HYBRID RESIN COMPOSITION FOR THE 3D-PRINTING OF OBJECTS

Abstract

A hybrid resin composition for the 3D-printing of objects, including at least one monofunctional, light-curable component A functioning as a reactive diluent (RD), at least one mono- or multifunctional, light-curable component B functioning as a toughness modifier (TNM), and at least one mono- or multifunctional, heat curable component C functioning as a T.sub.g-enhancer (TGE).

Claims

1-29. (canceled)

30. A hybrid resin composition for the 3D-printing of objects, comprising components A, B and C, wherein, a) component A is at least one monofunctional, light-curable component having the formula (I) comprising a reactive species Y that is susceptible of radical polymerization and a side group X, said component A upon light-induced curing forming a polymer backbone, said backbone preferably having a T.sub.g>25? C.,
XYFormula (I) b) component B is at least one mono- or multifunctional, light-curable component, which copolymerizes with component A, having a molecular weight of >500 g mol.sup.?1, said component B upon light-induced curing preferably forming a polymerized network with an elongation at break >10% and a T.sub.g>0? C., c) component C is at least one mono- or multifunctional, heat-curable component forming a second polymerized network with a T.sub.g>100? C., wherein the amount of the light-curable component A ranges from 5 wt % to 80 wt %, the amount of the light-curable component B ranges from 10 wt % to 90 wt %, and the amount of the heat-curable component C ranges from 1 wt % to 50 wt %, based on the total weight of components A, B and C; and wherein the component C comprises one or more compound(s) selected from the group consisting of allyl, vinyl, maleimide, citraconimide, benzoxazine, epoxy, phenol, cyanate ester, phthalonitrile and oligomers or polymers thereof and/or isomers thereof and/or combinations thereof, in particular one or more chemical species chosen from the group consisting of monomers and/or oligomers and/or prepolymers of maleimide and citraconimide derivatives according to formula (II), ##STR00006## as well as isomers thereof, wherein n is an integer between 1 and 10 RI.sub.1 represents H, CH.sub.3 or CH.sub.2, R.sub.2 independently represents a linear, branched or cy-clic C.sub.5-C.sub.40 aliphatic or aromatic residue of one or more of the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, 2-ethylhexyl, octyl, decanyl, dodecanyl, acetic, propanoic, butanoic, pentanoic, undecanoic, dodecanoic, benzoic acid and corresponding esters, alkyl or aromatic esters, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-isobutylcyclohexyl, cycloheptyl, cyclooctyl, adamantyl, isobornyl, salicyl, cholesteryl, phenyl, benzyl, phenethyl, propenyl, biphenyl, naphthyl, anthracenyl, pyrenyl, bis(methylene)oxy, bis(ethylene)oxy, bis(phenyl)methane, bis(phenyl)ethane, bis(phenyl)propane, bis(phenyl)butane, bis(phenyl)ether, bis(phenyl)thioether, bis(phenyl)amino and bis(phenyl)sulfone, where one or more of these groups are optionally, individually linked via an ester, amide, urea, urethane, carbonate, ether, thioether group, which are optionally substituted with one or more C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 thioether, halogen, NO.sub.2, SO.sub.3H, CF.sub.3, OH, NH.sub.2, SH, CN, -trimethoxysilyl, -triethoxysilyl or a polymerisable group from the substance classes of maleimide and citraconimide compounds and/or isomers thereof.

31. The hybrid resin composition according to claim 30, wherein: the amount of light-curable component A ranges from 5 wt % to 80 wt %, based on the total weight of components A, B and C; the amount of the light-curable component B ranges from 10 wt % to 90 wt %, based on the total weight of components A, B and C; and the amount of the heat-curable component C ranges from 1 wt % to 50 wt %, based on the total weight of components A, B and C.

32. The hybrid resin composition according to claim 30, wherein: component B is partly substituted by a crosslinking component D, which is at least one light-curable crosslinking agent (CA) that copolymerizes with components A and B; and the amount of the crosslinking component D ranges from 3 wt % to 70 wt % based on the total weight of components B and D within the resin composition.

33. The hybrid resin composition according to claim 30, wherein component A comprises one or more compound(s) selected from the group consisting of monofunctional (meth)acrylates, (meth)acrylamides, vinyl ester and N-vinyl compounds, in particular one or more compound(s) selected from the group consisting of isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, trimethyl-cyclohexyl (meth)acrylate, glycerol formal (meth)acrylate, tricyclodecane methanol mono(meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, salicylate (meth)acrylates such as 2-(methacryloyloxy)benzoic acid cyclopentyl ester, 2-(methacryloyloxy)benzoic acid cyclohexyl ester, 2-(methacryloyloxy)benzoic acid-2-isopropyl-5-methylcyclohexyl ester, 3-(methacryloyloxy)benzoic acid-2-isopropyl-5-methylcyclohexyl ester, 4-(methacryloyloxy)benzoic acid-2-isopropyl-5-methylcyclohexyl ester, 2-(methacryloyloxy)benzoic acid-3,3,5-trimethylcyclohexyl ester, 2-(acryloyloxy)benzoic acid-3,3,5-trimethylcyclohexyl ester, 2-(methacryloyloxy)benzoic acid decahydronaphthalen-2-yl ester, 2-(methacryloyloxy)benzoic acid-1,3,3-trimethyl-2-bicyclo[2.2.1]heptanyl ester, 2-(methacryloyloxy)benzoic acid-1,7,7-trimethyl-2-bicyclo[2.2.1]heptanyl ester, 2-(methacryloyloxy)benzoic acid-bicyclo[2.2.1]heptan-2-yl methyl ester, 2-(methacryloyloxy)benzoic acid-2-cyclohexylethyl ester, 2-(methacryloyloxy)benzoic acid benzyl ester, 4-(methacryloyloxy)benzoic acid benzoate, 3-(methacryloyloxy)benzoic acid-4-isopropylbenzyl ester, 2-(acryloyloxy)benzoic acid benzyl ester, 2-(methacryloyloxy)benzoic acid phenethyl ester, 4-(methacryloyloxy)-3-methoxybenzoic acid-3-methoxybenzyl ester, 2-(methacryloyloxy)benzoic acid-1-phenylethyl ester, 4-((methacryloyloxy)methyl)benzoic acid cycloheptyl ester and 2-(methacryloyloxy)benzoic acid cyclohexyl methyl ester, cholesteryl (meth)acrylate, biphenyl (meth)acrylate, phenyl acrylamide, diacetone acrylamide, t-butyl acrylamide, N-acryloyl morpholine, N-vinyl pyrrolidone, N-vinyl caprolactam, N-vinyl formamide, vinyl cinnamate, vinyl methyl oxazolidinone, and 2-(allyloxymethyl)acrylic acid methyl ester.

34. The hybrid resin composition according to claim 30, wherein component B comprises multifunctional (meth)acrylates, in particular one or more compound(s) selected from the group consisting of ethoxylated bisphenol A di(meth)acrylates, aliphatic urethane di(meth)acrylates, polyether urethane (meth)acrylates, hydrophobic urethane (meth)acrylates, polyester urethane (meth)acrylates, polyester di(meth)acrylates, modified epoxy di(meth)acrylates, and oligomeric polycarbonate di(meth)acrylates.

35. The hybrid resin composition according to claim 30, wherein component C comprises multifunctional allyl compounds comprising rigid substituents responsible for the formation of polymer backbones or polymer networks providing the required high T.sub.g, such as aromatic and/or cycloaliphatic and/or heterocyclic groups and/or groups exhibiting strong intermolecular forces and/or a high functionality (>2) with respect to reactive groups, in particular one or more compound(s) selected from the group consisting of 1,3,5-triallyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,4,6-triallyloxy-1,3,5-triazine, triallyl borate, triallyl 1,3,5-benzenetricarboxylate, triallyl citrate, triallyl phosphate, tetraallyl pyromellitate, tetraallyloxyethane, diallyl propyl isocyanurate, diallyl isocyanurate, diallyl phthalate, 2,2-bis(4-allyloxy-3,5-dibromophenyl)propane, diallyl dicarbonate, diallyl carbonate, diallyl 1,4-cyclohexanedicarboxylate, 2,2-diallyl bisphenol A diacetate ether, diallyl terephthalate, diallyl isophthalate, diethyl diallylmalonate, 1,3-diallylurea, 1,3-diallyl-2-thiourea, 2,4-diamino-6-diallylamino-1,3,5-triazine, diallyl oxalate, diallyl malonate, diallyl tetrabromophthalate, 2,6-dially-meta-cresol, N,N-diallylaniline, diallyl cyanamide, N,N-diallylmelamine, 2,2-diallylbisphenol A, N,N-diallylpiperazine, 2,2-diallylpyrrolidine, diallyl-carbamic acid tert-butyl ester, diallyl ether bisphenol A, diallyl phenylphosphonate, 5,5-diallyl-[1,1-biphenyl]-2,2-diol, cyclohexanone diallyl acetal, 4,4-diallyl-1,1-biphenyl, and 2,2-diallyl-4,4-biphenol.

36. The hybrid resin composition according to claim 30, wherein component C comprises multifunctional epoxy compounds comprising rigid substituents responsible for the formation of polymer backbones or polymer networks providing the required high T.sub.g, such as aromatic and/or cycloaliphatic and/or heterocyclic groups, and/or groups exhibiting strong intermolecular forces and/or a high functionality (>2) with respect to reactive groups, in particular one or more compound(s) selected from the group consisting of bisphenol A, bisphenol F and bisphenol S derivatives such as bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether and diglycidyl 1,2-cyclohexanedicarboxylate, 4,4-methylenebis(N,N-diglycidylaniline), trimethylolpropane triglycidyl ether, (3,4-epoxycyclohexane)methyl-3,4-epoxycyclohexylcarboxylate, condensation products of 1-2-epoxy-4(2-oxiranyl)-cyclohexane and 2,2-bis(hydroxy methyl)1-butanol, bisphenol A novolac epoxy resins and oligomers and prepolymers of these derivatives.

37. The hybrid resin composition according to claim 32, wherein component D comprises one of: i) multifunctional (meth)acrylates and/or a mixture of multifunctional (meth)acrylates; ii) aromatic or cycloaliphatic groups; and iii) tri-, tetra-, penta- and/or hexafunctional (meth)acrylates and/or hyperbranched and/or dendritic (meth)acrylates having even more functional sites.

38. The hybrid resin composition according to claim 32, wherein component D comprises one or more compounds selected from the group consisting of: i) 1,4-butanedioldi(meth)acrylate, 1,6-hexanedioldi(meth)acrylate, 1,10-decanedioldi(meth)acrylate and 1,12-dodecanedioldi-(meth)acrylate, tri- or tetraethylenglycol-di(meth)acrylate, pentaerythrittetra(meth)acrylate, and trimethylolpropantri(meth)acrylate, or ii) 2-(2-biphenyloxy)-ethyl(meth)acrylate, bisphenol-A-di(meth)acrylate (an addition product from (meth)acrylic acid and bisphenol-A-diglycidylether), ethoxy- or propoxylated bisphenol-A-di(meth)acrylate (e.g., 2-[4-(2-(meth)acryloyloxyethoxyethoxy)phenyl]-2-[4-(2-(meth)acryloyloxyethoxy)phenyl]-propane), 2,2-bis[4-(2-(meth)acryloxypropoxy)phenyl]propane, tricyclodecanedimethanol di(meth)acrylate, isophorone urethane di(meth)acrylate, and tris(2-hydroxy ethyl)isocyanurate tri(meth)acrylate.

39. The hybrid resin composition according to claim 30, wherein the hybrid resin formulation further comprises at least one of a comonomer, cooligomer, and coprepolymer, which is able to copolymerize with component C as well as with derivatives thereof.

40. The hybrid resin composition according to claim 30, wherein the resin composition comprises at least one photoinitiator suitable for radical polymerization upon light excitation.

41. The hybrid resin composition according to claim 30, wherein the resin composition comprises at least one thermal initiator and/or catalyst for the thermal curing of component C.

42. The hybrid resin composition according to claim 30, wherein the resin composition comprises one or more initiators for radical polymerization.

43. The hybrid resin composition according to claim 30, wherein the composition comprises toughness modifiers, said toughness modifiers preferably being terminated or functionalized with one or multiple reactive groups susceptible of radical or ionic polymerization.

44. The hybrid resin composition according to claim 30, wherein the resin composition comprises at least one or multiple components chosen from the groups of polymerization initiators, polymerization inhibitors, solvents, fillers, antioxidants, pigments, dyes, surface modifiers, core-shell particles and/or mixtures thereof.

45. The hybrid resin composition according to claim 40, wherein photoinitiators, thermal initiators, catalysts, curing agents, polymerization initiators, polymerization inhibitors, solvents, fillers, antioxidants, pigments, dyes, surface modifiers, core-shell particles and/or mixtures thereof are of polymeric nature and/or additionally functionalized with a polymerizable functional group, which can undergo polymerization either with components A, B and D and/or component C.

46. The hybrid resin composition according to claim 30, wherein the resin composition at room temperature has a viscosity >2 Pa s, preferably >10 Pa s.

47. The hybrid resin composition according to claim 30, wherein the resin composition further comprises mineral flame retardants, in particular aluminum hydroxide, magnesium hydroxide, calcium hydroxide, antimony oxide, tin oxide, borax and/or zinc borate, red phosphorous, expanded graphite and/or organic additives such as nitrogen donors and/or phosphorous containing substances, preferably ammonium polyphosphate, melamine polyphosphate, organic phosphates, triphenyl phosphine, phosphinates, 9,10-dihydro-9-oxa-10-phosphaphenanthren-10-oxide, halogenated organic flame retardants such as halogenated phosphates, halogenated diphenylether, halogenated styrene, halogenated epoxides, halogenated (meth)acrylates and/or halogenated paraffins, preferably in amounts of 0.5 wt % to 50 wt %, preferably 1 wt % to 30 wt %, more preferably 2 wt % to 25 wt % based on the total weight of components A, B, C and D, wherein preferably the organic additives are functionalized with a polymerizable group, in particular (meth)acrylate.

48. A method of manufacturing an object by 3D-printing, wherein a resin composition according to claim 30 is subjected to a light-induced structuring step, and followed by a heat-induced curing step.

49. The method according to claim 48, wherein the light-induced structuring step is carried out at a processing temperature of the resin composition of between 30? C. and 150? C.

50. The method according to claim 48, wherein the light-induced structuring step is carried out utilizing an NIR- or UV/Vis light source and corresponding optics, wherein the NIR-configuration is selected to enable 3D-fabrication via two photon photopolymerization, and the UV/Vis configuration is selected from the group consisting of laser/DLP, LED/DLP, laser/LCD, and LED/LCD.

51. The method according to claim 48, wherein the light-induced structuring step comprises building the object on a construction platform layer-by-layer to obtain a stack of structured layers, wherein each structured layer is obtained by the steps of: forming an unstructured layer of predetermined thickness of the resin composition, and selectively projecting light onto the unstructured layer according to a desired pattern, thereby curing the resin composition to obtain the structured layer.

52. The method according to claim 51, wherein the unstructured layer of the resin composition has a viscosity at said processing temperature of 0.01 to 70 Pa s.

53. The method according to claim 48, wherein the heat-induced curing step is performed at a temperature that is higher than the processing temperature of the light-induced structuring step.

54. The method according to claim 48, wherein the heat-induced curing step comprises at least one of: heating the object in an oven; subjecting the object to electromagnetic radiation; and inducing secondary exothermic reactions.

55. An object manufactured from a resin composition by a method according to claim 48.

56. The object according to claim 55, wherein the object comprises an interpenetrating polymer network.

57. The object according to claim 55, wherein the object exhibits: i) a tensile modulus of 800 MPa or more, a tensile strength of 25 MPa or more, an elongation at break of 20% or more, a glass transition temperature of 45? C. or more and a temperature value at 1 GPa storage modulus of 30? C. or more; or ii) a tensile modulus of 1500 MPa or more, a tensile strength of 35 MPa or more, an elongation at break of 5% or more, a glass transition temperature of 90? C. or more and a temperature value at 1 GPa storage modulus of 45? C. or more; or iii) a tensile modulus of 2000 MPa or more, a tensile strength of 50 MPa or more, an elongation at break of 5% or more, a glass transition temperature of 100? C. or more and a temperature value at 1 GPa storage modulus of 60? C. or more; or iv) a tensile modulus of 1300 MPa or more, a tensile strength of 35 MPa or more, an elongation at break of 20% or more, and a heat deflection temperature of 70? C. or more; or v) a tensile modulus of 2000 MPa or more, a tensile strength of 55 MPa or more, an elongation at break of 10% or more, and a heat deflection temperature of 85? C. or more.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0222] FIG. 1 shows a schematic configuration of a high temperature additive manufacturing device used for light-curing the curable compositions according to the present invention by means of a 3D printing process,

[0223] FIG. 2 represents a schematic example for the network formation via a first light-curing step with components A (RD) and B (TNM) and subsequent heat-curing step with component C (TGE),

[0224] FIG. 3 represents a schematic example for the network formation via a first light curing-step with components A (RD), B (TNM) and D (CA) and subsequent heat-curing step with component C (TGE),

[0225] FIG. 4 shows the data retrieved from the photorheology experiments (light-curing step) with comparative example resin CE3 and heat-curable components C (TGEs being TAIC and DAP),

[0226] FIG. 5 shows the data retrieved from the thermal rheology experiments (mimicking the heat-curing step) with components C (TGEs being TAIC, DAP, OBCI, BMIDPM and BADGE),

[0227] FIG. 6a shows the data retrieved from the DMA of the printed (light-curing step) and post-cured (heat-curing step) photopolymer E1 in comparison to CE1 and CE3 (storage modulus plot - top, tand plot - bottom),

[0228] FIG. 6b shows the (thermo)mechanical performance of the printed (light-curing step) and post-cured (heat-curing step) photopolymer E1 in comparison to CE3 and compares CE1 and CE3 with respect to their percentage deviations,

[0229] FIG. 6c shows the data retrieved from the DMA of the printed (light-curing step) and post-cured (heat-curing step) photopolymers E2 and E3 in comparison to CE2 and CE3 (storage modulus plottop, tand plotbottom),

[0230] FIG. 6d shows the (thermo)mechanical performance of the printed (light-curing step) and post-cured (heat-curing step) photopolymer E2 in comparison to CE2 and CE3 and compares CE2 and CE3 with respect to their percentage deviations,

[0231] FIG. 7a shows the data retrieved from the DMA of the printed (light-curing step) and post-cured (heat-curing step) photopolymer E4 in comparison to CE4 (storage modulus plottop, tand plotbottom),

[0232] FIG. 7b shows the data retrieved from the DMA of the printed (light-curing step) and post-cured (heat-curing step) photopolymer E5 in comparison to CE5 (storage modulus plottop, tand plotbottom),

[0233] FIG. 8a shows the data retrieved from the DMA of the printed (light-curing step) and post-cured (heat-curing step) photopolymer E6.1 in comparison to CE6.1 and CE6.3 (storage modulus plottop, tand plotbottom),

[0234] FIG. 8b shows the (thermo)mechanical performance of the printed (light-curing step) and post-cured (heat-curing step) photopolymer E6.1 in comparison to CE6.1 and CE6.3 and compares CE6.1 and CE6.3 with respect to their percentage deviations,

[0235] FIG. 8c shows the data retrieved from the DMA of the printed (light-curing step) and post-cured (heat-curing step) photopolymers E6.2 and E6.3 in comparison to CE6.2 and CE6.3 (storage modulus plottop, tand plotbottom),

[0236] FIG. 8d shows the (thermo)mechanical performance of the printed (light-curing step) and post-cured (heat-curing step) photopolymer E6.2 in comparison to CE6.2 and CE6.3 and compares CE6.2 and CE6.3 with respect to their percentage deviations,

[0237] FIG. 8e shows the (thermo)mechanical performance of the printed (light-curing step) and post-cured (heat-curing step) photopolymer E6.3 in comparison to CE6.2 and CE6.3 and compares CE6.2 and CE6.3 with respect to their percentage deviations.

DETAILED DESCRIPTION

[0238] In FIG. 1, reference numeral 1 denotes a material support, on which a material layer 11 is arranged. Spaced from the material support 1, a construction platform 8 is arranged, which is height-adjustable in the z direction and is tiltably mounted about the axis 4. Between the build platform 8 and the material support 1, some material layers 11 are already constructed. The material support 1 is translationally movable along the x-direction perpendicular to the z-direction.

[0239] Furthermore, a material introduction device 3 is provided which comprises a first recoater blade 5 and a second re-coater blade 6. The first recoater blade 5 is height adjustable by means of a recoater motor 10 in the z direction and the second recoater blade 6 has a spring 7 which holds the second recoater blade 6 in abutment with the material support 1 in the z direction. Between the two recoater blades 5 and 6 a material reservoir 2 is formed, which can be supplied by means of a conveyor 9 with the inventive resin composition.

[0240] In the phase of the method shown in FIG. 1, the material support 1 is in the second position. The construction platform 8 is lowered in the direction of the material support 1, so that a new material layer 11 of the inventive resin composition can be formed by the material layer 11 and is irradiated selectively on the material support 1 by means of a radiation source, not shown, from below through the material support 1 and thereby structured and solidified. The material layer 11 was applied during the movement of the material support 1 in the second position by the first recoater blade 5.