 response Effects 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000007171 acid catalysis Methods 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 238000002525 ultrasonication Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 125000002362 bornane-2,3-dione group Chemical group 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 8
- 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 abstract description 4
- 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 abstract description 4
- 239000003999 initiator Substances 0.000 abstract description 3
- 239000011858 nanopowder Substances 0.000 abstract 4
- 239000002105 nanoparticle Substances 0.000 abstract 2
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 abstract 1
- 239000006087 Silane Coupling Agent Substances 0.000 abstract 1
- 239000011350 dental composite resin Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 30
- 238000002156 mixing Methods 0.000 description 28
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- 239000011521 glass Substances 0.000 description 14
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- 238000012856 packing Methods 0.000 description 11
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- 239000011256 inorganic filler Substances 0.000 description 6
- 229910003475 inorganic filler Inorganic materials 0.000 description 6
- 230000000379 polymerizing effect Effects 0.000 description 6
- 239000002344 surface layer Substances 0.000 description 6
- FCSYVLNEFRBFMA-UHFFFAOYSA-N [B].[Pb] Chemical compound [B].[Pb] FCSYVLNEFRBFMA-UHFFFAOYSA-N 0.000 description 5
- CNKUAUGVOXURRM-UHFFFAOYSA-N [Ba].[Sr].[B] Chemical compound [Ba].[Sr].[B] CNKUAUGVOXURRM-UHFFFAOYSA-N 0.000 description 5
- DUPIXUINLCPYLU-UHFFFAOYSA-N barium lead Chemical compound [Ba].[Pb] DUPIXUINLCPYLU-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- YLIZNYFVRHGNKF-UHFFFAOYSA-N 2-[2-(2-hydroxyethoxy)ethoxy]ethanol;methyl 2-methylprop-2-enoate Chemical class COC(=O)C(C)=C.OCCOCCOCCO YLIZNYFVRHGNKF-UHFFFAOYSA-N 0.000 description 4
- UEKHZPDUBLCUHN-UHFFFAOYSA-N 2-[[3,5,5-trimethyl-6-[2-(2-methylprop-2-enoyloxy)ethoxycarbonylamino]hexyl]carbamoyloxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOC(=O)NCCC(C)CC(C)(C)CNC(=O)OCCOC(=O)C(C)=C UEKHZPDUBLCUHN-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000005728 strengthening Methods 0.000 description 4
- 229910052712 strontium Inorganic materials 0.000 description 4
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 4
- 229910052581 Si3N4 Inorganic materials 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000001154 acute effect Effects 0.000 description 3
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 208000002925 dental caries Diseases 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 208000015181 infectious disease Diseases 0.000 description 3
- 239000002932 luster Substances 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 3
- 229910010271 silicon carbide Inorganic materials 0.000 description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
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- 239000010410 layer Substances 0.000 description 2
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 235000010215 titanium dioxide Nutrition 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910052586 apatite Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
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- 239000007943 implant Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
- 150000002989 phenols Chemical group 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
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Landscapes
- Dental Preparations (AREA)
Abstract
The invention relates to a preparation method of multicomponent composite materials used for single paste type cavity filling, belonging to the field of preparation for dental use. The technical proposal aims at solving the problem that current dental composite resin materials used for cavity filling urgently need to be further improved in the aspects of wear-resisting properties and toughness. The method comprises the following steps: silane coupling agent is adopted to carry out surface modification on inorganic nano powder; the modified inorganic nano powder is evenly mixed with monomers such as bisphenol A glycidyl methacrylate, thinners such as triethylene- glycol dimethacrylate, light initiators such as camphorquinone, coinitiators such as dimethylamino ethyl methacrylate and the like in the absence of light; bubbles are eliminated in vacuum. The technical proposal has the key point that the inorganic nano powder contains short-rod like nano-particle hydroxyapatite accounting for10-80% of the inorganic nano powder by weight. The short-rod like nano-particle hydroxyapatite added in the multicomponent composite materials helps to improve the wear-resisting properties and tough ness of the materials.
Description
Technical field
The present invention relates to a kind of multicomponent composite materials used for single paste type cavity filling preparation method, belong to that A61K is medical, the dental preparation field.
Background technology
Countries in the world dental caries incidence rate still was in higher level in recent years, using the cavity packing material in the dental caries curative activity in a large number, based on this reality, for further alleviating patient's misery, simultaneously, reduce medical treatment cost, increase and fill out dental caries reliability of material and durability, this class material is carried out degree of depth research and development have practical significance.Advantages such as dentistry composite resin is because of having higher mechanical strength, and thermal coefficient of expansion is similar to tooth, and polishing performance is good, is insoluble to saliva, and color and luster and tooth are close just are being applied to the repairing filling of cavity at present gradually.But the anti-wear performance of dentistry composite resin is still not ideal enough at present.
The dentistry compound resin material of single paste prescription also claims visible-light curing composite resin (VLC), is that the visible light with specific wavelength and intensity comes initiated polymerization.The product in past mostly is ultraviolet light (UV) curing materials.Two paste type composite resin materials can be after mixing self-solidifying, also can after mixing, reach dual cure by using visible light.The composite resin prescription that occurs on the current international market has kind more than 50, and they can be divided into different classifications, and has bigger difference on composition and performance.Its composition introduction of the dentistry compound resin material that manufacturer announced is more rough usually, and important data then need could obtain by chemical analysis.The basic composition of dentistry compound resin material comprises: resinous substrates, inorganic filler, polymerizing curable cause material, polymerization inhibitor and coloring agent; The effect of resinous substrates is to give plasticity, curing characteristics and intensity, resinous substrates commonly used is the polyfunctional group methacrylate monomer, the polyfunctional group methacrylate monomer relates to miscellaneous similar chemical substance, actual polyfunctional group methacrylate monomer commonly used is the selection of having taken all factors into consideration the each side factor in the dentistry compound resin material, concrete example such as BIS-GMA, UDMA and TEGDMA, BIS-GMA wherein, UDMA or their combination have viscosity higher, and TEGDMA joins BIS-GMA for reducing viscosity as diluent, in UDMA or their combination; The effect of inorganic filler is to gain in strength and wearability, inorganic filler commonly used such as silica flour, silicon dioxide powder, glass dust; The effect that polymerizing curable causes material is the trigger monomer polymerizing curable, polymerizing curable causes material and generally includes initiator and coinitiator, at present, the mode of visible-light curing is main flow gradually, for utilizing radiation of visible light to carry out the situation of resin solidification, described initiator and coinitiator can be respectively camphorquinone and tertiary amine; Inhibitor action is to keep effective life, and described polymerization inhibitor mostly is phenols; The effect of coloring agent is to give the natural teeth color and luster, described coloring agent such as titanium white, chrome yellow.The dummy suffix notation BIS-GMA acute pyogenic infection of finger tip bisphenol-A glycidyl methacrylate that above relates to; Dummy suffix notation UDMA acute pyogenic infection of finger tip carbamate double methyl methacrylate; Dummy suffix notation TEGDMA acute pyogenic infection of finger tip double methyl methacrylate triethylene glycol ester.More than the Chinese of cited various related substanceses and the art-recognized meanings of English alphabet dummy suffix notation indication, for the dental profession technical staff, its art-recognized meanings is known.
In each composition of dentistry composite resin, for amorphous granular is adopted in the inorganic filler of gaining in strength and wearability adds more, the effect that amorphous granular can be brought into play in composite resin is similar to spheroidal particle, surface layer at the dentistry composite resin after polyreaction is solidified, faying face between amorphous granular and the resin matrix is less, anchor force thus a little less than, in friction process, peel off easily, this factor makes amorphous granular make a discount in the effect aspect the lifting dentistry composite resin wearability, on the other hand, in the dentistry composite resin body after solidifying, amorphous granular is contributed also because of fully not taking into account for the Strengthening and Toughening of dentistry composite resin and is extracted toughening mechanisms some shortcomings have been arranged.
Extract toughening mechanisms and come the Strengthening and Toughening dentistry composite resin for utilizing fully, in recent years, the glass fibre that draw ratio is very high, silicon carbide whisker, silicon nitride crystal whisker and aluminium borate whisker etc. are as considerable inorganic filler, obtain some research staff's concern, undoubtedly, the inorganic filler that this class draw ratio is very high is if can sneak into equably in the resin, benefiting of a front will be provided the Strengthening and Toughening of dentistry composite resin, but, the glass fibre that draw ratio is very high, silicon carbide whisker, silicon nitride crystal whisker and aluminium borate whisker etc. are difficult to sneak into equably in the resin matrix because of its inherent physics pattern, in other words, uniform mixing becomes and is difficult for the obstacle gone beyond together, this factor, make the glass fibre that draw ratio is very high, silicon carbide whisker, the application of inorganic material such as silicon nitride crystal whisker and aluminium borate whisker in dentistry composite resin can be not fully, put to good use all sidedly, about this point, in cavity is filled with the dentistry compound resin material field, show particularly evidently.
Summary of the invention
Technical problem to be solved by this invention is, demand the further technical development actual requirement of raising urgently at existing dentistry composite resin anti-wear performance and toughness and tenacity, develop a kind of new preparation method for dental fortified resin, this method should be taken the raising of wearability into account, also to take into account and extract toughening mechanisms the front of Strengthening and Toughening is benefited, simultaneously, this method should avoid occurring described mixing obstacle again.
The present invention solve the technical problem by following scheme, and this scheme provides a kind of multicomponent composite materials used for single paste type cavity filling preparation method, and this method may further comprise the steps:
A forms silane coupler hydrolysis under acetic acid catalysis the water alcohol system that contains coupling agent;
B adds ultra-sonic dispersion in the water alcohol system that contains coupling agent with nano inorganic powder, and after reacting completely, washing, drying obtain the inorganic nano-filler of modification;
C adds an amount of diluent dilution with resin monomer, forms the resinous substrates with good miscibility;
D under the lucifuge condition, adds light trigger and coinitiator with the resinous substrates for preparing, and after stirring, adds the inorganic nano-filler of modification again, behind the mix homogeneously, removes interlaminar resin and has bubble, prepares nano-composite resin material;
This case main points are, it is 10%～80% corynebacterium nanometer hydroxyapatite that described nano inorganic powder contains the percetage by weight that accounts for nano inorganic powder weight; The radial width of described corynebacterium nanometer hydroxyapatite is less than 100 nanometers, and the aspect ratio distribution of corynebacterium nanometer hydroxyapatite is between 2 and 6.
The radial width of described corynebacterium nanometer hydroxyapatite can be the arbitrarily selected width less than 100 nanometers, and still, the preferred value of corynebacterium nanometer hydroxyapatite radial width is between 5 nanometers and 30 nanometers; The draw ratio of corynebacterium nanometer hydroxyapatite can be distributed in 2 and 6 between any set point value, still, its scope of draw ratio of further preferred corynebacterium nanometer hydroxyapatite is distributed between 2 and 4.
Described resin monomer comprises the low molecular weight monomers form and is so-called oligomer form by the bigger morphon of the molecular weight of low molecular weight monomers after low polymerization that the preferred value of described its molecular weight of resin monomer is between 200～5000; Described resin monomer is a polyfunctional group methyl acrylic ester material, the polyfunctional group methacrylate monomer relates to miscellaneous similar chemical substance, this class material all is easy to realize polymerizing curable between monomer fast under the initiation of polymerizing curable initiation material, described resin monomer preferred material is a kind of or both combinations in bisphenol-A glycidyl methacrylate, the carbamate double methyl methacrylate; Because above-mentioned preferred monomer is the bisphenol-A glycidyl methacrylate, class materials such as carbamate double methyl methacrylate have higher viscosity, for ease of the adding operation of inorganic nano-filler and the practical application of making finished product, the operation that an amount of diluent of adding dilutes in step c is necessary, the adding diluent can reduce the viscosity of composite resin paste, the optional material of diluent that is suitable for this case purpose is more, and described diluent preferred material is a double methyl methacrylate triethylene glycol ester, Ethylene glycol dimethacrylate, the combination of one or more in the hydroxyethyl methylacrylate.Described diluent is participating in there is no too big-difference with materials such as described bisphenol-A glycidyl methacrylate and carbamate double methyl methacrylates aspect the cross-linking and curing reaction, distinguish with diluent one speech, be that mainly this class material is for reducing the composition that viscosity adds from function.
This case dentistry composite resin is applicable to that light radiation causes the application mode of curing cross-linking reaction, the preferred camphorquinone of light trigger, coinitiator preferable methyl acrylic acid diformazan ammonia ethyl ester.
Silane coupler is used for the surface modification of nano inorganic powder, commercially available silane coupler applicable to this case purpose has multiple, concrete example such as KH-550, KH-560, KH-570 etc., comprehensive many-sided factor, the KH-570 of the preferred medical grade of described silane coupler, all there is introduction in each corresponding producer of the condition of manipulating of above-mentioned various commercially available silane couplers, for example, situation to the KH-570 that selects medical grade for use, when disposing described water alcohol system, wherein the scope that water and the volume ratio of alcohol are optionally suitable is 5 to 95～70 to 30.
Utilize silane coupler nano inorganic powder to be carried out the result of modification, just coat the coupling agent molecule layer of about one deck molecular layers thick of skim on the surface of nano inorganic powder, thereby, the actual coupling agent requirement that plays a role is also few, in described water alcohol system, the suitable weight percentage of silane coupler is 0.5%～10%, and, in step b, nano inorganic powder is 1 to 20～1 to 2 with the suitable weight ratio scope of water alcohol system.
In the described step b of this case, the reaction temperature preferable range is 50 ℃～100 ℃, and the response time, preferred yardstick was between 2h～24h.Certainly, reaction temperature and response time also can allow to do as required other selection.
Not allowing bubble in the finished product dentistry composite resin is mingled with therebetween, in addition, unnecessary tool is volatile to be mingled with the complementary composition that other permission therebetween is added into and also must to remove in operating process, there is kind of mode can reach this purpose, in the described steps d of this case, preferably remove the mode of bubble and other volatile impurity, be by ultrasonication 10min～2h then the mode of vacuum drying effect 10h～24h remove the bubble that exists in the resin.
In the described steps d of this case, the weight percentage apportioning cost of each component can be the rational arbitrarily apportioning cost of setting as required in the nanocomposite, but, based on the demand of the described dentistry composite resin of this case at aspect of performance, the preferable range of the weight percentage of each component is respectively in the described nanocomposite:
Resin monomer 8%～70%;
Diluent 5%～25%;
Light trigger 0.25%～2%;
Coinitiator 0.5%～3%;
Inorganic nano-filler 20%～85% after the modification.
Above address, it is 1%～80% corynebacterium nanometer hydroxyapatite that the described nano inorganic powder of this case contains the percetage by weight that accounts for nano inorganic powder weight; It is other the selected arbitrarily inorganic material that is suitable for that all the other compositions of described inorganic nano-filler can allow; The preferred material of all the other compositions of described inorganic nano-filler is a kind of of following material at least: biological glass powder, commercially available barium lead glass powder, strontium glass powder, boron lead glass powder, barium strontium boron glass powder, certainly, also can be the combination of two or more listed alternative materials.
The technology of preparing of the related corynebacterium nanometer hydroxyapatite of this case, can be with reference to relevant scientific and technical literature, described relevant scientific and technical literature is for example: one piece of paper that is entitled as " wet method of the light basic apatite of corynebacterium nanometer is synthetic and characterize ", China's " silicate journal " the 30th volume the 2nd phase magazine that this paper publishing was published in April, 2002, this paper has described a kind of technology of preparing of corynebacterium nanometer hydroxyapatite in detail, and the author of this paper is the Guo Dagang of Strength of Metallic Materials National Key Laboratory of Xi'an Communications University etc.
Related other related reagent of this case and material all have finished product commercially available; The corresponding technology of preparing that related other related reagent and material also can utilize relevant speciality Gao Ke company to provide with compensation prepares to be obtained; Certainly, related other related reagent and material can also be obtained by the mode to relevant speciality Gao Ke company customization finished product.
In described step a, step c, can add ultrasound wave effect operation, utilize ultrasound wave to be used for promoting reaction or acceleration uniform mixing, certainly, the operation that can add the ultrasound wave effect in described step a, step c is optional; At the mix stages of steps d, can further add ultrasound wave effect operation, this helps to facilitate the uniform mixing of each composition, but that ultrasound wave acts on this link is optional, because the conventional mode that mixes is also effective.
This case method can also comprise some other steps certainly, described other step for example adds an amount of polymerization inhibitor in described nano-composite resin material system, add an amount of polymerization inhibitor and its objective is the effective life of keeping nanocomposite, described polymerization inhibitor can be selected aldehydes matter for use, and the step that adds polymerization inhibitor is optional; Described other step also for example adds an amount of coloring agent in described nano-composite resin material system, adding an amount of coloring agent its objective is and give resin with the natural teeth color and luster, be suitable for optional coloring agent such as the titanium white of this purpose and chrome yellow etc., described coloring agent also can add wherein.
Advantage of the present invention is, utilize the corynebacterium nanometer hydroxyapatite composition that is added as critical increase wearability, increase flexible material composition, hydroxyapatite has the hardness that is similar to human body natural's tooth, and, in resin surface layer is constructed after solidifying in application, the bar-shaped pattern of corynebacterium nanometer hydroxyapatite, also make the corynebacterium nanometer hydroxyapatite be positioned on the surface layer to have more multimachine can implant resin matrix more deeply than circular granular or amorphous granular, in other words, more strong comparatively speaking at corynebacterium nanometer hydroxyapatite on the surface layer and the adhesion between the composite resin matrix, this factor, make the corynebacterium nanometer hydroxyapatite that is positioned on the surface layer among using, be difficult for being peeled off by friction strength, therefore the corynebacterium nanometer hydroxyapatite that is positioned on the surface layer can be anchored on the surface of composite resin more muchly, bringing into play the front to increasing wearability that its hardness that is similar to the nature tooth brings more muchly benefits, that is to say that this helps to reduce the abrasion speed of composite resin; On the other hand, composite resin matrix inside after in application, solidifying, disperse a large amount of corynebacterium nanometer hydroxyapatite therebetween changes bending, distortion and fracture more intense drag, this stems to a great extent extracts toughening effect, and this factor helps to improve the toughness of composite resin; And, have the corynebacterium nanometer hydroxyapatite of benefiting in front, above-mentioned two aspect and also have the pattern of the less corynebacterium of draw ratio because of it, comparatively speaking, in preparation process than other composition uniform mixing that is easier to composite resin, in other words, be not prone to the mixing obstacle in the preparation process.
The specific embodiment
Embodiment 1:
Take by weighing 10.00 gram corynebacterium nanometer hydroxyapatites, and, 50.00 gram barium strontium boron glass powder, and 40.00 gram boron lead glass powder carry out uniform mixing by churned mechanically mode with above three kinds of compositions, make gross weight and be the nano inorganic powder that contains multiple composition of 100.00 grams, standby; The radial width of wherein related corynebacterium nanometer hydroxyapatite is less than 100 nanometers, and its aspect ratio distribution is between 2 and 6, and all corynebacterium nano hydroxyapatite materials that satisfies described radial width qualification and draw ratio qualification all can use.
With 2.50 gram medical grade silane coupler KH-570 hydrolysis under the effect of acetic acid, add 40 ml water alcoholic solutions, water in this water-alcohol solution, the alcohol volume ratio is 70 to 30, subsequently, add the above-mentioned mixed in advance nano inorganic powder that contains multiple composition of 22.00 grams, in ultrasound wave, disperse, afterwards, reaction is 24 hours under 50 ℃ of temperature, moves to baking oven, dries 10 hours down at 80 ℃, then, with described water-alcohol solution washing, dried 10 hours down in 100 ℃ again, after the drying, pulverize, make the nano inorganic powder after the modification, standby, reserve level is slightly greater than requirement.
In 70.00 gram bisphenol-A glycidyl methacrylate, add 5.00 gram double methyl methacrylate triethylene glycol ester dilutions, stir, make resinous substrates, thereafter, under the lucifuge condition, the resinous substrates made and 2.00 gram camphorquinones and 3.00 gram dimethylaminoethyl acrylate methyl ammonia ethyl esters are mixed, after mixing, add therein 20.00 the gram these routine described modifications after nano inorganic powder, carrying out mechanical agitation mixes, after the mechanical agitation married operation was finished, ultrasound wave effect 10 minutes placed vacuum desiccator with mixture, application of vacuum 24 hours, remove the bubble and other volatile impurity that are mingled with in the mixture, make nano-composite resin material, be i.e. the described multicomponent composite materials used for single paste type cavity filling of this case; Can under lucifuge condition according to usual use amount carry out finished product packing thereafter.
Embodiment 2:
Take by weighing 80.00 gram corynebacterium nanometer hydroxyapatites, and 20.00 gram barium strontium boron glass powder carry out uniform mixing by churned mechanically mode with above three kinds of compositions, make gross weight and are the nano inorganic powder that contains multiple composition of 100.00 grams, and are standby; The radial width of wherein related corynebacterium nanometer hydroxyapatite is less than 100 nanometers, and its aspect ratio distribution is between 2 and 6, and all corynebacterium nano hydroxyapatite materials that satisfies described radial width qualification and draw ratio qualification all can use.
With 2.00 gram medical grade silane coupler KH-570 hydrolysis under the effect of acetic acid, add 400 ml water alcoholic solutions, water in this water-alcohol solution, the alcohol volume ratio is 5 to 95, subsequently, add the above-mentioned mixed in advance nano inorganic powder that contains multiple composition of 87.00 grams, in ultrasound wave, disperse, under 100 ℃ of temperature, reacted 2 hours afterwards, move to baking oven, dried 2 hours down at 80 ℃ earlier, then, with described water-alcohol solution washing, again in 80 ℃ of down oven dry 2 hours, after be warming up to 100 ℃ and continue oven dry 5 hours, after the drying, pulverize, make the nano inorganic powder after the modification, standby, reserve level is slightly greater than requirement.
Get 8.00 gram bisphenol-A glycidyl methacrylate, add 6.25 gram double methyl methacrylate triethylene glycol ester dilutions therein, both are stirred, make resinous substrates, thereafter, under the lucifuge condition, the resinous substrates made and 0.25 gram camphorquinone and 0.50 gram dimethylaminoethyl acrylate methyl ammonia ethyl ester are mixed, after mixing, add the nano inorganic powder after these routine described modifications of 85.00 grams therein, carry out mechanical agitation and mix, after the mechanical agitation married operation is finished, ultrasound wave effect 2 hours, mixture is placed vacuum desiccator, and the bubble and other volatile impurity that are mingled with in the mixture are removed in application of vacuum 10 hours, make nano-composite resin material, i.e. the described multicomponent composite materials used for single paste type cavity filling of this case; Can under lucifuge condition according to usual use amount carry out finished product packing thereafter.
Embodiment 3:
Take by weighing 45.00 gram corynebacterium nanometer hydroxyapatites, and, 25.00 gram barium strontium boron glass powder, and, 10.00 gram strontium glass powder, and, 10.00 gram boron lead glass powder, and, 10.00 restrain commercially available barium lead glass powder, by churned mechanically mode above multiple composition is carried out uniform mixing, make gross weight and be the nano inorganic powder that contains multiple composition of 100.00 grams, standby; The radial width of wherein related corynebacterium nanometer hydroxyapatite is less than 100 nanometers, and its aspect ratio distribution is between 2 and 6, and all corynebacterium nano hydroxyapatite materials that satisfies described radial width qualification and draw ratio qualification all can use.
With 10.00 gram medical grade silane coupler KH-570 hydrolysis under the effect of acetic acid, add 200 ml water alcoholic solutions, water in this water-alcohol solution, the alcohol volume ratio is 2.4 to 1.0, subsequently, add the above-mentioned mixed in advance nano inorganic powder that contains multiple composition of 55.00 grams, in ultrasound wave, disperse, under 100 ℃ of temperature, reacted 2 hours afterwards, move to baking oven, dried 2 hours down at 80 ℃ earlier, then, with described water-alcohol solution washing, again in 80 ℃ of down oven dry 12 hours, after be warming up to 100 ℃ and continue oven dry 5 hours, after the drying, pulverize, make the nano inorganic powder after the modification, standby, reserve level is slightly greater than requirement.
Get 39.00 gram bisphenol-A glycidyl methacrylate, add 5.59 gram double methyl methacrylate triethylene glycol ester dilutions therein, both are stirred, make resinous substrates, thereafter, under the lucifuge condition, the resinous substrates made and 1.16 gram camphorquinones and 1.75 gram dimethylaminoethyl acrylate methyl ammonia ethyl esters are mixed, after mixing, add the nano inorganic powder that contains multiple composition after these routine described modifications of 52.50 grams therein, carry out mechanical agitation and mix, after the mechanical agitation married operation is finished, ultrasound wave effect 45 minutes, mixture is placed vacuum desiccator, and the bubble and other volatile impurity that are mingled with in the mixture are removed in application of vacuum 16 hours, make nano-composite resin material, i.e. the described multicomponent composite materials used for single paste type cavity filling of this case; Can under lucifuge condition according to usual use amount carry out finished product packing thereafter.
Embodiment 4:
Take by weighing 30.00 gram corynebacterium nanometer hydroxyapatites, and, 30.00 gram barium strontium boron glass powder, and, 10.00 gram biological glass powders, and, 5.00 gram strontium glass powder, and, 5.00 gram boron lead glass powder, and, 20.00 restrain commercially available barium lead glass powder, by churned mechanically mode above multiple composition is carried out uniform mixing, make gross weight and be the nano inorganic powder that contains multiple composition of 100.00 grams, standby; The radial width of wherein related corynebacterium nanometer hydroxyapatite is less than 100 nanometers, and its aspect ratio distribution is between 2 and 6, and all corynebacterium nano hydroxyapatite materials that satisfies described radial width qualification and draw ratio qualification all can use.
With 5.00 gram medical grade silane coupler KH-570 hydrolysis under the effect of acetic acid, add 200 ml water alcoholic solutions, water in this water-alcohol solution, the alcohol volume ratio is 1.0 to 10.0, subsequently, add the above-mentioned mixed in advance nano inorganic powder that contains multiple composition of 35.00 grams, in ultrasound wave, disperse, under 100 ℃ of temperature, reacted 2 hours afterwards, move to baking oven, dried 2 hours down at 80 ℃ earlier, then, with described water-alcohol solution washing, again in 80 ℃ of down oven dry 12 hours, after be warming up to 100 ℃ and continue oven dry 5 hours, after the drying, pulverize, make the nano inorganic powder after the modification, standby, reserve level is slightly greater than requirement.
Get 40.00 gram bisphenol-A glycidyl methacrylate, add 25.00 gram double methyl methacrylate triethylene glycol ester dilutions therein, both are stirred, make resinous substrates, thereafter, under the lucifuge condition, the resinous substrates made and 1.00 gram camphorquinones and 1.20 gram dimethylaminoethyl acrylate methyl ammonia ethyl esters are mixed, after mixing, add the nano inorganic powder after these routine described modifications of 32.80 grams therein, carry out mechanical agitation and mix, after the mechanical agitation married operation is finished, ultrasound wave effect 20 minutes, mixture is placed vacuum desiccator, and the bubble and other volatile impurity that are mingled with in the mixture are removed in application of vacuum 20 hours, make nano-composite resin material, i.e. the described multicomponent composite materials used for single paste type cavity filling of this case; Can under lucifuge condition according to usual use amount carry out finished product packing thereafter.
Embodiment 5:
Take by weighing 60.00 gram corynebacterium nanometer hydroxyapatites, and the commercially available barium lead glass powder of 40.00 grams carries out uniform mixing by churned mechanically mode with above two kinds of compositions, makes gross weight and is the nano inorganic powder that contains two kinds of compositions of 100.00 grams, and is standby; The radial width of wherein related corynebacterium nanometer hydroxyapatite is less than 100 nanometers, and its aspect ratio distribution is between 2 and 6, and all corynebacterium nano hydroxyapatite materials that satisfies described radial width qualification and draw ratio qualification all can use.
With 3.00 gram medical grade silane coupler KH-570 hydrolysis under the effect of acetic acid, add 100 ml water alcoholic solutions, water in this water-alcohol solution, the alcohol volume ratio is 1.0 to 10.0, subsequently, add the above-mentioned mixed in advance nano inorganic powder that contains two kinds of compositions of 35.00 grams, in ultrasound wave, disperse, under 100 ℃ of temperature, reacted 2 hours afterwards, move to baking oven, dried 2 hours down at 80 ℃ earlier, then, with described water-alcohol solution washing, again in 80 ℃ of down oven dry 12 hours, after be warming up to 100 ℃ and continue oven dry 5 hours, after the drying, pulverize, make the nano inorganic powder after the modification, standby, reserve level is slightly greater than requirement.
Get 50.00 gram carbamate double methyl methacrylates, add 15.00 gram Ethylene glycol dimethacrylate dilutions therein, both are stirred, make resinous substrates, thereafter, under the lucifuge condition, the resinous substrates made and 1.00 gram camphorquinones and 1.20 gram dimethylaminoethyl acrylate methyl ammonia ethyl esters are mixed, after mixing, add the nano inorganic powder after these routine described modifications of 32.80 grams therein, carry out mechanical agitation and mix, after the mechanical agitation married operation is finished, ultrasound wave effect 20 minutes, mixture is placed vacuum desiccator, and the bubble and other volatile impurity that are mingled with in the mixture are removed in application of vacuum 20 hours, make nano-composite resin material, i.e. the described multicomponent composite materials used for single paste type cavity filling of this case; Can under lucifuge condition according to usual use amount carry out finished product packing thereafter.
Embodiment 6:
Take by weighing 70.00 gram corynebacterium nanometer hydroxyapatites, and the strontium glass powder of 30.00 grams carries out uniform mixing by churned mechanically mode with above two kinds of compositions, makes gross weight and is the nano inorganic powder that contains two kinds of compositions of 100.00 grams, standby; The radial width of wherein related corynebacterium nanometer hydroxyapatite is less than 100 nanometers, and its aspect ratio distribution is between 2 and 6, and all corynebacterium nano hydroxyapatite materials that satisfies described radial width qualification and draw ratio qualification all can use.
With 3.00 gram medical grade silane coupler KH-570 hydrolysis under the effect of acetic acid, add 100 ml water alcoholic solutions, water in this water-alcohol solution, the alcohol volume ratio is 1.0 to 10.0, subsequently, add the above-mentioned mixed in advance nano inorganic powder that contains two kinds of compositions of 35.00 grams, in ultrasound wave, disperse, under 100 ℃ of temperature, reacted 2 hours afterwards, move to baking oven, dried 2 hours down at 80 ℃ earlier, then, with described water-alcohol solution washing, again in 80 ℃ of down oven dry 12 hours, after be warming up to 100 ℃ and continue oven dry 5 hours, after the drying, pulverize, make the nano inorganic powder after the modification, standby, reserve level is slightly greater than requirement.
Get 20.00 gram carbamate double methyl methacrylates, and get 30.00 gram bisphenol-A glycidyl methacrylate, in the above two mixture, add 15.00 gram hydroxyethyl methylacrylate dilutions, this mixture system is stirred, make resinous substrates, thereafter, under the lucifuge condition, the resinous substrates made and 1.00 gram camphorquinones and 1.20 gram dimethylaminoethyl acrylate methyl ammonia ethyl esters are mixed, after mixing, add therein 32.80 the gram these routine described modifications after the nano inorganic powder that contains multiple composition, carrying out mechanical agitation mixes, after the mechanical agitation married operation was finished, ultrasound wave effect 20 minutes placed vacuum desiccator with mixture, application of vacuum 20 hours, remove the bubble and other volatile impurity that are mingled with in the mixture, make nano-composite resin material, be i.e. the described multicomponent composite materials used for single paste type cavity filling of this case; Can under lucifuge condition according to usual use amount carry out finished product packing thereafter.
Embodiment 7:
Take by weighing 75.00 gram corynebacterium nanometer hydroxyapatites, and the commercially available barium lead glass powder of 25.00 grams carries out uniform mixing by churned mechanically mode with above two kinds of compositions, makes gross weight and is the nano inorganic powder that contains two kinds of compositions of 100.00 grams, standby; The radial width of wherein related corynebacterium nanometer hydroxyapatite is less than 100 nanometers, and its aspect ratio distribution is between 2 and 6, and all corynebacterium nano hydroxyapatite materials that satisfies described radial width qualification and draw ratio qualification all can use.
With 3.00 gram medical grade silane coupler KH-570 hydrolysis under the effect of acetic acid, add 100 ml water alcoholic solutions, water in this water-alcohol solution, the alcohol volume ratio is 1.0 to 10.0, subsequently, add the above-mentioned mixed in advance nano inorganic powder that contains two kinds of compositions of 35.00 grams, in ultrasound wave, disperse, under 100 ℃ of temperature, reacted 2 hours afterwards, move to baking oven, dried 2 hours down at 80 ℃ earlier, then, with described water-alcohol solution washing, again in 80 ℃ of down oven dry 12 hours, after be warming up to 100 ℃ and continue oven dry 5 hours, after the drying, pulverize, make the nano inorganic powder after the modification, standby, reserve level is slightly greater than requirement.
Get 20.00 gram carbamate double methyl methacrylates, and get 20.00 gram bisphenol-A glycidyl methacrylate, in the above two mixture, add 10.00 gram double methyl methacrylate triethylene glycol esters, 10.00 gram Ethylene glycol dimethacrylate, 5.00 gram hydroxyethyl methylacrylate dilution, this mixture system is stirred, make resinous substrates, thereafter, under the lucifuge condition, the resinous substrates made and 1.00 gram camphorquinones and 1.20 gram dimethylaminoethyl acrylate methyl ammonia ethyl esters are mixed, after mixing, add therein 32.80 the gram these routine described modifications after the nano inorganic powder that contains multiple composition, carrying out mechanical agitation mixes, after the mechanical agitation married operation was finished, ultrasound wave effect 20 minutes placed vacuum desiccator with mixture, application of vacuum 20 hours, remove the bubble and other volatile impurity that are mingled with in the mixture, make nano-composite resin material, be i.e. the described multicomponent composite materials used for single paste type cavity filling of this case; Can under lucifuge condition according to usual use amount carry out finished product packing thereafter.
Embodiment 8:
Take by weighing 65.00 gram corynebacterium nanometer hydroxyapatites, and the commercially available boron lead glass powder of 35.00 grams carries out uniform mixing by churned mechanically mode with above two kinds of compositions, makes gross weight and is the nano inorganic powder that contains two kinds of compositions of 100.00 grams, standby; The radial width of wherein related corynebacterium nanometer hydroxyapatite is less than 100 nanometers, and its aspect ratio distribution is between 2 and 6, and all corynebacterium nano hydroxyapatite materials that satisfies described radial width qualification and draw ratio qualification all can use.
With 3.00 gram medical grade silane coupler KH-570 hydrolysis under the effect of acetic acid, add 100 ml water alcoholic solutions, water in this water-alcohol solution, the alcohol volume ratio is 1.0 to 10.0, subsequently, add the above-mentioned mixed in advance nano inorganic powder that contains two kinds of compositions of 35.00 grams, in ultrasound wave, disperse, under 100 ℃ of temperature, reacted 2 hours afterwards, move to baking oven, dried 2 hours down at 80 ℃ earlier, then, with described water-alcohol solution washing, again in 80 ℃ of down oven dry 12 hours, after be warming up to 100 ℃ and continue oven dry 5 hours, after the drying, pulverize, make the nano inorganic powder after the modification, standby, reserve level is slightly greater than requirement.
Get 10.00 gram carbamate double methyl methacrylates, and get 30.00 gram bisphenol-A glycidyl methacrylate, in the above two mixture, add 15.00 gram double methyl methacrylate triethylene glycol esters, 10.00 gram Ethylene glycol dimethacrylate dilution, this mixture system is stirred, make resinous substrates, thereafter, under the lucifuge condition, the resinous substrates made and 1.00 gram camphorquinones and 1.20 gram dimethylaminoethyl acrylate methyl ammonia ethyl esters are mixed, after mixing, add therein 32.80 the gram these routine described modifications after the nano inorganic powder that contains multiple composition, carrying out mechanical agitation mixes, after the mechanical agitation married operation was finished, ultrasound wave effect 20 minutes placed vacuum desiccator with mixture, application of vacuum 20 hours, remove the bubble and other volatile impurity that are mingled with in the mixture, make nano-composite resin material, be i.e. the described multicomponent composite materials used for single paste type cavity filling of this case; Can under lucifuge condition according to usual use amount carry out finished product packing thereafter.
Embodiment 9:
Take by weighing 10.00 gram corynebacterium nanometer hydroxyapatites, and the commercially available biological glass powder of 90.00 grams carries out uniform mixing by churned mechanically mode with above two kinds of compositions, makes gross weight and is the nano inorganic powder that contains two kinds of compositions of 100.00 grams, standby; The radial width of wherein related corynebacterium nanometer hydroxyapatite is less than 100 nanometers, and its aspect ratio distribution is between 2 and 6, and all corynebacterium nano hydroxyapatite materials that satisfies described radial width qualification and draw ratio qualification all can use.
With 4.00 gram medical grade silane coupler KH-570 hydrolysis under the effect of acetic acid, add 100 ml water alcoholic solutions, water in this water-alcohol solution, the alcohol volume ratio is 1.0 to 6.0, subsequently, add the above-mentioned mixed in advance nano inorganic powder that contains two kinds of compositions of 35.00 grams, in ultrasound wave, disperse, under 75 ℃ of temperature, reacted 15 hours afterwards, move to baking oven, dried 2 hours down at 80 ℃ earlier, then, with described water-alcohol solution washing, again in 80 ℃ of down oven dry 12 hours, after be warming up to 100 ℃ and continue oven dry 5 hours, after the drying, pulverize, make the nano inorganic powder after the modification, standby, reserve level is slightly greater than requirement.
Get 30.00 gram carbamate double methyl methacrylates, and get 10.00 gram bisphenol-A glycidyl methacrylate, in the above two mixture, add 10.00 gram double methyl methacrylate triethylene glycol esters, 15.00 gram Ethylene glycol dimethacrylate dilution, this mixture system is stirred, make resinous substrates, thereafter, under the lucifuge condition, the resinous substrates made and 1.00 gram camphorquinones and 1.20 gram dimethylaminoethyl acrylate methyl ammonia ethyl esters are mixed, after mixing, add therein 32.80 the gram these routine described modifications after the nano inorganic powder that contains multiple composition, carrying out mechanical agitation mixes, after the mechanical agitation married operation was finished, ultrasound wave effect 20 minutes placed vacuum desiccator with mixture, application of vacuum 20 hours, remove the bubble and other volatile impurity that are mingled with in the mixture, make nano-composite resin material, be i.e. the described multicomponent composite materials used for single paste type cavity filling of this case; Can under lucifuge condition according to usual use amount carry out finished product packing thereafter.
Embodiment 10:
Take by weighing 40.00 gram corynebacterium nanometer hydroxyapatites, and the biological glass powder of 60.00 grams carries out uniform mixing by churned mechanically mode with above two kinds of compositions, makes gross weight and is the nano inorganic powder that contains two kinds of compositions of 100.00 grams, standby; The radial width of wherein related corynebacterium nanometer hydroxyapatite is less than 100 nanometers, and its aspect ratio distribution is between 2 and 6, and all corynebacterium nano hydroxyapatite materials that satisfies described radial width qualification and draw ratio qualification all can use.
With 5.00 gram medical grade silane coupler KH-570 hydrolysis under the effect of acetic acid, add 100 ml water alcoholic solutions, water in this water-alcohol solution, the alcohol volume ratio is 1.0 to 5.0, subsequently, add the above-mentioned mixed in advance nano inorganic powder that contains two kinds of compositions of 35.00 grams, in ultrasound wave, disperse, under 60 ℃ of temperature, reacted 20 hours afterwards, move to baking oven, dried 2 hours down at 80 ℃ earlier, then, with described water-alcohol solution washing, again in 80 ℃ of down oven dry 12 hours, after be warming up to 100 ℃ and continue oven dry 5 hours, after the drying, pulverize, make the nano inorganic powder after the modification, standby, reserve level is slightly greater than requirement.
Get 30.00 gram carbamate double methyl methacrylates, and get 20.00 gram bisphenol-A glycidyl methacrylate, in the above two mixture, add 10.00 gram double methyl methacrylate triethylene glycol esters, 5.00 gram Ethylene glycol dimethacrylate dilution, this mixture system is stirred, make resinous substrates, thereafter, under the lucifuge condition, the resinous substrates made and 1.00 gram camphorquinones and 1.20 gram dimethylaminoethyl acrylate methyl ammonia ethyl esters are mixed, after mixing, add therein 32.80 the gram these routine described modifications after the nano inorganic powder that contains multiple composition, carrying out mechanical agitation mixes, after the mechanical agitation married operation was finished, ultrasound wave effect 20 minutes placed vacuum desiccator with mixture, application of vacuum 20 hours, remove the bubble and other volatile impurity that are mingled with in the mixture, make nano-composite resin material, be i.e. the described multicomponent composite materials used for single paste type cavity filling of this case; Can under lucifuge condition according to usual use amount carry out finished product packing thereafter.
Claims (5)
1. multicomponent composite materials used for single paste type cavity filling preparation method may further comprise the steps:
A forms silane coupler hydrolysis under acetic acid catalysis the water alcohol system that contains coupling agent;
B adds ultra-sonic dispersion in the water alcohol system that contains coupling agent with nano inorganic powder, and after reacting completely, washing, drying obtain the inorganic nano-filler of modification;
C adds an amount of diluent dilution with resin monomer, forms the resinous substrates with good miscibility;
D under the lucifuge condition, adds light trigger and coinitiator with the resinous substrates for preparing, and after stirring, adds the inorganic nano-filler of modification again, behind the mix homogeneously, removes interlaminar resin and has bubble, prepares nano-composite resin material;
It is characterized in that it is 10%～80% corynebacterium nanometer hydroxyapatite that described nano inorganic powder contains the percetage by weight that accounts for nano inorganic powder weight; The radial width of described corynebacterium nanometer hydroxyapatite is less than 100 nanometers, and the aspect ratio distribution of corynebacterium nanometer hydroxyapatite is between 2 and 6; The molecular weight ranges of described resin monomer is 200～5000; Described resin monomer is a kind of or both combinations in bisphenol-A glycidyl methacrylate, the carbamate double methyl methacrylate; Diluent is one or more the combination in double methyl methacrylate triethylene glycol ester, Ethylene glycol dimethacrylate, the hydroxyethyl methylacrylate; Light trigger is a camphorquinone; Coinitiator is a dimethylaminoethyl acrylate methyl ammonia ethyl ester; Described silane coupler is medical grade KH-570; Water is 5 to 95～70 to 30 with the volume ratio of alcohol in the described water alcohol system; In steps d, the weight percentage of each component is respectively in the nanocomposite: the inorganic nano-filler 20%～85% after resin monomer 8%～70%, diluent 5%～25%, light trigger 0.25%～2%, coinitiator 0.5%～3%, the modification.
2. multicomponent composite materials used for single paste type cavity filling preparation method according to claim 1, it is characterized in that, the radial width of described corynebacterium nanometer hydroxyapatite is between 5 nanometers and 30 nanometers, and the aspect ratio distribution of corynebacterium nanometer hydroxyapatite is between 2 and 4.
3. multicomponent composite materials used for single paste type cavity filling preparation method according to claim 1, it is characterized in that, the weight percentage of silane coupler is 0.5%～10% in the water alcohol system, and, in step b, nano inorganic powder is 1 to 20～1 to 2 with the weight ratio of water alcohol system.
4. multicomponent composite materials used for single paste type cavity filling preparation method according to claim 1 is characterized in that, in step b, reaction temperature is 50 ℃～100 ℃, and the response time is 2h～24h.
5. multicomponent composite materials used for single paste type cavity filling preparation method according to claim 1, it is characterized in that, in steps d, be by ultrasonication 10min～2h then the mode of vacuum drying effect 10h～24h remove the bubble that exists in the resin.
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