CN104940027A - Low-shrinkage dental restoration resin and preparation method thereof - Google Patents

Abstract

The invention discloses a low-shrinkage dental restoration resin and a preparation method thereof. The low-shrinkage dental restoration resin consists of methacrylate monomers, modified Boltorn type second-generation hyperbranched polyester monomers, diluents and epoxy resins. system and initiators, in which: methacrylate monomers account for 25-60% of the entire resin system; modified Boltorn type second-generation hyperbranched polyester monomers account for 0-40%; diluents and Epoxy system accounts for 30~50%; initiator accounts for 1~5%. According to the above-mentioned ingredients, mix them uniformly, pour them into a specific mold for light-curing molding, and obtain a low-shrinkage dental restoration resin material. The dental restorative resin of the present invention has low shrinkage, reduces micro-leakage, eliminates triethylene glycol dimethacrylate, and has ideal effects in double bond conversion rate, shrinkage rate and other properties. The introduction of diluent, epoxy system and modified Boltorn type second-generation hyperbranched polyester monomer greatly reduces the polymerization shrinkage of the composite resin.

Description

Low shrinkage dental restorative resin and preparation method thereof

technical field

The invention belongs to the technical field of dental restoration materials, in particular to a low-shrinkage dental restoration resin and a preparation method thereof.

technical background

Dental restoration materials have experienced a long course of development from natural substances-metal materials-ceramic-polymer materials-composite materials since their birth. The introduction of resin-based dental composites is a significant leap in the field of dental materials. In the middle of the 20th century, light-curing molding technology gradually entered people's lives. Light-curing has unique advantages: fast curing speed, high curing efficiency, high mechanical properties, complete polymerization at room temperature, large selectivity of curing parts, zero pollution, etc. After the 1960s, light-curing composite resin was first used in the field of dental restoration. The composition of light-curing composite resin system includes resin matrix, inorganic filler and corresponding photoinitiation system. The preparation of light-cured composite resin is simple, easy to operate, good in color, high in strength and plasticity, good in bonding effect, and can be polished after curing. Multiple advantages make it widely concerned in the field of tooth restoration.

When used as a dental resin matrix, certain requirements must be met: 1) The degree of photopolymerization is high, and the cured polymer is cross-linked, which ensures the mechanical performance requirements of the restoration; 2) The volume shrinkage after polymerization should be low, so that it can Ensure that there are no air bubbles and no gaps in the restoration. In clinical use, monomers with diluting and crosslinking effects are often added in a certain proportion together with bisphenol A-glycidyl methacrylate (Bis-GMA) to form a resin matrix. At present, the commonly used diluting monomer is triethylene glycol dimethacrylate (TEGDMA), which has a very low viscosity and has methacryloyloxy functional groups at both ends of the molecule. It also participates in the diluting of the system polymerization. But the addition of TEGDMA will increase the polymerization shrinkage of the system. And studies have shown that TEGDMA monomers will exhibit certain cytotoxicity and may cause allergies, so the amount of TEGDMA added needs to be limited. Moreover, the occurrence of secondary caries after restoration is mainly due to the growth of oral bacteria adhered between the restoration and the tooth interface, forming dental plaque to corrode the tooth and restoration materials, making the restoration fail.

Contents of the invention

The object of the present invention is to provide a low shrinkage dental restoration resin with low shrinkage rate and a preparation method thereof.

The technical solution that realizes the object of the present invention is: a kind of low-shrinkage dental restorative resin, by methacrylate monomer, modified Boltorn type second generation hyperbranched polyester monomer, diluent and epoxy system and initiator prepared in which:

Methacrylate monomers account for 25-60% of the mass of the entire resin system;

Modified Boltorn type second-generation hyperbranched polyester monomer accounts for 0-40% of the mass of the entire resin system;

Diluent and epoxy system account for 30~50% of the whole resin system;

The initiator accounts for 1-5% of the mass of the whole resin system.

Preferably, the methacrylate monomer is bisphenol A-glycidyl dimethacrylate Bis-GMA.

Preferably, the modified Boltorn-type second-generation hyperbranched polyester monomer is obtained by reacting Boltorn-type second-generation hyperbranched polyester with a modified monomer, and contains carbon-carbon double bonds and hydroxyl groups after modification.

Preferably, the diluent and epoxy system include expansion monomer and epoxy resin, the mass ratio of expansion monomer and epoxy resin is (1~4):4, wherein epoxy resin is 3,4-ring Oxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, methylbis[2-(7-oxabicyclo[4.1.0]hept-3-yl)-ethyl]phenylsilane or 2,4,6,8-tetramethyl-2,4,6,8-tetrakis[2-(7-oxabicyclo[4.1.0]hept-3-yl)-ethyl]-1,3 ,5,7-tetraoxa-2,4,6,8-tetrasilacyclobutane, the expanded monomer is 3,9-diethyl-3,9-propenyloxymethyl-1,5,7, 11-tetraoxaspira[5,5]undecane.

Preferably, in the ternary photoinitiator system.

Preferably, the modified monomer is a combination of methacryloyl chloride and propionyl chloride, wherein the molar ratio of methacryloyl chloride and Boltorn type second-generation hyperbranched polyester is (7 ~ 10): 1, and propionyl chloride and The molar ratio of Boltorn type second-generation hyperbranched polyester is (6~9):1.

Preferably, the ternary photoinitiating system comprises a photoacidic compound, a visible light photosensitizer and an electron donor compound group, and the photoacidic compound is diaryliodonium hexafluorophosphate, triarylsulfonium hexafluorophosphate or Triarylselenium hexafluorophosphate, the visible light photosensitizer is camphorquinone, benzophenone, acetophenone, benzoin ether or thioxanthraquinone, and the electron donor compound is N,N-dimethylaminoethyl methacrylate , dimethylvinylaminobenzoic acid or N,N-dimethyl-p-vinylaniline, wherein the mass ratio of photoacidic compound, visible light photosensitizer and electron donor compound is (1~3):(0.1~1) :0.1.

A method for preparing the above-mentioned low-shrinkage dental restoration resin, using 25-60% (weight) of methacrylate monomers and 0-40% (weight) of modified Boltorn type second-generation hyperbranched polyester monomers 30-50% (weight) of diluent and epoxy system and 1-5% (weight) of initiator are used as ingredients, mixed evenly, poured into a specific mold for light-curing molding, and obtain a low-shrinkage dental restoration resin material.

Compared with the prior art, the present invention has the following remarkable advantages: (1) it forms a solid cured body under light, reduces the shrinkage rate of the repair resin, and has ideal hardness; (2) expands the monomer and epoxy resin The introduction of the replacement of triethylene glycol dimethacrylate (TEGDMA), which is cytotoxic to the dental pulp, reduces the cytotoxicity of the restorative resin.

Detailed ways

The low-shrinkage dental restoration resin of the present invention is prepared from methacrylate monomers, modified Boltorn type second-generation hyperbranched polyester monomers, diluents, epoxy systems and initiators, wherein:

Methacrylate monomers account for 25-60% of the mass of the entire resin system;

Modified Boltorn type second-generation hyperbranched polyester monomer accounts for 0-40% of the mass of the entire resin system;

Diluent and epoxy system account for 30~50% of the whole resin system;

The initiator accounts for 1-5% of the mass of the whole resin system.

Preferably, the methacrylate monomer is bisphenol A-glycidyl dimethacrylate Bis-GMA.

Preferably, the modified Boltorn-type second-generation hyperbranched polyester monomer is obtained by reacting Boltorn-type second-generation hyperbranched polyester with a modified monomer, and contains carbon-carbon double bonds and hydroxyl groups after modification. Among them, the Boltorn type second-generation hyperbranched polyester is synthesized by reacting pentaerythritol and bismethylolpropionic acid, and after dissolving, acetone precipitation, suction filtration, and then adding modified monomers at low temperature, centrifugation, filtration, washing, and drying are obtained. hyperbranched polyester. Described modified monomer is the combination of methacryloyl chloride and propionyl chloride, wherein the molar ratio of methacryloyl chloride and Boltorn type second-generation hyperbranched polyester is (7～10):1, propionyl chloride and Boltorn type two The molar ratio of hyperbranched polyester is (6~9):1.

The above-mentioned modified Boltorn type second-generation hyperbranched polyester monomer replaces part of bisphenol A-glycidyl methacrylate (Bis-GMA), which reduces the polymerization shrinkage of the entire resin system.

Preferably, the diluent and epoxy system include expansion monomer and epoxy resin, the mass ratio of expansion monomer and epoxy resin is (1~4):4, wherein epoxy resin is 3,4-ring Oxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, methylbis[2-(7-oxabicyclo[4.1.0]hept-3-yl)-ethyl]phenylsilane or 2,4,6,8-tetramethyl-2,4,6,8-tetrakis[2-(7-oxabicyclo[4.1.0]hept-3-yl)-ethyl]-1,3 ,5,7-tetraoxa-2,4,6,8-tetrasilacyclobutane, the expanded monomer is 3,9-diethyl-3,9-propenyloxymethyl-1,5,7, 11-tetraoxaspira[5,5]undecane.

The above diluent and epoxy system replace triethylene glycol dimethacrylate (TEGDMA), which is commonly used clinically, which not only reduces the shrinkage rate of the entire repair resin, but also reduces the cytotoxicity of the repair resin.

Preferably, the initiator is a ternary photosensitive initiating system. The ternary photosensitive initiating system includes a photoacidic compound, a visible light photosensitizer and an electron donor compound group, and the photoacidic compound is a diaryl iodonium hexafluorophosphate, a triarylsulfonium hexafluorophosphate or a triaryl selenium Onium hexafluorophosphate, the visible light photosensitizer is camphorquinone, benzophenone, acetophenone, benzoin ether or thiaxanthraquinone, and the electron donor compound is N,N-dimethylaminoethyl methacrylate, methyl Vinylaminobenzoic acid or N,N-dimethyl-p-vinylaniline, wherein the mass ratio of photoacidic compound, visible light photosensitizer and electron donor compound is (1~3):(0.1~1):0.1, because The addition amount of each component of the ternary photoinitiator system in the entire resin system is relatively small, and if added sequentially, it will cause errors, so they are mixed and stirred evenly in advance, and stored in the refrigerator away from light for later use.

The following example 1 provides the mass ratio of resin Bis-GMA and TEGDMA used clinically, and examples 2 to 16 provide the mass percentages of each raw material accounting for the entire resin system, wherein: the methacrylate monomer is Bis- GMA; Modified Boltorn type second generation hyperbranched polyester monomer is 7:6:1 modified Boltorn type second generation hyperbranched polyester (i.e. methacryloyl chloride, propionyl chloride, Boltorn type second generation hyperbranched polyester The molar ratio is 7:6:1); the epoxy resin in the diluent and epoxy system is 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexyl carboxylate (EE), expansion monomer It is 3,9-diethyl-3,9-propenyloxymethyl-1,5,7,11-tetraoxaspira[5,5]undecane (BAOM), and the mass ratio of EE:BAOM is 1 : 1; The ternary photoinitiating system consists of diphenyliodonium hexafluorophosphate, camphorquinone and dimethylaminoethyl methacrylate DMAEMA, and the mass ratio of the three is 3:1:0.1. Embodiment 17 provides the detection results of shrinkage rate and double bond conversion rate of Examples 1-16.

Example 1

Bis-GMA50%, TEGDMA45%, ternary photosensitive trigger system 5%

Example 2

EE: BAOM is 1:1 diluent and epoxy system 30%, Bis-GMA 25%, 7:6:1 modified Boltorn type second-generation hyperbranched polyester 40%, ternary photosensitive initiator system 5%

Example 3

EE: BAOM is 1:1 diluent and epoxy system 30%, Bis-GMA 35%, 7:6:1 modified Boltorn type second-generation hyperbranched polyester 30%, ternary photosensitive initiator system 5%

Example 4

EE: BAOM is 1:1 diluent and epoxy system 30%, Bis-GMA 45%, 7:6:1 modified Boltorn type second generation hyperbranched polyester 20%, ternary photosensitive initiator system 5%

Example 5

EE: BAOM is 1:1 diluent and epoxy system 30%, Bis-GMA 50%, 7:6:1 modified Boltorn type second-generation hyperbranched polyester 15%, ternary photosensitive initiation system 5%

Example 6

EE: BAOM is 1:1 diluent and epoxy system 30%, Bis-GMA 55%, 7:6:1 modified Boltorn type second generation hyperbranched polyester 10%, ternary photosensitive initiator system 5%

Example 7

EE: BAOM is 1:1 diluent and epoxy system 30%, Bis-GMA60%, 7:6:1 modified Boltorn type second-generation hyperbranched polyester 5%, ternary photosensitive initiator system 5%

Example 8

EE: BAOM is 1:1 diluent and epoxy system 40%, Bis-GMA 30%, 7:6:1 modified Boltorn type second-generation hyperbranched polyester 25%, ternary photosensitive initiator system 5%

Example 9

EE: BAOM is 1:1 diluent and epoxy system 40%, Bis-GMA35%, 7:6:1 modified Boltorn type second-generation hyperbranched polyester 20%, ternary photosensitive initiator system 5%

Example 10

EE: BAOM is 1:1 diluent and epoxy system 40%, Bis-GMA 45%, 7:6:1 modified Boltorn type second-generation hyperbranched polyester 10%, ternary photosensitive initiator system 5%

Example 11

EE: BAOM is 1:1 diluent and epoxy system 40%, Bis-GMA 50%, 7:6:1 modified Boltorn type second-generation hyperbranched polyester 5%, ternary photosensitive initiation system 5%

Example 12

EE: BAOM is 1:1 diluent and epoxy system 40%, Bis-GMA 55%, 7:6:1 modified Boltorn type second-generation hyperbranched polyester 0%, ternary photosensitive initiator system 5%

Example 13

EE: BAOM is 1:1 diluent and epoxy system 50%, Bis-GMA 30%, 7:6:1 modified Boltorn type second generation hyperbranched polyester 15%, ternary photosensitive initiator system 5%

Example 14

EE: BAOM is 1:1 diluent and epoxy system 50%, Bis-GMA 35%, 7:6:1 modified Boltorn type second generation hyperbranched polyester 10%, ternary photosensitive initiator system 5%

Example 15

EE: BAOM is 1:1 diluent and epoxy system 50%, Bis-GMA 40%, 7:6:1 modified Boltorn type second-generation hyperbranched polyester 5%, ternary photosensitive initiation system 5%

Example 16

EE: BAOM is 1:1 diluent and epoxy system 50%, Bis-GMA 45%, 7:6:1 modified Boltorn type second generation hyperbranched polyester 0%, ternary photosensitive initiator system 5%

Example 17

After testing, table 1 lists Bis-GMA, 7:6:1 modified Boltorn type second generation hyperbranched polyester that embodiment 1～16 provides, EE: BAOM is the diluent and epoxy system of 1:1 and Shrinkage rate and double bond conversion rate after photocuring at different mass ratios.

Table 1

Example Shrinkage/% Double bond conversion rate/% 1 5.8 49.6 2 2.34 90.55 3 2.73 89.56 4 3.09 93.23 5 3.27 96 6 3.66 90 7 3.77 89.83 8 1.96 85.75 9 2.16 86.64 10 2.59 90.24 11 2.96 92.28 12 3.1 90.07 13 2.1 76.36 14 2.27 80.3 15 2.46 81.1 16 2.55 82.64

Can find out that embodiment 2,8,9,13,14,15 shrinkage rate is all below 2.5% by table 1, except embodiment 13, the double bond transformation rate of other examples is all higher, by the shrinkage rate of these embodiments rate and double bond conversion rate, preferred embodiment 2, 8, 9, and thus it can be seen that the most preferred proportion of each component is: Bis-GMA selected amount accounts for 25 ~ 35% of the whole resin system quality, diluted The amount of agent and expansion system used accounted for 30-40% of the mass of the entire resin system, and the amount of modified hyperbranched polyester accounted for 20-40% of the mass of the entire resin system.

In Examples 18 to 24, the following names are adopted: (1) The modified Boltorn type second-generation hyperbranched polyester monomer is marked as A, and A is composed of methacryloyl chloride, propionyl chloride and Boltorn type second-generation hyperbranched polyester monomer. The product obtained by reacting the ester according to the molar ratio of 7:6:1, 7:8:1, 7:9:1, 8:6:1, 8:8:1, 10:6:1 or 9:7:1 . (2) Record the diluent and epoxy system as B. B is obtained by mixing the epoxy resin and the expansion monomer at a mass ratio of 1:4, 1:2, or 1:1, where the epoxy resin is 3 ,4-Epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, Methylbis[2-(7-oxabicyclo[4.1.0]hept-3-yl)-ethyl] Phenylsilane or 2,4,6,8-tetramethyl-2,4,6,8-tetrakis[2-(7-oxabicyclo[4.1.0]hept-3-yl)-ethyl] -One of 1,3,5,7-tetraoxa-2,4,6,8-tetrasilacyclobutane, the expansion monomer is 3,9-diethyl-3,9-propenyloxymethyl -1,5,7,11-tetraoxaspira[5,5]undecane (BAOM). (3) The ternary photoinitiator is denoted as C, and C is composed of photoacidic compound, visible light photosensitizer and electron donor compound according to the mass ratio of 3:1:0.1, 3:0.1:0.1, 3:0.5: 0.1, 1:0.1:0.1, 1:0.5:0.1 or 1:1:0.1 mixed evenly, wherein the photoacidic compound is diaryl iodide catium salt, triaryl sulfur anchor salt or triaryl selenium salt, visible light photosensitivity The agent is camphorquinone, benzophenone, acetophenone, benzoin ether or thioxanthraquinone, and the electron donor compound is N,N-dimethylaminoethyl methacrylate, dimethylvinylaminobenzoic acid or N , N-dimethyl-p-vinylaniline.

Example 18

The low-shrinkage dental restorative resin of the present invention, the mass percentages of raw materials are: B 30%, Bis-GMA 60%, A5%, C5%.

A is a product obtained by reacting methacryloyl chloride, propionyl chloride and Boltorn type second-generation hyperbranched polyester according to the molar ratio of 7:6:1.

B is obtained by uniformly mixing epoxy resin and expansion monomer at a mass ratio of 1:4, wherein the epoxy resin is 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexyl carboxylate, and the expansion The monomer is 3,9-diethyl-3,9-propenyloxymethyl-1,5,7,11-tetraoxaspira[5,5]undecane (BAOM).

C is obtained by mixing a photoacidic compound, a visible light photosensitizer and an electron donor compound group according to a mass ratio of 3:1:0.1, wherein the photoacidic compound is diaryliodonium hexafluorophosphate, and the visible light photosensitizer is Camphorquinone, the electron donor compound is N,N-dimethylaminoethyl methacrylate.

Example 19

The low-shrinkage dental restorative resin of the present invention, the mass percentages of raw materials are: B 30%, Bis-GMA 25%, A 40%, Sanyuanguang C 5%.

A is the product obtained by reacting methacryloyl chloride, propionyl chloride and Boltorn type second-generation hyperbranched polyester according to the molar ratio of 7:8:1.

B is obtained by uniformly mixing epoxy resin and expansion monomer at a mass ratio of 1:4, wherein the epoxy resin is methyl bis[2-(7-oxabicyclo[4.1.0]hept-3-yl) -Ethyl]phenylsilane, the expanding monomer is 3,9-diethyl-3,9-propenyloxymethyl-1,5,7,11-tetraoxaspira[5,5]undecane ( BAOM).

C is obtained by uniformly mixing the photoacidic compound, visible light photosensitizer and electron donor compound group according to the mass ratio of 3:0.1:0.1, wherein the photoacidic compound is triarylsulfonium hexafluorophosphate, and the visible light photosensitizer is di Benzophenone, the electron donor compound is dimethylvinylaminobenzoic acid.

Example 20

The low-shrinkage dental restorative resin of the present invention has the following mass percentages of raw materials: B 30%, Bis-GMA 37%, A 30%, and Sanyuanguang C 3%.

A is the product obtained by reacting methacryloyl chloride, propionyl chloride and Boltorn type second-generation hyperbranched polyester according to the molar ratio of 7:9:1.

B is obtained by uniformly mixing epoxy resin and expansion monomer at a mass ratio of 1:2, wherein the epoxy resin is 2,4,6,8-tetramethyl-2,4,6,8-tetra[2- (7-Oxabicyclo[4.1.0]hept-3-yl)-ethyl]-1,3,5,7-tetraoxa-2,4,6,8-tetrasilacyclobutane, expanded The monomer is 3,9-diethyl-3,9-propenyloxymethyl-1,5,7,11-tetraoxaspira[5,5]undecane (BAOM).

C is obtained by uniformly mixing photoacidic compound, visible light photosensitizer and electron donor compound group according to the mass ratio of 3:0.5:0.1, wherein the photoacidic compound is diaryliodonium hexafluorophosphate, visible light photosensitizer It is acetophenone, and the electron donor compound is N,N-dimethyl-p-vinylaniline.

Example 21

The low-shrinkage dental restorative resin of the present invention has the following mass percentages of raw materials: B 40%, Bis-GMA 32%, A 25%, and Sanyuanguang C 3%.

A is a product obtained by reacting methacryloyl chloride, propionyl chloride and Boltorn type second-generation hyperbranched polyester according to the molar ratio of 8:6:1.

B is obtained by uniformly mixing epoxy resin and expansion monomer at a mass ratio of 1:2, wherein the epoxy resin is methyl bis[2-(7-oxabicyclo[4.1.0]hept-3-yl) -Ethyl]phenylsilane, the expanding monomer is 3,9-diethyl-3,9-propenyloxymethyl-1,5,7,11-tetraoxaspira[5,5]undecane ( BAOM).

C is obtained by uniformly mixing photoacidic compound, visible light photosensitizer and electron donor compound group according to the mass ratio of 3:0.5:0.1, wherein the photoacidic compound is triarylsulfonium hexafluorophosphate, and the visible light photosensitizer is benzoin Ether, the electron donor compound is N,N-dimethylaminoethyl methacrylate.

Example 22

The low-shrinkage dental restorative resin of the present invention, the mass percentages of raw materials are: B 40%, Bis-GMA 57%, A0%, Sanyuanguang C3%.

A is the product obtained by reacting methacryloyl chloride, propionyl chloride and Boltorn type second-generation hyperbranched polyester according to the molar ratio of 8:8:1.

B is obtained by uniformly mixing epoxy resin and expansion monomer at a mass ratio of 1:1, wherein the epoxy resin is 2,4,6,8-tetramethyl-2,4,6,8-tetra[2- (7-Oxabicyclo[4.1.0]hept-3-yl)-ethyl]-1,3,5,7-tetraoxa-2,4,6,8-tetrasilacyclobutane, expanded The monomer is 3,9-diethyl-3,9-propenyloxymethyl-1,5,7,11-tetraoxaspira[5,5]undecane (BAOM).

C is obtained by mixing a photoacidic compound, a visible light photosensitizer and an electron donor compound group according to a mass ratio of 1:0.1:0.1, wherein the photoacidic compound is diaryliodonium hexafluorophosphate, and the visible light photosensitizer is Thioxanthraquinone, the electron donor compound is N,N-dimethyl-p-vinylaniline.

Example 23

The low-shrinkage dental restoration resin of the present invention, the mass percentages of raw materials are: B 50%, Bis-GMA 40%, A9%, Sanyuanguang C1%.

A is a product obtained by reacting methacryloyl chloride, propionyl chloride and Boltorn type second-generation hyperbranched polyester according to the molar ratio of 10:6:1.

B is obtained by uniformly mixing epoxy resin and expansion monomer at a mass ratio of 1:1, wherein the epoxy resin is 2,4,6,8-tetramethyl-2,4,6,8-tetra[2- (7-Oxabicyclo[4.1.0]hept-3-yl)-ethyl]-1,3,5,7-tetraoxa-2,4,6,8-tetrasilacyclobutane, expanded The monomer is 3,9-diethyl-3,9-propenyloxymethyl-1,5,7,11-tetraoxaspira[5,5]undecane (BAOM).

C is obtained by mixing a photoacidic compound, a visible light photosensitizer and an electron donor compound group according to a mass ratio of 1:0.5:0.1, wherein the photoacidic compound is diaryliodonium hexafluorophosphate, and the visible light photosensitizer is Camphorquinone, the electron donor compound is N,N-dimethylaminoethyl methacrylate.

Example 24

The low-shrinkage dental restorative resin of the present invention, the mass percentages of raw materials are: B 50%, Bis-GMA 30%, A 19%, Sanyuanguang C 1%.

A is a product obtained by reacting methacryloyl chloride, propionyl chloride and Boltorn type second-generation hyperbranched polyester according to the molar ratio of 9:7:1.

B is obtained by uniformly mixing epoxy resin and expansion monomer at a mass ratio of 1:1, in which 2,4,6,8-tetramethyl-2,4,6,8-tetra[2-(7-oxo Heterobicyclo[4.1.0]hept-3-yl)-ethyl]-1,3,5,7-tetraoxa-2,4,6,8-tetrasilacyclobutane, expanded monomer of 3 ,9-diethyl-3,9-propenyloxymethyl-1,5,7,11-tetraoxaspira[5,5]undecane (BAOM).

C is obtained by uniformly mixing photoacidic compound, visible light photosensitizer and electron donor compound group according to the mass ratio of 1:1:0.1, wherein the photoacidic compound is triaryl selenium hexafluorophosphate, and the visible light photosensitizer is sulfur Xanthraquinone, the electron donor compound is dimethylvinylaminobenzoic acid.

In summary, the present invention forms a solid cured body under light, reduces the shrinkage rate of the repair resin, and has ideal hardness; the introduction of expansion monomer and epoxy resin replaces the diluent bis that is cytotoxic to the dental pulp. Triethylene glycol methacrylate (TEGDMA), which reduces the cytotoxicity of repair resins.

Claims (8)

1. a low-shrinkage dental restoration resin, is characterized in that, is prepared from by methacrylate monomer, modified Boltorn type second generation hyperbranched polyester monomer, diluent and epoxy system and initiator, in: Methacrylate monomers account for 25-60% of the mass of the entire resin system; Modified Boltorn type second-generation hyperbranched polyester monomer accounts for 0-40% of the mass of the entire resin system; Diluent and epoxy system account for 30~50% of the whole resin system; The initiator accounts for 1-5% of the mass of the whole resin system. 2. The low-shrinkage dental restoration resin according to claim 1, wherein the methacrylate monomer is bisphenol A-glycidyl dimethacrylate Bis-GMA. 3. low-shrinkage dental restoration resin according to claim 1, is characterized in that, described modified Boltorn type second generation hyperbranched polyester monomer reacts with modified monomer by Boltorn type second generation hyperbranched polyester Obtained, modified to contain carbon-carbon double bonds and hydroxyl groups. 4. low-shrinkage dental restoration resin according to claim 1, is characterized in that, described diluent and epoxy system comprise expansion monomer and epoxy resin, and the mass ratio of expansion monomer and epoxy resin is (1 ~4): 4, wherein the epoxy resin is 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexyl carboxylate, methyl bis[2-(7-oxabicyclo[4.1. 0]hept-3-yl)-ethyl]phenylsilane or 2,4,6,8-tetramethyl-2,4,6,8-tetra[2-(7-oxabicyclo[4.1. 0]hept-3-yl)-ethyl]-1,3,5,7-tetraoxa-2,4,6,8-tetrasilacyclobutane, expanded monomer is 3,9-diethyl -3,9-propenyloxymethyl-1,5,7,11-tetraoxaspira[5,5]undecane. 5. The low-shrinkage dental restoration resin according to claim 1, wherein the initiator is a ternary photosensitive initiator system. 6. The low-shrinkage dental restoration resin according to claim 3, wherein the modified monomer is a combination of methacryloyl chloride and propionyl chloride, wherein methacryloyl chloride and Boltorn type second-generation hyperbranched polymer The molar ratio of ester is (7~10):1, and the molar ratio of propionyl chloride to Boltorn type second-generation hyperbranched polyester is (6~9):1. 7. The low-shrinkage dental restoration resin according to claim 5, wherein the ternary photoinitiating system comprises a photoacidic compound, a visible light photosensitizer and an electron donor compound group, and the photoacidic compound is a diaryl Ionium hexafluorophosphate, triarylsulfonium hexafluorophosphate or triarylselenium hexafluorophosphate, visible light photosensitizer is camphorquinone, benzophenone, acetophenone, benzoin ether or thiaxanthraquinone, electron donating The body compound is N,N-dimethylaminoethyl methacrylate, dimethylvinylaminobenzoic acid or N,N-dimethyl-p-vinylaniline, among which photoacidic compound, visible light photosensitizer and electron donor The mass ratio of body compound is (1~3):(0.1~1):0.1. 8. A preparation method of low-shrinkage dental restorative resin as claimed in claim 1, characterized in that, with methacrylate monomer 25 ~ 60% (weight), modified Boltorn type second generation hyperbranched polyester 0-40% (weight) of monomer, 30-50% (weight) of diluent and epoxy system and 1-5% (weight) of initiator are used as ingredients, mixed evenly and poured into a specific mold for photocuring molding to obtain Low shrinkage dental restorative resin material.