CN101507687A - Preparation method of dentistry composite resin material capable of improving abrasion resistance and obdurability - Google Patents
Preparation method of dentistry composite resin material capable of improving abrasion resistance and obdurability Download PDFInfo
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Abstract
The invention relates to a method for preparing a dental composite resin material aiming to improve the wear resistance and the toughness, which belongs to the field of preparations for dentistry. The wear resistance and the toughness of the prior dental composite resin material used for tooth cavity filling need to be further improved, and the proposal devotes to solving the problem. The method of the proposal comprises the following steps that: a silane coupling agent is utilized to perform surface modification on nano-inorganic powder, the modified nano-inorganic powder and materials such as a monomer (such as bisphenol A-glycidyl methacrylate), a diluting agent (such as triethylene-glycol dimethacrylate), a photo initiator (such as camphorquinone), and a coinitiator (such as 2-(dimethylamino)ethyl methacrylate) are mixed evenly under dark conditions, and bubbles are removed under vacuum conditions. The key point of the proposal is that the nano-inorganic powder contains silicon dioxide nano-rods which account for 10 to 80 percent of the weight of the nano-inorganic powder. The silicon dioxide nano-rods added into the material help to improve the wear resistance and the toughness of the material.
Description
Technical field
The present invention relates to a kind of dentistry compound resin material preparation method that is intended to improve wearability and obdurability, belong to that A61K is medical, the dental preparation field.
Background technology
The dental care development of technology depends on the technological progress of dental materials to a great extent; Dental materials relates to the beauty treatment of oral medical purposes and oral cavity and modifies many aspects such as applications, this wherein, the cavity packing material be use in all kinds of dental materialss frequently, a class material that use amount is bigger.
The dental caries that cavity is a symptom to occur, its public's incidence rate also is in higher numerical value level at present, no matter be in developed country, still in undeveloped country, the incidence rate of dental caries is all higher, with China is example, the caries prevalence rate per capita of China is 40%, and wherein child's caries prevalence rate is 80%, and adolescence's caries prevalence rate is 60～70%, old people's caries prevalence rate is 52%, and each patient on average relates to 2～3 teeth.Above-mentioned numeral shows, dental filling material great demand arranged.Dentistry composite resin is because of having higher mechanical strength, advantage such as 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 and be widely used in the repairing filling of cavity.But the anti-wear performance of dentistry composite resin is still not ideal enough at present.
Dentistry composite resin also is called tooth section composite resin, and it is a kind of teeth repairing material that is combined by organic resin substrate and surface treated inorganic filler and initiator system, is widely used in directly and indirectly repairing of all kinds of dental defect.For a long time, for overcoming the disadvantage of traditional teeth repairing material-silver amalgam, people are seeking a kind of repair materials safely and effectively can replace silver amalgam always.It is that organic resin and adamantine bonding maintenance have found a kind of effective ways that Buonocore adopts phosphoric acid pretreatment facing the fifties, Bowen successfully synthesizes a kind of important resin monomer BIS-GMA with special construction and performance in the sixties, on this basis, dentistry composite resin is developed rapidly.Dentistry composite resin has become the requisite important materials of dental defect repairing and treating, runs neck and neck with silver amalgam.
Dentistry compound resin material is at present many to be configured to single paste type or two paste type for clinical use by manufacturer.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, described initiator and coinitiator can be respectively peroxide and tertiary amine for the situation of chemosetting, peroxide concrete example such as BPO, tertiary amine concrete example such as DHET, 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; Dummy suffix notation BPO acute pyogenic infection of finger tip benzoyl peroxide, benzoyl peroxide has another name called dibenzoyl peroxide; Dummy suffix notation DHET acute pyogenic infection of finger tip N, the N-dihydroxyethyl p-toluidine.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 it can be brought into play in composite resin also 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, the rough approximation substantially of amorphous granular is in spheric pattern, also extracts toughening mechanisms some shortcomings have been arranged because of fully not taking into account for the Strengthening and Toughening contribution of dentistry composite resin.
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 dentistry compound resin material preparation method that is intended to improve wearability and obdurability, 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 dentistry compound resin material;
This case main points are, it is 10%～80% silicon dioxide nano rod that described nano inorganic powder contains the percetage by weight that accounts for nano inorganic powder weight; The radial width of described silicon dioxide nano rod is less than 200 nanometers, and the aspect ratio distribution of silicon dioxide nano rod is between 3 and 20.
The radial width of described silicon dioxide nano rod can be the arbitrarily selected width less than 200 nanometers, and still, the preferred value of silicon dioxide nano rod radial width is between 5 nanometers and 195 nanometers.
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 compound resin material 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 dentistry compound resin material, but, based on the demand of the described dentistry compound resin material 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% silicon dioxide nano rod 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: nanometer hydroxyapatite, 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.
About the related silicon dioxide nano rod raw material of this case, that its technology of preparing can be from the public information platform is known, understand the open source information.
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 dentistry compound resin material system, add an amount of polymerization inhibitor and its objective is the effective life of keeping dentistry compound resin material, 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 dentistry compound 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 silicon dioxide nano rod composition that is added as critical increase wearability, increase flexible material composition, silicon dioxide nano rod has the inherent moderate hardness of silicon dioxide, and, in resin surface layer is constructed after solidifying in application, the bar-shaped pattern of silicon dioxide nano rod, the also feasible silicon dioxide nano rod that is positioned on the surface layer can have more than amorphous granular, and multimachine can be rooted in resin matrix dearly, in other words, adhesion between silicon dioxide nano rod on the surface layer and composite resin matrix is more strong comparatively speaking, this factor, make the silicon dioxide nano rod that is positioned on the surface layer among using, be difficult for being peeled off by friction strength, therefore the silicon dioxide nano rod 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 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 silicon dioxide nano rod therebetween changes bending, distortion and fracture more intense drag, and this stems to a great extent extracts toughening effect, and this factor helps to improve the toughness of composite resin; And, have the silicon dioxide nano rod 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 silicon dioxide nano rods, 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; Wherein the radial width of related silicon dioxide nano rod is less than 200 nanometers, and its aspect ratio distribution is between 3 and 20, and all silicon dioxide nano rod 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 is finished, ultrasound wave effect 10 minutes places vacuum desiccator with mixture, application of vacuum 24 hours, remove the bubble and other volatile impurity that are mingled with in the mixture, make described dentistry compound resin material; Can under lucifuge condition according to usual use amount carry out finished product packing thereafter.
Embodiment 2:
Take by weighing 80.00 gram silicon dioxide nano rods, and, 15.00 gram barium strontium boron glass powder, and 5.00 gram nanometer hydroxyapatites 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; Wherein the radial width of related silicon dioxide nano rod is less than 200 nanometers, and its aspect ratio distribution is between 3 and 20, and all silicon dioxide nano rod 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 therein 85.00 the gram these routine described modifications after nano inorganic powder, carry out mechanical agitation and mix, after the mechanical agitation married operation is finished, ultrasound wave effect 2 hours, mixture is placed vacuum desiccator, the bubble and other volatile impurity that are mingled with in the mixture are removed in application of vacuum 10 hours, make described dentistry compound resin material; Can under lucifuge condition according to usual use amount carry out finished product packing thereafter.
Embodiment 3:
Take by weighing 45.00 gram silicon dioxide nano rods, and, 25.00 gram barium strontium boron glass powder, and, 10.00 gram nanometer hydroxyapatites, and, 5.00 gram strontium glass powder, and, 5.00 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; Wherein the radial width of related silicon dioxide nano rod is less than 200 nanometers, and its aspect ratio distribution is between 3 and 20, and all silicon dioxide nano rod 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 therein 52.50 the gram these routine described modifications after the nano inorganic powder that contains multiple composition, carry out mechanical agitation and mix, after the mechanical agitation married operation is finished, ultrasound wave effect 45 minutes, mixture is placed vacuum desiccator, the bubble and other volatile impurity that are mingled with in the mixture are removed in application of vacuum 16 hours, make described dentistry compound resin material; Can under lucifuge condition according to usual use amount carry out finished product packing thereafter.
Embodiment 4:
Take by weighing 30.00 gram silicon dioxide nano rods, 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; Wherein the radial width of related silicon dioxide nano rod is less than 200 nanometers, and its aspect ratio distribution is between 3 and 20, and all silicon dioxide nano rod 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 therein 32.80 the gram these routine described modifications after nano inorganic powder, carry out mechanical agitation and mix, after the mechanical agitation married operation is finished, ultrasound wave effect 20 minutes, mixture is placed vacuum desiccator, the bubble and other volatile impurity that are mingled with in the mixture are removed in application of vacuum 20 hours, make described dentistry compound resin material; Can under lucifuge condition according to usual use amount carry out finished product packing thereafter.
Embodiment 5:
Take by weighing 60.00 gram silicon dioxide nano rods, 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; Wherein the radial width of related silicon dioxide nano rod is less than 200 nanometers, and its aspect ratio distribution is between 3 and 20, and all silicon dioxide nano rod 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 therein 32.80 the gram these routine described modifications after nano inorganic powder, carry out mechanical agitation and mix, after the mechanical agitation married operation is finished, ultrasound wave effect 20 minutes, mixture is placed vacuum desiccator, the bubble and other volatile impurity that are mingled with in the mixture are removed in application of vacuum 20 hours, make described dentistry compound resin material; Can under lucifuge condition according to usual use amount carry out finished product packing thereafter.
Embodiment 6:
Take by weighing 70.00 gram silicon dioxide nano rods, 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; Wherein the radial width of related silicon dioxide nano rod is less than 200 nanometers, and its aspect ratio distribution is between 3 and 20, and all silicon dioxide nano rod 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 methylacrylic acid diformazan ammonia ethyl esters are mixed, after mixing, add the nano inorganic powder that contains multiple composition 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 places vacuum desiccator with mixture, application of vacuum 20 hours, remove the bubble and other volatile impurity that are mingled with in the mixture, make described dentistry compound resin material; Can under lucifuge condition according to usual use amount carry out finished product packing thereafter.
Embodiment 7:
Take by weighing 75.00 gram silicon dioxide nano rods, 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; Wherein the radial width of related silicon dioxide nano rod is less than 200 nanometers, and its aspect ratio distribution is between 3 and 20, and all silicon dioxide nano rod 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 is finished, ultrasound wave effect 20 minutes is put mixture in the fourth vacuum desiccator, application of vacuum 20 hours, remove the bubble and other volatile impurity that are mingled with in the mixture, make described dentistry compound resin material; Can under lucifuge condition according to usual use amount carry out finished product packing thereafter.
Embodiment 8:
Take by weighing 65.00 gram silicon dioxide nano rods, 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; Wherein the radial width of related silicon dioxide nano rod is less than 200 nanometers, and its aspect ratio distribution is between 3 and 20, and all silicon dioxide nano rod 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 is finished, ultrasound wave effect 20 minutes places vacuum desiccator with mixture, application of vacuum 20 hours, remove the bubble and other volatile impurity that are mingled with in the mixture, make described dentistry compound resin material; Can under lucifuge condition according to usual use amount carry out finished product packing thereafter.
Embodiment 9:
Take by weighing 10.00 gram silicon dioxide nano rods, 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; Wherein the radial width of related silicon dioxide nano rod is less than 200 nanometers, and its aspect ratio distribution is between 3 and 20, and all silicon dioxide nano rod 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 is finished, ultrasound wave effect 20 minutes places vacuum desiccator with mixture, application of vacuum 20 hours, remove the bubble and other volatile impurity that are mingled with in the mixture, make described dentistry compound resin material; Can under lucifuge condition according to usual use amount carry out finished product packing thereafter.
Embodiment 10:
Take by weighing 40.00 gram silicon dioxide nano rods, and, the biological glass powder of 30.00 grams, 30.00 the nanometer hydroxyapatite of gram, by churned mechanically mode above two kinds of compositions are carried out uniform mixing, make gross weight and be the nano inorganic powder that contains two kinds of compositions of 100.00 grams, standby; Wherein the radial width of related silicon dioxide nano rod is less than 200 nanometers, and its aspect ratio distribution is between 3 and 20, and all silicon dioxide nano rod 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 is finished, ultrasound wave effect 20 minutes places vacuum desiccator with mixture, application of vacuum 20 hours, remove the bubble and other volatile impurity that are mingled with in the mixture, make described dentistry compound resin material; Can under lucifuge condition according to usual use amount carry out finished product packing thereafter.
Claims (10)
1. be intended to improve the dentistry compound resin material preparation method of wearability and obdurability, 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 dentistry compound resin material;
It is characterized in that it is 10%～80% silicon dioxide nano rod that described nano inorganic powder contains the percetage by weight that accounts for nano inorganic powder weight; The radial width of described silicon dioxide nano rod is less than 200 nanometers, and the aspect ratio distribution of silicon dioxide nano rod is between 3 and 20.
2. the dentistry compound resin material preparation method that is intended to improve wearability and obdurability according to claim 1 is characterized in that the radial width of described silicon dioxide nano rod is between 5 nanometers and 195 nanometers.
3. the dentistry compound resin material preparation method that is intended to improve wearability and obdurability according to claim 1 is characterized in that 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.
4. the dentistry compound resin material preparation method that is intended to improve wearability and obdurability according to claim 1 is characterized in that light trigger is a camphorquinone, and coinitiator is a dimethylaminoethyl acrylate methyl ammonia ethyl ester.
5. the dentistry compound resin material preparation method that is intended to improve wearability and obdurability according to claim 1 is characterized in that described silane coupler is medical grade KH-570, and water is 5 to 95～70 to 30 with the volume ratio of alcohol in the described water alcohol system.
6. be intended to improve the dentistry compound resin material preparation method of wearability and obdurability according to claim 1 or 5, 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.
7. the dentistry compound resin material preparation method that is intended to improve wearability and obdurability according to claim 1 is characterized in that, in step b, reaction temperature is 50 ℃～100 ℃, and the response time is 2h～24h.
8. the dentistry compound resin material preparation method that is intended to improve wearability and obdurability 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.
9. the dentistry compound resin material preparation method that is intended to improve wearability and obdurability according to claim 1 is characterized in that, in steps d, the weight percentage of each component is respectively in the dentistry compound resin material:
Resin monomer 8%～70%;
Diluent 5%～25%;
Light trigger 0.25%～2%;
Coinitiator 0.5%～3%;
Inorganic nano-filler 20%～85% after the modification.
10. the dentistry compound resin material preparation method that is intended to improve wearability and obdurability according to claim 1, it is characterized in that all the other compositions of described inorganic nano-filler are a kind of of following material at least: nanometer hydroxyapatite, biological glass powder, commercially available barium lead glass powder, strontium glass powder, boron lead glass powder, barium strontium boron glass powder.
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| CN101690696B (en) * | 2009-09-25 | 2012-02-01 | 李榕生 | Method for preparing anti-secondary caries cavity repairing material |
| CN101703450B (en) * | 2009-09-29 | 2012-07-25 | 李榕生 | Fluoridated dental composite resin material contributing to resisting secondary caries |
| CN104524638A (en) * | 2014-11-19 | 2015-04-22 | 上海纳米技术及应用国家工程研究中心有限公司 | Silicon oxide-calcium phosphate class composite nano-filler and preparation method thereof |
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| CN109199874A (en) * | 2018-11-07 | 2019-01-15 | 西南交通大学 | A kind of compound resin and preparation method thereof |
| CN111821201A (en) * | 2019-03-26 | 2020-10-27 | 株式会社松风 | Dental stereolithography three-dimensional printing material for producing dental three-dimensional molded object |
| CN113081859A (en) * | 2021-03-15 | 2021-07-09 | 山东沪鸽口腔材料股份有限公司 | Anti-staining hard resin denture and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101690696B (en) * | 2009-09-25 | 2012-02-01 | 李榕生 | Method for preparing anti-secondary caries cavity repairing material |
| CN101703450B (en) * | 2009-09-29 | 2012-07-25 | 李榕生 | Fluoridated dental composite resin material contributing to resisting secondary caries |
| CN104524638A (en) * | 2014-11-19 | 2015-04-22 | 上海纳米技术及应用国家工程研究中心有限公司 | Silicon oxide-calcium phosphate class composite nano-filler and preparation method thereof |
| CN107595644A (en) * | 2017-09-29 | 2018-01-19 | 郑州大学第附属医院 | A kind of compound nuclear resin of dentistry and preparation method thereof |
| CN107595644B (en) * | 2017-09-29 | 2018-10-09 | 郑州大学第一附属医院 | A kind of compound nuclear resin of dentistry and preparation method thereof |
| CN109199874A (en) * | 2018-11-07 | 2019-01-15 | 西南交通大学 | A kind of compound resin and preparation method thereof |
| CN111821201A (en) * | 2019-03-26 | 2020-10-27 | 株式会社松风 | Dental stereolithography three-dimensional printing material for producing dental three-dimensional molded object |
| CN113081859A (en) * | 2021-03-15 | 2021-07-09 | 山东沪鸽口腔材料股份有限公司 | Anti-staining hard resin denture and preparation method thereof |
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