CN103622837A - Self-etch amphiphilic dental adhesive and preparation method thereof - Google Patents
Self-etch amphiphilic dental adhesive and preparation method thereof Download PDFInfo
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- CN103622837A CN103622837A CN201310638270.0A CN201310638270A CN103622837A CN 103622837 A CN103622837 A CN 103622837A CN 201310638270 A CN201310638270 A CN 201310638270A CN 103622837 A CN103622837 A CN 103622837A
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Abstract
The invention discloses a self-etch amphiphilic dental adhesive and a preparation method thereof. The adhesive is a one-component adhesive and comprises the following components in parts by weight: 100 parts of polymerizable monomer, 0.2 to 0.8 part of photoinitiator, 0.1 to 0.5 parts of an accelerating agent, 0.001 to 0.5 parts of a polymerization inhibitor and 1 to 20 parts of filler; the polymerizable monomer comprises the following components in weight percent: 40% to 60% of resinous monomer, 1% to 10% of amphiphilic monomer, 2% to 10% of acidic monomer and 35% to 50% of dilute monomer. The self-etch amphiphilic dental adhesive provided by the invention can be used for acid etching of dentin, has the characteristic of amphipathicity, and is relatively high in bonding strenth; not only does the development of the adhesive update the conventional clinical adhesive, but also the adhesive has a relatively good dentin bonding effect.
Description
Technical field
The present invention relates to the preparing technical field of nano material and composite thereof, be specifically related to a kind of from amphiphilic gear division binding agent of acid etching and preparation method thereof.
Background technology
For filling the reparation defect of tooth and the material of dental caries, commonly use clinically light-cured composite.One solidifies this composite resin filling nest hole post polymerization, but because this material itself can not maintain the caking property with tooth, need to be used in conjunction with the dental bonding material that composite resin is used, and is commonly called as binding agent.Binding agent is often divided into enamel binding agent and dentin binding agent.At present, along with making rapid progress and the raising of living standards of the people of science and technology, binding agent is through experimentation and the Clinical Exploration of decades, constantly towards attractive in appearance, adhesion strength is high, persistency good, future development easy to use, from many components of the first generation, comprised that etching agent, silane coupling agent, binding agent etc. were now developed to for the 7th generation, it is the self-etch adhesives of one-component, only need a step can complete the use of binding agent, to doctor, bring great convenience, accelerate therapeutic process, reduced sufferer painful.At present conventional binding agent has 3M ESPS Relyx ARC clinically, 3M ESPS RelyX Unicem, 3M ESPS Valux Plus, 3M ESPS Relyx luting2, Ivoclar Variolink, Clearfil DC Core Automix, Clearfil SAC, DMG smartmix dual, superbond etc.These clinical conventional binding agents are higher to adamantine adhesion strength, and its reason is that enamel surface can become coarse and uneven after suitable acid etching, is special alveolate texture.Resin forms resin after infiltrating, solidifying prominent chimeric with enamel micromechanics.But Dentin Structure is different from enamel, in dentin, inorganic matter accounts for 70%, and Organic substance and water account for 30%, and Organic substance is mainly collagen protein (accounting for organic 90%).Because Dentinal surface is fluffy collagen fiber and the opening of dentinal tubule, if collagen fiber overdrying will subside, in dentinal tubule, there is TF simultaneously, so dentin surface is a permanent moistening surface, and all resinoid bonds are all hydrophobic, this just makes bonding become very difficult.Therefore, in order to promote resin and Dentinal bonding, need exploitation to have good cohesive force with resin, also can there is with dentin the amphiphilic binding agent of good cohesive force.The patent No. is that 200880123336 patent discloses a kind of dental binding agent, and this binding agent focuses on the binding agent of exploitation removability excellence when semi-cured state, owing to being multicomponent binding agent, during use, to doctors and patients, makes troubles.The patent No. is that 201010224479 patent discloses a kind of orthodontic visible light curing cross-linking agent, Epocryl, reactive diluent, functional monomer, initiator, photoiniator and polymerization inhibitor, consists of.The patent No. is that 7041714 United States Patent (USP) discloses a kind of gear division binding agent, has comprised acid monomer, non-acidic monomers, chemical polymerisation initiator, filler etc., and the photocuring time of gained binding agent is controlled, and the tone of binding agent weakens.The patent No. is that 8198388 United States Patent (USP) discloses a kind of one-component and forms from the gear division binding agent injecting from acid etching, mainly contains polymerisable phosphate ester monomer, the acid monomer of polymerizable, polymerizable acrylic amide monomer, organic or inorganic acid, water-miscible organic solvent or water, polymerization initiator, polymerization inhibitor and stabilizing agent etc.The exploitation of these binding agents has all comprised the function ingredients of binding agent, but is difficult to solve the problem of surface wettability between binding agent and dentin.The adhesion strength of binding agent is the important indicator of judgement binding agent quality, and its power depends on the wettability that binding agent is good and repairs the identical tightness degree between interface.The patent No. is the composition that 7304096 United States Patent (USP) discloses high functionality gear division binding agent, can carry out a step photocuring, the mixture that mainly contains multi-functional prepolymer, as Bisphenol A-glycidyl Methacrylate and the multi-functional compound that adopts the hydrogen atom substituting on hydroxyl wherein such as methacrylate based to form, the acid monomer of energy remove portion smear layer, there is hydrophilic and hydrophobic bonding monomer simultaneously, can in wet environment, play the hydrophilic monomer of cementation, play the inorganic filler of potentiation, light initiation system, water, and other additives.Although this patent for improve the bond effect of binding agent in wet environment and binding agent from acid etching effect, added therein and had hydrophilic and hydrophobic monomer concurrently, and containing the monomer of carboxylic acid or carboxylic acid anhydrides.But in this patent, only adopt silane coupler to carry out the finishing of inorganic filler, perhaps, the filler that is modified with silane coupler can improve the dispersibility of filler in bonding system, but filler can not participate in polyreaction, and be difficult to be penetrated in the collagen fiber at dentin interface, a little less than causing bond effect, and also which kind of silane coupler of unexposed use of this patent.Filler can increase the body intensity of binding agent, if but can carry out suitable finishing to filler, make it more easily and have an effect in dentin interface, and participate in polyreaction when light initiation polymerization, the effect of filler will be more remarkable.Therefore, the bond effect important of the finishing of filler to binding agent in binding agent.
Self-etch adhesives is mainly the polymerizable monomer that adds therein phosphate ester-containing, because acidic-group has demineralization function to dentin, has reduced operating procedure, makes pretreatment synchronize and carry out with bonding.Although self-etch adhesives is operation technique, bring great convenience, its bond effect still carries out pretreated binding agent not as the early stage phosphoric acid that directly adopts, and therefore also needs further to improve the adhesion strength of self-etch adhesives.Current binding agent main component is hydrophobic polymerizable monomer, and due to Dentinal hydrophilic and be different from the characteristic of enamel surface porous, binding agent is difficult to penetrate in dentinal tubule, has caused adhesion strength effect not good enough.
Summary of the invention
The object of the invention is to overcome the deficiency that above-mentioned prior art exists, and provides a kind of from amphiphilic gear division binding agent of acid etching and preparation method thereof.Owing to take binding agent that acrylate is main component in clinical use for many years, there is good biocompatibility, and initiated polymerization is gentle under illumination, the impact bringing to patient is less, the present invention has carried out a large amount of experiments on this basis, develops from the amphiphilic binding agent of acid etching.In order to make to have amphiphilic from the binding agent of acid etching, added on the one hand amphiphatic monomer, on the other hand inorganic filler has been carried out to finishing, it is not only disperseed in binding agent better, and can better be combined with dentin surface's collagen, in infiltration dentin, and can participate in photopolymerization reaction, thereby produce better bond effect.
The object of the invention is to be achieved through the following technical solutions:
First aspect, the present invention relates to that a kind of described binding agent is one-component binding agent from the amphiphilic gear division binding agent of acid etching, comprises each component of following parts by weight:
Described polymerizable monomer comprises each component of following weight percent content:
Preferably, described resinousness monomer is difunctional or multi-functional acrylic ester monomer.
Further preferably, described resinousness monomer is one or more in Bisphenol A-glycidyl Methacrylate, bisphenol-A ethoxyl methyl glycidyl acrylate, bisphenol-A methacrylate 2-methoxyl group dipropyl alcohol ester, bisphenol-A methacrylate siloxanes glyceride, bisphenol-A methacrylate dimethyl isopropyl siloxanes glyceride, trimethylol-propane trimethacrylate, trimethylolethane trimethacrylate methacrylate, pentaerythritol acrylate trimethyl, pentaerythritol tetramethylacrylate, tetramethylol methane tetraacrylate.
When preferably, described amphiphilic monomer is hydroxyl or carboxyl, there is hydrophilic and hydrophobic esters of acrylic acid material.
Further preferably, described amphiphilic monomer is one or more in hydroxyethyl methylacrylate, hydroxypropyl acrylate, hydroxyethylmethacry,ate, dipentaerythritol acrylate, ethylene glycol dimethacrylate.
Preferably, described acid monomer is one or more in 4-methylacryoyloxyethyl trimellitic anhydride, two [2-(methacryloxy) ethyl] phosphate ester, methacryloxypropyl decyl phosphate ester, phosphoric acid hydrogen two (methylacryoyloxyethyl) ester.
Preferably, described diluting monomer is bifunctional acrylic ester monomer.
Further preferably, described diluting monomer is TEGDMA, diethylene glycol dimethacrylate, diethylene glycol dimethylacrylate, diethylene glycol dimethacrylate, TEG dimethylacrylate, 2-methyl-2-acrylic acid-1,12 pairs of alcohol esters of 12-, 2-methyl-2-acrylic acid-1,10-diester in the last of the ten Heavenly stems, 1, one or more in 4-butanediol dimethylacrylate, 1,3 butylene glycol dimethylacrylate etc.
Preferably, described light trigger is camphorquinone.
Preferably, described promoter is 2-(dimethylamino) ethyl methacrylate, 4-N, N-dimethylaminobenzoic acid ethyl ester, 4-N, N-dimethylaminobenzoic acid methyl ester, N, N-dimethylaminobenzoic acid n-butoxy ethyl ester, 4-N, one or more in N-dimethylamino benzophenone, benzene sulfinic acid sodium salt.
Preferably, described polymerization inhibitor is 2,6-di-tert-butyl-4-methy phenol.
Preferably, one or several in the silicon dioxide that described filler is surface modification, eight poly-cage-type silsesquioxanes, hydroxyapatite, calcium phosphate, calcium carbonate, aluminium oxide, zirconium dioxide, silicon oxide-titanium oxide, silicate, borosilicate, fluorine aluminosilicate, montorillonite clay, CNT.
Further preferably, described finishing is specially and adopts polymerisable monomer filler contain to the modification of pair key groups; Described polymerisable monomer is acrylic acid, acrylic anhydride, methacrylic acid, methacrylic anhydride, hydroxyethyl methylacrylate, hydroxypropyl acrylate, hydroxyethylmethacry,ate, dipentaerythritol acrylate, ethylene glycol dimethacrylate, 4-methylacryoyloxyethyl trimellitic anhydride, two [2-(methacryloxy) ethyl] phosphate ester, methacryloxypropyl decyl phosphate ester or phosphoric acid hydrogen two (methylacryoyloxyethyl) ester).
Second aspect, the present invention relates to a kind of aforesaid preparation method from the amphiphilic gear division binding agent of acid etching, comprises the steps:
A, by described resinousness monomer, diluting monomer at 40～70 ℃ of mix homogeneously, add amphiphilic monomer, acid monomer after being cooled to room temperature, mix, form polymerizable monomer solution;
B, filler is added in polymerizable monomer solution, by ultrasonic or mechanical agitation or magnetic agitation, uniform filling is dispersed in polymerizable monomer solution, obtain the mixed solution of polymerizable monomer-filler;
C, in the mixed solution of described polymerizable monomer-filler, add successively described light trigger, promoter, polymerization inhibitor, after lucifuge stirs, obtain described from the amphiphilic gear division binding agent of acid etching.
Compared with prior art, the present invention has following beneficial effect:
1, of the present invention can not only be for to Dentinal acid etching from the amphiphilic binding agent of acid etching, and there is amphiphilic feature, there is higher adhesion strength.
2, clinical existing adhesive techniques has not only been upgraded in the exploitation of binding agent of the present invention, and has better dentin bond effect.
Accompanying drawing explanation
By reading the detailed description of non-limiting example being done with reference to the following drawings, it is more obvious that the other features, objects and advantages of patent of the present invention will become:
Fig. 1 is the scanning electron microscope (SEM) photograph after the silicon dioxide of HEMA modification adds in binding agent;
Fig. 2 is the scanning electron microscope (SEM) photograph after the POSS of acrylic anhydride modification adds in binding agent;
Fig. 3 is the scanning electron microscope (SEM) photograph after the silicon dioxide of APTES modification adds in binding agent.
The specific embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.Following examples will contribute to those skilled in the art further to understand the present invention, but not limit in any form the present invention.It should be pointed out that to those skilled in the art, without departing from the inventive concept of the premise, can also make some distortion and improvement.These all belong to protection scope of the present invention.
The performance test methods of the binding agent of following embodiment is as follows:
1, photocuring time test method
With the LED lamp of 400-500nm wavelength, as light source, binding agent sample is dropped on microscope slide abreast, be placed on vertical dimension 10cm place under light source, the solid needed time of log, be adhesive cures required time.
2, phototranstormation efficiency method of testing
Get a certain amount of spectroscopic pure potassium bromide, after pulverizing, be pressed into the wafer that KBr is transparent, binding agent is dropped in a wafer wherein, and cover and drip the face that has binding agent by another wafer, after photocuring, on infrared spectrometer (Nicolet6700), carry out the mensuration of infrared spectrum.The computational methods of phototranstormation efficiency are: DC=(1-(I
solidify rear 1637/ I
after solidifying 1715)/(I
solidify front 1637/ I
solidify front 1715)) * 100%; I
solidify rear 1637refer to that sample after solidifying is at 1637cm
-1time ratio of infrared absorption intensity, I
solidify rear 1715refer to that sample after solidifying is at 171Scm
-1time ratio of infrared absorption intensity, I
solidify front 1637refer to and solidify front sample at 1637cm
-1time ratio of infrared absorption intensity, I
solidify front 1715refer to and solidify front sample at 171Scm
-1time ratio of infrared absorption intensity.
3, hydrophilic method of testing
Use the contact angle of JC2000C1 contact angle measurement test sample surface, use No. 22 syringe needles that the distilled water of approximately 5 μ L is dropped in to the binding agent sample surfaces after solidifying, in 10s, take rapidly photo, by supporting computed in software, go out contact angle.
4, bond strength testing method
Adopt micro-stretching test instrument, in advance by resin in die for molding, length and width height is the batten of 1cm*2mm*1mm, get fresh people's third molar, with microtome, be cut into the thin slice of the high 1cm*2mm*1mm of being of length and width, and make one side keep smooth, respectively two battens are fixed on micro-stretching test instrument, make smooth one side as adhesive surface, at the surface uniform of resin sheet and tooth sheet, coat after binding agent respectively, two battens are close to, with the LED lamp of 400-500nm wavelength, carry out photocuring, then at the velocity pull-down of 10mm/min, stretch sample, by value of thrust, calculate adhesion strength.
embodiment 1
The present embodiment relates to a kind of from the amphiphilic binding agent of acid etching.
1.1, the HEMA of silicon dioxide (hydroxyethyl methylacrylate) finishing
Take a certain amount of nano silica powder and slowly add (ethanol: water=19:1 in alcoholic solution, mass ratio), after stirring, in immigration there-necked flask, use magnetic stirring apparatus rapid stirring, after disperseing completely, drip 12% silane coupling A PTES (3-aminopropyl triethoxysilane), after dropwising, temperature is risen to 110 ℃ gradually, with condensing tube, reflux, continue to stir 3h, be down to after room temperature, with second alcohol and water, carry out repeatedly centrifuge washing, dry, obtain amido modified silicon dioxide a.
In 50mL dimethyl sulfoxide (DMSO), add HEMA; the mol ratio of HEMA and APTES is 1:1; after dissolving completely, add respectively and the equimolar NHS of HEMA (N-hydroxy-succinamide), EDC (1-ethyl-3-(3-dimethyl aminopropyl)-carbodiimides) and TEA (triethanolamine); under nitrogen protection; stirring at room 24 hours, obtains solution b.
A is added in solution b, stir after 24 hours, product is filtered, with dehydrated alcohol, water washing three times, vacuum is drained, and obtains the silicon dioxide that HEMA modifies.
1.2 preparations from the amphiphilic binding agent of acid etching
Be proportionally 1.5, by Bis-GMA (Bisphenol A-glycidyl Methacrylate), at 60 ℃, be dissolved in TEGDMA (TEGDMA), stir the solution that 30min becomes homogeneous above, then solution is cooling, then according to the ratio of 3:95 and 2:95, HEMA and 4-methylacryoyloxyethyl trimellitic anhydride are joined in above solution, after stirring, the silicon dioxide that adds the above-mentioned HEMA making to modify by 10% of the gross mass of above each monomer mixture solution again, stir 6 hours, make its mix homogeneously, by 0.4% of the gross mass of above each monomer mixture solution, add light trigger CQ (camphorquinone) subsequently, by 0.3% of the gross mass of above each monomer mixture solution, add DMAMA (2-(dimethylamino) ethyl methacrylate), by 0.1% of the gross mass of above each monomer mixture solution, add BHT (2, 6-di-tert-butyl-4-methy phenol), stir, in whipping process, note lucifuge, finally obtain binding agent.Binding agent solidified in 5 seconds, and transformation efficiency is 60%, and solidifying rear surface contact angle is 65 °, and adhesion strength is 15.5MPa.Scanning electron microscope (SEM) photograph after the silicon dioxide of modifying through HEMA adds in binding agent is shown in Fig. 1, in binding agent, disperses better.
embodiment 2
The present embodiment relates to a kind of from the amphiphilic binding agent of acid etching.It is prepared as follows:
Be proportionally 1.5, by Bis-GMA (Bisphenol A-glycidyl Methacrylate), at 60 ℃, be dissolved in TEGDMA (TEGDMA), stir the solution that 30min becomes homogeneous above, solution is cooling, then according to the ratio of 2:95 and 3:95, respectively HEMA (methacrylic acid dihydroxy ethyl ester) and MEP (two [2-(methacryloxy) ethyl] phosphate ester) are joined in above solution, stir, by 0.4% of the gross mass of above each monomer mixture solution, add light trigger CQ (camphorquinone) subsequently, by 0.3% of the gross mass of above each monomer mixture solution, add DMAMA (2-(dimethylamino) ethyl methacrylate), by 0.1% of the gross mass of above each monomer mixture solution, add BHT (2, 6-di-tert-butyl-4-methy phenol), after stirring, by 10% of the gross mass of above each monomer mixture solution, add again the silicon dioxide of the HEMA modification being obtained by embodiment 1, stir 6 hours, make its mix homogeneously, in whipping process, note lucifuge, finally obtain binding agent.Binding agent solidified in 5 seconds, and transformation efficiency is 60%, and solidifying rear surface contact angle is 67 °, and adhesion strength reaches 22MPa.
embodiment 3
The present embodiment relates to a kind of from the amphiphilic binding agent of acid etching.
3.1, the acrylic anhydride of POSS (eight poly-cage-type silsesquioxanes) is modified
Get a certain amount of amido modified POSS, put into the four neck flasks that reflux condensing tube is housed, add wherein the acrylic anhydride of 8 times of its moles, add wherein subsequently the solvent of triethylamine and dimethyl formamide, then at N
2under protection, 80 ℃ of heated and stirred obtained product after 24 hours, then product is scattered in ether, and centrifugalize 6 times, being placed in vacuum drying oven, normal temperature drying 24h, obtains the POSS that acrylamido is modified.
3.2, from the preparation of the amphiphilic binding agent of acid etching
Be proportionally 1.5, by Bis-GMA (Bisphenol A-glycidyl Methacrylate), at 60 ℃, be dissolved in TEGDMA (TEGDMA), stir the solution that 30min becomes homogeneous above, solution is cooling, then according to the ratio of 2:95 and 3:95, respectively HEMA (methacrylic acid dihydroxy ethyl ester) and MEP (two [2-(methacryloxy) ethyl] phosphate ester) are joined in above solution, stir, the POSS that adds the above-mentioned acrylamido making to modify by 20% of the gross mass of above each monomer mixture solution again, stir 6 hours, ultrasonic dispersion 3 minutes, it is uniformly dispersed, in mixed process, note lucifuge, by 0.4% of the gross mass of above each monomer mixture solution, add light trigger CQ (camphorquinone) subsequently, by 0.3% of the gross mass of above each monomer mixture solution, add DMAMA (2-(dimethylamino) ethyl methacrylate), by 0.1% of the gross mass of above each monomer mixture solution, add BHT (2, 6-di-tert-butyl-4-methy phenol), after stirring, finally obtain binding agent.Binding agent solidified in 5 seconds, and transformation efficiency is 61%, and solidifying rear surface contact angle is 62 °, and adhesion strength reaches 25MPa.Scanning electron microscope (SEM) photograph after the POSS modifying through acrylic anhydride adds in binding agent is shown in Fig. 2, in binding agent, disperses better.
embodiment 4
The present embodiment relates to a kind of from the amphiphilic binding agent of acid etching.
4.1, the hydroxyethylmethacry,ate finishing of silicon dioxide
The preparation method of amido modified silicon dioxide a is as embodiment 1.1.
In 50mL dimethyl sulfoxide (DMSO), add hydroxyethylmethacry,ate; the mol ratio of hydroxyethylmethacry,ate and APTES is 1:1; after dissolving completely, add respectively and the equimolar NHS of hydroxyethylmethacry,ate, EDC and TEA; under nitrogen protection; stirring at room 24 hours, obtains solution b.
A is added in solution b, stir after 24 hours, product is filtered, with dehydrated alcohol, water washing three times, vacuum is drained, and obtains the silicon dioxide that hydroxyethylmethacry,ate is modified.
4.2, from the preparation of the amphiphilic binding agent of acid etching
Polymerisable monomer forms: bisphenol-A methacrylate 2-methoxyl group dipropyl alcohol ester 60%, hydroxyethylmethacry,ate 1%, methacryloxypropyl decyl phosphate ester 4%, BDO dimethylacrylate 35%, bisphenol-A methacrylate 2-methoxyl group dipropyl alcohol ester is dissolved in to 1 at 70 ℃, in 4-butanediol dimethylacrylate, stir the solution that 30min becomes homogeneous above, solution is cooled to room temperature, then respectively hydroxyethylmethacry,ate and methacryloxypropyl decyl phosphate ester are joined in above solution in proportion, stir, by 1% of the gross mass of above polymerizable monomer mixed solution, add the above-mentioned silicon dioxide making again, stir 6 hours, ultrasonic dispersion 3 minutes, it is uniformly dispersed, in mixed process, note lucifuge, by 0.2% of the gross mass of above each monomer mixture solution, add light trigger CQ (camphorquinone) subsequently, by 0.1% of the gross mass of above polymerizable monomer mixed solution, add DMAMA (2-(dimethylamino) ethyl methacrylate), by 0. () () of the gross mass of above polymerizable monomer mixed solution 1%, add BHT (2, 6-di-tert-butyl-4-methy phenol), after stirring, finally obtain binding agent.Binding agent solidified in 10 seconds, and transformation efficiency is 42%, and solidifying rear surface contact angle is 69 °, and adhesion strength reaches 12MPa.
embodiment 5
The present embodiment relates to a kind of from the amphiphilic binding agent of acid etching.
5.1, the silicon dioxide that hydroxyethylmethacry,ate is modified is as embodiment 4.1.
5.2, from the preparation of the amphiphilic binding agent of acid etching
Polymerisable monomer forms: bisphenol-A methacrylate 2-methoxyl group dipropyl alcohol ester 40%, hydroxyethylmethacry,ate 10%, methacryloxypropyl decyl phosphate ester 10%, BDO dimethylacrylate 40%, bisphenol-A methacrylate 2-methoxyl group dipropyl alcohol ester is dissolved in to 1 at 70 ℃, in 4-butanediol dimethylacrylate, stir the solution that 30min becomes homogeneous above, solution is cooled to room temperature, then respectively hydroxyethylmethacry,ate and methacryloxypropyl decyl phosphate ester are joined in above solution in proportion, stir, by 10% of the gross mass of above polymerizable monomer mixed solution, add the above-mentioned silicon dioxide making again, stir 6 hours, ultrasonic dispersion 3 minutes, it is uniformly dispersed, in mixed process, note lucifuge, by 0.8% of the gross mass of above each monomer mixture solution, add light trigger CQ (camphorquinone) subsequently, by 0.5% of the gross mass of above polymerizable monomer mixed solution, add DMAMA (2-(dimethylamino) ethyl methacrylate), by 0.5% of the gross mass of above polymerizable monomer mixed solution, add BHT (2, 6-di-tert-butyl-4-methy phenol), after stirring, finally obtain binding agent.Binding agent solidified in 20 seconds.
embodiment 6
The present embodiment relates to a kind of from the amphiphilic binding agent of acid etching.
6.1, the silicon dioxide that hydroxyethyl methylacrylate is modified is as embodiment 1.1.
6.2, from the preparation of the amphiphilic binding agent of acid etching
Polymerisable monomer forms: bisphenol-A methacrylate 2-methoxyl group dipropyl alcohol ester 40%, hydroxyethylmethacry,ate 5%, methacryloxypropyl decyl phosphate ester 5%, BDO dimethylacrylate 50%, bisphenol-A methacrylate 2-methoxyl group dipropyl alcohol ester is dissolved in to 1 at 70 ℃, in 4-butanediol dimethylacrylate, stir the solution that 30min becomes homogeneous above, solution is cooled to room temperature, then respectively hydroxyethylmethacry,ate and methacryloxypropyl decyl phosphate ester are joined in above solution in proportion, stir, by 5% of the gross mass of above polymerizable monomer mixed solution, add the above-mentioned silicon dioxide making again, stir 6 hours, it is uniformly dispersed, in mixed process, note lucifuge, by 0.5% of the gross mass of above each monomer mixture solution, add light trigger CQ (camphorquinone) subsequently, by 0.3% of the gross mass of above polymerizable monomer mixed solution, add DMAMA (2-(dimethylamino) ethyl methacrylate), by 0.1% of the gross mass of above polymerizable monomer mixed solution, add BHT (2, 6-di-tert-butyl-4-methy phenol), after stirring, finally obtain binding agent.Binding agent solidified in 10 seconds.
embodiment 7
The present embodiment relates to a kind of from the amphiphilic binding agent of acid etching.
7.1, the silicon dioxide that hydroxyethyl methylacrylate is modified is as embodiment 1.1.
7.2, from the preparation of the amphiphilic binding agent of acid etching
Polymerisable monomer forms: bisphenol-A methacrylate 2-methoxyl group dipropyl alcohol ester 45%, hydroxyethyl methylacrylate 2%, methacryloxypropyl decyl phosphate ester 3%, TEGDMA 50%, bisphenol-A methacrylate 2-methoxyl group dipropyl alcohol ester is dissolved in TEGDMA at 40 ℃, stir the solution that 1h becomes homogeneous above, solution is cooled to room temperature, then respectively hydroxyethyl methylacrylate and methacryloxypropyl decyl phosphate ester are joined in above solution in proportion, stir, by 1% of the gross mass of above polymerizable monomer mixed solution, add the above-mentioned silicon dioxide making again, stir 6 hours, it is uniformly dispersed, in mixed process, note lucifuge, by 0.6% of the gross mass of above each monomer mixture solution, add light trigger CQ (camphorquinone) subsequently, by 0.3% of the gross mass of above polymerizable monomer mixed solution, add 4-N, N-dimethylaminobenzoic acid ethyl ester, by 0.05% of the gross mass of above polymerizable monomer mixed solution, add BHT (2, 6-di-tert-butyl-4-methy phenol), after stirring, finally obtain binding agent.Binding agent solidified in 10 seconds.
comparative example 1
This comparative example relates to a kind of amphiphilic binding agent.
1.1, the finishing of silicon dioxide
Get that a certain amount of silicon dioxide is ultrasonic to be scattered in toluene, disperse 30min, obtain unit for uniform suspension, add 3-aminopropyl triethoxysilane (APTES), continue ultrasonic 5min, transfer in the four neck flasks that reflux condensing tube is housed, under room temperature, stir 24 hours.Ultrasonicly be scattered in ethanol, centrifugalize 6 times, be placed in vacuum drying oven, normal temperature drying 24h, obtains the nano silicon of APTES modification.
1.2, the preparation of binding agent
Be proportionally 1.5, by Bis-GMA (Bisphenol A-glycidyl Methacrylate), at 60 ℃, be dissolved in TEGDMA (TEGDMA), stir the solution that 30min becomes homogeneous above, solution is cooling, then according to the ratio of 5:95, HEMA (methacrylic acid dihydroxy ethyl ester) is joined in above solution, stir, by 0.4% of the gross mass of above each monomer mixture solution, add light trigger CQ (camphorquinone) subsequently, by 0.3% of the gross mass of above each monomer mixture solution, add DMAMA (2-(dimethylamino) ethyl methacrylate), by 0.1% of the gross mass of above each monomer mixture solution, add BHT (2, 6-di-tert-butyl-4-methy phenol), after stirring, the silicon dioxide that adds the above-mentioned APTES making to modify by 10% of the gross mass of above each monomer mixture solution again, stir 6 hours, make its mix homogeneously, in whipping process, note lucifuge, finally obtain binding agent.Binding agent solidified in 5 seconds, and transformation efficiency is 58%, and solidifying rear surface contact angle is 70 °, and adhesion strength is 8MPa.Scanning electron microscope (SEM) photograph after the silicon dioxide that APTES modifies adds in binding agent as shown in Figure 3.As shown in Figure 3, although silicon dioxide can be uniformly dispersed in binding agent, crosslinked insufficient with the organic constituents in binding agent.
Above specific embodiments of the invention are described.It will be appreciated that, the present invention is not limited to above-mentioned specific implementations, and those skilled in the art can make various distortion or modification within the scope of the claims, and this does not affect flesh and blood of the present invention.
Claims (14)
1. from the amphiphilic gear division binding agent of acid etching, it is characterized in that, described binding agent is one-component binding agent, comprises each component of following parts by weight:
Described polymerizable monomer comprises each component of following weight percent content:
2. as claimed in claim 1ly from the amphiphilic gear division binding agent of acid etching, it is characterized in that, described resinousness monomer is difunctional or multi-functional acrylic ester monomer.
3. as claimed in claim 2 from the amphiphilic gear division binding agent of acid etching, it is characterized in that, described resinousness monomer is Bisphenol A-glycidyl Methacrylate, bisphenol-A ethoxyl methyl glycidyl acrylate, bisphenol-A methacrylate 2-methoxyl group dipropyl alcohol ester, bisphenol-A methacrylate siloxanes glyceride, bisphenol-A methacrylate dimethyl isopropyl siloxanes glyceride, trimethylol-propane trimethacrylate, trimethylolethane trimethacrylate methacrylate, pentaerythritol acrylate trimethyl, pentaerythritol tetramethylacrylate, one or more in tetramethylol methane tetraacrylate.
4. as claimed in claim 1ly from the amphiphilic gear division binding agent of acid etching, it is characterized in that, described amphiphilic monomer has hydrophilic and hydrophobic esters of acrylic acid material when being hydroxyl or carboxyl.
5. as claimed in claim 4 from the amphiphilic gear division binding agent of acid etching, it is characterized in that, described amphiphilic monomer is one or more in hydroxyethyl methylacrylate, hydroxypropyl acrylate, hydroxyethylmethacry,ate, dipentaerythritol acrylate, ethylene glycol dimethacrylate.
6. as claimed in claim 1 from the amphiphilic gear division binding agent of acid etching, it is characterized in that, described acid monomer is one or more in 4-methylacryoyloxyethyl trimellitic anhydride, two [2-(methacryloxy) ethyl] phosphate ester, methacryloxypropyl decyl phosphate ester, phosphoric acid hydrogen two (methylacryoyloxyethyl) ester.
7. as claimed in claim 1ly from the amphiphilic gear division binding agent of acid etching, it is characterized in that, described diluting monomer is bifunctional acrylic ester monomer.
8. as claimed in claim 7 from the amphiphilic gear division binding agent of acid etching, it is characterized in that, described diluting monomer is TEGDMA, diethylene glycol dimethacrylate, diethylene glycol dimethylacrylate, diethylene glycol dimethacrylate, TEG dimethylacrylate, 2-methyl-2-acrylic acid-1,12 pairs of alcohol esters of 12-, 2-methyl-2-acrylic acid-1,10-diester in the last of the ten Heavenly stems, 1, one or more in 4-butanediol dimethylacrylate, 1,3 butylene glycol dimethylacrylate etc.
9. as claimed in claim 1ly from the amphiphilic gear division binding agent of acid etching, it is characterized in that, described light trigger is camphorquinone.
10. as claimed in claim 1 from the amphiphilic gear division binding agent of acid etching, it is characterized in that, described promoter is 2-(dimethylamino) ethyl methacrylate, 4-N, N-dimethylaminobenzoic acid ethyl ester, 4-N, N-dimethylaminobenzoic acid methyl ester, N, N-dimethylaminobenzoic acid n-butoxy ethyl ester, 4-N, one or more in N-dimethylamino benzophenone, benzene sulfinic acid sodium salt.
11. as claimed in claim 1ly is characterized in that from the amphiphilic gear division binding agent of acid etching, and described polymerization inhibitor is 2,6-di-tert-butyl-4-methy phenol.
12. is as claimed in claim 1 from the amphiphilic gear division binding agent of acid etching, it is characterized in that one or several in the silicon dioxide that described filler is surface modification, eight poly-cage-type silsesquioxanes, hydroxyapatite, calcium phosphate, calcium carbonate, aluminium oxide, zirconium dioxide, silicon oxide-titanium oxide, silicate, borosilicate, fluorine aluminosilicate, montorillonite clay, CNT.
13. as claimed in claim 12ly is characterized in that from the amphiphilic gear division binding agent of acid etching, and described finishing is specially and adopts polymerisable monomer filler contain to the modification of pair key groups; Described polymerisable monomer is acrylic acid, acrylic anhydride, methacrylic acid, methacrylic anhydride, hydroxyethyl methylacrylate, hydroxypropyl acrylate, hydroxyethylmethacry,ate, dipentaerythritol acrylate, ethylene glycol dimethacrylate, 4-methylacryoyloxyethyl trimellitic anhydride, two [2-(methacryloxy) ethyl] phosphate ester, methacryloxypropyl decyl phosphate ester or phosphoric acid hydrogen two (methylacryoyloxyethyl) ester).
14. 1 kinds of preparation methoies from the amphiphilic gear division binding agent of acid etching as claimed in claim 1, is characterized in that, comprise the steps:
A, by described resinousness monomer, diluting monomer at 40～70 ℃ of mix homogeneously, add amphiphilic monomer, acid monomer after being cooled to room temperature, mix, form polymerizable monomer solution;
B, filler is added in polymerizable monomer solution, by ultrasonic or mechanical agitation or magnetic agitation, uniform filling is dispersed in polymerizable monomer solution, obtain the mixed solution of polymerizable monomer-filler;
C, in the mixed solution of described polymerizable monomer-filler, add successively described light trigger, promoter, polymerization inhibitor, after lucifuge stirs, obtain described from the amphiphilic gear division binding agent of acid etching.
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