RADIATION-CURABLE COMPOSITION FOR USE IN RAPID PROTOTYPING OR RAPID MANUFACTURING METHODS

Abstract

A polymerisable radiation-curable composition comprising: (i) monomers, comprising at least (a) a first monomer having a TG (glass-transition point) of the homopolymer of said first monomer? 120? C. and at least (b) a second monomer having a TG (glass-transition point) of the homopolymer of the second monomer? 100? C., wherein at least one of the at least one first monomer or of the at least one second monomer has an alicyclic group, and comprising (ii) at least one further component, comprising at least one photo-initiator for the UV and/or Vis spectral region or a photo-initiator system for the UV and/or Vis spectral region. Also disclosed is a blank in the form of a three-dimensional moulded body of a polymerised composition, in particular a radiation-cured composition, for producing 3D moulded bodies, dental prosthetic parts, orthopaedic appliances or dental pre-forms in a rapid prototyping, rapid manufacturing, or rapid tooling method.

Claims

1. Polymerisable radiation-curable composition comprising (i) monomers and (ii) at least one further component, wherein (i) the monomers comprise at least (a) one first monomer having a TG (glass-transition point) of the homopolymer of said first monomer of greater than or equal to 120? C. comprising di-functional acrylates having a bivalent alicyclic group and/or di-functional methacrylates having a bivalent alicyclic group and at least one di-functional urethane (meth)acrylate selected from di-functional urethane (meth)acrylates having a bivalent alkylene group and at least one di-functional urethane (meth)acrylate selected from di-functional urethane (meth)acrylates having a bivalent alkylene group, and at least (b) one second monomer having a TG (glass-transition point) of the homopolymer of the second monomer of less than or equal to 100? C. comprising at least one mono-functional acrylate having an alicyclic group and/or mono-functional methacrylate having an alicyclic group, and (ii) the at least one further component comprises at least one photo-initiator for the UV and/or Vis spectral region or a photo-initiator system for the UV and/or Vis spectral region, wherein the viscosity of the composition at approx. 20? C. to 23? C. is less than or equal to 3000 m.Math.Pas.

2. Composition according to claim 1, wherein the viscosity of the composition at approx. 20? C. to 23? C. is from 500 to less than 2500 m.Math.Pas.

3. Composition according to claim 1, wherein (i) the monomers comprise (a) at least one first monomer or a mixture of first monomers having a TG (glass-transition point) of the homopolymer of the respective first monomer of greater than or equal to 120? C., wherein the first monomer or the mixture of first monomers comprises di-functional acrylates having a bivalent alicyclic group and/or di-functional methacrylates having a bivalent alicyclic group and selected from tricyclodecane dimethanol diacrylate, tricyclodecane dimethanol dimethacrylate, tricyclodecane diethanol diacrylate, tricyclodecane diethanol dimethacrylate and/or mixtures thereof, or a mixture thereof, and (b) at least one second monomer or a mixture of second monomers each having a TG (glass-transition point) of the homopolymer of the respective second monomer of less than or equal to 100? C., wherein the second monomer or the mixture of second monomers comprises at least one mono-functional acrylate having an alicyclic group and/or mono-functional methacrylate having an alicyclic group and selected from (octahydro-4,7-methano-1H-indenyl) methanol acrylate, (octahydro-4,7-methano-1H-indenyl) methanol methacrylate, (octahydro-4,7-methano-1H-indenyl) ethanol acrylate and (octahydro-4,7-methano-1H-indenyl) ethanol methacrylate.

4. Composition according to claim 3, wherein (i) in the composition are present 15 to 25% by weight of at least one mono-functional acrylate having an alicyclic group and/or mono-functional methacrylate having an alicyclic group and selected from (octahydro-4,7-methano-1H-indenyl) methanol acrylate, (octahydro-4,7-methano-1H-indenyl) methanol methacrylate, (octahydro-4,7-methano-1H-indenyl) ethanol acrylate and (octahydro-4,7-methano-1H-indenyl) ethanol methacrylate, and optionally 5 to 15% by weight of di-functional acrylates having a bivalent alicyclic group and/or di-functional methacrylates having a bivalent alicyclic group and selected from tricyclodecane dimethanol diacrylate, tricyclodecane dimethanol dimethacrylate, tricyclodecane diethanol diacrylate, tricyclodecane diethanol dimethacrylate and/or mixtures thereof, wherein the total composition amounts to 100% by weight, or (ii) 5 to 15% by weight of di-functional acrylates having a bivalent alicyclic group and/or di-functional methacrylates having a bivalent alicyclic group and selected from tricyclodecane dimethanol diacrylate, tricyclodecane dimethanol dimethacrylate, tricyclodecane diethanol diacrylate, tricyclodecane diethanol dimethacrylate and/or mixtures thereof, and 15 to 25% by weight mono-functional acrylic ester being based on a tricyclodecane alkanol, with alkanol comprising 1 to 6 C-atoms, optionally in (ii) with no presence of triacrylate derived from 1,3,5-tris(hydroxyalkyl) isocyanurate, wherein the total composition amounts to 100% by weight, or (iii) 15 to 45% by weight of a mixture comprising at least one mono-functional acrylate having an alicyclic group and/or mono-functional methacrylate having an alicyclic group and selected from (octahydro-4,7-methano-1H-indenyl) methanol acrylate, (octahydro-4,7-methano-1H-indenyl) methanol methacrylate, (octahydro-4,7-methano-1H-indenyl) ethanol acrylate and (octahydro-4,7-methano-1H-indenyl) ethanol methacrylate, and at least one di-functional acrylate having a bivalent alicyclic group and/or di-functional methacrylates having a bivalent alicyclic group and selected from tricyclodecane dimethanol diacrylate, tricyclodecanedimethanoldimethacrylate, tricyclodecane diethanol diacrylate, tricyclodecane diethanol dimethacrylate and/or mixtures thereof, optionally in (iii) with no presence of triacrylate derived from 1,3,5-tris(hydroxyalkyl) isocyanurate, wherein the total composition amounts to 100% by weight.

5. Composition according to claim 1, wherein the di-functional acrylates having a bivalent alicyclic group and/or di-functional methacrylates having a bivalent alicyclic group are selected from tricyclodecane dimethanol diacrylate, tricyclodecane dimethanol dimethacrylate, tricyclodecane diethanol diacrylate, tricyclodecane diethanol dimethacrylate and/or mixtures thereof.

6. Composition according to claim 3, wherein (i) the first monomer comprises (f.1) at least one mono-, tri-, tetra- or multi-functional monomer, optionally not being a urethane (meth)acrylate.

7. Composition according to claim 6, wherein the first monomer comprises acrylic esters and/or methacrylic esters of polyethers selected from di-methacrylic esters of polyethers, tri-, tetra- or multi-functional methacrylic esters of polyethers, di-acrylic esters of polyethers, and tri-, tetra- and/or multi-functional acrylic esters of polyethers.

8. Composition according to claim 1, wherein (i) the second monomer comprises (c) at least one mono-functional acrylate having an alicyclic group and/or mono-functional methacrylate having an alicyclic group, selected from (octahydro-4,7-methano-1H-indenyl) methanol acrylate, (ctahydro-4,7-methano-1H-indenyl) methanol methacrylate, (octahydro-4,7-methano-1H-indenyl) ethanol acrylate, and (octahydro-4,7-methano-1H-indenyl) ethanol methacrylate.

9. Composition according to claim 1, wherein the (i) monomers and the (ii) at least one further component are present in the composition according to the following formula, $1/\mathrm{TG}\left(\mathrm{total}\right)=w1/{\mathrm{TG}}_{\left(1\right)}+w2/{\mathrm{TG}}_{\left(2\right)}+w3/{\mathrm{TG}}_{\left(3\right)}+\mathrm{optionally}w4/{\mathrm{TG}}_{\left(4\right)}+\mathrm{optionally}w5/{\mathrm{TG}}_{\left(5\right)}+\mathrm{optionally}\mathrm{wn}/{\mathrm{TG}}_{\left(n\right)},$ with w1, w2, w3, w4, w5 and wn each weight proportion of the monomer in the total mixture of the first and second monomers and optionally third monomers of 100% by weight, with n=6 to 50, wherein TG is greater than or equal to 100? C., and the viscosity of the composition at approx. 20?? C. to 23? C. is less than or equal to 3000 m.Math.Pas, optionally from 500 to less than 2500 m.Math.Pas.

10. Composition according to claim 1, wherein the viscosity is suitable for use of the composition in generative radiation-curing methods.

11. Composition according to claim 1, wherein (d) at least one disubstituted 4,4-di(oxabenzol) dialkyl methane of formula I is present in the composition as a monomer, optionally as at least one third monomer, ##STR00002## wherein R.sup.1, R.sup.2, R.sup.5 and R.sup.6 each independently are selected from H or C1- to C4-alkyl, and R.sup.3 and R.sup.4 each independently are bivalent C1- to C4-alkylene, with n=0 to 6 and m=0 to 6.

12. Composition according to claim 11, wherein the disubstituted 4,4-di(oxabenzol) dialkyl methane of formula I is a first or a third monomer depending on the substitution pattern, wherein it is a first or a third monomer, depending on the selection of residues R.sup.1 to R.sup.6 and indices n and m, if the TG is greater than or equal to 120? C., or it is a first monomer if the TG is greater than or equal to 100? C. and optionally less than 120? C.

13. Composition according to claim 12, wherein the disubstituted 4,4-di(oxabenzol) dialkyl methane of formula I is a third monomer and the composition is free of monomers of formula I with n and m greater than or equal to 4 or contains them from 0 to less than or equal to 7.5% by weight, based on the total composition.

14. Polymerised composition according to claim 1, wherein the (i) monomers are present in the composition according to the following formula, $1/\mathrm{TG}\left(\mathrm{total}\right)=w1/{\mathrm{TG}}_{\left(1\right)}+w2/{\mathrm{TG}}_{\left(2\right)}+w3/{\mathrm{TG}}_{\left(3\right)}+\mathrm{optionally}w4/{\mathrm{TG}}_{\left(4\right)}+\mathrm{optionally}w5/{\mathrm{TG}}_{\left(5\right)}+\mathrm{optionally}\mathrm{wn}/{\mathrm{TG}}_{\left(n\right)},$ with w1, w2, w3, w4, w5 and wn each weight proportion of the monomer in the total mixture of the first and second monomers and optionally of the third monomer of 100% by weight, with n=6 to 50, wherein TG is greater than or equal to 100? C., and the polymerised composition has a flexural strength of greater than or equal to 40 MPa (following DIN EN ISO 20795-2), optionally measured in water at 55? C., and/or b) an E-modulus of greater than or equal to 800 MPa (following DIN EN ISO 20795-2), optionally measured in water at 55? C.

15. Polymerised composition according to claim 14, wherein the polymerised composition has, alternatively or cumulatively, i) a) a flexural strength of greater than or equal to 75 MPa (following DIN EN ISO 20795-2), and/or b) an E-modulus of greater than or equal to 2000 MPa (following DIN EN ISO 20795-2), and/or ii) a) a flexural strength of greater than or equal to 70 MPa (following DIN EN ISO 20795-2), optionally measured in water at 37? C., and/or b) an E-modulus of greater than or equal to 2000 MPa (following DIN EN ISO 20795-2), optionally measured in water at 37? C., and/or iii) a) a flexural strength of greater than or equal to 50 MPa (following DIN EN ISO 20795-2), optionally measured in water at 45? C., and/or b) an E-modulus of greater than or equal to 1500 MPa (following DIN EN ISO 20795-2), optionally measured in water at 45? C., and/or iv) a) a flexural strength of greater than or equal to 40 MPa (following DIN EN ISO 20795-2), optionally measured in water at 55? C., and/or b) an E-modulus of greater than or equal to 900 MPa (following DIN EN ISO 20795-2), optionally measured in water at 55? C.

16. Blank in the form of a three-dimensional moulded body of a polymerised composition according to claim 14 adapted for producing dental prosthetic parts, orthopaedic appliances or dental pre-forms, wherein the blank has a.1) a flexural strength of greater than or equal to 75 MPa (following DIN EN ISO 20795-2), and/or b.1) an E-modulus of greater than or equal to 2000 MPa (following DIN EN ISO 20795-2), and optionally a.2) a flexural strength of greater than or equal to 50 MPa (following DIN EN ISO 20795-2), optionally measured in water at 45? C., and/or b.2) an E-modulus of greater than or equal to 1500 MPa (following DIN EN ISO 20795-2), optionally measured in water at 45? C.

17. Method for producing a dental product selected from anatomical models, anatomical table-top models, dental working models, dental full models, dental die models, anatomical or dental saw-cut models, situation models, counter-bite models, functional models, pre-models, repair models, precision models, anatomical models for replacement of a dental plaster model of a patient's dentition, aligners, dental splints, prosthetic pars, dental prosthetic parts, orthopaedic appliances, and dental pre-forms, said method comprising 3D-printing a composition according to claim 1 and polymerizing and curing the composition under radiation.

18. Method according to claim 17, wherein the dental prosthetic parts comprise prosthesis base or parts thereof, artificial teeth, dental arches having at least two to 16 artificial teeth being interdentally connected in an integral manner, crowns, provisional crowns, total prostheses, total crowns, splints for orthodontic corrections (similar to Invisalign), dental bridges, abutments, suprastructures, dental bars, inlays, onlays, orthopaedic appliances, occlusal splints, dental pre-forms of artificial teeth, surgical guides for implantology, mouthguards, and/or implants.

Description

EXEMPLARY EMBODIMENTS

[0117] General example of production: the initiators are pre-dissolved in (octahydro-4,7-methano-1H-indenyl) methyl acrylate or tricyclodecane dimethanol diacrylate. Subsequently, the other monomers are added and the mixture is homogenised. Pigment concentrates or pigments may be added. The composition is then preferably homogenised. The composition produced is processable with a 3D printer. It is to be noted that the light-sensitive initiators may react to an undesired polymerisation in connection with the ambient light (the composition is preferably transferred into the pressure bath under appropriate measures). Lighting is carried out at 385-405 nm and post-curing or post-tempering, respectively, is carried out e.g. with a laboratory light device HiLite Power 3D.

[0118] The mixture produced is used to print test specimens according to ISO 20795-2 (50 ?m) for the following tests on a 3D precision printer having the wavelength 405 nm (Cara Print 4.0). The test specimens were washed up with isopropanol after the printing process and subjected to a post-tempering process. The said was carried out by lighting on both sides in a laboratory light device HiLite Power 3D, 200 W (Kulzer GmbH) for 3 to 5 min respectively or as specified by the manufacturer. Properties of the mixture according to the invention for modelling materials, tested according to DIN EN ISO 20795-2 or following the norm, respectively:

TABLE-US-00001 TABLE 1 Comparative example TG Functional TG VG1 VG2 tris(2-hydroxyethyl) 3 270 17.7 isocyanurate triacrylate ethoxylated (2) bisphenol-A 2 115 30 30 dimethacrylate (octahydro-4,7-methano-1H- 1 35 17.7 indenyl) methylacrylate tricyclodecane dimethanol 2 185 10 10 diacrylate aliphatic urethane acrylate 2 148 amine-modified polyether 4 25 35 35 acrylate ethoxylated (4) bisphenol-A 2 60 6 6 diacrylate stabiliser/photo-initiator 0.5 bis 0.5 bis 2.0 2.00 Flexural strength in MPa 35.4 54.2 E-modulus in MPa 1081 1761 Bending fracture in MPa 0.67 0.47 m.sup.1/2 ? 1.1 Fracture work in J/m.sup.2 > 250 75.6 33.49

[0119] Comparative examples 1 and 2 show a high amount of quad crosslinkers alone does not guarantee for good mechanical properties, as the comparative examples do not exhibit acceptable mechanical properties even at ambient room temperature. Although the compositions of the comparative examples have a viscosity of good usability for 3D printing applications, however the requirements for the mechanical properties following ISO-20795 are not achieved.

TABLE-US-00002 TABLE 2a VG3 and Examples 1 and 2 Compositions VG3 1 2 tris(2-hydroxyethyl) isocyanurate triacrylate ethoxAated (2) bisphenol-A dimethacrylate 30 36 42.25 (octahydro-4,7-methano-1H-indenyl) 19.86 19.86 19.86 methyl acrylate tricyclodecane dimethanol diacrylate 10 10 10 carboxyacrylate* 28.25 6.25 ethoxylated (4) bisphenol-A diacrylate 11.25 UDMA 27.25 27.25 Calculated TG 79 107 111 *TG: 39? C.

TABLE-US-00003 TABLE 2b Flexural strength and E-modulus Test Compositions Storage Testing VG3 1 2 Storage dry dry Flexural strength in [MPa] 113.3 82 81.3 ISO/20795 E-modulus in [MPa] 2880 2494 2319 Storage dry in water Flexural strength in [MPa] 68.7 76.6 63.2 ISO/20795 (37? C.) E-modulus in [MPa] 2131 2012 1797 Storage dry in water Flexural strength in [MPa] 45.6 59.2 55.7 ISO/20795 (45? C.) E-modulus in [MPa] 1329 1624 1528 Storage dry in water Flexural strength in [MPa] 21.1 46.8 43.9 ISO/20795 (55? C.) E-modulus in [MPa] kein 1121 987

TABLE-US-00004 TABLE 3a Examples 3 to 6 Compositions 3 4 5 6 tris(2-hydroxyethyl) isocyanurate triacrylate 13.34 11 10 12 ethoxylated (2) bisphenol-A dimethacrylate 40 40 45 40 (octahydro-4,7-methano-1H-indenyl) methyl 13.34 11 10 12 acrylate tricyclodecane dimethanol diacrylate 13.34 11 10 12 Carboxyacrylate ethoxylated (4) bisphenol-A diacrylate UDMA 17.8 24.7 22.7 22 Calculated TG 137 135.5 133 130

TABLE-US-00005 TABLE 3b Examples 3 to 6 Mechanics following Storage Pr?fung ISO-20795 3 4 5 6 Storage dry dry Flexural strength 85.5 93 105.5 104.3 ISO/20795 in [MPa] E-modulus in 2592 2841 2883 2726 [MPa] Storage dry in water Flexural strength 72.2 87.5 88.1 84.5 ISO/20795 (37? C.) in [MPa] E-modulus in 2134 2447 2344 2264 [MPa] Storage dry in water Flexural strength 62.1 65.1 70.6 68.5 ISO/20795 (45? C.) in [MPa] E-modulus in 1799 1831 1958 1813 [MPa] Storage dry in water Flexural strength 45.8 58.2 54.8 51.1 ISO/20795 (55? C.) in [MPa] E-modulus in 1120 1428 1346 1194 [MPa]

TABLE-US-00006 TABLE 4a Thermostability of compositions according to the invention Thermostability Mechanics Beispiel 7 Beispiel 8 Beispiel 9 following Calculated TG Storage Testing ISO-20795 135 186 201 Storage dry Flexural strength 84.2 90.6 95.3 dry in [MPa] E-modulus in 2615 2785 2859 [MPa] Storage in water Flexural strength 81.2 71 79.4 dry (37? C.) in [MPa] E-modulus in 2185 2316 2412 [MPa] Storage in water Flexural strength 58.2 66.4 75.7 dry (45? C.) in [MPa] E-modulus in 1559 1889 1993 [MPa] Storage in water Flexural strength 44.9 59.3 60.2 dry (55? C.) in [MPa] E-modulus in 940 1485 1582 [MPa] Shrinkage [%] 5.5 6.41 6.76 according to Watts Viscosity 1390 1560 2224 [m .Math. Pas]

TABLE-US-00007 TABLE 4b Compositions according to the invention Example Example Example 7 8 9 135? C. 186? C. 201? C. Calculated Amount Amount Amount TG in % by in % by in % by Monomers TG weight weight weight aliphatic urethane 148 27.7 32.5 dimethacrylate ethoxylated (2) bisphenol-A 105 40 32.5 dimethacrylate tris(2-hydroxyethyl) 270 10 32.5 32.5 isocyanurate triacrylate (octahydro-4,7-methano- 35 10 1H-indenyl) methylacrylate tricyclodecane dimethanol 185 10 32.5 32.5 diacrylate