阅读说明：本技术 一种嵌入纳米颗粒的光固化口腔隔离树脂及其制备方法 (Light-cured oral cavity isolation resin embedded with nanoparticles and preparation method thereof ) 是由 李燕燕 张良芬 其他发明人请求不公开姓名 于 2019-10-08 设计创作，主要内容包括：本发明旨在提供一种光固化口腔应用树脂,尤其提供一种嵌入纳米颗粒的光固化口腔隔离树脂及其制备方法。口腔隔离树脂的性能由基体树脂、光引发剂、纳米填料等共同决定,每一个组份都非常重要。其中纳米填料可以满足一般增强材料的基本要求外,还对光线具有很好的透过性和较小的吸收率,光固化时,减少光能量的损耗,使复合树脂的转化率高、固化充分。本发明将经过表面处理的纳米填料引入到光固化树脂体系中,纳米起到很好的小尺寸效应、表面效应、量子尺寸效应和宏观量子隧道效应等特征,使隔离树脂具有优异的光固化性能、理想的机械强度和隔离效果好等特点。(The invention aims to provide a light-cured oral cavity application resin, in particular to a light-cured oral cavity isolation resin embedded with nano-particles and a preparation method thereof. The properties of the mouth barrier resin are determined by the matrix resin, the photoinitiator, the nanofiller and the like, and each component is very important. The nano filler can meet the basic requirements of general reinforcing materials, has good transmittance and small absorptivity for light, reduces the loss of light energy during photocuring, and ensures that the composite resin has high conversion rate and full curing. The surface-treated nano filler is introduced into a light-cured resin system, and the nano filler has the characteristics of good small-size effect, surface effect, quantum size effect, macroscopic quantum tunneling effect and the like, so that the isolation resin has the characteristics of excellent light-cured performance, ideal mechanical strength, good isolation effect and the like.)

1. A light-cured oral cavity isolation resin embedded with nano-particles and a preparation method thereof are characterized by comprising the following components: prepolymer, diluent, solvent, surface modified nano-particles, photoinitiator, cross-linking agent, essence and other auxiliary agents;

the components comprise the following components in parts by weight: 35-75 parts of prepolymer, 10-30 parts of diluent, 15-80 parts of solvent, 5-35 parts of surface modified nano particles, 0.5-4 parts of photoinitiator, 0.5-2 parts of cross-linking agent, 0-4 parts of essence and 0-4 parts of other auxiliary agents.

2. The nanoparticle-embedded photocurable oral barrier resin of claim 1 wherein the prepolymer includes but is not limited to one or a combination of two or more of the group consisting of a diamine-based dimethacrylate resin, a urethane-based dimethacrylate resin, a polyethylene glycol-modified urethane-based dimethacrylate resin, a bisphenol a glyceryl dimethacrylate resin, a triethylene glycol dimethacrylate resin, and an epoxy resin E-44.

3. The nanoparticle-embedded photocurable oral barrier resin of claim 1 wherein the diluent comprises but is not limited to one or a combination of two or more of methacrylic acid, dimethylacrylic acid, polyethylene glycol modified methacrylic acid, triethylene glycol dimethacrylate, hydroxyethyl methacrylate.

4. The nanoparticle-embedded photocurable oral barrier resin of claim 1 wherein the solvent includes but is not limited to one or a combination of acetone, ethanol, methanol, toluene, ethyl acetate, butyl acetate.

5. The nanoparticle-embedded photocurable oral barrier resin of claim 1 wherein the photoinitiator comprises but is not limited to camphorquinone, 2-methyl-2- (4-morpholino) -1- [4- (methylthio) phenyl ] -1-propanone, diethyl trimethylbenzoylphosphonate, benzophenone (BP for short), Diethylthioxanthone (DETX), 4- (phenylthio) phenyldiphenylsulfonium hexafluorophosphate, 4-isobutylphenyl-4' -methylphenyliodilium hexafluorophosphate, N, -dimethylaminoethyl methacrylate.

6. The nanoparticle-embedded photocurable oral cavity barrier resin of claim 1, wherein the crosslinking agent is a monomer having two double bonds, such as one or more of ethylene glycol dimethacrylate, polyethylene glycol diacrylate, and methylene bisacrylamide.

7. The nanoparticle-embedded photocurable oral barrier resin of claim 1 wherein the surface-modified nanoparticles are nanoparticles surface-modified with a silane coupling agent in a ratio of 1:3 to 1:10, in parts by weight;

the nano particles are one or more of fumed silica, talcum powder and mica powder, wherein the specific surface area of the fumed silica, the talcum powder and the mica powder is more than 1000 meshes;

the silane coupling agent is siloxane containing unsaturated double bonds, and comprises but is not limited to one or more of gamma-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, allyltriethoxysilane, 5-hexenyltrimethoxysilane, 11-acetoxyundecyltriethoxysilane, 10-alkenylundecyltrimethoxysilane, unsaturated double-bond trimethoxysilane, unsaturated double-bond triethoxysilane, methyl unsaturated double-bond diethoxysilane, methyl unsaturated double-bond dimethoxysilane and tetramethyl di-unsaturated double-bond siloxane.

8. The surface-modified nanoparticles of claim 7, wherein the preparation process comprises the steps of:

⑴ respectively weighing silane coupling agent and nanoparticles;

⑵ adding the nanometer particles into the reaction kettle, adding the silane coupling agent while stirring, and stirring at constant speed for 1-2 hours for standby.

9. The nanoparticle-embedded photocurable oral barrier resin of claim 1 wherein the nanoparticle-embedded photocurable oral barrier resin is prepared by the steps of:

1) uniformly mixing a diluent and a solvent, adding a prepolymer, and uniformly stirring;

2) adding the cross-linking agent and the surface modified nano-particles into the mixture, and uniformly stirring;

3) weighing the photoinitiator, and adding and stirring uniformly;

4) adding essence, pigment or antioxidant and other adjuvants, stirring, and vacuum degassing to obtain the light-curable oral cavity isolation resin embedded with nanoparticles.

Technical Field

The invention belongs to the field of photocuring functional resin, and particularly relates to a nanoparticle-embedded photocuring oral cavity isolation resin and a preparation method thereof.

Background

The photo-curing means that the photo-curing agent is composed of a resin monomer (monomer) and a prepolymer (oligomer), contains an active functional group, and can initiate polymerization reaction by a photosensitizer (light initiator) under the irradiation of ultraviolet light. The light-cured resin is also called photosensitive resin, is a photosensitive resin with relatively low molecular mass, and is an oligomer which can rapidly generate physical and chemical changes in a short time after being irradiated by light so as to be crosslinked and cured. The light-cured resin is an environment-friendly energy-saving resin material developed by German Bayer company in the end of the 60 th century. China entered the field of light-cured resin from the 70 s of the 20 th century. In recent years, with the enhancement of energy-saving and environment-friendly consciousness of people, the variety and the performance of the light-cured resin are continuously enhanced, the application field is continuously expanded, the yield is rapidly increased, and the development trend is rapid.

At present, the light-cured composite resin is a commonly used filling and repairing material in stomatology, plays an important role in clinical application because of attractive color and certain compressive strength, and is commonly used for obtaining satisfactory effects on repairing various defects and cavities of anterior teeth. Bowen succeeded in synthesizing a resin monomer Bis-GMA (bisphenol A-glycidyl methacrylate) with special structure and performance in the 60 s, which opened a new era of dental resin-based composite materials and started recognizing the important significance of surface treatment on inorganic fillers. On the basis of this, various composite resins have been rapidly developed. The composite resin has the advantages of beautiful color, high strength, good bonding retention effect, good plasticity, capability of being polished and polished after being cured, and the like, can be used for repairing the tooth defects by preparing mixed slurry with proper viscosity and curing after specific light irradiation, thereby greatly meeting the requirements of clinicians and patients on the tooth cosmetic repair, becoming an important material essential in the tooth defect repair treatment, and being widely used for the direct or indirect repair of various tooth defects.

In order to improve the physical properties of composite resins, inorganic fillers are essential as main components in dental composite resins, and the principle thereof is mainly a particle reinforcing effect. The inorganic filler is used as the disperse phase of the composite resin, can enhance the mechanical property, the wear resistance and the rigidity of the material, reduce the linear expansion coefficient, reduce the polymerization volume shrinkage, adjust the refractive index property, increase the X-ray radiation resistance property and the like, and can adjust the viscosity of the matrix and realize the clinical operation hand feeling and the performance of the composite resin. The performance of the composite resin depends on the characteristics of the inorganic filler such as granularity and morphology, so the type, the particle size, the content, the bonding strength with the resin and the like of the inorganic filler are all key factors influencing the performance of the material. The inorganic filler not only needs to meet the basic requirements of general reinforcing materials, but also needs to have good light transmittance and smaller absorptivity, and the loss of light energy is reduced as much as possible during photocuring, so that the conversion rate of the composite resin is high, and the curing is sufficient.

When the filler with larger particle size is used in the dental composite resin, although the large-particle filler increases the strength of the composite resin, the filler with larger particle size is easy to generate spatial fluctuation in the material along with different aggregation degrees of the filler, so the surface of the repair material is not smooth, the surface of the resin is not easy to polish, and the defects of easy coloring and the like are overcome. In contrast, small particle size fillers have unique advantages and have attracted considerable attention, particularly nanofillers. The invention aims to prepare a tooth isolation resin, which needs to have elasticity and stretchability after photocuring, can be well attached to oral cavity micro-tissues and is easy to remove. The surface-treated nano filler is introduced into a light-cured resin system, and the nano filler has the characteristics of good small-size effect, surface effect, quantum size effect, macroscopic quantum tunneling effect and the like, so that the isolation resin has the characteristics of excellent light-cured performance, ideal mechanical strength, good isolation effect and the like.

Disclosure of Invention

The invention aims to provide a light-cured oral cavity application resin, in particular to a light-cured oral cavity isolation resin embedded with nano-particles and a preparation method thereof.

The light-cured oral cavity isolation resin embedded with the nano particles mainly comprises the following components: prepolymer, diluent, solvent, surface modified nano-particles, photoinitiator, cross-linking agent, essence and other auxiliary agents.

The components comprise the following components in parts by weight: 35-75 parts of prepolymer, 10-30 parts of diluent, 15-80 parts of solvent, 5-35 parts of surface modified nano particles, 0.5-4 parts of photoinitiator, 0.5-2 parts of cross-linking agent, 0-4 parts of essence and 0-4 parts of other auxiliary agents.

The prepolymer includes but is not limited to one or a combination of two or more of diamine-based dimethacrylate resin, urethane-based dimethacrylate resin, polyethylene glycol modified urethane-based dimethacrylate resin, bisphenol A glyceryl dimethacrylate, triethylene glycol dimethacrylate and epoxy resin E-44.

The diluent includes but is not limited to one or a combination of two or more of methacrylic acid, dimethyl acrylic acid, polyethylene glycol modified methacrylic acid, triethylene glycol dimethacrylate and hydroxyethyl methacrylate.

The solvent includes but is not limited to one or more of acetone, ethanol, methanol, toluene, ethyl acetate and butyl acetate.

The photoinitiator includes, but is not limited to, one or more of camphorquinone, 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone, diethyl trimethylbenzoylphosphonate, benzophenone (BP for short), Diethylthianthrone (DETX), 4- (phenylthio) phenyldiphenylsulfonium hexafluorophosphate, 4-isobutylphenyl-4' -methylphenyliodilium hexafluorophosphate, N-dimethylaminoethyl methacrylate.

The crosslinking agent is a monomer with two double bonds, such as one or more of ethylene glycol dimethacrylate, polyethylene glycol diacrylate, and methylene bisacrylamide.

The essence includes one or more of fructus Citri Junoris, herba Menthae, strawberry, herba Coriandri, rhizoma Steudnerae Henryanae, and ilex.

The other auxiliary agents comprise pigments, antioxidants, preservatives, heat stabilizers and the like.

The surface-modified nano-particles are surface-modified by adopting a silane coupling agent, and the ratio of the silane coupling agent to the nano-particles is 1: 3-1: 10 in parts by mass.

The nano particles are one or more of fumed silica, talcum powder and mica powder, wherein the specific surface area of the fumed silica, the talcum powder and the mica powder is more than 1000 meshes.

The silane coupling agent is siloxane containing unsaturated double bonds, and comprises but is not limited to one or more of gamma-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, allyltriethoxysilane, 5-hexenyltrimethoxysilane, 11-acetoxyundecyltriethoxysilane, 10-alkenylundecyltrimethoxysilane, unsaturated double-bond trimethoxysilane, unsaturated double-bond triethoxysilane, methyl unsaturated double-bond diethoxysilane, methyl unsaturated double-bond dimethoxysilane and tetramethyl di-unsaturated double-bond siloxane.

The preparation method of the surface modified nano-particles comprises the following steps:

⑴ respectively weighing silane coupling agent and nanoparticles;

⑵ adding the nanometer particles into the reaction kettle, adding the silane coupling agent while stirring, and stirring at constant speed for 1-2 hours for standby.

The preparation method of the light-cured oral cavity isolation resin embedded with the nano-particles comprises the following steps:

1) uniformly mixing a diluent and a solvent, adding a prepolymer, and uniformly stirring;

2) adding the cross-linking agent and the surface modified nano-particles into the mixture, and uniformly stirring;

3) weighing the photoinitiator, and adding and stirring uniformly;

4) adding essence, pigment or antioxidant and other adjuvants, stirring, and vacuum degassing to obtain the light-curable oral cavity isolation resin embedded with nanoparticles.

The method of making the nanoparticle-embedded, photocurable oral barrier resin of the present invention does not represent the only form in which the present invention may be made or utilized. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The photo-curing oral cavity isolation resin embedded with the nano particles provided by the invention is added with essence, so that the oral cavity adaptability of a user can be adjusted. The nano-particle-embedded photocuring oral cavity isolation resin provided by the invention has small shrinkage volume during curing, the formed polymer has strong adhesive force, the heat release is small during curing, and the isolation effect is good during clinical use.

Detailed Description