阅读说明：本技术 一种齿科修复用可光固化牙本质粘结剂及其制备方法 (Photocurable dentin binder for dental restoration and preparation method thereof ) 是由 张青红 涂宝丽 李耀刚 王宏志 侯成义 于 2020-03-18 设计创作，主要内容包括：本发明涉及一种齿科修复用可光固化牙本质粘结剂及其制备方法,所述粘结剂中的填料为改性SiC晶须。本方法工艺简单可靠,产品体系稳定,力学性能优异,具有广泛的应用前景。(The invention relates to a photo-curable dentin adhesive for dental restoration and a preparation method thereof. The method has simple and reliable process, stable product system, excellent mechanical property and wide application prospect.)

1. A photocurable dentin binder composition, the binder component comprising, in mass fraction: 40-50% of resin monomer, 35-45% of crosslinking monomer and monofunctional group comonomer, 0.1-0.3% of photoinitiator, 0.7-0.9% of co-initiator, 2-10% of acid etching monomer, 0.01-0.2% of polymerization inhibitor, 5-15% of solvent and 0-0.7% of filler; the method is characterized in that the filler is modified SiC whisker; the molar ratio of the resin monomer to the crosslinking monomer is 4:1 to 1: 4.

2. The composition of claim 1, wherein the resin monomer is bisphenol a-glycidyl methacrylate Bis-GMA; the crosslinking monomer is triethylene glycol dimethacrylate (TEGDMA); the monofunctional group comonomer is hydroxyethyl methacrylate HEMA; the photoinitiator is camphorquinone CQ; the auxiliary initiator is ethyl p-dimethylaminobenzoate 4-EDMAB; the acid etching monomer is 10- (2-methacryloyloxy) phosphoric acid monodecanyl ester 10-MDP; the polymerization inhibitor is 2, 6-di-tert-butyl-4-methylphenol BHT; the solvent is water.

3. The composition of claim 1, wherein the modified SiC whiskers have a particle size of 0.05-2.5 μm and an aspect ratio of 20 or more.

4. The composition according to claim 1, wherein the modified SiC whiskers are in particular: ultrasonically dispersing the SiC crystal whisker into an organic solvent, dropwise adding a surface modifier, heating and stirring, and carrying out rotary evaporation and vacuum drying to obtain the modified SiC crystal whisker.

5. The composition of claim 4, wherein the surface modifier is one or more of gamma-methacryloxypropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, and 3-aminopropyltriethoxysilane.

6. The composition of claim 1, wherein the molar ratio of the resin monomer to the crosslinking monomer is 3: 2; the mass percentage of the filler is 0.1-0.5%.

7. A method of preparing a photocurable dentin adhesive composition comprising:

(1) ultrasonically dispersing SiC crystal whiskers into an organic solvent, dropwise adding a surface modifier, heating and stirring, performing rotary evaporation, and performing vacuum drying to obtain modified SiC crystal whiskers;

(2) mixing 40-50% of resin monomer, 35-45% of crosslinking monomer and monofunctional group comonomer according to mass fraction, stirring, cooling, adding 0.1-0.3% of photoinitiator, 0.7-0.9% of initiator aid, 2-10% of acid etching monomer, 0.01-0.2% of polymerization inhibitor, 5-15% of solvent and 0-0.7% of modified SiC whisker, and stirring in a dark place to obtain the light-curable dentin adhesive.

8. The preparation method according to claim 7, wherein the organic solvent in step (1) is one or more of cyclohexane, n-propylamine and absolute ethyl alcohol; the surface modifier is one of gamma-methacryloxypropyltrimethoxysilane, gamma-aminopropyltriethoxysilane and 3-aminopropyltriethoxysilane.

9. The preparation method according to claim 7, wherein the heating in the step (1) is oil bath heating, and the heating temperature is 60-80 ℃; stirring for at least 30min by magnetic stirring; the rotary evaporation temperature is 60-90 ℃; the vacuum drying temperature is 80-100 ℃.

10. Use of the photocurable dentin adhesive of claim 1.

Technical Field

The invention belongs to the field of dental self-acid etching binders and preparation thereof, and particularly relates to a light-curable dentin binder for dental restoration and a preparation method thereof.

Background

The silicon carbide whisker is commonly used for strengthening and toughening metal-based, ceramic-based and high polymer-based composite materials, and can be used as artificial teeth, bones, joints and the like in the aspect of biological ceramics.

The binder is a liquid substance matched with the dental restoration composite resin, the self-acid-etching binder is acidic, the phosphoric acid etching step in the restoration process is reduced, and acid etching is completed by the polymerizable acidic functional monomer in the composition. Most resin-based binders, the main components of which are bisphenol a-glycidyl methacrylate (Bis-GMA), triethylene glycol dimethacrylate (TEGDMA), hydroxyethyl methacrylate (HEMA), and the like. In general, dental adhesives always contain fillers. The development of fillers, from glass frits, silicates to nano-sized fumed silica and ion leachable glass fillers, to POSS particles (polyhedral oligomeric silsesquioxanes) with unique cage structures, and the like. The filler added into the adhesive has high activity and polarity, the surface of the adhesive is generally hydrophilic, the polarity of the resin matrix is weaker, and the interface problem exists between the two, so the filler added into the adhesive needs to be pre-activated. In the traditional test, phosphate and silane compounds are used for surface treatment of minerals. The silane compounds are most commonly gamma-methylpropylacyloxypropyltrimethoxysilane (gamma-MPS or KH-570).

At present, the edges of a restoration body cannot be completely sealed by self-acid-etching adhesive commodities, nano leakage is possible, the aperture of the nano leakage is generally 20-100 nm, and gaps appear due to stress at an adhesive interface along with curing shrinkage of resin, and finally micro leakage is developed. Therefore, the method has important significance for practical application by regulating and controlling the components of the self-acid-etching binder, improving the binding performance of the self-acid-etching binder and endowing the self-acid-etching binder with antibacterial performance.

CN109758371A discloses a photo-curable dentin adhesive for dental restoration and preparation and application thereof, but the adhesive strength is not high, and the occurrence of postoperative micro-leakage cannot be relieved.

Disclosure of Invention

The invention aims to solve the technical problem of providing a photocurable dentin adhesive for dental restoration and a preparation method thereof, which overcome the defects that the prior art can not obviously improve the adhesive strength of a self-acid-etching adhesive and micro leakage is easy to occur after operation.

The invention provides a photo-curable dentin bonding agent composition, which comprises the following components in percentage by mass: 40-50% of resin monomer, 35-45% of crosslinking monomer and monofunctional group comonomer, 0.1-0.3% of photoinitiator, 0.7-0.9% of co-initiator, 2-10% of acid etching monomer, 0.01-0.2% of polymerization inhibitor, 5-15% of solvent and 0-0.7% of filler; the filler is modified SiC whisker; the molar ratio of the resin monomer to the crosslinking monomer is 4:1 to 1: 4.

The resin monomer is bisphenol A-glycidyl methacrylate Bis-GMA; the crosslinking monomer is triethylene glycol dimethacrylate (TEGDMA); the monofunctional group comonomer is hydroxyethyl methacrylate HEMA; the photoinitiator is camphorquinone CQ; the auxiliary initiator is ethyl p-dimethylaminobenzoate 4-EDMAB; the acid etching monomer is 10- (2-methacryloyloxy) phosphoric acid monodecanyl ester 10-MDP; the polymerization inhibitor is 2, 6-di-tert-butyl-4-methylphenol BHT; the solvent is water.

The particle size of the modified SiC crystal whisker is 0.05-2.5 mu m, and the length-diameter ratio is not less than 20 and not more than 300.

The modified SiC whisker is specifically as follows: ultrasonically dispersing the SiC crystal whisker into an organic solvent, dropwise adding a surface modifier, heating and stirring, and carrying out rotary evaporation and vacuum drying to obtain the modified SiC crystal whisker.

The surface modifier is one or more of gamma-methacryloxypropyltrimethoxysilane, gamma-aminopropyltriethoxysilane and 3-aminopropyltriethoxysilane.

The molar ratio of the resin monomer to the crosslinking monomer is 3: 2; the mass percentage of the filler is 0.1-0.5%.

The present invention provides a method for preparing a photocurable dentin adhesive composition, comprising:

(1) ultrasonically dispersing SiC crystal whiskers into an organic solvent, dropwise adding a surface modifier, heating and stirring, performing rotary evaporation, and performing vacuum drying to obtain modified SiC crystal whiskers;

(2) mixing 40-50% of resin monomer, 35-45% of crosslinking monomer and monofunctional group comonomer according to mass fraction, stirring, cooling, adding 0.1-0.3% of photoinitiator, 0.7-0.9% of initiator aid, 2-10% of acid etching monomer, 0.01-0.2% of polymerization inhibitor, 5-15% of solvent and 0-0.7% of modified SiC whisker, and stirring in a dark place to obtain the light-curable dentin adhesive.

The preferred mode of the above preparation method is as follows:

in the step (1), the SiC whiskers are ultrasonically dispersed into an organic solvent according to the concentration of 0.025-0.1 g/m L, wherein the organic solvent is gamma-methacryloxypropyl trimethoxysilane and cyclohexane in a ratio of 0.005-0.02: 1.

The organic solvent in the step (1) is one or more of cyclohexane, n-propylamine and absolute ethyl alcohol; the surface modifier is one of gamma-methacryloxypropyltrimethoxysilane, gamma-aminopropyltriethoxysilane and 3-aminopropyltriethoxysilane.

The heating in the step (1) is oil bath heating, and the heating temperature is 60-80 ℃; stirring for at least 30min by magnetic stirring; the rotary evaporation temperature is 60-90 ℃; the vacuum drying temperature is 80-100 ℃.

And (3) stirring in the step (2) at the temperature of 40-60 ℃ for 1-3 h.

And (3) keeping away from light and stirring for 5-10 h.

The invention provides an application of the light-curable dentin adhesive.

Advantageous effects

(1) The preparation method is simple, mild in condition and strong in operability;

(2) the light-cured dentin adhesive prepared by the invention and taking the SiC crystal whiskers as the filler has good filler dispersibility and stable adhesive system;

(3) the invention modifies SiC crystal whiskers by using the silane coupling agent and uniformly disperses the modified SiC crystal whiskers in the binder matrix, and the prepared self-acid etching binder has simple and reliable process, high binding strength and wide application prospect.

Drawings

FIG. 1 is a scanning electron micrograph of a modified SiC whisker;

FIG. 2 is a scanning electron micrograph of the bonding interface of the resulting photocurable dentin adhesive and resin;

FIG. 3 is a graph showing the relationship between the bonding strength of a photo-curable dentin adhesive and the content of modified SiC whiskers;

FIG. 4 is a microleakage test chart of the resulting light-curable dentin adhesive;

fig. 5 is the viscosity of the adhesive.

Detailed Description

The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.

The SiC crystal whisker adopted in the embodiment of the invention adopts a commercial product (Xuzhou Jie Innovation materials science and technology Co., Ltd.), the model is D500, and the length-diameter ratio is about 100; the particle size was 1 μm.

The method for testing the bonding strength in the embodiment of the invention comprises the steps of filling 3M purchased resin in a 25mm × 2mm × 2mm silicon rubber mold, filling half of the length at one time, curing the front side and the back side for 60s, then coating a proper amount of bonding agent on one end of the mold, blowing for at least 5s by using strong air flow, curing for 20s by using a visible light curing lamp, filling the other half of the mold and curing, preparing 8 samples in total for each group of materials, setting the loading speed to be 0.75mm/min after the mold is fixed on a universal tester, stretching until the mold is broken, and recording the maximum tensile bonding strength at the time of the breakage.