CN101703451B - Drug release mechanism based fluorine-containing dental restorative material - Google Patents
Drug release mechanism based fluorine-containing dental restorative material Download PDFInfo
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- CN101703451B CN101703451B CN2009102051204A CN200910205120A CN101703451B CN 101703451 B CN101703451 B CN 101703451B CN 2009102051204 A CN2009102051204 A CN 2009102051204A CN 200910205120 A CN200910205120 A CN 200910205120A CN 101703451 B CN101703451 B CN 101703451B
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Abstract
The invention relates to a drug release mechanism based fluorine-containing dental restorative material, belonging to the field of dental preparation. The invention aims at solving the problem that the current cavity-filling compound resin materials in the simple fluorine doped salt are fast in fluorine release, poor in interfacial compatibility and have no rigid support for the cavity-filling bodies. The material comprises the following components in percentage by weight: 20-85% of inorganic nanopowder subjected to surface modification by silane coupling agents, 8-70% of resin monomers such as bisphenol A-glycidyl methacrylate, 5-25% of diluents such as triethylene-glycol dimethacrylate, 0.25-2% of photoinitiators such as camphorquinone and 0.5-3% of coinitiators such as dimethylaminoethyl methacrylate. The technical scheme is characterized in that the inorganic nanopowder contains fluorine-carrying zirconia nanotubes which account for 10-80% of the inorganic nanopowder by weight. The fluorine-carrying zirconia nanotubes have the functions of resisting secondary caries by releasing fluorine and reinforcing structures.
Description
Technical field
The present invention relates to a kind of fluorine-containing dental restorative material, belong to that A61K is medical, the dental preparation field based on drug release mechanism.
Background technology
In view of its comprehensive advantage, composite resin be clinically at present gradually popular employing fill out the dental caries material.
Fill out dental caries and can be divided into single paste type composite resin and two big types of two paste type composite resins substantially with composite resin; Difference between them is only in the initiation mode of cross-linking and curing reaction, these two types of composite resins in solidification process all with certain volume contraction, therefore; No matter fill out the dental caries operation with any composite resin; All be easy to generate microfissure filling out dental caries obturator edge, and cause the little seepage in edge thus, and then cause recurrent caries.
Many researchs show; If the cavity filling material has the releasing fluoride ion ability, the recurrent caries at cavity filling body edge will significantly reduce, because the fluorion that discharges can diffuse in the adjacent hard tooth tissue; Combine with hydroxyapatite, improve the anti-bad ability of recurrent caries of hard tooth tissue.
About in composite resin, adding the experimental evidence that fluoride can produce good effect; Can be referring to paper " kind of fluoride and content be to the influence of composite resin fluorion release characteristics "; The author of this paper is the Li Dong, Zhao Xinyi of Stomatologic Medical College, No.4 Military Medicine Univ. doctor religion portion etc., and this article was delivered at Third Military Medical University's journal in July, 2003.The work of this paper is useful, constructive work.
That introduces in above-mentioned this paper fills out dental caries with mixing the fluorine composite resin, and its preparation method has certain representativeness in now; This type that this paper is introduced filled out dental caries with the method for preparing of mixing the fluorine composite resin; Be with inorganic fluoride salt oven dry, levigate, sieve, afterwards, with the inorganic filler mix homogeneously of inorganic fluoride salt and composite resin; And mix with resinous substrates and diluent etc., be mixed with two paste type composite resins.The experimental data of this paper shows that this type composite resin after the curing truly has releases the fluorine effect, still, this type composite resin release the fluorine persistence, stability is not ideal enough, releases fluorine amount decay rapidly.
And, mix in the fluorine composite resin material in above-mentioned this type, the inorganic fluoride salt that is mixed be solubility or say water miscible inorganic fluoride salt, for example sodium fluoride (NaF), potassium fluotitanate (K
2TiF
6) etc.; The uncomfortable cooperating surfaces modification of this type inorganic fluoride salt that is to say, inorganic fluoride salt that can surface modification be awkwardly embed with the inconsistent organic resin matrix of its polarity in; And; The solubility that exists in this way and inorganic fluoride salt that very easily pulverize itself does not have constructive rigidity, except that releasing the fluorine effect, composite resin is not had rigid support; This has just produced a negative effect; There is form in the character of the no rigidity of inorganic fluoride salt, very easily pulverizing together with its inconsistent embedding of material peripheral with it, makes that the structural continuity of resin matrix is interfered, destroys, and this will cause composite resin being subdued aspect toughness and tenacity and the anti-wear performance.
Summary of the invention
Technical problem to be solved by this invention is; Release the fluorine instability problem to the existing dental caries of filling out with mixing the inorganic fluoride salt that exists in the fluorine composite resin; And; The consumption problem of following the naked doping of inorganic fluoride salt of generation and bringing to whole toughness and tenacity of composite resin and anti-wear performance, research and develop a kind of newly help to prevent recurrent caries fill out dental caries with mixing the fluorine composite resin material.
The present invention solve the technical problem through following scheme; This scheme provides a kind of fluorine-containing dental restorative material based on drug release mechanism, and the weight percentage of each composition is following in this material: 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; Wherein, the inorganic nano-filler after the said modification is to be handled through silane coupler by nano inorganic powder, and through powder body material dry, that pulverizing forms afterwards; Said nano inorganic powder contains the percetage by weight that the accounts for nano inorganic powder weight Nano tube of zirconium dioxide of solubility inorganic fluoride salt that has been its inner surface load of 10%～80%; Said its inner surface load the Nano tube of zirconium dioxide of solubility inorganic fluoride salt be to carry a fluorodioxy zirconium nanotube; This year, fluorodioxy zirconium nanotube was to carry fluorodioxy zirconium nanotube via what following main step of preparation process was processed: the Nano tube of zirconium dioxide that 1. Nano tube of zirconium dioxide is flooded, 2. will flood the inorganic fluoride salt aqueous solution in the inorganic fluoride salt aqueous solution carries out drying, 3. dried year fluorodioxy zirconium nanotube aggregate is pulverized at 40 ℃～100 ℃ warm areas; Said inorganic fluoride salt is sodium fluoride or potassium fluotitanate, and the weight percentage of inorganic fluoride salt is between 0.5%～5.0% in the inorganic fluoride salt aqueous solution; The external diameter of said Nano tube of zirconium dioxide is between 20 nanometers and 300 nanometers, and the length of said Nano tube of zirconium dioxide is between 0.2 micron and 200 microns, and the ratio of the length of said Nano tube of zirconium dioxide and external diameter is between 3 and 100.
The external diameter of said Nano tube of zirconium dioxide can be the arbitrary value between 20 nanometers and 300 nanometers; But; Smaller external diameter helps combining of Nano tube of zirconium dioxide and resin matrix; Based on this, the preferred external diameter scope of said Nano tube of zirconium dioxide is between 20 nanometers and 200 nanometers; It is the arbitrary value between 0.2 micron and 200 microns that the length of said Nano tube of zirconium dioxide can allow; But; Because the Nano tube of zirconium dioxide of smaller length more helps reducing the operation easier of raw materials mix operation; Therefore, the even more ideal length range of Nano tube of zirconium dioxide is that the preferred length scope is between 0.2 micron and 2 microns; It is the arbitrary value between 3 and 100 that the ratio of the length of said Nano tube of zirconium dioxide and external diameter can allow; Be based on the consideration that reduces raw materials mix process operations difficulty equally; It is more favourable that the length of said Nano tube of zirconium dioxide and the preferred value of the ratio of external diameter are got smaller value; So, the preferable range of this value is that more better scope is between 3 and 10.The Nano tube of zirconium dioxide of low draw ratio and short and small yardstick not only helps reducing the operation easier of raw materials mix operation; And obviously, it also helps the stability that increases the finished product paste; Simultaneously; Increase the flowability of finished product paste, and the raising of the mobile performance of finished product paste, then help to reduce the operation easier of this finished product paste clinical practice.
Said 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 said its molecular weight of resin monomer is between 200～5000; Said resin monomer is a polyfunctional group methyl acrylic ester material; The polyfunctional group methacrylate monomer relates to miscellaneous similar chemical substance; This type material all is easy to realize polymerizing curable between monomer fast under the initiation of polymerizing curable initiation material, said resin monomer preferred material is a kind of or both combinations in bisphenol-A GMA, the carbamate double methyl methacrylate; Because above-mentioned preferred monomer is that class materials such as bisphenol-A GMA, carbamate double methyl methacrylate have higher viscosity; For ease of the adding operation of inorganic nano-filler and the practical application of processing finished product; Diluent components is necessary in the compositions; The existence of diluent can reduce the viscosity of composite resin paste; The optional material of diluent that is suitable for this case purpose is more, and said diluent preferred material is one or more the combination in double methyl methacrylate triethylene glycol ester, GDMA, the hydroxyethyl methacrylate.Said diluent is participating in not having too big-difference with materials such as said bisphenol-A GMA and carbamate double methyl methacrylates aspect the cross-linking and curing reaction; Distinguish with diluent one speech; Be mainly this type material sees it is for reducing the composition that viscosity adds more significantly from function.
This case is applicable to that based on the fluorine-containing dental restorative material of drug release mechanism 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 said silane coupler; All there is introduction in each corresponding producer of the condition of manipulating of above-mentioned various commercially available silane couplers, and the condition of manipulating of all kinds of commercially available silane couplers is known.
Preceding text are addressed, the said nano inorganic powder of this case contain the percetage by weight that accounts for nano inorganic powder weight be 10%～80% carry fluorodioxy zirconium nanotube; It is other the selected arbitrarily inorganic material that is suitable for that all the other compositions of said inorganic nano-filler can allow; The preferred material of all the other compositions of said 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.
The said fluorine-containing dental restorative material based on drug release mechanism of this case also is that dentistry compound resin material is used in a kind of single paste type photocuring cavity filling certainly.
The technology of preparing of the related Nano tube of zirconium dioxide of this case can be sought from existing scientific and technical literature; Relevant scientific and technical literature is for example: the application for a patent for invention case that is entitled as " method for preparing of Nano tube of zirconium dioxide " that the Hebei University of Technology of China submitted on May 23rd, 2007; Open day of this case is on October 10th, 2007; The publication number of this case is CN101049964, and the application number of this application case is 200710057426.0.When needs use the Nano tube of zirconium dioxide raw material of low draw ratio; Grinding, the fragmentation that can carry out appropriateness through the Nano tube of zirconium dioxide raw material with high length-diameter ratio form the Nano tube of zirconium dioxide raw material of low relatively draw ratio; Obtain the Nano tube of zirconium dioxide raw material of required low draw ratio in this way; Certainly, the approach that obtains the Nano tube of zirconium dioxide raw material of low draw ratio is not limited thereto.
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 relevant speciality Gao Ke also capable of using company provide with compensation prepares to be obtained; Certainly, related other related reagent and material can also be obtained through the mode to relevant speciality Gao Ke company customization finished product.
This case can also comprise some other compositions certainly based on the fluorine-containing dental restorative material of drug release mechanism; The for example an amount of polymerization inhibitor of said other composition; An amount of polymerization inhibitor can be kept the effective life of dental resin composition; Said polymerization inhibitor can be selected aldehydes matter for use, and the polymerization inhibitor composition is optional; The coloring agent that said other composition is also for example an amount of, an amount of coloring agent can be given dental resin composition after the curing with the natural teeth color and luster, are suitable for optional coloring agent such as titanium white and chrome yellow of this purpose etc., and said coloring agent component is optional.
Advantage of the present invention is that the space relies on the capillary tube adsorption effect to realize that the pipe of Nano tube of zirconium dioxide contains fluorine as the bearing space of inorganic fluoride salt in the pipe of this material use Nano tube of zirconium dioxide; Carry the elongated tubulose storage construct of fluorodioxy zirconium nanotube; Help slow, gentle, long-acting, the stable release of inorganic fluoride salt, meanwhile, can also realize carrying the modified-reaction of normal and silane coupler of the outer surface of fluorodioxy zirconium nanotube; Its outer surface is able to year fluorodioxy zirconium nanotube of normal modification; Good with the organic substrate compatibility of composite resin, be that Nano tube of zirconium dioxide self has inherent high hardness of zirconium dioxide and high obdurability owing to carry the base material of fluorodioxy zirconium nanotube, in resin surface layer is constructed after in application, solidifying; Carry the pattern of fluorodioxy zirconium nanotube; Determined that these years, fluorodioxy zirconium nanotube can be rooted in the resin matrix dearly, in other words, more strong in the adhesion of carrying between fluorodioxy zirconium nanotube and the composite resin matrix on the surface layer; This factor; The feasible fluorodioxy zirconium nanotube that carries that is positioned on the surface layer is difficult for being peeled off by friction strength among using, and therefore year fluorodioxy zirconium nanotube that is positioned on the surface layer can be anchored on the surface of composite resin, when slowly releasing fluorine more muchly; Can also bring into play its nanotube base material high rigidity and the front to the composite resin wearability that high-strength tenacity brought muchly benefits; That is to say, can slowly release fluorine, can help to reduce the abrasion speed of composite resin again; And; The composite resin matrix is inner after in application, solidifying; A disperse a large amount of year fluorodioxy zirconium nanotube therebetween is long lasting inner reserve fluorine source of slowly releasing fluorine; Simultaneously, disperse has more intense drag in the inner a large amount of fluorodioxy zirconium nanotube that carries of composite resin matrix to bending, the distortion of composite resin matrix and the variation of rupturing, and its strengthening action is similar to the strengthening action of reinforcing bar in the armored concrete; This strengthening action stems from extracts toughening effect, and this effect helps to improve the toughness and tenacity of composite resin.In brief, what this case material had both been realized said composite resin slowly releases fluorine, relies on slowly to release fluorine mechanism and resist recurrent caries, has realized the reinforcement to composite resin again simultaneously, has improved the anti-wear performance and the toughness and tenacity of composite resin.
The specific embodiment
The fluorodioxy zirconium nanotube that carries that relates in this case material is year fluorodioxy zirconium nanotube of processing via following main step of preparation process:
1. Nano tube of zirconium dioxide is flooded in the inorganic fluoride salt aqueous solution;
The Nano tube of zirconium dioxide that 2. will flood the inorganic fluoride salt aqueous solution carries out drying at 40 ℃～100 ℃ warm areas;
3. dried year fluorodioxy zirconium nanotube aggregate pulverized;
Said inorganic fluoride salt is sodium fluoride or potassium fluotitanate, and the weight percentage of inorganic fluoride salt is between 0.5%～5.0% in the inorganic fluoride salt aqueous solution; The external diameter of said Nano tube of zirconium dioxide is between 20 nanometers and 300 nanometers, and the length of said Nano tube of zirconium dioxide is between 0.2 micron and 200 microns, and the ratio of the length of said Nano tube of zirconium dioxide and external diameter is between 3 and 100.
The molecular formula of said sodium fluoride is NaF, and the molecular formula of said potassium fluotitanate is K
2TiF
6Utilizing the inorganic fluoride salt aqueous solution can be room temperature or higher temperature to the operative temperature that Nano tube of zirconium dioxide carries out impregnation process, all can.The dried temperature of having flooded the Nano tube of zirconium dioxide of inorganic fluoride salt aqueous solution can be any warm spot in 40 ℃～100 ℃ temperature ranges; Difference is a length consuming time; Dry at relative low temperature warm spot; Consuming time slightly long, and carry out drying process at the relatively-high temperature warm spot, then process is accomplished very fast.Be used for Nano tube of zirconium dioxide is carried out the inorganic fluoride salt aqueous solution of impregnation process, the weight percentage of inorganic fluoride salt wherein can be the selected arbitrarily value between 0.5%～5.0%, and difference is only being carried on the fluorine amount; It is bigger to carry the fluorine amount, can supply to release more for a long time fluorine, otherwise, release fluorine effectiveness time limit weak point; Select for use the dipping of which kind of concentration to use inorganic fluoride salt solution, can confirm as required.
This case material that has comprised said year fluorodioxy zirconium nanotube composition, i.e. the said fluorine-containing dental restorative material of this case based on drug release mechanism, some related embodiment are explained in detail as follows:
Embodiment 1:
Take by weighing 10.00 grams and carry fluorodioxy zirconium nanotube, and, 50.00 gram barium strontium boron glass powder; And 40.00 gram boron lead glass powder carry out uniform mixing through churned mechanically mode with above three kinds of compositions; Process gross weight and be the nano inorganic powder that contains multiple composition of 100.00 grams, subsequent 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, pure volume ratio are 70 to 30 in this water-alcohol solution, subsequently; Add the good nano inorganic powder that contains multiple composition of above-mentioned premix of 22.00 grams, in ultrasound wave, disperse, afterwards, reaction is 24 hours under 50 ℃ of temperature; Move to baking oven, dried 10 hours down at 80 ℃, then, with said water-alcohol solution washing; Dried 10 hours down in 100 ℃ again, after the drying, pulverize; Process the nano inorganic powder after the modification, subsequent use, reserve level is slightly greater than requirement.
In 70.00 gram bisphenol-A GMAs, add 5.00 gram double methyl methacrylate triethylene glycol ester dilutions, stir, process resinous substrates; Under lucifuge condition, the resinous substrates processed and 2.00 gram camphorquinones and 3.00 gram dimethylaminoethyl acrylate methyl ammonia ethyl esters mixed thereafter; After mixing, add the nano inorganic powder after this routine described modifications of 20.00 grams therein, carry out mechanical agitation and mix; After the mechanical agitation married operation is accomplished; 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, processing dental resin composition is the said fluorine-containing dental restorative material based on drug release mechanism 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 grams and carry fluorodioxy zirconium nanotube, and, 15.00 gram barium strontium boron glass powder; And 5.00 gram nanometer hydroxyapatites carry out uniform mixing through churned mechanically mode with above three kinds of compositions; Process gross weight and be the nano inorganic powder that contains multiple composition of 100.00 grams, subsequent 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, pure volume ratio are 5 to 95 in this water-alcohol solution, subsequently; Add the good nano inorganic powder that contains multiple composition of above-mentioned premix of 87.00 grams, in ultrasound wave, disperse, under 100 ℃ of temperature, reacted 2 hours afterwards, move to baking oven; Elder generation dried 2 hours down at 80 ℃, then, with said water-alcohol solution washing, dried 2 hours down in 80 ℃ again; After be warming up to 100 ℃ and continue oven dry 5 hours, after the drying, pulverize; Process the nano inorganic powder after the modification, subsequent use, reserve level is slightly greater than requirement.
Get 8.00 gram bisphenol-A GMAs, add 6.25 gram double methyl methacrylate triethylene glycol ester dilutions therein, both are stirred; Process resinous substrates, thereafter, under the lucifuge condition; The resinous substrates of processing 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 this routine described modifications of 85.00 grams therein; Carry out mechanical agitation and mix, after the mechanical agitation married operation is accomplished, 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, and processing dental resin composition is the said fluorine-containing dental restorative material based on drug release mechanism 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 grams and carry fluorodioxy zirconium nanotube, and, 25.00 gram barium strontium boron glass powder, and; 10.00 the gram nanometer hydroxyapatite, and, 5.00 gram strontium glass powders, and; 5.00 gram boron lead glass powder, and, the commercially available barium lead glass powder of 10.00 grams; Carry out uniform mixing through multiple composition more than the churned mechanically mode general, process gross weight and be the nano inorganic powder that contains multiple composition of 100.00 grams, subsequent 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, pure volume ratio are 2.4 to 1.0 in this water-alcohol solution, subsequently; Add the good nano inorganic powder that contains multiple composition of above-mentioned premix of 55.00 grams, in ultrasound wave, disperse, under 100 ℃ of temperature, reacted 2 hours afterwards, move to baking oven; Elder generation dried 2 hours down at 80 ℃, then, with said water-alcohol solution washing, dried 12 hours down in 80 ℃ again; After be warming up to 100 ℃ and continue oven dry 5 hours, after the drying, pulverize; Process the nano inorganic powder after the modification, subsequent use, reserve level is slightly greater than requirement.
Get 39.00 gram bisphenol-A GMAs, add 5.59 gram double methyl methacrylate triethylene glycol ester dilutions therein, both are stirred; Process resinous substrates, thereafter, under the lucifuge condition; The resinous substrates of processing 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 this routine described modifications of 52.50 grams therein; Carry out mechanical agitation and mix, after the mechanical agitation married operation is accomplished, 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, and processing dental resin composition is the said fluorine-containing dental restorative material based on drug release mechanism 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 grams and carry fluorodioxy zirconium nanotube, and, 30.00 gram barium strontium boron glass powder, and; 10.00 the gram biological glass powder, and, 5.00 gram strontium glass powders, and; 5.00 gram boron lead glass powder, and, the commercially available barium lead glass powder of 20.00 grams; Carry out uniform mixing through multiple composition more than the churned mechanically mode general, process gross weight and be the nano inorganic powder that contains multiple composition of 100.00 grams, subsequent 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, pure volume ratio are 1.0 to 10.0 in this water-alcohol solution, subsequently; Add the good nano inorganic powder that contains multiple composition of above-mentioned premix of 35.00 grams, in ultrasound wave, disperse, under 100 ℃ of temperature, reacted 2 hours afterwards, move to baking oven; Elder generation dried 2 hours down at 80 ℃, then, with said water-alcohol solution washing, dried 12 hours down in 80 ℃ again; After be warming up to 100 ℃ and continue oven dry 5 hours, after the drying, pulverize; Process the nano inorganic powder after the modification, subsequent use, reserve level is slightly greater than requirement.
Get 40.00 gram bisphenol-A GMAs, add 25.00 gram double methyl methacrylate triethylene glycol ester dilutions therein, both are stirred; Process resinous substrates, thereafter, under the lucifuge condition; The resinous substrates of processing 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 this routine described modifications of 32.80 grams therein; Carry out mechanical agitation and mix, after the mechanical agitation married operation is accomplished, 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, and processing dental resin composition is the said fluorine-containing dental restorative material based on drug release mechanism 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 grams and carry fluorodioxy zirconium nanotube, and the commercially available barium lead glass powder of 40.00 grams carries out uniform mixing through churned mechanically mode with above two kinds of compositions, processes gross weight and is the nano inorganic powder that contains two kinds of compositions of 100.00 grams, and is subsequent 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, pure volume ratio are 1.0 to 10.0 in this water-alcohol solution, subsequently; Add the good nano inorganic powder that contains two kinds of compositions of above-mentioned premix of 35.00 grams, in ultrasound wave, disperse, under 100 ℃ of temperature, reacted 2 hours afterwards, move to baking oven; Elder generation dried 2 hours down at 80 ℃, then, with said water-alcohol solution washing, dried 12 hours down in 80 ℃ again; After be warming up to 100 ℃ and continue oven dry 5 hours, after the drying, pulverize; Process the nano inorganic powder after the modification, subsequent use, reserve level is slightly greater than requirement.
Get 50.00 gram carbamate double methyl methacrylates, add 15.00 gram GDMA dilutions therein, both are stirred; Process resinous substrates, thereafter, under the lucifuge condition; The resinous substrates of processing 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 this routine described modifications of 32.80 grams therein; Carry out mechanical agitation and mix, after the mechanical agitation married operation is accomplished, 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, and processing dental resin composition is the said fluorine-containing dental restorative material based on drug release mechanism 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 grams and carry fluorodioxy zirconium nanotube, and the strontium glass powder of 30.00 grams carries out uniform mixing through churned mechanically mode with above two kinds of compositions, processes gross weight and is the nano inorganic powder that contains two kinds of compositions of 100.00 grams, subsequent 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, pure volume ratio are 1.0 to 10.0 in this water-alcohol solution, subsequently; Add the good nano inorganic powder that contains two kinds of compositions of above-mentioned premix of 35.00 grams, in ultrasound wave, disperse, under 100 ℃ of temperature, reacted 2 hours afterwards, move to baking oven; Elder generation dried 2 hours down at 80 ℃, then, with said water-alcohol solution washing, dried 12 hours down in 80 ℃ again; After be warming up to 100 ℃ and continue oven dry 5 hours, after the drying, pulverize; Process the nano inorganic powder after the modification, subsequent use, reserve level is slightly greater than requirement.
Get 20.00 gram carbamate double methyl methacrylates, and get 30.00 gram bisphenol-A GMAs, in the above two mixture, add 15.00 gram hydroxyethyl methacrylate dilutions; This mixture system is stirred, process resinous substrates, thereafter; Under the lucifuge condition, the resinous substrates of processing 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 this routine described modification after the nano inorganic powder that contains multiple composition; Carry out mechanical agitation and mix, after the mechanical agitation married operation is accomplished, 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, and processing dental resin composition is the said fluorine-containing dental restorative material based on drug release mechanism 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 grams and carry fluorodioxy zirconium nanotube, and the commercially available barium lead glass powder of 25.00 grams carries out uniform mixing through churned mechanically mode with above two kinds of compositions, processes gross weight and is the nano inorganic powder that contains two kinds of compositions of 100.00 grams, subsequent 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, pure volume ratio are 1.0 to 10.0 in this water-alcohol solution, subsequently; Add the good nano inorganic powder that contains two kinds of compositions of above-mentioned premix of 35.00 grams, in ultrasound wave, disperse, under 100 ℃ of temperature, reacted 2 hours afterwards, move to baking oven; Elder generation dried 2 hours down at 80 ℃, then, with said water-alcohol solution washing, dried 12 hours down in 80 ℃ again; After be warming up to 100 ℃ and continue oven dry 5 hours, after the drying, pulverize; Process the nano inorganic powder after the modification, subsequent use, reserve level is slightly greater than requirement.
Get 20.00 gram carbamate double methyl methacrylates, and get 20.00 gram bisphenol-A GMAs, in the above two mixture, add 10.00 gram double methyl methacrylate triethylene glycol esters, 10.00 gram GDMAs, 5.00 gram hydroxyethyl methacrylate dilutions; This mixture system is stirred, process resinous substrates, thereafter; Under the lucifuge condition, the resinous substrates of processing 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 this routine described modification after the nano inorganic powder that contains multiple composition; Carry out mechanical agitation and mix, after the mechanical agitation married operation is accomplished, 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, and processing dental resin composition is the said fluorine-containing dental restorative material based on drug release mechanism 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 grams and carry fluorodioxy zirconium nanotube, and the commercially available boron lead glass powder of 35.00 grams carries out uniform mixing through churned mechanically mode with above two kinds of compositions, processes gross weight and is the nano inorganic powder that contains two kinds of compositions of 100.00 grams, subsequent 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, pure volume ratio are 1.0 to 10.0 in this water-alcohol solution, subsequently; Add the good nano inorganic powder that contains two kinds of compositions of above-mentioned premix of 35.00 grams, in ultrasound wave, disperse, under 100 ℃ of temperature, reacted 2 hours afterwards, move to baking oven; Elder generation dried 2 hours down at 80 ℃, then, with said water-alcohol solution washing, dried 12 hours down in 80 ℃ again; After be warming up to 100 ℃ and continue oven dry 5 hours, after the drying, pulverize; Process the nano inorganic powder after the modification, subsequent use, reserve level is slightly greater than requirement.
Get 10.00 gram carbamate double methyl methacrylates, and get 30.00 gram bisphenol-A GMAs, in the above two mixture, add 15.00 gram double methyl methacrylate triethylene glycol esters, 10.00 gram GDMA dilutions; This mixture system is stirred, process resinous substrates, thereafter; Under the lucifuge condition, the resinous substrates of processing 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 this routine described modification after the nano inorganic powder that contains multiple composition; Carry out mechanical agitation and mix, after the mechanical agitation married operation is accomplished, 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, and processing dental resin composition is the said fluorine-containing dental restorative material based on drug release mechanism 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 grams and carry fluorodioxy zirconium nanotube, and the commercially available biological glass powder of 90.00 grams carries out uniform mixing through churned mechanically mode with above two kinds of compositions, processes gross weight and is the nano inorganic powder that contains two kinds of compositions of 100.00 grams, subsequent 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, pure volume ratio are 1.0 to 6.0 in this water-alcohol solution, subsequently; Add the good nano inorganic powder that contains two kinds of compositions of above-mentioned premix of 35.00 grams, in ultrasound wave, disperse, under 75 ℃ of temperature, reacted 15 hours afterwards, move to baking oven; Elder generation dried 2 hours down at 80 ℃, then, with said water-alcohol solution washing, dried 12 hours down in 80 ℃ again; After be warming up to 100 ℃ and continue oven dry 5 hours, after the drying, pulverize; Process the nano inorganic powder after the modification, subsequent use, reserve level is slightly greater than requirement.
Get 30.00 gram carbamate double methyl methacrylates, and get 10.00 gram bisphenol-A GMAs, in the above two mixture, add 10.00 gram double methyl methacrylate triethylene glycol esters, 15.00 gram GDMA dilutions; This mixture system is stirred, process resinous substrates, thereafter; Under the lucifuge condition, the resinous substrates of processing 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 this routine described modification after the nano inorganic powder that contains multiple composition; Carry out mechanical agitation and mix, after the mechanical agitation married operation is accomplished, 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, and processing dental resin composition is the said fluorine-containing dental restorative material based on drug release mechanism 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 grams and carry fluorodioxy zirconium nanotube, and, the biological glass powder of 30.00 grams; 30.00 the nanometer hydroxyapatite of gram; Through churned mechanically mode above two kinds of compositions are carried out uniform mixing, process gross weight and be the nano inorganic powder that contains two kinds of compositions of 100.00 grams, subsequent 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, pure volume ratio are 1.0 to 5.0 in this water-alcohol solution, subsequently; Add the good nano inorganic powder that contains two kinds of compositions of above-mentioned premix of 35.00 grams, in ultrasound wave, disperse, under 60 ℃ of temperature, reacted 20 hours afterwards, move to baking oven; Elder generation dried 2 hours down at 80 ℃, then, with said water-alcohol solution washing, dried 12 hours down in 80 ℃ again; After be warming up to 100 ℃ and continue oven dry 5 hours, after the drying, pulverize; Process the nano inorganic powder after the modification, subsequent use, reserve level is slightly greater than requirement.
Get 30.00 gram carbamate double methyl methacrylates, and get 20.00 gram bisphenol-A GMAs, in the above two mixture, add 10.00 gram double methyl methacrylate triethylene glycol esters, 5.00 gram GDMA dilutions; This mixture system is stirred, process resinous substrates, thereafter; Under the lucifuge condition, the resinous substrates of processing 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 this routine described modification after the nano inorganic powder that contains multiple composition; Carry out mechanical agitation and mix, after the mechanical agitation married operation is accomplished, 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, and processing dental resin composition is the said fluorine-containing dental restorative material based on drug release mechanism of this case; Can under lucifuge condition according to usual use amount carry out finished product packing thereafter.
Claims (2)
1. based on the fluorine-containing dental restorative material of drug release mechanism, the weight percentage of each composition is following in this material: 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; Wherein, the inorganic nano-filler after the said modification is to be handled through silane coupler by nano inorganic powder, and through powder body material dry, that pulverizing forms afterwards; Said nano inorganic powder contains the percetage by weight that the accounts for nano inorganic powder weight Nano tube of zirconium dioxide of solubility inorganic fluoride salt that has been its inner surface load of 10%～80%; Said its inner surface load the Nano tube of zirconium dioxide of solubility inorganic fluoride salt be to carry a fluorodioxy zirconium nanotube; This year, fluorodioxy zirconium nanotube was to carry fluorodioxy zirconium nanotube via what following main step of preparation process was processed: the Nano tube of zirconium dioxide that 1. Nano tube of zirconium dioxide is flooded, 2. will flood the inorganic fluoride salt aqueous solution in the inorganic fluoride salt aqueous solution carries out drying, 3. dried year fluorodioxy zirconium nanotube aggregate is pulverized at 40 ℃～100 ℃ warm areas; Said inorganic fluoride salt is sodium fluoride or potassium fluotitanate, and the weight percentage of inorganic fluoride salt is between 0.5%～5.0% in the inorganic fluoride salt aqueous solution; The external diameter of said Nano tube of zirconium dioxide is between 20 nanometers and 300 nanometers, and the length of said Nano tube of zirconium dioxide is between 0.2 micron and 200 microns, and the ratio of the length of said Nano tube of zirconium dioxide and external diameter is between 3 and 100; Said silane coupler is the KH-570 of medical grade; The molecular weight ranges of said resin monomer is 200～5000; Said resin monomer is a kind of or both combinations in bisphenol-A GMA, the carbamate double methyl methacrylate; Diluent is one or more the combination in double methyl methacrylate triethylene glycol ester, GDMA, the hydroxyethyl methacrylate; Light trigger is a camphorquinone, and coinitiator is a dimethylaminoethyl acrylate methyl ammonia ethyl ester.
2. the fluorine-containing dental restorative material based on drug release mechanism according to claim 1; It is characterized in that; The external diameter of said Nano tube of zirconium dioxide is between 20 nanometers and 200 nanometers, and the length of said Nano tube of zirconium dioxide is between 0.2 micron and 2 microns; And the ratio of the length of said Nano tube of zirconium dioxide and external diameter is between 3 and 10.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US9168114B2 (en) | 2013-10-17 | 2015-10-27 | B & D Dental Corp. | Method of making a dental prosthesis |
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| CN115778826A (en) * | 2022-12-20 | 2023-03-14 | 桂林凯文彼德科技有限公司 | Dental flowable composite resin with long-term fluorine release property |
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| CN1951358A (en) * | 2006-11-09 | 2007-04-25 | 深圳清华大学研究院 | A method for preparing nano compound resin prosthetics material |
| CN101412517A (en) * | 2008-11-14 | 2009-04-22 | 华东理工大学 | Preparation and use of pore diameter controllable mesoporous silicon dioxide microsphere |
| CN101507686A (en) * | 2009-04-07 | 2009-08-19 | 李榕卿 | Teeth composition capable of increasing abrasion resistance and obdurability based on composite modification theory |
| CN101518501A (en) * | 2009-03-25 | 2009-09-02 | 李榕卿 | Dental resin composition utilizing reinforcing mechanism with mixed nanometer |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1951358A (en) * | 2006-11-09 | 2007-04-25 | 深圳清华大学研究院 | A method for preparing nano compound resin prosthetics material |
| CN101412517A (en) * | 2008-11-14 | 2009-04-22 | 华东理工大学 | Preparation and use of pore diameter controllable mesoporous silicon dioxide microsphere |
| CN101518501A (en) * | 2009-03-25 | 2009-09-02 | 李榕卿 | Dental resin composition utilizing reinforcing mechanism with mixed nanometer |
| CN101507686A (en) * | 2009-04-07 | 2009-08-19 | 李榕卿 | Teeth composition capable of increasing abrasion resistance and obdurability based on composite modification theory |
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| US9168114B2 (en) | 2013-10-17 | 2015-10-27 | B & D Dental Corp. | Method of making a dental prosthesis |
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