CN114522107A - Dental adhesive and method for preparing dental product - Google Patents
Dental adhesive and method for preparing dental product Download PDFInfo
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- CN114522107A CN114522107A CN202011324560.4A CN202011324560A CN114522107A CN 114522107 A CN114522107 A CN 114522107A CN 202011324560 A CN202011324560 A CN 202011324560A CN 114522107 A CN114522107 A CN 114522107A
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/30—Compositions for temporarily or permanently fixing teeth or palates, e.g. primers for dental adhesives
- A61K6/35—Preparations for stabilising dentures in the mouth
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/70—Preparations for dentistry comprising inorganic additives
- A61K6/71—Fillers
- A61K6/74—Fillers comprising phosphorus-containing compounds
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/70—Preparations for dentistry comprising inorganic additives
- A61K6/71—Fillers
- A61K6/77—Glass
Abstract
The application provides a dental adhesive and a method for preparing a dental product, which consists of paste A and liquid B: the paste A comprises the following components in percentage by mass: 13-50% by weight of an ethylenically unsaturated compound bearing an acid or ester function, 65-85% by weight of a filler and 0.1-2% by weight of an auxiliary; the liquid agent B comprises the following components in percentage by mass: 75-99.9% by weight of an ethylenically unsaturated compound bearing an acid or ester function and 0.1-25% by weight of an auxiliary; wherein the filler comprises a modified bioactive glass. The application can obviously reduce the curing shrinkage rate of the adhesive by adding the modified bioactive glass material into the dental adhesive, and avoids the increase of gaps between orthodontic accessories and tooth surface bonding interfaces caused by excessive shrinkage of the adhesive in the curing process of the adhesive, thereby avoiding enamel demineralization caused by the aggregation and growth of dental bacteria in the gaps.
Description
Technical Field
The application relates to the field of medical materials, in particular to a dental adhesive and a method for preparing a dental product.
Background
The existing orthodontic direct bonding technology is widely applied to correction treatment of dentognathic deformity, improves stimulation to gum by directly bonding the bracket on the labial and buccal surfaces of the dental crown, is beneficial to cavity sanitation, takes little time and is deeply popular with doctors and patients.
The bracket is fixed on the tooth surface for 1 to 2 years, and common clinical complications are as follows: the contact surface of the tooth and the bracket is demineralized, which causes the formation of chalk spots and even caries. Epidemiological investigation results show that the incidence rate of enamel demineralization of orthodontic patients is 50-80%, which not only violates the aesthetic principle of orthodontic treatment, but also impairs the health of teeth, so that the enamel demineralization phenomenon is a problem that orthodontic doctors cannot ignore.
Orthodontic adhesives are currently classified according to the method of curing in use, and three types are available: chemical curing-type, non-curing type, and photo-curing type. For simplicity, photocurable and non-curable chemical curing adhesives are currently the mainstream adhesives. However, none of the above adhesives satisfactorily solves the problem of demineralization of the tooth-bracket interface.
Disclosure of Invention
The invention aims to provide a dental adhesive and a method for preparing a dental product, wherein the obtained dental adhesive has low curing shrinkage rate, dental plaque can be prevented from being accumulated on an adhesive interface, and the enamel demineralization phenomenon is reduced.
The application is realized by adopting the following technical scheme:
in a first aspect, the present application provides a dental adhesive consisting of a paste a and a liquid B:
paste a, by mass percent, comprising: 13-33% by weight of an ethylenically unsaturated compound bearing an acid or ester function, 65-85% by weight of a filler and 0.1-2% by weight of an auxiliary;
liquid agent B comprises the following components in percentage by mass: 75-99.9% by weight of an ethylenically unsaturated compound bearing an acid or ester function and 0.1-25% by weight of an auxiliary;
wherein the filler comprises bioactive glass; an ethylenically unsaturated compound with acid or ester functional groups, which comprises a monomer or oligomer with at least two ethylenic bonds and acid or ester functional groups, wherein the acid functional groups are selected from at least one of carboxylic acid functional groups, phosphonic acid functional groups and phosphoric acid functional groups, and the ester functional groups are selected from at least one of acrylate and phosphate.
Further, in the preferred embodiment of the present application, the ethylenically unsaturated compound bearing an acid or ester functionality is selected from at least one of bisphenol A glycerol dimethacrylate, bisphenol A ethoxy dimethacrylate, bisphenol A polyethoxylated dimethacrylate, diurethane dimethacrylate (UDMA), bis [2- (methacryloyloxy) ethyl ] phosphate, 1, 6-hexanediol dimethacrylate, triethylene glycol dimethacrylate (TEDMA), polyethylene glycol dimethacrylate, 2-methyl-2-phosphinyl tris (oxy-2, 1-ethylene) acrylate, or hydroxyethyl methacrylate dimethacrylate glyceryl dimethacrylate.
Further, in the preferred embodiment of the present application, the bioactive glass is P2O5-SiO2CaO bioactive glass, wherein, in mass ratio, P2O5：SiO2：CaO＝(0.5-68)：(13.2-99)： (0.5-80)。
Further, in the preferred embodiment of the present application, the bioglass is modified with 3- (trimethoxysilyl) propyl methacrylate;
the inorganic filler is modified by 3- (trimethoxysilyl) propyl methacrylate.
Further, in the preferred embodiment of the present application, the bioglass is modified with 3- (trimethoxysilyl) propyl methacrylate.
Further, in the preferred embodiment of the present application, the filler further comprises other modified inorganic fillers, and the other inorganic fillers are preferably at least one selected from quartz, fused quartz, quartz glass, fumed silica, liquid phase silica, barium glass, strontium glass, alumina, zirconia, titania, and hydroxyapatite.
Further, in the preferred embodiment of the present application, the bioglass or other inorganic filler has a particle size of no greater than 150 microns, preferably in the range of 10 nanometers to 100 microns.
Further, in the preferred embodiment of the present application, the auxiliary agent comprises an initiator and a stabilizer; and/or the initiator is a thermal initiator, preferably benzoyl peroxide; and/or the stabilizer is at least one of triphenyl antimony, hydroquinone or 2, 6-di-tert-butyl-4-cresol.
Further, in the preferred embodiment of the present application, the auxiliary agents include initiators, stabilizers, and accelerators; and/or the initiator is a photoinitiator, preferably diphenyl iodonium hexafluorophosphate or camphorquinone; and/or the stabilizer is at least one of triphenyl antimony, hydroquinone or 2, 6-di-tert-butyl-4-cresol; and/or the accelerant is at least one of 4- (dimethylamino) ethyl benzoate, N-dihydroxyethyl-p-methylaniline or dimethylaminoethyl methacrylate.
Further, in the preferred embodiment of the present application, the curing shrinkage of the dental adhesive is less than 3%, preferably less than 2.5%.
In a second aspect, the present application also provides a method of making a dental article comprising hardening the above dental adhesive to make an orthodontic attachment.
Compared with the prior art, the dental adhesive and the method for preparing the dental product provided by the preferred embodiment of the application have the advantages that:
according to the dental adhesive, the bioactive glass material is added into the dental adhesive, so that the curing shrinkage rate of the adhesive can be remarkably reduced, the phenomenon that the excessive shrinkage of the adhesive causes the increase of the gap between the orthodontic accessory and the tooth surface bonding interface in the curing process of the adhesive is avoided, and the enamel demineralization caused by the aggregation and growth of dental plaque in the gap is avoided. Meanwhile, the bioactive glass material also has the natural remineralization function of enhancing the tooth structure, can repair damaged enamel and further reduce the occurrence of enamel demineralization.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application are described below.
In the present application, "adhesive" or "dental adhesive" refers to a composition that bonds a "dental material" (e.g., an orthodontic appliance) to a tooth structure. Where the tooth surface needs to be pretreated prior to bonding, for example, by acid etching or otherwise treating the tooth surface to enhance the adhesion of the "dental material" to the tooth surface.
In this application, "curing" or "hardening" refers to polymerization and/or crosslinking reactions, including, for example, photopolymerization reactions and chemical polymerization techniques involving one or more compounds capable of hardening or curing (e.g., ionic reactions or chemical reactions that form radicals effective to polymerize ethylenically unsaturated compounds).
The composite resin is an orthodontic adhesive which is commonly used clinically at present, has high adhesive property and convenient operation, and is generally accepted in the field. The general composite resin adhesive is composed of a liquid agent and a paste agent, wherein the liquid agent is mainly used for infiltrating the enamel surface after acid etching treatment, and the paste agent is used for bonding the orthodontic bracket to the tooth surface.
However, in practical applications, it has been found that bacteria tend to aggregate around the composite resin, resulting in demineralization of the enamel surrounding the resin. In order to avoid the occurrence of enamel demineralization, the resin reinforced glass ion adhesive is introduced into the oral cavity field, the mechanical property of the adhesive after curing can be greatly improved by adding a small amount of resin monomers into glass ions, and simultaneously, fluoride in the resin reinforced glass ion adhesive can release fluorine ions in the oral cavity, thereby slowing down the occurrence of enamel demineralization.
However, since the time for fixing the bracket to the tooth surface is generally 1 to 2 years, the phenomenon of enamel removal still occurs during orthodontic treatment by adhering the orthodontic bracket using the resin-reinforced glass ionomer adhesive, and there is no difference in the probability of enamel removal occurring between the tooth using the composite resin bonded bracket and the tooth.
In view of the above problems with adhering dental adhesives to orthodontic brackets, the present application provides a dental adhesive consisting of a paste a and a liquid B:
paste a, by mass percent, comprising: 13-30 wt% of an ethylenically unsaturated compound with an acid or ester function, 65-85 wt% of a filler and 0.1-2 wt% of an auxiliary;
liquid agent B comprises the following components in percentage by mass: 75-99.9% by weight of an ethylenically unsaturated compound bearing an acid or ester function and 0.1-25% by weight of an auxiliary;
wherein the filler comprises a modified bioactive glass; ethylenically unsaturated compounds with acid or ester functions, comprising monomers or oligomers with at least two ethylenic bonds, bearing acid or ester functions, chosen from at least one carboxylic acid function, phosphonic acid function, phosphoric acid function, chosen from at least one acrylate, phosphate.
Illustratively, the proportion of ethylenically unsaturated compounds bearing acid or ester functional groups in paste A is between 13 and 30 wt%, and may be, for example, 13, 15, 16, 18, 20, 21, 22, 24, 26, 28, or 30 wt%, and so forth.
In paste A, the filler content is 65-85 wt%, and may be, for example, 65 wt%, 66 wt%, 70 wt%, 72 wt%, 75 wt%, 78 wt%, 80 wt%, 82 wt%, or 85 wt%, and so forth.
In liquid formulation B, the proportion of ethylenically unsaturated compound having an acid or ester functional group is 75 to 99.9% by weight, and may be, for example, 75%, 77%, 79%, 82%, 85%, 90%, 91%, 93%, 95%, 98%, 99%, or 99.9% by weight, or the like.
In the liquid agent B, the proportion of the auxiliary agent is 0.5 to 25% by weight, and may be, for example, 0.5%, 1%, 5%, 7%, 9%, 10%, 13%, 15%, 19%, 20%, 25% by weight, or the like.
In the process of adhering the orthodontic bracket on the tooth surface by using the adhesive, the adhesive shrinks during the curing process, so that gaps exist between the adhesive and the tooth surface, and a space is provided for the breeding of dental plaque. After eating daily on a sugar diet, the bacteria in the plaque break down the sugar to produce acid, and the local increase in acid concentration causes calcium phosphorus plasma dissolution in the enamel, resulting in demineralization of the enamel. Therefore, it is possible to prevent the adhesive from generating a gap with the tooth surface by reducing the curing shrinkage of the adhesive, thereby reducing the occurrence of enamel demineralization.
The inventor finds in the research process that the curing shrinkage of the adhesive can be remarkably reduced by adding the bioactive glass into the paste, so that gaps can be prevented from being generated at the bonding interface of the adhesive and the tooth surface in the curing process of the adhesive, and the incidence rate of enamel demineralization of orthodontic patients can be reduced.
Suitable photopolymerizable compositions that can be used as dental materials and dental adhesive compositions herein can include epoxy resins, vinyl ether resins, ethylenically unsaturated compounds containing free-radically reactive unsaturated groups, e.g., acrylates and methacrylates, and combinations thereof. Considering the adhesive property and the curing property of the resin, the application selects the use of the ethylenic unsaturated compound, which has the advantages of fast curing and good adhesive property.
Among these, ethylenically unsaturated compounds bearing acid or ester functionality are more suitable as the resin component of the binder herein, such as, but not limited to, at least one of bisphenol A glycerol dimethacrylate, bisphenol A ethoxy dimethacrylate, bisphenol A polyethoxylated dimethacrylate, diurethane dimethacrylate, bis [2- (methacryloyloxy) ethyl ] phosphate, 1, 6-hexanediol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 2-methyl-2-acryloxy phosphinyl tris (oxy-2, 1-ethylene) acrylate, or hydroxyethyl methacrylate dimethacrylate.
In some embodiments, the dental adhesive is photopolymerizable, i.e. the dental adhesive contains a photoinitiator system in its adjuvant to initiate polymerization (or hardening) of the ethylenically unsaturated compound upon irradiation with light radiation.
Photoinitiators suitable for use in the polymerization of the above ethylenically unsaturated compounds may include free radical polymerization photoinitiators and cationic polymerization photoinitiators.
Free radical polymerization photoinitiators include, but are not limited to, monoketones and diketones that absorb light within the range of 400nm to 520nm (preferably, 450nm to 500nm), preferably alpha-diketones, more preferably camphorquinone, benzil, furiluoyl, 3,3,6, 6-tetramethylcyclohexanedione, phenanthrenequinone or 1-phenyl-1, 2-propanedione, with camphorquinone being most preferred.
The cationic polymerization photoinitiator may be selected from one or more of iodonium salts, sulfonium salts, and ferriaromatic hydrocarbons, including diaryliodonium salts, e.g., diphenyliodonium chloride, diphenyliodonium hexafluorophosphate, diphenyliodonium tetrafluoroborate, and tolylcumylium tetrakis (pentafluorophenyl) borate. Diphenyliodonium hexafluorophosphate is an option used in this application.
In order to accelerate the photocuring, in certain embodiments, an accelerator may also be added. The promoter may be at least one selected from ethyl 4- (dimethylamino) benzoate, N-dihydroxyethyl-p-methylaniline or dimethylaminoethyl methacrylate.
In some embodiments, the dental adhesive is of the chemical type, i.e. the dental adhesive contains a chemical curing type initiator system in its adjuvant, so that the polymerization curing of the ethylenically unsaturated compound is initiated without relying on irradiation with light rays.
Chemical initiators suitable for the polymerization of the above ethylenically unsaturated compounds may include azo-type initiators, peroxy-type initiators, and redox initiators. In view of the conditions for specific adhesion, benzoyl peroxide is preferably used in the present application.
The present application optionally incorporates stabilizers in the dental adhesive, according to the actual need. The stabilizer may be selected from, for example, but not limited to, at least one of triphenylantimony, hydroquinone or 2, 6-di-t-butyl-4-methylphenol.
In the present application, "bioactive glass" means a glass predominantly composed of P2O5、SiO2And inorganic material taking CaO as a main body, which can generate ionic reaction with body fluid, and finally a hydroxyapatite structure layer is formed on the surface of the bioglass, so that the tooth surface can be repaired. As an example, the bioactive glass of the present application is P2O5-SiO2CaO bioactive glass, wherein, in mass ratio, P2O5：SiO2： CaO＝(0.5-68)：(13.2-99)：(0.5-80)。
For example, P2O5-SiO2The molar ratio of-CaO may be 0.5: 13.2: 0.5, 1: 15: 20. 20: 13.2: 0.5, 1:1:1, 1: 80:80, 68: 13.2: 80. 68:99:0.5, and so on.
Further, in order to improve polymerizability of the bioactive resin so that the bioactive material can participate in polymerization of the ethylenically unsaturated compound, further improving mechanical properties of the dental adhesive, the bioglass of the present application is preferably modified using an ethylenic linkage-containing silane coupling agent. Wherein the silane coupling agent containing olefinic bond includes, but is not limited to, at least one of 3- (trimethoxysilyl) propyl methacrylate, vinyltrimethoxysilane, vinyltris (2-methoxyethoxy) silane, and vinyltriethoxysilane, preferably 3- (trimethoxysilyl) propyl methacrylate.
Further, in order to further improve the mechanical properties of the adhesive, other inorganic fillers that are modified, such as, but not limited to, at least one of quartz, fused quartz, quartz glass, fumed silica, liquid phase silica, barium glass, strontium glass, alumina, zirconia, titanium dioxide, or hydroxyapatite, may be added to the filler.
In some embodiments of the present application, the bioglass is modified with 3- (trimethoxysilyl) propyl methacrylate;
the inorganic filler is modified by 3- (trimethoxysilyl) propyl methacrylate.
The filler is preferably finely dispersed, and may have a monomodal or multimodal particle size distribution, preferably having a particle size of no more than 150 microns, preferably in the range of 10 nm to 100 microns.
For example, the particle size of the filler can be 10 nanometers, 100 nanometers, 200 nanometers, 500 nanometers, 920 nanometers, 1 micron, 10 microns, 20 microns, 80 microns, 100 microns, 120 microns, 150 microns, or the like.
The resulting dental adhesive has a cure shrinkage of less than 3%, preferably less than 2.5%.
For example, the curing shrinkage of the finally obtained dental adhesive may be 0.1%, 0.5%, 0.9%, 1.1%, 1.5%, 1.9%, 2%, 2.5%, 3%, and the like.
The density of the paste before and after curing was tested using a balance density module (sartorius YDKO3) according to archimedes' principle, and the cure shrinkage was calculated according to the following formula:
where ρ isuncuredDensity before curing of the paste, pcuredIs the density of the paste after curing.
Another aspect of the present application also provides a method of making a dental article comprising hardening the above dental adhesive to make an orthodontic attachment.
Specifically, when the orthodontic bracket is used, firstly, an acid etching agent is used for acid etching of the surface of the enamel, after the enamel is dried, the liquid B is used for infiltrating the treated enamel, meanwhile, the paste A is coated on the bracket, and finally, the orthodontic bracket with the paste is bonded with the liquid B, so that the orthodontic bracket is bonded on the tooth surface, and the adhesive is hardened under the irradiation of a curing lamp or under the chemical curing condition at room temperature, so that the orthodontic bracket is bonded on the tooth surface.
Objects and advantages of this invention are further illustrated by the following examples, but the particular materials and amounts thereof recited in these examples, as well as other conditions and details, should not be construed to unduly limit this invention. All parts and percentages are by weight and all water is deionized water, unless otherwise indicated. In the present invention, all numbers disclosed herein are approximate values, regardless of whether the word "about" or "approximately" is used. There may be differences below 10% in the value of each number or reasonably considered by those skilled in the art, such as differences of 1%, 2%, 3%, 4% or 5%. The following explains the aspects of the present invention with reference to examples.
Preparation example 1: preparation of modified bioactive glass and modified quartz
70mL of ethanol, 30mL of water, 10g of bioglass (purchased from Wakui science and technology Tay, Co., Ltd., particle size range of 1-100 microns) and 2mL of 3- (trimethoxysilyl) propyl methacrylate are sequentially added into a round-bottom flask, then stirred at 80 ℃ for 24 hours, then a liquid phase is removed, the remaining solid phase is washed with ethanol for three times, and then vacuum drying is carried out at 100 ℃ for 24 hours to obtain the modified bioactive glass.
The method for modifying quartz powder (with particle size ranging from 1-100 microns) is the same as the method for modifying bioactive glass. The modified bioactive glass and the modified quartz described above were used in paste a of dental adhesive in the subsequent examples.
Example 1 preparation of pure modified bioactive glass-filled Photocurable type Material
The paste A comprises 0.100g bisphenol A glycerol dimethacrylate, 0.150g bisphenol A ethoxy dimethacrylate, 0.740g modified bioactive glass, 0.001g hydroquinone, 0.004g camphorquinone and 0.005g dimethylaminoethyl methacrylate
The liquid agent B includes: 0.693g bisphenol A glycerol dimethacrylate, 0.300g triethylene glycol dimethacrylate, 0.001g hydroquinone, 0.004g camphorquinone and 0.005g dimethylaminoethyl methacrylate;
the material curing method comprises the following steps: dripping 10 microliters of the liquid B into the bottom of a mold with the inner cavity diameter of 5mm and the thickness of 1mm, filling the paste A, irradiating the material by using a light source with the wavelength of 400nm-500nm for 20s, and taking out the cured and molded wafer material.
Example 2 preparation of a light-curable type Material with modified bioactive glass Co-filled with other fillers
Paste A comprises 0.08g of bisphenol A glycerol dimethacrylate, 0.12g of bisphenol A ethyleneoxy dimethacrylate, 0.10g of modified bioactive glass, 0.69g of modified quartz, 0.001g of hydroquinone, 0.004g of camphorquinone and 0.005g of dimethylaminoethyl methacrylate;
the liquid agent B includes: 0.693g bisphenol A glycerol dimethacrylate, 0.300g triethylene glycol dimethacrylate, 0.001g hydroquinone, 0.004g camphorquinone and 0.005g dimethylaminoethyl methacrylate;
the material curing method comprises the following steps: the same as in example 1.
Example 3 preparation of modified bioactive glass-filled chemical Cure-type Material
Paste A comprises 0.100g of bisphenol A glycerol dimethacrylate, 0.150g of bisphenol A ethyleneoxy dimethacrylate, 0.740g of modified bioactive glass, 0.001g of hydroquinone and 0.009g of benzoyl peroxide.
The liquid agent B includes: 0.300g bisphenol A glycerol dimethacrylate, 0.450g triethylene glycol dimethacrylate, 0.100g polymethacrylate, 0.001g hydroquinone, 0.149g N, N-dihydroxyethyl p-toluidine;
the material curing method comprises the following steps: firstly, 10 microliters of the liquid B is dripped into the bottom of a mold with the inner cavity diameter of 5mm and the thickness of 1mm, then the paste A is filled, then a glass slide containing 10 microliters of the liquid B is covered on the upper surface, then the glass slide is placed for 10 minutes at room temperature, and then the solidified and molded wafer material is taken out.
Example 4 preparation of a chemically curable type Material with Co-filling of modified bioactive glass with other fillers
The paste A comprises 0.08g of bisphenol A glycerol dimethacrylate, 0.120g of bisphenol A ethoxy dimethacrylate, 0.100g of modified bioactive glass, 0.690g of modified quartz, 0.001g of hydroquinone and 0.009g of benzoyl peroxide.
The liquid agent B includes: 0.300g bisphenol A glycerol dimethacrylate, 0.450g triethylene glycol dimethacrylate, 0.100g polymethacrylate, 0.001g hydroquinone, 0.149g N, N-dihydroxyethyl p-toluidine;
the material curing method comprises the following steps: same as example 3
Comparative example 1 preparation of modified Quartz-filled Photocurable type Material
Paste a composition: 0.080g of bisphenol A glycerol dimethacrylate, 0.120g of bisphenol A ethyleneoxy dimethacrylate, 0.790g of modified quartz, 0.001g of hydroquinone, 0.004g of camphorquinone and 0.005g of dimethylaminoethyl methacrylate;
the liquid agent B includes: 0.693g bisphenol A glycerol dimethacrylate, 0.300g triethylene glycol dimethacrylate, 0.001g hydroquinone, 0.004g camphorquinone and 0.005g dimethylaminoethyl methacrylate;
the material curing method comprises the following steps: same as example 1
Comparative example 2 preparation of modified Quartz filled chemical Cure type Material
The paste A comprises 0.080g bisphenol A glycerol dimethacrylate, 0.120g bisphenol A ethoxy dimethacrylate, 0.790g modified quartz, 0.001g hydroquinone, and 0.009g benzoyl peroxide.
The liquid agent B includes: 0.300g bisphenol A glycerol dimethacrylate, 0.450g triethylene glycol dimethacrylate, 0.100g polymethacrylate, 0.001g hydroquinone, 0.149g N, N-dihydroxyethyl p-toluidine;
the material curing method comprises the following steps: same as example 3
Comparative example 3 light-cured product on the market
Liquid agent: 3M Unitek Transbond XT Primer
Paste: 3M transbond XT light curve additive
The material curing method comprises the following steps: same as example 1
Comparative example 4 now-marketed non-tempered chemical cured product
Liquid agent: 3M Unitek Unite Primer
Paste: 3M United Unit Adhesive
The material curing method comprises the following steps: the same as in example 3.
The disc materials of examples 1-4 and comparative examples 1-4 were tested for cure shrinkage and the results are shown in table 1.
TABLE 1
| Material | Shrinkage rate |
| Example 1 | 0.7％ |
| Example 2 | 2.3％ |
| Example 3 | 0.5％ |
| Example 4 | 2.2％ |
| Comparative example 1 | 5.4％ |
| Comparative example 2 | 5.0％ |
| Comparative example 3 | 6.9％ |
| Comparative example 4 | 10.5％ |
As can be seen from Table 1, the shrinkage rates of examples 1 to 4 of the present application are smaller than those of comparative examples 1 to 4.
It will be evident to those skilled in the art that the present disclosure is not limited to the foregoing illustrative embodiments, but may be embodied in other specific forms without departing from the essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive. Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that those skilled in the art can make changes, modifications, substitutions and alterations to the above embodiments without departing from the spirit and scope of the present invention.
Claims (10)
1. A dental adhesive consisting of a paste a and a liquid B:
the paste A comprises the following components in percentage by mass: 13-33% by weight of an ethylenically unsaturated compound bearing an acid or ester function, 65-85% by weight of a filler and 0.1-2% by weight of an auxiliary;
the liquid agent B comprises the following components in percentage by mass: 75-99.5% by weight of an ethylenically unsaturated compound bearing an acid or ester function and 0.5-25% by weight of an auxiliary;
wherein the filler comprises a modified bioactive glass; the ethylenically unsaturated compound with acid or ester functional group comprises a monomer or oligomer which has at least two ethylenic bonds and has acid or ester functional groups, wherein the acid functional groups are selected from at least one of carboxylic acid functional groups, phosphonic acid functional groups and phosphoric acid functional groups, and the ester functional groups are selected from at least one of acrylate and phosphate.
2. Dental adhesive according to claim 1, wherein the ethylenically unsaturated compound carrying an acid or ester functionality is selected from at least one of bisphenol a glycerol dimethacrylate, bisphenol a ethoxy dimethacrylate, bisphenol a polyethoxylated dimethacrylate, diurethane dimethacrylate (UDMA), bis [2- (methacryloyloxy) ethyl ] phosphate, 1, 6-hexanediol dimethacrylate, triethylene glycol dimethacrylate (temma), polyethylene glycol dimethacrylate, 2-methyl-2-phosphinyl tris (oxy-2, 1-ethylene) acrylate or hydroxyethyl methacrylate dimethacrylate.
3. Dental adhesive according to claim 1, wherein the bioactive glass is P2O5-SiO2CaO bioactive glass, wherein, in terms of mass ratio, P2O5：SiO2：CaO＝(0.5-68)：(13.2-99)：(0.5-80)。
4. Dental adhesive according to claim 1, wherein the filler further comprises a modified further inorganic filler, preferably selected from at least one of quartz, fused quartz, quartz glass, fumed silica, liquid silica, barium glass, strontium glass, alumina, zirconia, titania or hydroxyapatite.
5. Dental adhesive according to claim 4, wherein the bioactive glass is modified with 3- (trimethoxysilyl) propyl methacrylate;
the inorganic filler is modified by 3- (trimethoxysilyl) propyl methacrylate.
6. Dental adhesive according to claim 4, wherein the bioactive glass or the further inorganic filler has a particle size of not more than 150 microns, preferably a particle size in the range of 10 nm to 100 microns.
7. Dental adhesive according to claim 1, wherein the auxiliary agents comprise initiators and stabilizers; and/or the initiator is a thermal initiator, preferably benzoyl peroxide; and/or the stabilizer is at least one of triphenyl antimony, hydroquinone or 2, 6-di-tert-butyl-4-cresol.
8. Dental adhesive according to claim 1, wherein the auxiliary agents comprise initiators, stabilizers and accelerators; and/or the initiator is a photoinitiator, preferably diphenyl iodonium hexafluorophosphate or camphorquinone; and/or the stabilizer is at least one of triphenyl antimony, hydroquinone or 2, 6-di-tert-butyl-4-cresol; and/or the accelerant is at least one of 4- (dimethylamino) ethyl benzoate, N-dihydroxyethyl-p-methylaniline or dimethylaminoethyl methacrylate.
9. Dental adhesive according to claim 1, wherein the curing shrinkage of the dental adhesive is less than 3%, preferably less than 2.5%.
10. A method of making a dental article comprising hardening the dental adhesive of any one of claims 1-9 to make an orthodontic attachment.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011324560.4A CN114522107A (en) | 2020-11-23 | 2020-11-23 | Dental adhesive and method for preparing dental product |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011324560.4A CN114522107A (en) | 2020-11-23 | 2020-11-23 | Dental adhesive and method for preparing dental product |
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