阅读说明：本技术 牙科复合材料以及所述复合材料的铣削坯料 (Dental composite material and milled blank of said composite material ) 是由 A.乌特罗特 K.赖施尔 N.申霍夫 M.埃克 R.科科格卢 J.施奈德 C.肯普卡 于 2018-10-01 设计创作，主要内容包括：本发明涉及可聚合牙科复合材料,其包含(i)70~85重量%的至少一种无机填料组分,其包含至少一种牙科玻璃以及任选的至少一种无定形金属氧化物,(ii)10~30重量%的至少两种不同的氨基甲酸酯(甲基)丙烯酸酯的混合物,(iii)0.01~5重量%的至少一种二官能单体、三官能单体、四官能单体或多官能单体,其不同于氨基甲酸酯(甲基)丙烯酸酯,和(iv)0.01~10重量%的至少一种引发剂、引发剂体系以及任选的至少一种稳定剂和任选的至少一种颜料,其中该复合材料的总组成共计100重量%。本发明还涉及用于制备间接假牙的具有大于或等于200 MPa的挠曲强度和15~20 GPa的弹性模量的聚合的复合材料。(The present invention relates to a polymerizable dental composite comprising (i)70 to 85 wt% of at least one inorganic filler component comprising at least one dental glass and optionally at least one amorphous metal oxide, (ii)10 to 30 wt% of a mixture of at least two different urethane (meth) acrylates, (iii)0.01 to 5 wt% of at least one di-, tri-, tetra-or multifunctional monomer which is different from the urethane (meth) acrylates, and (iv)0.01 to 10 wt% of at least one initiator, initiator system and optionally at least one stabilizer and optionally at least one pigment, wherein the total composition of the composite totals 100 wt%. The invention also relates to a polymeric composite material having a flexural strength greater than or equal to 200 MPa and an elastic modulus of 15-20 GPa for the preparation of an indirect dental prosthesis.)

1. A polymerizable dental composite comprising:

(i) 70-85 wt% of an inorganic filler component comprising at least one having an average particle size d of 0.7-7.5 μm₅₀And optionally at least one amorphous metal oxide,

(ii)10 to 30 wt. -% of a mixture of at least two different urethane (meth) acrylates, wherein the mixture comprises at least one difunctional urethane (meth) acrylate with a divalent cycloaliphatic group comprising bis (4',7' -dioxa-3 ',8' -dioxo-2 ' -aza-dec-9 ' -enyl) tetrahydrodicyclopentadiene, bis (4',7' -dioxa-3 ',8' -dioxo-2 ' -aza-9 ' -methyl-dec-9 ' -enyl) tetrahydrodicyclopentadiene and/or mixtures thereof and optionally 3, 8-isomer/3, 9-isomer/4, 8-isomer/3 of the above-mentioned compounds, 10-isomer/4, 10-isomer and/or a mixture of cis-and trans-isomers,

(iii)0.01 to 5 wt% of at least one difunctional, trifunctional, tetrafunctional or multifunctional monomer other than urethane (meth) acrylate,

(iv)0.01 to 10 wt% of at least one initiator, an initiator system, and optionally at least one stabilizer and optionally at least one pigment, wherein the total composition of the composite totals 100 wt%.

2. Dental composite according to claim 1, characterized in that:

a) the dental glass has an average particle size d of 1.5 [ mu ] m₅₀And preferably has a d of less than or equal to 10 [ mu ] m₉₉Or is or

b) The dental glass comprises a mixture of dental glasses having different fractions of the following average particle size: i) 2-8 mu m d₅₀Ii) d of 1.0 to 2.0 [ mu ] m₅₀And iii) d of 0.5 to 1.2 mu m₅₀Wherein the ratio of the portion i) to the portion ii) to the portion iii) is 1 to 4: 1: 4 to 8, particularly 2 to 3: 1: 6 to 7.

3. Dental composite according to claim 1 or 2, characterized in that the amorphous metal oxide comprises at least one non-agglomerated amorphous metal oxide having a primary particle size of 2-45 nm, and the amorphous metal oxide optionally comprises precipitated silica, pyrogenic silica, zirconia or mixed oxides.

4. Dental composite according to any of claims 1 to 3, characterized in that the composite comprises as (i) inorganic filler component:

(i.1) 70 to 84% by weight of at least one dental glass, and optionally

(i.2) 1-15% by weight of an amorphous metal oxide, in particular fumed silica and/or precipitated silica.

5. Dental composite according to any of claims 1 to 4, characterized in that (ii) comprises a mixture of at least two different urethane (meth) acrylates, wherein said mixture comprises at least one difunctional urethane (meth) acrylate with a divalent cycloaliphatic group and a difunctional urethane (meth) acrylate with a divalent alkylene group and optionally at least one at least tetrafunctional dendritic urethane (meth) acrylate, preferably at least one hexafunctional dendritic urethane (meth) acrylate.

6. Dental composite according to any of claims 1 to 5, characterized in that (ii) is selected from the group consisting of dimethacrylate of polyether, trifunctional, tetrafunctional or multifunctional methacrylate of polyether.

7. Dental composite according to any of claims 1 to 6, characterized in that the at least one stabilizer comprises water, at least one benzophenone derivative and/or at least one phenol derivative.

8. Dental composite according to any of claims 1 to 7, characterized in that said at least one pigment comprises fluorescent pigments, organic colour pigments, and inorganic colour pigments, in particular comprising diethyl 2, 5-dihydroxyterephthalate; n, N' -bis (3, 5-xylyl) perylene-3, 4:9, 10-bis (dicarboximide); copper phthalocyanine; titanate pigments, in particular antimony chromium titanate (rutile structure); spinel black, especiallyBased on black iron oxide (Fe)₃O₄) Wherein iron (Fe) is partially substituted by chromium and copper or nickel and chromium or manganese; zinc iron chromium spinel; brown spinel; cobalt zinc aluminate blue spinel and/or titanium oxide.

9. Polymerized dental composite obtainable by polymerization of a composite according to any of claims 1 to 8, in particular obtainable by polymerization at a pressure of 50 to 300 MPa and/or at an elevated temperature, preferably at 90 to 150 ℃, in particular for 10 minutes to 10 hours.

10. The polymeric dental composite according to claim 9, having a flexural strength (7 days, 23 ± 2 ℃, dry storage) of greater than or equal to 200 MPa to 260 MPa and an elastic modulus (7 days, 23 ± 2 ℃, dry storage) of greater than or equal to 15 to 20 GPa according to EN ISO6872: 2008.

11. The polymeric dental composite according to claim 9, having a flexural strength according to EN ISO6872:2008 greater than or equal to 160MPa to 260 MPa (storage in deionized water at 37 ℃ for 7 days followed by greater than or equal to 1000 cycles (5 ℃ to 55 ℃, retention time greater than or equal to 30 seconds)) and a modulus of elasticity greater than or equal to 14 to 21GPa (storage in deionized water at 37 ℃ for 7 days followed by greater than or equal to 1000 cycles (5 ℃ to 55 ℃, retention time greater than or equal to 30 seconds)).

12. A polymeric dental composite comprising:

70 to 85 wt% of at least one inorganic filler compound comprising at least one average particle size d₅₀0.7 to 7.5 [ mu ] m dental glass and optionally at least one amorphous silanized metal oxide with a primary particle size of 2 to 45 nm,

10 to 30% by weight of at least one polymer based on at least one monomer comprising at least one biscarbamate derivative of tetrahydrodicyclopentadiene, at least one dicarbamate (meth) acrylate having a divalent alkylene group, at least one tetrafunctional to decafunctional dendritic carbamate methacrylate and at least one difunctional, trifunctional, tetrafunctional or multifunctional methacrylate of a polyether, preferably triethylene glycol dimethacrylate, and

-0.01 to 10% by weight of at least one pigment, in particular at least one fluorescent pigment and at least one organic colour pigment and/or at least one inorganic colour pigment, wherein the total composition of the composite totals 100% by weight.

13. Polymeric dental composite according to any of claims 8-12, characterized in that the polymeric dental composite is present in the form of a block of material, in particular as a three-dimensional geometric moulded body, in particular as a milled blank without joints, or as a milled blank with joints for fastening in an automated device for removing material.

14. Use of a dental composite according to any one of claims 1-13 for the production of dental prostheses during material removal, in particular during removal of said polymerized composite by means of milling, cutting, polishing, breaking, cutting and/or drilling, in particular during removal of said composite by means of laser energy, or for the production of directly bonded dental prostheses, as hoof repair materials, as bone cements for bonding artificial joint prostheses, orthodontic appliances and appliances.

15. Use according to claim 14 for the preparation of a dental prosthetic restoration comprising a crown, an inlay, an onlay, a superstructure, an artificial tooth, a bridge, a dental strip, a spacer, an abutment or a veneer.

Example (b):

three point bending flexure test

The flexural properties were determined using a three-point bending flexural test according to ISO6872:2008 (ISO 6872:2008 dentistry-ceramic material, 3 rd edition, international organization for standardization, geneva, 2008.) rod samples of 4.0 mm in width, 14.0 mm in length and 1.2 mm in thickness were prepared using a low speed diamond saw (Isomet, Buehler, L ake Bluff, I L.) all samples were wet milled and polished using #600 and #1000 diamond wheels (Maruto, Tokyo, japan) and a #1000 diamond blade (Maruto) mounted on a metallographic grinder (Dia-L ap, M L-150P, Maruto) to achieve the desired dimensions of 4.0 ± 0.2 × 14.0.14.0 ± 0.2 × 1.2.2 ± 0.2 mm, to minimize edge breakage of the rod sample during the bending test, a grinder with a #1000 diamond blade was used to incorporate the 0.15 mm wide MDC 38.2 ± 0.2 mm in order to minimize edge breakage of the rod sample during the bending test, after the bending test was performed using a thermal cycle test under a t-cycle test set of # 20 mm (tako) and a thermal cycle test under room temperature, storage, and storage, under room temperature, storage, under room temperature, storage, temperature, storage, under 30 ℃ conditions, 30 ℃ of 30 mm, 30 ℃, 30 mm, 1.7 ℃ of a thermal cycle, 1.7 ℃ of a thermal test, 1.7 ℃ of a thermal cycle, 1.7 ℃ and a thermal test environment, using a thermal test, a thermal test environment, using a thermal test environment, a thermal test environment, a thermal test under the following three:

E=FL ³ /4bh ³ d

whereinFRepresenting the load at the appropriate point in the linear portion having spring characteristics, L representing the support span (12.00mm), b representing the width of the sample, h representing the thickness of the sample, and d representing the bending under load Fσ)：

σ=3F ₁ L/2bh ²

Wherein F₁Representing the maximum load during the bending deflection test.

Hardness testing was performed using Zwick general purpose equipment: the samples according to the invention have measured values in the range of 800 to 850.

In the following, comparative examples of Venus Diamond (VD) and Venus Pearl (VP) photo-cured products were measured according to ISO4049 and ISO6872 (exposure was performed point by point according to the method described in EN ISO 4049: 20097.11 using Translux 2Wave (1200 mW/cm) with exposure times of 20 seconds/exposure point, respectively), and compared with example 1 according to the present invention.

Table 2: example 1 comparison with Venus product

Table 3: examples 1 to 3

The polymerization of the dental composite according to the invention is typically carried out at 95 ℃ for about 3 h.

Table 4: flexural Strength (according to EN ISO 6872)

After polymerization, after 7 days,¹⁾the particle size distribution of the three dental glass parts is according to b) 2-3: 1: 6-7,²⁾particle size distribution according to a) d₅₀Is 1.5 mu m

Table 5: e-modulus (modulus of elasticity)

After polymerization, after 7 days,¹⁾the particle size distribution of the three dental glass parts is according to b) 2-3: 1: 6-7,²⁾particle size distribution according to a) d₅₀Is 1.5 mu m.