阅读说明：本技术 一种含支化聚硅氧烷（甲基）丙烯酸酯的牙科复合树脂 (Dental composite resin containing branched polysiloxane (methyl) acrylate ) 是由 何经纬 刘芳 李爽 于 2019-10-22 设计创作，主要内容包括：本发明公开了一种含支化聚硅氧烷(甲基)丙烯酸酯的牙科复合树脂。所述的复合树脂包括20-50重量份的(甲基)丙烯酸酯树脂基体和光引发体系混合物、50-80重量份无机填料。(甲基)丙烯酸酯树脂基体和光引发体系混合物中,(甲基)丙烯酸树脂基体占混合物重量的95%-99.6%,光引发体系占混合物重量的0.4%-5%。本发明所述的含支化聚硅氧烷(甲基)丙烯酸酯的牙科复合树脂具有抗细菌黏附功能并可保持复合树脂的力学性能,可降低复合树脂修复牙齿窝洞时由于二次龋齿导致修复失败的现象。(The invention discloses a dental composite resin containing branched polysiloxane (methyl) acrylate. The composite resin comprises 20-50 parts by weight of (methyl) acrylate resin matrix, a photoinitiation system mixture and 50-80 parts by weight of inorganic filler. In the mixture of the (methyl) acrylic resin matrix and the photoinitiation system, the (methyl) acrylic resin matrix accounts for 95 to 99.6 percent of the weight of the mixture, and the photoinitiation system accounts for 0.4 to 5 percent of the weight of the mixture. The dental composite resin containing the branched polysiloxane (methyl) acrylate has an antibacterial adhesion function, can maintain the mechanical property of the composite resin, and can reduce the phenomenon of restoration failure caused by secondary decayed teeth when the composite resin restores cavities of teeth.)

1. A dental composite resin containing branched polysiloxane (meth) acrylate, characterized by consisting of 20 to 50 parts by weight of a mixture of a (meth) acrylate resin matrix and a photoinitiating system, 50 to 80 parts by weight of an inorganic filler; the (methyl) acrylate resin matrix accounts for 95-99.6% of the weight of the mixture, and the photoinitiation system accounts for 0.4-5% of the weight of the mixture.

2. The branched polysiloxane (meth) acrylate-containing dental composite resin of claim 1, wherein the (meth) acrylate resin matrix comprises a branched polysiloxane (meth) acrylate, (meth) acrylate oligomer, and a (meth) acrylate reactive diluent; the weight percentage of the branched polysiloxane (methyl) acrylate is 10-40%, the weight percentage of the (methyl) acrylate oligomer is 40-70%, and the weight percentage of the (methyl) acrylate reactive diluent is 20-50%.

3. A branched polysiloxane (meth) acrylate-containing dental composite resin according to claim 3, wherein the branched polysiloxane (meth) acrylate has the following structure:

structural formula AR₁R₂In R₁Is methyl or hydrogen, R₂Is methyl or ethyl, wherein n is 10-100;

structural formula BR₁R₂In R₁Can be methyl or hydrogen, R₂And can be methyl or ethyl, wherein n is 10-100.

4. Dental composite resin containing branched polysiloxane (meth) acrylate according to claim 3, characterized in that branched polysiloxane (meth) acrylate AR₁R₂The preparation method comprises the following steps:

adding branched amino polysiloxane and an acid-binding agent into a reaction vessel, dropwise adding (methyl) acryloyl chloride into the reaction vessel at-10-0 ℃, reacting at room temperature for 12-48 hours after dropwise adding, and then purifying a reaction product; the acid-binding agent is selected from: one of triethylamine, N' -dimethylbenzylamine, pyridine and 4-dimethylaminopyridine;

the molar ratio of the branched amino polysiloxane to the (methyl) acryloyl chloride is 1:2-1:3, and the molar number of the acid-binding agent is equal to the molar amount of the (methyl) acryloyl chloride.

5. The branched polysiloxane (meth) acrylate-containing dental composite resin of claim 3, wherein the branched polysiloxane (meth) acrylate BR₁R₂The preparation method comprises the following steps:

adding branched amino polysiloxane and a catalyst into a reaction container, dropwise adding (methyl) isocyano ethyl acrylate into the reaction container at-10-0 ℃, reacting at room temperature for 3-24 hours after dropwise adding, and then purifying a reaction product; the catalyst is selected from: one of triethylamine, triethylenediamine, tetramethylbutanediamine, N-dimethylbenzylamine, dibutyltin dilaurate and stannous octoate;

the molar ratio of the branched amino polysiloxane to the isocyano ethyl (meth) acrylate is 1:2-1:3, and the amount of the catalyst is 0.1-1.0% of the total mass of the reactants.

6. A branched polysiloxane (meth) acrylate-containing dental composite resin according to claim 2, wherein the (meth) acrylate oligomer is selected from the group consisting of: one or more of diurethane dimethacrylate, bisphenol A diglycidyl ether di (meth) acrylate, and ethoxylated bisphenol A di (meth) acrylate; the (meth) acrylate reactive diluent is selected from: one or more of ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1, 6-hexanediol dimethacrylate, isobornyl (meth) acrylate, and tricyclo [5.2.1.02,6] decane dimethanol acrylic acid.

7. A dental composite resin containing branched polysiloxane (meth) acrylate according to claim 1, wherein said photoinitiating system comprises a photoinitiator and an accelerator; the photoinitiator is selected from: one or more of camphorquinone, benzophenone and 1-phenyl-1, 2-propanedione; the accelerator is selected from: one or more of ethyl dimethylaminobenzoate, N, N-dimethylaminoethyl ester and methacrylic ester dimethylaminoethyl ester.

8. Dental composite resin containing branched polysiloxane (meth) acrylate according to claim 7, characterized in that the mass ratio of photoinitiator and accelerator is between 1:1 and 1: 4.

9. Dental composite resin containing branched polysiloxane (meth) acrylate according to claim 1, characterized in that the inorganic filler is selected from: more than one of silicon dioxide, hydroxyapatite, barium-containing silicate glass powder, zirconium-containing silicate glass powder, strontium-containing silicate glass powder and aluminosilicate-containing glass powder.

Technical Field

The invention belongs to the field of dental restoration materials, and particularly relates to a dental composite resin containing branched polysiloxane (methyl) acrylate.

Technical Field

Dental caries is a common bacterial dental disease, has high morbidity and wide distribution, can be developed into pulpitis and periapical periodontitis if not treated in time, and seriously affects the physical health of patients, so that the carious part needs to be treated timely and effectively. At present, the main method for treating the decayed tooth is filling treatment, namely, decayed tissues are cleaned to prepare cavities, and the cavities are disinfected and then filled and repaired by filling materials.

With the increasing demand of people for tooth beauty, the composite resin is more and more widely applied to tooth restoration due to good color performance and simple and convenient operation performance. Compared with other material restoration, the composite resin restoration has less grinding amount to tooth tissues, can reserve healthy tooth tissues to the maximum extent, has the appearance similar to the tooth tissues, and improves the aesthetic property after restoration, so the composite resin becomes an important material for tooth defect restoration. The composite resin commonly used in clinic at present consists of light-curable methacrylate matrix resin and glass powder with X-ray radiation resistance. Compared with metal repair materials such as gold, silver, amalgam and the like and glass ion type repair materials, bacteria easily accumulate and grow on the surface of the composite resin, so that the incidence rate of secondary caries is high, and the secondary caries is a main reason for repair failure and replacement of a repair body.

In order to impart antibacterial properties to composite resins, currently, an antibacterial agent such as chlorhexidine, cetylpyridinium chloride, a quaternary ammonium salt antibacterial monomer, or the like is added to the composite resin. The monomethacrylate monomer methacryloyloxydodecyl bromopyridine (MDPB) containing a pyridinium structure synthesized by Imazato et al is the first clinically used dental material antibacterial additive. Although the antibacterial agent can kill bacteria adhered to the surface of the composite resin, in the oral environment, oral salivary proteins form an "acquired film" on the surface of the composite resin, and the antibacterial efficiency is reduced because the "acquired film" can prevent the bacteria from contacting the antibacterial agent. L. wang et al add 2-Methacryloyloxyethyl Phosphorylcholine (MPC) to the composite resin, and because MPC is added to make the surface of the composite resin super-hydrophilic, the super-hydrophilic surface has good resistance to adhesion of protein and bacteria, the composite resin with MPC can effectively reduce the adsorption of protein and bacteria on the surface of the composite resin. However, the water absorption of the composite resin is increased due to the hydrophilicity of the MPC, and the mechanical property and long-term service performance of the composite resin under a humid environment are affected by higher water absorption.

Disclosure of Invention

The invention provides a dental composite resin containing branched polysiloxane (methyl) acrylate, aiming at the problem that bacteria are easy to accumulate and grow on the surface of the existing dental composite resin.

The dental composite resin containing branched polysiloxane (methyl) acrylate comprises 20-50 parts by weight of a mixture of a (methyl) acrylate resin matrix and a photoinitiation system and 50-80 parts by weight of an inorganic filler.

The dental composite resin containing the branched polysiloxane (methyl) acrylate comprises 95-99.6% of (methyl) acrylate resin matrix and 0.4-5% of photoinitiation system.

The dental composite resin containing the branched polysiloxane (methyl) acrylate innovatively adopts a novel branched polysiloxane-containing (methyl) acrylate as a component of a resin matrix, and the branched polysiloxane-containing (methyl) acrylate contains a siloxy structure, so that the interaction between the resin matrix and an inorganic filler in the composite resin can be enhanced. The (methyl) acrylate resin matrix of the composite resin comprises the following components in percentage by weight:

10-40 of branched polysiloxane-containing (meth) acrylate

(meth) acrylate oligomer 40-70

20-50 of (methyl) acrylate reactive diluent

The invention relates to a dental composite resin containing branched polysiloxane (methyl) acrylate, wherein the branched polysiloxane (methyl) acrylate in a (methyl) acrylate resin matrix comprises the following structure:

structural formula AR₁R₂In R₁Can be methyl (CH)₃) Or hydrogen (H), R₂Can be methyl (CH)₃) Or ethyl (CH)₂CH₃) Wherein n is 10-100;

structural formula BR₁R₂In R₁Can be methyl (CH)₃) Or hydrogen (H), R₂Can be methyl (CH)₃) Or ethyl (CH)₂CH₃) Wherein n is 10-100

The invention relates to a dental composite resin containing branched polysiloxane (methyl) acrylate, wherein the synthesis method of the branched polysiloxane (methyl) acrylate in a (methyl) acrylate resin matrix comprises the following steps:

AR₁R₂the synthesis method comprises the following steps: adding branched amino polysiloxane and an acid binding agent into a reaction vessel, dropwise adding (methyl) acryloyl chloride into the reaction vessel at-10-0 ℃, reacting at room temperature for 12-48 hours after dropwise adding, and then purifying the reaction product. The acid scavenger is selected from but not limited to: one of triethylamine, N' -dimethylbenzylamine, pyridine and 4-dimethylaminopyridine.

In the method, the molar ratio of the branched amino polysiloxane to the (methyl) acryloyl chloride is 1:2-1:3, and the molar number of the acid-binding agent is equal to the molar amount of the (methyl) acryloyl chloride.

The chemical reaction formula of the above steps is as follows:

BR₁R₂the synthesis method comprises the following steps: in the reactionAdding branched amino polysiloxane and a catalyst into a container, dropwise adding (methyl) isocyano ethyl acrylate into the reaction container at-10-0 ℃, reacting at room temperature for 3-24 hours after dropwise adding, and then purifying the reaction product. The catalyst is selected from, but not limited to: triethylamine, triethylenediamine, tetramethylbutanediamine, N-dimethylbenzylamine, dibutyltin dilaurate and stannous octoate.

In the method, the molar ratio of the branched amino polysiloxane to the isocyano ethyl (meth) acrylate is 1:2-1:3, and the amount of the catalyst accounts for 0.1% -1.0% of the total mass of the reactants.

The chemical reaction formula of the above steps is as follows:

the (meth) acrylate oligomer in the (meth) acrylate resin matrix of the dental composite resin containing branched polysiloxane (meth) acrylate is selected from one or more of, but not limited to, diurethane dimethacrylate, bisphenol A diglycidyl ether di (meth) acrylate, and ethoxylated bisphenol A di (meth) acrylate.

The dental composite resin containing branched polysiloxane (meth) acrylate is characterized in that the (meth) acrylate reactive diluent in the (meth) acrylate resin matrix is selected from one or more of ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1, 6-hexanediol dimethacrylate, isobornyl (meth) acrylate, and tricyclo [5.2.1.02,6] decane dimethanol acrylate.

The dental composite resin containing the branched polysiloxane (methyl) acrylate comprises a photoinitiator and an accelerator in a photoinitiation system.

The photoinitiator is selected from one or more of camphorquinone, benzophenone and 1-phenyl-1, 2-propanedione.

The accelerant is selected from one or more of ethyl dimethylaminobenzoate, N, N-dimethylaminoethyl ester and methacrylic ester dimethylaminoethyl ester.

The mass ratio of the photoinitiator to the accelerator is 1:1-1: 4.

The inorganic filler of the dental composite resin containing branched polysiloxane (methyl) acrylate is selected from one or more of silicon dioxide, hydroxyapatite, barium-containing silicate glass powder, zirconium-containing silicate glass powder, strontium-containing silicate glass powder and aluminosilicate-containing glass powder.

Compared with the prior art, the invention has the advantages that:

the dental composite resin containing the branched polysiloxane (methyl) acrylate creatively adopts a novel (methyl) acrylate containing the branched polysiloxane as a component of a resin matrix, and the (methyl) acrylate containing the branched polysiloxane contains a siloxy structure, so that the interaction between the resin matrix and an inorganic filler in the composite resin can be enhanced while the antibacterial adhesion of the composite resin is endowed, and the mechanical property and the medium resistance of the composite resin are improved. Therefore, the dental composite resin containing the branched polysiloxane (methyl) acrylate prepared by the invention has the application as a dental prosthetic material in oral clinic.

Detailed Description

The present invention is further described with reference to the following specific examples, which do not limit the scope of the present invention.