Radically polymerisable dental material, cured product and usage

• US 9,381,140 B2
• Filed: 08/30/2013
• Issued: 07/05/2016
• Est. Priority Date: 08/31/2012
• Status: Active Grant

• Current Assignee: Kettenbach GmbH & Co. KG
• Original Assignee: Kettenbach GmbH & Co. KG
• Inventors: Bublewitz, Alexander, Reber, Jens-Peter, Theis, Alexander
• Primary Examiner(s): Choi, Ling
• Assistant Examiner(s): WHITELEY, JESSICA
• Application Number:
  US14/424,729
• Publication Number:
  US 20150231041A1
• Time in Patent Office: 1,040 Days
• Field of Search: None
• US Class Current: 1/1
• CPC Class Codes: A61K 6/16 Refractive index
• CPC Class Codes: A61K 6/76 comprising silicon-containing compounds
• CPC Class Codes: A61K 6/887 Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
• CPC Class Codes: A61K 6/889 Polycarboxylate cements; Glass ionomer cements
• CPC Class Codes: C08L 33/00 Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers

Abstract

The invention relates to a polymerizable dental material containing a) at least one curable aliphatic and/or cycloaliphatic monomer system having a refractive index that is measured at 23° C. and a wavelength of 589 nm of less than or equal to 1.50 that contains at least one aliphatic and/or cycloaliphatic bis(meth)acrylate and/or at least one aliphatic and/or cycloaliphatic bis(meth)acrylamide; and b) 15 to 80% by weight relative to the total mass of the dental material of at least one filler selected from the group of fused silica having a refractive index that is measured at 23° C. and a wavelength of 589 nm of 1.45 to 1.47, or cristobalite with a refractive index that is measured at 23° C. and a wavelength of 589 nm of 1.48 to 1.49, or combinations thereof. The radically polymerizable dental material has excellent storage properties and is formulated, in particular, as a two-component mixture containing components A and B. Subsequent to mixing components A and B, the polymerizable mixture cures quickly in the conditions present in the mouth and forms cured masses having outstanding mechanical and optical properties. The cured products can be used, in particular, for producing crowns and bridge material and as core buildup material.

Claims

1. A radically polymerizable dental material containing the components:

a) at least one curable aliphatic and/or cycloaliphatic monomer system having a refractive index as measured at 23°

C. and at a wavelength of 589 nm of less than or equal to 1.50, that contains at least one aliphatic and/or cycloaliphatic bis(meth)acrylate and/or at least one aliphatic and/or cycloaliphatic bis(meth)acrylamide in a mixture comprising aliphatic and/or cycloaliphatic bis(meth)acrylate monomers,

wherein at least one of the monomers comprises one or several urethane groups, and at least one of the monomers does not comprise a urethane group,

wherein the content of urethane-group-containing (meth)acrylate monomers in the monomer mixture is ≧

50% by weight, relative to the monomer mixture, and

wherein the monomer mixture contains 1 to 20% by weight relative to the total amount of component a) of low viscous (meth)acrylate and/or bis(meth)acrylate free of aromatic compounds, urethane groups and urea groups, having a viscosity of less than 2000 mPa·

s as measured at a temperature of 23°

C. with a cone/plate geometry of (35 mm, 4°

), and a shear stress of 50 Pa,

b) 15 to 80% by weight relative to the total mass of the dental material of at least one filler selected from the group of

fused silica having a refractive index as measured at 23°

C. and at a wavelength of 589 nm of 1.45 to 1.47, and

cristobalite having a refractive index measured at 23°

C. and at a wavelength of 589 nm of 1.48 to 1.49,

or their combinations, and

e) an initiator for radical polymerization,

wherein the dental material contains in component a) 1 to 20% by weight relative to the total amount of the component a) of a polytetramethylene glycol di(meth)acrylate having an average molecular weight of 300 g/mol to 1000 g/mol, a viscosity of less than 2000 mPa·

s as measured at a temperature of 23°

C. with a cone/plate geometry of (35 mm, 4°

) and a shear stress of 50 Pa, as an impact strength modifying (meth)acrylate monomer,

provided, that the radically polymerizable dental material does not contain compounds comprising Bisphenol A groups.

2. The radically polymerizable dental material as recited in claim 1, wherein the at least one filler b) has an average grain size d₅₀ of between 0.2 and 1.0 μ

m as determined by means of sediment analysis.

3. The radically polymerizable dental material as recited in claim 1, wherein the dental material is devoid of radically polymerizable (meth)acrylates comprising aromatic groups.

4. The radically polymerizable dental material as recited in claim 1, wherein the dental material contains in component a) 1 to 20% by weight relative to the total amount of component a) of low viscous (meth)acrylate and/or bis(meth)acrylate that is free of aromatic compounds, urethane groups and urea groups, having a viscosity of less than 500 mPa·

s as measured at a temperature of 23°

C. with a cone/plate geometry of (35 mm, 4°

), and a shear stress of 50 Pa.

5. The radically polymerizable dental material as recited in claim 1, wherein the filler b) is a mixture of fused silica and cristobalite.

6. The radically polymerizable dental material as recited in claim 1, wherein the at least one filler b) has an average grain size d₅₀ between 0.3 and 0.8 μ

m, and a surface area between 10 and 20 m²/g as determined according to BET.

7. The radically polymerizable dental material as recited in claim 1, further comprising d) nanoparticular fillers consisting of 0.1 to 15% by weight relative to the dental mass and having a BET surface area of 30 to 400 m²/g.

8. The radically polymerizable dental material as recited in claim 1, further comprising white, black, red and/or yellow organic or inorganic pigment.

9. The radically polymerizable dental material as recited in claim 1, wherein the dental material is present in the form of a two-component paste system consisting of base paste A and of an initiator paste B,

wherein the base paste A has the following components:

19 to 80% by weight relative to the total mass of base paste A consisting of a mixture of mono and multifunctional acrylates and/or methacrylates a) having a refractive index as measured at 23°

C. and at a wavelength of 589 nm between 1.46 and 1.50,

19 to 80% by weight relative to the total mass of base paste A of a cristobalite and/or fused silica b), having an average grain size d₅₀ of 0.3 to 0.8 μ

m, and a specific surface area of 10 to 20 m²/g as determined according to the BET method,

wherein the cristobalite has a refractive index as measured at 23°

C. and at a wavelength of 589 nm of 1.484 to 1.487, and the fused silica has a refractive index at 23°

C. and at a wavelength of 589 nm of 1.455 to 1.465,

1 to 15% by weight relative to the total mass of base paste A of a fumed silica d) having a specific surface area of 30 to 400 m²/g as determined according to the BET method,

at least one metal compound f),

at least one halogenide and/or pseudohalogenide compound g), and

optionally, one or more photoinitiators and/or photo co-initiators e),

wherein the initiator paste B contains the following components;

19 to 80% by weight relative to the total mass of the initiator paste B of a paste-forming agent j) having a refractive index at 23°

C. and at a wavelength of 589 nm between 1.460 and 1.520,

0 to 80% by weight relative to the total mass of the initiator paste B of a cristobalite and/or fused silica b), having an average grain size d₅₀ of 0.3 to 0.8 μ

m, and a specific surface area of 10 to 20 m²/g as determined according to the BET method,

wherein the fused silica has a refractive index at 23°

C. and at a wavelength of 589 nm of 1.455 to 1.465, and wherein the cristobalite has a refractive index at 23°

C. and at a wavelength of 589 nm of 1.484 to 1.487,

0 to 80% by weight relative to the total mass of the initiator paste B of other conventional dental fillers with the exception of fused silica and cristobalite,

1 to 15% by weight relative to the total mass of the initiator paste B of a barbituric acid derivative and/or a malonyl sulfamide e), and

0 to 2% by weight relative to the total mass of initiator paste B of an organic peroxygen compound h), and

optionally, one or several photo hardening initiators and/or photo co-initiators e).

10. The radically polymerizable dental material as recited in claim 1, wherein the dental material is present in the form of a pasty two-component system consisting of base paste A and of initiator paste B,

wherein the base paste A contains the following components:

18.99 to 80% by weight relative to the total mass of the base paste A of a mixture consisting of mono-functional and multifunctional acrylates and/or methacrylates a) that have a refractive index at 23°

C. and at a wavelength of 589 nm between 1.46 and 1.50,

18.99 to 80% by weight relative to the total mass of the base paste A of a cristobalite and/or fused silica b), having an average grain size d₅₀ of 0.3 to 0.8 μ

m, and a specific surface area of 10 to 20 m²/g as determined according to the BET method,

wherein the cristobalite has a refractive index at 23°

C. and at a wavelength of 589 nm of 1.484 to 1.487, and the fused silica has a refractive index at 23°

C. and at a wavelength of 589 nm of 1.455 to 1.465,

1 to 15% by weight relative to the total mass of the base paste A of a fumed silica d) having a specific surface area of 30 to 400 m²/g as determined according to the BET method, and

0.01 to 2% by weight relative to the total mass of base paste A of an amine,

and optionally one or several photoinitiators and/or additional co-initiators e), and

wherein the initiator paste B contains the following components;

19.99 to 80% by weight relative to the total mass of the initiator paste B of a mixture consisting of mono-functional and multifunctional acrylates and/or methacrylates a) that have a refractive index at 23°

C. and at a wavelength of 589 nm between 1.46 and 1.50,

19.99 to 80% by weight relative to the total mass of the initiator paste B of a cristobalite and/or fused silica b) that has an average grain size d₅₀ of 0.3 to 0.8 μ

m, as well as a specific surface area of 10 to 20 m²/g as determined according to the BET method,

wherein the fused silica has a refractive index at 23°

C. and at a wavelength of 589 nm of 1.455 to 1.465, and wherein the cristobalite has a refractive index at 23°

C. and at a wavelength of 589 nm of 1.484 to 1.487,

0.01 to 2% by weight relative to the total mass of the initiator paste B, of at least one organic peroxide h), and

optionally, one or several photoinitiators and/or co-initiators e).

11. A cured dental material that is obtainable by curing the radically polymerizable dental material as recited in claim 1.

12. The cured dental material as recited in claim 11, wherein the dental material has a resistance to impact of at least 55 MPa.

13. The cured dental material as recited in claim 12, wherein the dental material has a flexural strength of at least 90 MPa and/or a translucence of at least 0.60.

14. A method for producing inlays, onlays, veneers, partial crowns, tooth fillings, artificial teeth, and model material for provisional crown, permanent crown and bridge material, the method comprising curing the polymerizable dental material as recited in claim 1.

15. A method for producing core buildup material, block and disc material for millable CAD-CAM restorations or for esthetic cement, the method comprising curing the polymerizable dental material as recited in claim 1.

16. The radically polymerizable dental material as recited in claim 5, wherein the weight ratio of fused silica to cristobalite is of 1:

1 to 10.

17. A cured dental material obtained by curing the radically polymerizable dental material as recited in claim 9, wherein base paste A and initiator paste B are present at a ratio of 20:

1 to 1;

1.

18. A cured dental material obtained by curing the radically polymerizable dental material as recited in claim 10, wherein base paste A and initiator paste B are present at a ratio of 20:

1 to 1;

1.

19. A radically polymerizable dental material containing the components:

a) at least one curable aliphatic and/or cycloaliphatic monomer system having a refractive index at 23°

C. and at a wavelength of 589 nm that is less than or equal to 1.50, that contains at least one aliphatic and/or cycloaliphatic bis(meth)acrylate and/or at least one aliphatic and/or cycloaliphatic bis(meth)acrylamide,

b) 15 to 80% by weight relative to the total mass of the dental material of at least one filler selected from the group of

fused silica having a refractive index at 23°

C. and at a wavelength of 589 nm of 1.45 to 1.47, and

cristobalite having a refractive index at 23°

C. and at a wavelength of 589 nm of 1.48 to 1.49,

or their combinations, and

c) 5 to 50% by weight relative to the total mass of the dental material of an X-ray-opaque filler c) that contains an irregularly shaped or spherical YbF₃—

or YF₃-powder having an average grain size of the primary particles of 40 nm to 1.5 μ

m, which is a core/shell combination product consisting of YF₃—

or YbF₃-core and SiO₂ shell, wherein the SiO₂ shell surface is silanized,

provided that the radically polymerizable dental material does not contain compounds comprising Bisphenol A groups.

20. The radically polymerizable dental material as recited in claim 19, wherein component a) contains at least one aliphatic and/or cycloaliphatic bis(meth)acrylate and/or at least one aliphatic and/or cycloaliphatic bis(meth)acrylamide in a mixture comprising aliphatic and/or cycloaliphatic bis(meth)acrylate monomers

wherein at least one of the monomers comprises one or several urethane groups, and at least one of the monomers does not comprise a urethane group,

wherein the content of urethane-group-containing (meth)acrylate monomers in the monomer mixture is 50% by weight, relative to the monomer mixture, and

wherein the monomer mixture contains 1 to 20% by weight relative to the total amount of component a) of low viscous (meth)acrylate and/or bis(meth)acrylate free of aromatic compounds, urethane groups and urea groups having a viscosity of less than 2000 mPa·

s as measured at a temperature of 23°

C. with a cone/plate geometry (35 mm, 4°

), and a shear stress of 50 Pa.

21. The radically polymerizable dental material as recited in claim 19, wherein the dental material contains no radically polymerizable (meth)acrylates comprising aromatic groups.

22. The radically polymerizable dental material as recited in claim 19, wherein the dental material is present in the form of a pasty two-component system consisting of base paste A and of initiator paste B,

wherein the base paste A contains the following components:

13.99 to 80% by weight relative to the total mass of the base paste A of a mixture consisting of mono-functional and multifunctional acrylates and/or methacrylates a) that have a refractive index at 23°

C. and at a wavelength of 589 nm between 1.46 and 1.50,

13.99 to 80% by weight relative to the total mass of the base paste A of a cristobalite and/or fused silica b) that has an average grain size d₅₀ of 0.8 to 20 μ

m, and a specific surface area of 1.0 to 20 m²/g as determined according to the BET method,

wherein the cristobalite has a refractive index at 23°

C. and at a wavelength of 589 nm of 1.484 to 1.487, and the fused silica has a refractive index at 23°

C. and at a wavelength of 589 nm of 1.455 to 1.465,

5 to 30% by weight relative to the total mass of the base paste A of an X-ray-opaque additive c) consisting of an irregularly shaped or spherical YbF₃—

or YF₃—

powder having an average grain size of the primary particles of 40 nm to 1.5 μ

m, which is a core/shell combination product consisting of a YF₃—

or YbF₃—

core and a SiO₂ shell, wherein the SiO₂ shell surface is silanized,

1 to 15% by weight relative to the total mass of the base paste A of a nanoscale silicon dioxide and/or SiO₂ d) that is present in the form of primary particles, clusters, aggregates and/or agglomerates having a specific surface area of 30 to 400 m²/g as determined according to the BET method, and

0.01 to 2% by weight relative to the total mass of the base paste A of an amine, and

optionally, one or several photoinitiators and/or additional co-initiators e), and

wherein the initiator paste B contains the following components;

13.99 to 80% by weight relative to the total mass of the initiator paste B of a mixture consisting of mono-functional and multifunctional acrylates and/or methacrylates a) that have a refractive index at 23°

C. and at a wavelength of 589 nm between 1.46 and 1.50,

13.99 to 80% by weight relative to the total mass of the initiator paste B of a cristobalite and/or fused silica b) that has an average grain size d₅₀ of 0.8 to 20 μ

m, and a specific surface area of 1.0 to 20 m²/g as determined by the BET method,

wherein the cristobalite has a refractive index at 23°

C. and at a wavelength of 589 nm of 1.484 to 1.487, and the fused silica has a refractive index at 23°

C. and at a wavelength of 589 nm of 1.455 to 1.465,

5 to 30% by weight relative to the total amount of the initiator paste B of X-ray-opaque additives c) that are irregularly shaped or spherical YbF₃—

or YF₃—

powders having an average grain size or primary particle size of 40 nm to 1.5 μ

m, which is a combination product consisting of a YF₃—

or YbF₃—

core and a SiO₂ shell, wherein the SiO₂ shell surface is silanized,

1 to 15% by weight relative to the total mass of the initiator paste B of a nanoscale silicon oxide and/or SiO₂ d) that is present in the form of primary particles, clusters, aggregates and/or agglomerates having a specific surface area of 30 to 400 m²/g as determined according to the BET method,

0.01 to 2% by weight relative to the total mass of the initiator paste B of at least one organic peroxide h), and

optionally, one or several photoinitiators and/or photo co-initiators e).

23. The radically polymerizable dental material as recited in claim 19, wherein

the average grain size d₅₀ of the at least one filler b) is between 1.0 and 50 μ

m as determined by using a laser refraction particle size measurement device Malvern Mastersizer 3000 with Hydro MV dispersion unit, and

the dental material contains 5 to 50% by weight relative to the total mass of the dental material of an X-ray-opaque filler c) that contains an irregularly shaped or spherical YbF₃—

or YF₃—

powder having an average grain size of the primary articles of 40 nm to 1.5 μ

m, which is a core/shell combination product consisting of a YF₃—

or YbF₃-core and a SiO₂ shell, wherein the SiO₂ shell surface is silanized.

24. The radically polymerizable dental material as recited in claim 19, wherein the dental material contains as component a) a mixture consisting of aliphatic and/or cycloaliphatic bis(meth)acrylate monomers,

wherein at least one of the monomers comprises one or several urethane groups, and at least one of the monomers does not comprise a urethane group.

25. The radically polymerizable dental material as recited in claim 19, wherein

the average grain size d₅₀ of the at least one filler b) is between 1.0 and 20 μ

m, and

the surface area of the at least one filler b) as determined according to BET is between 2 and 6 m²/g.

26. A cured dental material that is obtained by curing the radically polymerizable dental material as recited in claim 19.

27. A cured dental material obtained by curing the radically polymerizable dental material as recited in claim 22, wherein base paste A and initiator paste B are present at a ratio of 20:

1 to 1;

1.

28. A method for producing inlays, onlays, veneers, partial crowns, tooth fillings, artificial teeth, and model material for provisional crown, permanent crown and bridge material, the method comprising curing the polymerizable dental material as recited in claim 19.

29. A method for producing core buildup material, block and disc material for millable CAD-CAM restorations or for esthetic cement, the method comprising curing the polymerizable dental material as recited in claim 19.