High-impact, transparent prosthesis material having a low residual MMA content

Abstract

The subject matter of the invention is an autopolymerisable 2-component prosthetic base material, a kit containing the material as well as a method for its production comprising at least one liquid monomer component (A), and at least one powdered component (B), wherein the prosthetic material in component (A) besides methylmethacrylate contains at least one N-alkyl-substituted acryloyloxy carbamate having a molecular mass of less than or equal to 250 g/mol, optionally at least one at least di-functional urethane (meth)acrylate, a di-, tri-, tetra- or multi-functional monomer not being urethane (meth)acrylate, and optionally polymeric particles having a primary particle size of less than 800 nm, and the powdered component (B) comprises polymeric particles having at least three different particle size fractions, and both (A) and (B) contains at least one initiator or at least one component of an initiator system for autopolymerisation.

Claims

1. Autopolymerisable 2-component prosthetic base material comprising the following components: A) at least one liquid monomer component, B) at least one powdered component, wherein component (A) comprises (i) at least one methyl (meth)acrylate, (ii) at least one N-alkyl or N-alkenyl-substituted acryloyloxy carbamate having a molecular mass of less than or equal to 250 g/mol, (iii) optionally, at least one at least di-functional urethane (meth)acrylate, (iv) at least one di-, tri, tetra- or multi-functional monomer not being urethane (meth)acrylate, (v) optionally, polymeric particles having a primary particle size of less than 800 nm, (vi) at least one initiator or at least one component of an initiator system for autopolymerisation, and component (B) comprises (i) at least one powdered component of polymeric particles comprising at least three different fractions of particle sizes of polymeric particles, and (ii) at least one initiator or at least one component of an initiator system for autopolymerisation.

2. Prosthetic base material according to claim 1, wherein component (A) comprises said polymeric particles (v) present as core-shell particles modified by an elastic phase, and/or component (B) comprises at least one fraction of said polymeric particles (i) present as core-shell particles modified by an elastic phase.

3. Prosthetic base material according to claim 1, wherein an average particle size of each fraction of the at least three different fractions of particle sizes is at least 5 micrometers apart from an average particle size of the other two fractions.

4. Prosthetic base material according to claim 1, wherein component (B) comprises as powdered component polymeric particles with three different fractions, which are selected from 1) polymeric particles of an average particle size of a) 25 μm to less than 40 μm, b) 40 μm to less than 55 μm, c) 55 μm to 100 μm, or 2) polymeric particles of an average particle size of a) 35 μm with plus/minus 2.5 μm, b) 45 μm with plus/minus 2.5 μm, c) 60 μm with plus/minus 2.5 μm, wherein a weight ratio of a) to b) to c) is from 12 to 18:1:1 to 5.

5. Prosthetic base material according to claim 1, wherein the N-alkyl- or N-alkenyl-substituted acryloyloxy carbamate is an N-alkyl- or N-alkenyl-substituted acryloyloxy alkylene carbamate.

6. Prosthetic base material according to claim 1, wherein the N-alkyl-substituted acryloyloxy carbamate is n-butyl acryloyloxy ethyl carbamate (BAEC).

7. Prosthetic base material according to claim 1, wherein the polymeric particles (v) comprise core-shell particles, and the primary particle sizes of the core-shell particles are from 500 nm to 10 nm.

8. Prosthetic base material according to claim 1, wherein the at least one initiator or the at least one component of an initiator system for autopolymerisation comprises at least one initiator system selected from (A) a redox system comprising (i) an oxidising agent and (ii) a reducing agent selected from ascorbic acid, ascorbic acid derivative, barbituric acid, barbituric acid derivative, sulfinic acid, sulfinic acid derivative, (B) a redox system comprising (i) barbituric acid or thiobarbituric acid or a barbituric acid derivative or thiobarbituric acid derivative, and (ii) at least one copper salt or one copper complex, and (iii) at least one compound having an ionic halogen atom, and (C) a redox system comprising (i) 1-benzyl-5-phenylbarbituric acid, (ii) copper acetylacetonate and (iii) a triazine derivative, toluidine derivative and/or benzyldibutylammoniumchloride.

9. Prosthetic base material according to claim 1, wherein the prosthetic material comprising components (A) and (B) comprises (i) 20 to 50% by weight of methyl methacrylate, and, optionally, at least one 2-alkyl acrylic acid ester not being methyl methacrylate, (ii) 1 to 30% by weight of at least one N-alkyl- or N-alkenyl-substituted acryloyloxy carbamate having a molecular mass of less than or equal to 250 g/mol, (iii) 0.5 to 10% by weight of at least one at least di-functional urethane (meth)acrylate, (iv) 0.05 to 10% by weight of at least one di-, tri-, tetra- or multi-functional monomer not being urethane (meth)acrylate, (v) 0.1 to 10% by weight of polymeric particles (v) present as core-shell particles modified by an elastic phase, having a primary particle size of less than 800 nm, (vi) 0.05 to 2% by weight of at least one initiator or at least one component of an initiator system for autopolymerisation, and (vii) 48.3 to 78.3% by weight of at least one powdered component (i) of polymeric particles comprising at least three different fractions of particle sizes of polymeric particles, wherein the % by weight is based on the total amount of (A) and (B), wherein the three different fractions are selected from polymeric particles of an average particle size of a) 25 μm to less than 40 μm, present at 50 to 90% by weight, b) 40 μm to less than 55 μm, present at 0.1 to 20% by weight, and c) 55 μm to 100 μm, present at 0.5 to 30% by weight, wherein the % by weight of a), b) and c) are based on powdered component B.

10. Method for the production of a polymerised prosthetic base material comprising mixing and subsequently polymerizing components: A) at least one liquid monomer component, and B) at least one powdered component, of the prosthetic base material-according to claim 1.

11. Method according to claim 10, which further comprises mixing the liquid monomer component (A) and the powdered component (B) at a weight ratio of 1:10 to 10:1.

12. Polymerised prosthetic base material obtained according to the method of claim 10.

13. Polymerised prosthetic base material according to claim 12, comprising a residual monomer content of methyl methacrylate of less than or equal to 3% by weight determined according to ISO 20795-1:2013, with a total variability of +/−0.05% by weight.

14. Polymerised prosthetic base material according to claim 12, wherein the prosthetic base material has a transparency of greater than or equal to 95% (measured against color test bodies of 3 mm thickness produced in metal molds).

15. Kit comprising an autopolymerisable prosthetic base material, wherein the kit comprises separated components (A) and (B), wherein component (A) comprises (i) 60 to 85% by weight of methyl methacrylate, (ii) 5 to 20% by weight of at least one N-alkyl- or N-alkenyl-substituted acryloyloxy carbamate having a molecular mass of less than or equal to 250 g/mol, (iii) 0.5 to 10% by weight of at least one at least di-function urethane (meth)acrylate, (iv) 0.05 to 10% by weight of at least one di-, tri-, tetra- or multi-functional monomer not being urethane (meth)acrylate, (v) 0.1 to 10% by weight of polymeric particles (v) present as core-shell particles modified by an elastic phase, having a primary particle size of less than 800 nm, (vi) 0.05 to 2% by weight of at least one initiator or at least one component of an initiator system for autopolymerisation, wherein the % by weight of components (i) to (vi) are based on the total amount of component (A), and component (B) comprises (i) 90 to 99.95% by weight of at least one powdered component of polymeric particles (i) comprising at least three different fractions of particles sizes of polymeric particles, wherein the three different fractions are selected from polymeric particles of an average particle size of a) 25 μm to less than 40 μm, present at 50 to 90% by weight, b) 40 μm to less than 55 μm, present at 0.1 to 20% by weight, and c) 55 μm to 100 μm, present at 0.5 to 30% by weight, and (ii) 0.05 to 10% by weight of at least one initiator or at least one component of an initiator system for autopolymerisation, wherein the % by weight of components (i) to (ii) of component B are based on the total amount of component (B).

16. Method of using the prosthetic base material according to claim 1, said method comprising forming the prosthetic base material into a part, wherein the part is selected from dental prostheses, parts of prostheses, occlusal splints, surgical guides for implantology, and mouthguards.

17. Method of using the prosthetic base material according to claim 1, said method comprising cementing a part with the prosthetic base material, wherein the part is selected from artificial articular prostheses, crowns, telescopic prostheses, telescopic crowns, veneers, dental bridges, prosthetic teeth, implants, implant parts, abutments, superstructures, orthodontic appliances, and orthodontic instruments.

18. Method of using the prosthetic base material according to claim 1, said method comprising repairing a hoof of an animal by applying the prosthetic base material to said hoof.

Description

EXEMPLARY EMBODIMENTS

(1) Production of a powder mixture: A trimodal powder system is produced from three PMMA-based beads together with barbituric acid by mixing. The production of the liquid was made from the components indicated below by mixing.

(2) The measured values below were determined in accordance with norm DIN EN ISO 20795-1. The residual MMA content was also determined in accordance with this norm, analogous to article 8.8. Article 5.2.10 defines that the maximum factor of the stress intensity for materials having heightened impact resistance has to amount to at least 1.9 MPa m.sup.1/2. The determination is made according to article 8.6. Article 5.2.11 defines that the total fracture work has to amount to at least 900 J/m.sup.2. The measurement of the fracture toughness was performed according to article 8.6, analogous to norm EN ISO 20795-1:2013. The device was called: Zwick/Roell Z010, machine type TMT1-FR010TN.A50. In the examples, a core-shell bead, such as the 6681F, was used as fraction having the largest particle diameter, wherein normal beads may also be used. Examples 1-3: All the plastics were produced at the ratio of 10:7 and by means of casting methods. Example 4 was produced at the ratio of 10:5. The determination was made according to article 8.6. The test bodies were polymerised for 30 min at 55° C. and 2 bar pressure.

Example 1

(3) TABLE-US-00001 % by weight Liquid MMA 83.435 aliquat 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5- 0.15 ((hexyl)oxy)-phenol copper(II) chloride solution 0.07 UV stabilisers 0.25 N,N-bis(2(hydroxyethyl)-p-toluidine 0.1 n-butyl acryloxyethyl carbamate 10 di-functional, aliphatic urethane acrylate oligomer 3 tris-(2-hydroxyethyl) isocyanurate triacrylate 1 styrene-butyl acrylate core-shell particles 2 (200 to 400 nm) Powder bead 1 d.sub.50: 35 μm 77.56 bead 2 d.sub.50: 45 μm 5 bead 3 d.sub.50 60 μm 15 barbituric acid 2.44

(4) In accordance with the usual manner of processing for prosthetic base materials, test bodies were produced according to norm DIN EN ISO 20795-1 (39 mm×8 mm×4 mm) for determination of the physical properties at the ratio powder to liquid of 10:7.

(5) The following measured values were determined:

(6) TABLE-US-00002 Ex. 1 mechanics 10:7 - flexural strenght [Mpa] 70.8 mechanics 10:7 I - E-modulus [Mpa] 2171 mechanics 10:7 - fracture toughness as maximum factor of the 2.54 stress intensity Kmax [Mpa m.sup.1/2] mechanics 10:7 I - fracture toughness as total fracture work Wf 1298 [J/m.sup.2] maximum temperature 10:7 [° C.] 72° C.* *measured at RT started polymerisation.

(7) Colour test bodies produced in metal moulds show a transparency of 96%. The residual MMA content, 48 hours after production (standard testing), amounts to 2.0% by weight in the case of a polymerisation time of 30 min, to 1.8% by weight in the case of 60 min. The residual monomer content of MMA, 4 days after production, amounts to 1.8% by weight in the case of a polymerisation time of 30 min.

Example 2

(8) Test bodies are produced analogously to Example 1 in accordance with the composition indicated in the table.

(9) TABLE-US-00003 % by weight Liquid MMA 88.43 aliquat 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5- 0.15 ((hexyl)oxy)-phenol copper(II) chloride solution 0.07 UV stabilisers 0.25 N,N-bis(2(hydroxyethyl)-p-toluidine 0.1 n-butyl acryloxyethyl carbamate 5 di-functional, aliphatic urethane acrylate oligomer 3 tris-(2-hydroxyethyl) isocyanurate triacrylate 1 styrene-butyl acrylate core-shell particles 2 tot. 100 Powder bead 1 d.sub.50: 35 μm 67.56 bead 2 d.sub.50: 45 μm 15 bead 3 d.sub.50 60 μm 15 barbituric acid 2.44

(10) The following measured values were determined according to the norm stated above (DIN EN ISO 20795-1):

(11) TABLE-US-00004 mechanics 10:7 - flexural strenght [Mpa] 68.1 mechanics 10:7 I - E-modulus [Mpa] 2307 mechanics 10:7 - fracture toughness as maximum factor of 2.37 the stress intensity Kmax [Mpa m.sup.1/2] mechanics 10:7 I - fracture toughness as total fracture 952.7 work Wf [J/m.sup.2] maximum temperature 10:7 [° C.] 110.5* *measured at RT started polymerisation.

(12) The test bodies show low transparency since the PMMA beads are still visible. The processing time is clearly too short. Even though high-impact properties may be achieved, but the inappropriate mixing of the beads results in an unfavourable temperature profile in which the polymerisation temperatures increases to high, and thus results in losses in processing and transparency.

Example 3

(13) Test bodies are produced analogously to Example 1 in accordance with the composition indicated in the table.

(14) TABLE-US-00005 % by weight Liquid MMA 88.43 aliquat 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5- 0.15 ((hexyl)oxy)-phenol copper(ll) chloride solution 0.07 UV stabilisers 0.25 N,N-bis(2(hydroxyethyl)-p-toluidine 0.1 n-butyl acryloxyethyl carbamate 20 di-functional, aliphatic urethane acrylate oligomer 3 tris-(2-hydroxyethyl) isocyanurate triacrylate 1 styrene-butyl acrylate core-shell particles 2 tot. 100 Powder bead 1 d.sub.50: 35 μm 67.56 bead 2 d.sub.50: 45 μm 15 bead 3 d.sub.50 60 μm 15 barbituric acid 2.44

(15) The following measured values were determined:

(16) TABLE-US-00006 mechanics 10:7 - flexural strenght [Mpa] 61.0 mechanics 10:7 I - E-modulus [Mpa] 2159 mechanics 10:7 - fracture toughness as maximum factor of 1.92 the stress intensity Kmax [Mpa m.sup.1/2] mechanics 10:7 I - fracture toughness as total fracture 653.8 work Wf [J/m.sup.2] maximum temperature 10:7 [° C.] 66.7° C.* *measured at RT started polymerisation.

(17) The samples contain a residual MMA content of 0.9% by weight. However, the high-impact properties are not achieved according to norm mentioned above due to non-ideal conditions in the monomer matrix and bead mixture.

Example 4

(18) The powdered component as well as the liquid component were mixed at the ratio of 10:7 to give the following composition:

(19) TABLE-US-00007 (Ratio 10:7) % by weight MMA approx. 34 aliquat 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5- <1 ((hexyl)oxy)-phenol copper(II) chloride solution <1 UV stabilisers <1 N,N-bis(2(hydroxyethyl)-p-toluidine <1 n-butyl acryloxyethyl carbamate 4.2 di-functional, aliphatic urethane acrylate oligomer <2 tris-(2-hydroxyethyl) isocyanurate triacrylate <1 styrene-butyl acrylate core-shell particles <1 bead 1 d50: 35 μm approx. 46 bead 2 d50: 45 μm 3 bead 3 d50 60 μm 9 barbituric acid <2 to 100% by weight

Example 5

(20) The powdered component as well as the liquid component were mixed in the following at the ratio of 10:5 to give the following composition:

(21) TABLE-US-00008 (Ratio 10:5) % by weight MMA approx. 28 aliquat 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5- 0.5 ((hexyl)oxy)-phenol copper(II) chloride solution <1 UV stabilisers <1 N,N-bis(2(hydroxyethyl)-p-toluidine <1 n-butyl acryloxyethyl carbamate 3.3 di-functional, aliphatic urethane acrylate oligomer <1 tris-(2-hydroxyethyl) isocyanurate triacrylate <1 styrene-butyl acrylate core-shell particles <1 bead 1 d.sub.50: 35 μm 52 bead 2 d.sub.50: 45 μm 3.3 bead 3 d.sub.50 60 μm 10 barbituric acid 1.6 to 100% by weight

(22) The polymerised prosthetic material has a total fracture work of 1126.89 J/m.sup.2 and a maximum factor of the stress intensity of 2.53 MPa m.sup.1/2. The E-modulus amounts to 2273 kJ/mol. In order to generate prostheses with optimum fit, the paste mixed at the ratio powder to liquid of 10:5 is injected (into a plaster mould) by means of the injection device Palajet. High-impact values are achieved even with this application method.

(23) The prosthetic materials produced from the monomer mixture according to the invention show a significantly improved fracture toughness over all comparative examples, an increased transparency as well as the least residual monomer content of MMA.

(24) Colour Test Bodies:

(25) The following powder mixtures and monomer mixtures at a ratio of 10 g powder to:7 ml liquid are being vigorously mixed and test bodies with dimensions of 30×30×3 mm are being cast into a metal mould after the swelling phase (approx. 5 min at 23° C.) and being polymerised in Palamat elite for 30 min at 55° C. and 2 bar pressure. The transparency measurements were performed with colorimeter FS600 Datacolor.

(26) Test Bodies for Mechanical Strength:

(27) The following powder mixtures and monomer mixtures at a ratio of 10 g powder to:7 ml liquid are being vigorously mixed and test bodies with dimensions of 100×100×5 mm are being cast after the swelling phase (approx. 5 min at 23° C.) and being polymerised in Palamat elite for 30 min at 55° C. and 2 bar pressure. Subsequently, the test plates are being sawed to the geometry stated in ISO 20795-1 and are being polished. Test bodies for mechanical and colorimetric tests are produced in steel moulds.