Hybrid resin composition for 3D printing of objects

Abstract

A hybrid resin composition for 3D printing of objects, comprising at least one monofunctional photocurable component A acting as a reactive diluent (RD), at least one monofunctional or multifunctional photocurable component B acting as a toughness modifier (TNM), and at least one t-butyl ether or t-butyl ether. g and C, at least one mono- or multi-functional thermosetting component that functions as a thermal gradient enhancer (TGE).

Description

[Technical field]

[0001] The present invention relates to a hybrid resin composition for 3D printing objects having improved toughness and improved thermal properties.Furthermore, the present invention relates to a method for producing objects by 3D printing with the hybrid resin composition of the present invention, and to objects produced from the resin composition of the present invention.

[0002] Introduction Lithography-based additive manufacturing technologies (L-AMT) are progressing from the sole prototyping part towards industrial use in parts production. Many new process solutions (e.g., hot lithography - EP 3284583 A1, CLIP - US 2015 / 0072293 A1, HARP - WO 2020 / 185692 A2) are driving the technology forward in terms of material flexibility and manufacturing capacity (e.g., by increasing speed or increasing material throughput), and these innovations are driving a broad range of new material technologies (e.g., UV-curable elastomers - DOI: 10.1002 / adma. 201606000, Tough Photopolymers - EP 3090722 A1, High Temperature Resistant Materials - EP 3632941 A1) are occurring at the same time, realizing end uses in very important areas of technology (e.g. dentistry, orthopedics, tissue engineering, regenerative medicine), mobility (e.g. aerospace, railway, automotive), electronics market, consumer goods (e.g. sports, jewellery, cosmetics, personal care products) that can exploit the potential of additive manufacturing (e.g. design freedom, manufacturing flexibility).

[0003] Photocurable materials (resins or formulations) for L-AMT are typically composed of reactive components (e.g., monomers, oligomers, and photoinitiators) that polymerize and harden upon irradiation with light, and certain additives that further adjust the overall material performance. Typically, photoinitiators are activated via irradiation with light to generate reactive sites (e.g., radicals, cations, or anions) that can subsequently react with the respective reactive components (e.g., (meth)acrylates, (meth)acrylamides, vinyl esters, vinyl ethers, vinyl amides, N-vinyl compounds, vinyl carbonates, vinyl carbamates, maleimides, itaconates, fumarates, styrene compounds, epoxy compounds, or cyclic ethers such as oxetanes, benzoxazines, oxazolines, cyanoacrylates, etc.) to form hardened materials.

[0004] Processing of such photocurable formulations into 3D parts can be carried out by various L-AMTs. Non-limiting examples of these are stereolithography (SLA), digital light processing (DLP), digital inkjet printing, hot lithography, continuous liquid interface production (CLIP), high-area rapid printing (HARP), multi-jet modeling, two photon photopolymerization (TPP) or other liquid additive manufacturing techniques. The aforementioned techniques are mostly based on layer-by-layer build-up of the final 3D part and can be realized in various forms such as bottom-up or top-down, in a continuous manner and / or by using moving DLP or laser-type systems for larger print areas. Current resin formulations applied in such techniques are almost exclusively of low viscosity (less than 5 Pa·s). This is essential for the success of the build-up or build-up process, ensuring high feature resolution and preventing processing defects.

[0005] The applicant has developed a hot lithography process (EP 3284583 A1) that allows lithography-based three-dimensional modeling at high temperatures with photocurable resins that have a high viscosity at ambient temperature (20°C), typically above 5 Pa·s. In the context of EP 3284583 A1, high viscosity refers to the use of high molecular weight (500 gmol -1 More than 2000gmol, preferably -1 These are found when processing photocurable resins with a high content of monomers, oligomers and / or prepolymers (e.g., urethanes, ureas, carbonates, esters, amides) with high number average molecular weights (> 35°C) and / or high melting or softening temperatures (> 35°C) and / or strong intermolecular forces, and / or a high content of filler materials (e.g., ceramic, metal and / or polymer particles and / or fibers) that are added to the photocurable resin to optimize the final material performance. The combination of high temperature and processing of highly viscous formulations allows for three-dimensional modeling of photocurable materials that combine toughness, heat resistance and impact resistance.

[0006] Improved heat resistance (e.g., increased T g Resin compositions for lithography-based three-dimensional fabrication to form photopolymer materials exhibiting a high thermal conductivity and / or thermal conductivity of 1000 nm and vice versa are of significant interest to the entire radiation curing industry. Non-limiting examples of such resin compositions are coatings, adhesives, thin layer applications by sandwich construction or bulk processing techniques such as material extrusion, resin infusion, resin transfer molding, L-AMT, etc. Many material concepts have been summarized in the literature, but typically sacrifice heat resistance to improve toughness. i) Controlling the overall network formation mechanism, for example by tuning the radical or cationic curing mechanism via thiol-ene photopolymerization, or by using addition-fragmentation chain transfer reactions (e.g., vinyl sulfones in radical chemistry or alcohols in cationic polymerization), leads to photopolymer networks with lower crosslink density. Thus, higher toughness is achieved by T g This is achieved by significantly impairing ii) Another approach to achieving tough photopolymers is to use high molecular weight photocurable oligomers, preferably with a T below ambient conditions. g The use of high molecular weight photocurable oligomers with a long flexible linker provides the desired photopolymer network toughness. Thus, when larger amounts of monofunctional reactive diluents are used in place of crosslinking monomers in the resin formulation to allow processing of such high molecular weight oligomers, toughness is significantly improved, but heat resistance and strength are often compromised (DOI:10.1002 / adma.201606000). iii) Alternatively, such photocurable oligomeric compounds with higher molecular weight also preferably have a T g This can be used to significantly improve the printing performance and change the material properties of the target photopolymer. g , (thermo)mechanical performance such as elastic modulus and strength is improved while at the same time toughness is compromised (US Patent Application Publication No. 2019 / 0249018 A1 and WO 2019 / 204807 A1).

[0007] In recent years, hybrid resin systems composed of one or more additional material concepts different from the photopolymer network formation used in the stereolithography process of L-AMT have attracted much attention. Such promising hybrid material concepts show great potential for the formation of tough photopolymer resins for additive manufacturing, resulting in photopolymerized materials that are simultaneously tough and heat-resistant. Hybrid resin systems can be defined as resin materials that exhibit different curing steps triggered by different impulses (e.g., a photocuring step followed by a thermal curing step - US 2016 / 0160077 A1) and / or materials that exhibit multiple curing mechanisms (e.g., a combination of radical and cationic curing mechanisms or different radical curing mechanisms - WO 2016 / 200972 A1, WO 2018 / 191247 A1). The photopolymer network thus formed is considered a hybrid material composed of a first component and a second or further components, typically representing a fully interpenetrating network (IPN), semi-IPN, pseudo-IPN, double network or polymer blend. To maintain reactivity to light and thereby ensure processability in L-AMT, a formulation containing an effective amount of photocurable components needs to be formulated to obtain a material with sufficient green strength. Green strength is the mechanical strength (e.g., measured by tensile or bending tests) of the respective material subjected to the photocuring additive manufacturing process.

[0008] Materials formed from such hybrid resins through a first photocuring step and a second or multiple additional curing steps different from the first photocuring step via different curing mechanisms provide a powerful design strategy for high performance photopolymers that are simultaneously tough and heat resistant. The second or multiple additional curing steps can be performed either simultaneously with or subsequent to the first photocuring step (e.g., the building step of L-AMT). Examples of the second or multiple additional curing steps include: i) a thermal curing step which causes thermal curing of the resin portions that have not been cured via the first light curing step (e.g., thermal curing of an epoxy thermoset in an acrylate matrix); ii) a moisture or organic catalyst catalyzed curing step which causes the curing of uncured resin portions via a first photocuring step (e.g. curing of resins having free isocyanate or silane groups) and / or a curing step which first causes decomposition of the resin portions followed by subsequent curing of the uncured resin portions via a first photocuring step (e.g. curing and / or deblocking of resins having blocked isocyanate groups); iii) a photocuring step that induces a different curing mechanism than the first photocuring step to initiate curing of the resin portions that were not cured via the first photocuring step (e.g., acrylate / epoxy resin systems cured via radical and cationic photopolymerization); iv) A photocuring step induced at a wavelength different from the first photocuring step to initiate curing of resin portions not cured via the first photocuring step (e.g., acrylate resin portions cured at wavelengths greater than 390 nm and epoxy resin portions cured at wavelengths less than 380 nm).

[0009] Limited examples of such hybrid resins have been introduced into photocurable formulations for 3D printing, as they are often designed for easy application and fast curing (e.g., 2K systems that cure quickly at ambient conditions such as room temperature and / or humidity). This is therefore not ideal for more complex part manufacturing processes such as L-AMT, which critically require high processing stability with a stable raw material formulation, preferably a 1K system, with homogeneous and controlled resin curing and controlled post-curing in a defined manufacturing process. Such hybrid material systems significantly improve material performance through a second or multiple further curing steps that cause curing of resin parts that have not been cured through the first photocuring step, but it is necessary to ensure that the curing step, which is different from the photocuring step, is not automatically triggered or occurs slowly outside the area of ​​irradiation (photocuring) during the manufacturing process, especially in applications such as L-AMT, where the resin stability is short and inhomogeneous and / or uncontrolled curing and / or uncontrolled material gradients are typically undesirable.

[0010] As in the case of hybrid resins composed of radical and cationic curing components (e.g., acrylate / epoxy systems), the cationic ring-opening mechanism for curing the epoxy-based component is relatively slow and requires high energy doses of actinic radiation to support additive manufacturing. In a further aspect, such acrylate / epoxy resins exhibit poor liquid stability caused by the living nature of the cationic polymerization mechanism. This living nature further challenges part accuracy and resolution during the 3D printing process. Furthermore, such resin systems must use cationic photoinitiators composed of antimony salts, which severely lack biocompatibility, and the resulting polymer parts suffer from yellowing upon prolonged exposure to UV light. Summary of the Invention

[0011] It is therefore an object of the present invention to provide a hybrid resin composition adapted for use in L-AMT. The hybrid resin composition provides improved heat resistance (e.g., higher glass transition temperature T g This enables 3D printing of photopolymer materials and products that exhibit high mechanical properties (e.g., low deflection temperature under load, HDT, reduced temperature dependent elastic modulus degradation) and at the same time maintain toughness (e.g., as demonstrated by retention of elongation at break in a tensile test), or vice versa.

[0012] To achieve this goal, a hybrid resin composition for 3D printing of objects is provided, comprising polymerized components A, B and C (and optionally D). The resin composition comprises: At least one monofunctional photocurable component having formula (I), also referred to as reactive diluent (RD), comprising reactive species Y susceptible to radical or cationic polymerization and pendant groups X, said component A forming a polymer backbone upon light-induced curing, said backbone preferably exhibiting a T above 25° C. g Component A having the formula XY Formula (I) At least one monofunctional or polyfunctional photocurable component that copolymerizes with component A via the corresponding curing mechanism, and -1 and preferably has a molecular weight of more than 10%, and acts as a toughness-modifier (TNM), and has a T of more than 0° C. g and component B, which forms a polymeric network having At least one mono- or polyfunctional thermosetting component, preferably having a T of greater than 100° C. g forming a second polymerized network having T g Elevator (T g and component C, which functions as a tertiary glycerin enhancer (TGE), Optionally, a partial content of the photocurable component B is replaced by a photocurable crosslinking component D, also called crosslinking agent (CA), which copolymerizes with components A and B via a corresponding curing mechanism to improve processability; The amount of photocurable component A ranges from 5% to 80% by weight, based on the total weight of components A, B, and C; the amount of photocurable component B ranges from 10% to 90% by weight; the amount of thermosetting component C ranges from 1% to 50% by weight; and optionally, the amount of crosslinking component D ranges from 3% to 70% by weight, based on the total weight of components B and D.

[0013] In a preferred embodiment, the resin composition comprises a photoinitiating system that renders the composition photocurable and a thermal initiating system that renders the composition thermally curable. In another preferred embodiment, the resin composition is storage stable at ambient conditions and a second, or multiple, further curing steps are latent and selectively induced simultaneously or subsequent to the first photocuring step.

[0014] The resin compositions of the present invention can form tough materials with improved thermal properties through a two-step process that includes a first photocuring step in which components A and B (and, if present, optionally D) are preferentially polymerized or copolymerized, and a second, or multiple, further thermal curing steps in which component C is preferentially cured (see Figures 2 and 3). The resulting materials exhibit increased heat resistance (e.g., glass transition temperatures T gThe photopolymer network obtained can be identified as an interpenetrating network (IPN), and depending on the composition of the hybrid resin formulation, a full IPN, semi-IPN, pseudo-IPN, double network or polymer blend can be obtained. Within the scope of the resin composition of the present invention, the photocurable components A, B and optionally D are responsible for the formation of a tough photopolymer network via a photocuring step (e.g., allowing processing via L-AMT), and further heat resistance is obtained via the network formation of a second or multiple further resin parts to form a rigid secondary network (e.g., via a thermal curing step of component C). Using this strategy, the heat resistance of the photopolymer material can be improved without having to compromise the toughness, which is also a key challenge for state-of-the-art photopolymers in 3D printing.

[0015] Component A is preferably selected to form a polymer backbone upon light-induced curing, said backbone having a T above 25° C. g Preferably, the backbone has a T of greater than 40° C. g and even more preferably has a T of greater than 100° C. g Optional component A, when used alone, has a respective minimum T g It is believed that this requirement can be met by producing a polymer having a glass transition temperature, T g is characterized by the temperature range over which this glass transition occurs, as measured by dynamic mechanical analysis (DMA) as described in the Examples section of this application.

[0016] Component B is preferably selected to form a polymeric network upon light-induced curing, the polymeric network having an elongation at break of greater than 10% and a T g Preferably, the elongation at break is greater than 20%. gis greater than 25°C. Optional component B, when used alone, has the lowest elongation at break and the lowest T g It is believed that this requirement is met by producing a polymer with a tensile strength of 0.05% to 0.25%. The elongation at break was measured using 5A specimens with a Zwick / Roell ProLine Z010 TH materials testing machine according to the standardized tensile test method defined in the international standard ISO 527-1 (published February 2012). The tensile test was performed at 1 mm min within the range of 0.05 to 0.25% elongation. -1 The measurements were then carried out at a strain rate of 10 mm. -1 The strain rate continues at the glass transition temperature T g is measured as shown for component A above.

[0017] Component C is preferably selected to form a polymeric network upon thermally induced curing, the polymeric network having a T of greater than 100° C. g Optional component C, when used alone, has a T of greater than 100° C. after complete polymerization. g It is believed that this requirement is met by producing a polymer having a glass transition temperature T g is measured as shown for component A above.

[0018] According to a further aspect, the resin composition of the invention for 3D printing of objects comprises the following polymerized components A, B and C: A) a monofunctional photocurable component A, also referred to as reactive diluent or RD, having formula (I) and comprising a reactive species Y susceptible to radical or cationic polymerization and a pendant group X, said component A being capable of undergoing photoinduced curing at a T above 25° C. g , preferably with a T of more than 40°C g , and even more preferably a T of more than 100° C. g forming a polymer backbone having XY Formula (I) wherein -Y is a chemical species selected from the group of (meth)acrylates, (meth)acrylamides, vinyl esters, vinyl ethers, vinyl amides, N-vinyl compounds, vinyl carbonates, vinyl carbamates, maleimides, itaconates, fumarates, styrene compounds, epoxy compounds or cyclic ethers such as oxetanes, oxazolines, benzoxazines, cyanoacrylates and their derivatives, optionally substituted with one or more C1-C6 alkyl, C1-C6 alkoxy, C1-C6 thioethers, halogens, -NO2, -SO3H, -CF3, -OH, -NH2, -SH, -CN, -trimethoxysilyl or triethoxysilyl; -X is one or more linear, branched or cyclic, bicyclic or polycyclic C5-C alkyl radicals selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, 2-ethylhexyl, octyl, decanyl, dodecanyl, acetic acid, propanoic acid, butanoic acid, pentanoic acid, undecanoic acid, dodecanoic acid, benzoic acid and the corresponding esters, alkyl or aromatic esters, phenyl, benzyl, phenethyl, biphenyl, naphthyl, anthracenyl, pyrenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-isobutylcyclohexyl, cycloheptyl, cyclooctyl, adamantyl, isobornyl, salicyl and cholesteryl. 40 represents an aliphatic residue, a heterocyclic residue, or an aromatic residue, one or more of which groups can be independently linked via an ester, amide, urea, urethane, carbonate, ether, or thioether group to form component A, which can optionally be one or more of C1-C6 alkyl, C1-C6 alkoxy, C3-C7 cycloalkyl, C6-C 10 Substituted with aryl, C1-C6 thioether, halogen, -NO2, -SO3H, -CF3, -OH, -NH2, -SH, -CN, -trimethoxysilyl or triethoxysilyl.

[0019] Preferred components A are cyclic, bicyclic or polycyclic C5-C 40 These are monomers that contain anchoring groups such as aliphatic, heterocyclic or aromatic residues and that form homopolymers and / or polymer backbones upon curing.

[0020] Preferred component A has a T of higher than 40° C., higher than 60° C., higher than 80° C., higher than 100° C., or from 50° C. to 100° C., or from 80° C. to 120° C., or from 100° C. to 150° C., or from 120° C. to 160° C., or from 150° C. to 200° C. g These are monomers which form homopolymers or polymer backbones upon curing at 0.5-10 wt. %, respectively. The respective polymer backbones can be formed via thermal or photochemical curing reactions, polymerization methods known to those skilled in the art. For example, as thermal initiators, organic peroxides such as benzoyl peroxide can be used in amounts of 0.1-5 wt. %, or as photoinitiation species, radical photoinitiators such as 1-hydroxycyclohexyl phenyl ketone in amounts of 0.2-5 wt. %, or cationic photoinitiators such as triphenylsulfonium or diphenyliodonium salts with anions such as borate, phosphate, arsenic, antimonate, tetrakisborate in amounts of 0.5-10 wt. %. For thermal polymerization, the reaction temperature is adjusted to the respective thermal initiator used, or, in the case of photocuring, the applied light impulse is adjusted to the photoinitiation system implemented. The polymer samples can be cured as thin layers or bulk samples via molding, lamination or 3D printing techniques. The polymer backbones formed can be as high as 5000 gmol -1 It is characterized by having a number average molecular weight of more than

[0021] Some preferred, but non-limiting examples of component A include 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, 2-(methacryloyloxy)benzoic acid cyclopentyl ester, 2-(methacryloyloxy)benzoic acid cyclohexyl ester, 2-(methacryloyloxy)benzoic acid-2-isopropyl-5-methylcyclohexyl ester, 3 ... 4-(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-ylmethyl 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)benzo Examples of the monofunctional (meth)acrylates include salicylate (meth)acrylates such as cycloheptyl ester of aromatic acid and cyclohexyl methyl ester of 2-(methacryloyloxy)benzoate, cholesteryl (meth)acrylate, biphenyl (meth)acrylate, phenyl acrylamide, diacetone acrylamide, t-butyl acrylamide, N-acryloylmorpholine, N-vinyl pyrrolidone, N-vinyl caprolactam, N-vinyl formamide, vinyl cinnamate, vinyl methyl oxazolidinone, and 2-(allyloxymethyl)acrylic acid methyl ester, (meth)acrylamides, vinyl esters, and N-vinyl compounds.

[0022] Component A may also consist of a composition comprising two, three or more different components described by formula I.

[0023] B) A mono- or polyfunctional photocurable component B that copolymerizes with component A via the corresponding curing mechanism, 500 gmol -1 More than 1000 gmol, preferably -1and having a number average molecular weight of greater than 10 ... 10 A modified epoxy functionalized oligomer optionally substituted with aryl, C1-C6 thioether, halogen, -NO2, -SO3H, -CF3, -OH, -NH2, -SH, -CN, -trimethoxysilyl or triethoxysilyl, which acts as a toughness modifier (TNM) and preferably has an elongation at break of more than 10%, preferably more than 20%, and / or a T of more than 0°C, preferably more than 25°C. g A polymer network having the formula:

[0024] Preferred components B are multifunctional oligomers, prepolymers and / or polymers having an average reactive group functionality greater than 1.3, preferably greater than 1.5, more preferably greater than 1.9, or an average functionality of 0.9 to 2.1, or 0.9 to 3.1, or 2.9 to 3.1, or 1.9 to 2.1.

[0025] The preferred component B is a copolymer having a number average molecular weight of 500 gmol -1 More than 1000 gmol, preferably -1 More preferably, 5000 gmol -1 More preferably still, greater than 10,000 gmol -1 or number average molecular weight is 700 gmol -1 ~50000gmol -1 , or 1000 gmol -1 ~30000gmol -1 , or 1000 gmol-1 ~20000gmol -1 , or 2000 gmol -1 ~50000gmol -1 , or 2000 gmol -1 ~30000gmol -1 , or 2000 gmol -1 ~20000gmol -1 and wherein

[0026] Preferred component B has a T of higher than 25° C., higher than 40° C., higher than 60° C., higher than 80° C., higher than 100° C., or 0° C. to 30° C., or 10° C. to 40° C., or 30° C. to 60° C., or 40° C. to 80° C. g and / or polyfunctional oligomers, prepolymers and / or polymers that form homopolymers or crosslinked polymer networks upon curing, with an elongation at break of greater than 10%, or greater than 20%, or greater than 30%, or greater than 50%, or greater than 80%, or between 10% and 30%, or between 20% and 40%, or between 30% and 50%, or between 80% and 120%, or between 150% and 200%. The respective crosslinked polymer networks can be formed via thermal or photochemical curing reactions, polymerization methods known to those skilled in the art (see above). The polymer samples can be cured as thin layers or bulk samples via molding, lamination or 3D printing techniques.

[0027] Some preferred examples for component B are ethoxylated bisphenol A di(meth)acrylates (e.g., Miramer 2200, Miramer 2301), aliphatic urethane di(meth)acrylates (e.g., Ebecryl 8811, Ebecryl 8809, Ebecryl 8409, Ebecryl 246, Miramer PU2100, Miramer SC2404, Miramer SC2565, Miramer PU2564, BR-571 MB, BR-7432GB, CN9001, CN965, CN981, CN8881 NS), polyether urethane (meth)acrylates (e.g., BR-541 which already contains 10-25% of component D as CA). MB, BR-582H15), hydrophobic urethane (meth)acrylates (e.g., BRC-443D, which already contains 5-15% of component A as RD), polyester urethane (meth)acrylates (e.g., BR-744BT), polyester di(meth)acrylates (e.g., CN2608A, CN704, CN790), modified epoxy di(meth)acrylates (e.g., CN2003EU), oligomeric polycarbonate di(meth)acrylates, and other multifunctional (meth)acrylates.

[0028] Component B may also consist of a composition comprising two, three or more different components B as described.

[0029] C) a monofunctional and / or polyfunctional thermosetting component C; T g It acts as a TGE and preferably has a T of more than 100°C, preferably more than 150°C, even more preferably more than 200°C. gand one or more species selected from the group consisting of allyl, vinyl, maleimide, citraconimide, benzoxazine, epoxy, phenol, cyanate ester, phthalonitrile, and their oligomers or polymers, and / or their isomers, and / or combinations thereof, and further latent, with a second or further curing step selectively triggered simultaneously with or subsequent to the first photocuring step to render the final formulation storage stable at ambient conditions. The respective crosslinked polymer network may be formed via a thermal curing reaction, a polymerization method known to those skilled in the art (see above). The polymer sample may be cured as a thin layer or bulk sample via molding, lamination or 3D printing techniques.

[0030] Preferred component C has a T of more than 100° C., preferably more than 150° C., more preferably more than 180° C., even more preferably more than 200° C. g , or 80°C to 120°C, or 120°C to 150°C, or 150°C to 180°C, or 180°C to 220°C, or 220°C to 250°C, or 250°C to 300°C g and thus providing improved heat resistance (e.g., T ) while maintaining the toughness (e.g., as measured by elongation at break) of the final photopolymer network. g or HDT).

[0031] Preferred components C are i) The required high T groups, such as aromatic groups, and / or cycloaliphatic groups, and / or heterocyclic groups, and / or groups exhibiting strong intermolecular forces. g and further comprising fixed substituents which are responsible for the formation of a polymer backbone or polymer network which is less prone to polymerization shrinkage, such moieties preferably having higher molecular weights (500 gmol -1 and / or ii) A lower molecular weight (500 gmol -1 and / or iii) Mono- and / or multi-functional thermosetting components, which are of high functionality (greater than 2) on the reactive groups resulting in higher crosslink density and therefore higher overall heat resistance.

[0032] The preferred component C can be efficiently cured via a heat curing step carried out subsequent to the photocuring steps of components A, B and optionally D. The heat curing step is carried out at a temperature higher than the initial processing temperature of the photocuring step, preferably above 100°C, more preferably above 120°C, even more preferably above 140°C, and at a temperature at which the formed material still exhibits sufficient thermal stability, preferably below 250°C, more preferably below 200°C, even more preferably below 180°C.

[0033] The preferred component C can be efficiently cured via a heat curing step performed subsequent to a light curing step of components A, B and optionally D. The heat curing step is performed by applying heat directly via active heating in an oven (e.g. electric, gas or solar oven) or indirectly via microwave irradiation, other light impulses (such as infrared) or secondary exothermic reactions such as thermal polymerization and / or combinations thereof.

[0034] Some other preferred components C can be effectively cured via a second curing step carried out simultaneously or subsequently to a first photocuring step. The resin components are cured via different curing mechanisms (e.g., cationic curing vs. radical curing) simultaneously with light or simultaneously or subsequently with a second curing step with light of a different wavelength than the first photocuring step (e.g., radical curing at wavelengths greater than 390 nm and cationic curing at wavelengths less than 380 nm).

[0035] Some further preferred examples of component C exhibit a softening or melting temperature within the processing range for hot lithography, which is 30 to 150°C, more preferably 30 to 120°C, and / or exhibit a viscosity of 0.5 to 1000 Pa s at processing temperatures in the range of 30 to 150°C, more preferably 30 to 120°C.

[0036] In a preferred embodiment, the thermosetting component C is responsible for the formation of a secondary polymer network during the subsequent thermosetting process, which improves the network heterogeneity as suggested in Figures 2 and 3. In this way, the cured material is i) an interpenetrating network, or ii) semi-interpenetrating networks, or iii) a sequential interpenetrating network, or iv) polymer blends; Configure.

[0037] Some preferred examples of component C are compounds of formula (II) [ka] wherein -n is an integer from 1 to 10, -R1 represents H, CH3 or CH2; -R2 is one or more linear, branched or cyclic C5-C alkyl groups selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, 2-ethylhexyl, octyl, decanyl, dodecanyl, acetic acid, propanoic acid, butanoic acid, pentanoic acid, undecanoic acid, dodecanoic acid, benzoic acid and the corresponding esters, alkyl or aromatic esters, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-isobutylcyclohexyl, cycloheptyl, cyclooctyl, adamantyl, isobornyl, salicyl and 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. 40 independently represent an aliphatic or aromatic residue, one or more of which are independently bonded via one or more of an ester, amide, urea, urethane, carbonate, ether, thioether group, optionally substituted with one or more C1-C6 alkyl, C1-C6 alkoxy, C1-C6 thioether, halogen, -NO2, -SO3H, -CF3, -OH, -NH2, -SH, -CN, -trimethoxysilyl, -triethoxysilyl, or a polymerizable group derived from the substance classes of maleimide and citraconimide compounds and / or their isomers, in particular itaconimides; and their isomers, particularly itaconimide, monomers, and / or oligomers thereof, and / or prepolymers thereof.

[0038] Some more preferred examples of component C are mono- and polyfunctional maleimide species of formula II, where R2 represents an aromatic residue that provides higher heat resistance due to fixed molecular structure, high crosslinking degree, and reduced photocurability. This improves network heterogeneity, as suggested in Figures 2 and 3. Thus, component C preferably comprises species of formula II, where n is an integer between 1 and 10, and has an aromatic residue bonded to the N atom of the maleimide ring either directly or through a methylene spacer. Such preferred species of component C are of the following formula: [ka] [ka] and / or oligomers and / or prepolymers of these derivatives, as well as their isomers, in particular itaconimides.

[0039] Some other preferred examples of the preferred component C are those which have the required high T, such as aromatic groups, and / or cycloaliphatic groups, and / or heterocyclic groups, and / or groups exhibiting strong intermolecular forces. g and further comprising fixed substituents that are responsible for the formation of a polymer backbone or polymer network that is less prone to polymerization shrinkage, and such components have a higher molecular weight (500 gmol -1 Preferably already oligomers and / or prepolymers, or with a low molecular weight (number average molecular weight above 500 gmol -1 In particular, the preferred aryl groups are polyfunctional aryl compounds, which have a number average molecular weight of less than 100 nm, and / or a high functionality (greater than 2) on the reactive groups resulting in a higher crosslink density and therefore overall higher heat resistance.

[0040] Some preferred examples of polyfunctional allyl compounds as component C are: 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 pyromelitate, 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-Diallylbisphenol A diacetate ether, diallyl terephthalate, diallyl isophthalate, diethyl diallyl malonate, 1,3-Diallylurea, 1,3-Diallyl-2-thiourea, 2,4-Diamino-6-diallylamino-1,3,5-triazine, diallyl oxylate, diallyl malonate, diallyl tetrabromophthalate, 2,6-Diallyl-meta-cresol, N,N-Diallylaniline, diallyl cyanamide, N,N-Diallylmelamine, 2,2'-Diallylbisphenol A, N,N'-Diallylpiperazine, 2,2-Diallylpyrrolidine, Diallylcarbamic acid tert-butyl ester, diallyl ether bisphenol A, diallyl phenyl phosphonate, 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.

[0041] Some other preferred examples of the preferred component C are those which have the required high T, such as aromatic groups, and / or cycloaliphatic groups, and / or heterocyclic groups, and / or groups exhibiting strong intermolecular forces. g and further comprising fixed substituents that are responsible for the formation of a polymer backbone or polymer network that is less prone to polymerization shrinkage, and such components have a higher molecular weight (500 gmol -1 Preferably already oligomers and / or prepolymers, or with a low molecular weight (number average molecular weight above 500 gmol -1In particular, the epoxy compounds are multifunctional, having a number average molecular weight of less than 100 nm, and / or a high functionality (greater than 2) on the reactive groups resulting in a higher crosslink density and therefore overall higher heat resistance.

[0042] Some preferred examples of the polyfunctional epoxy compound as component C are: Bisphenol A, bisphenol F and / or bisphenol S derivatives such as bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, and / or diglycidyl 1,2-cyclohexanedicarboxylate, 4,4'-methylenebis(N,N-diglycidylaniline), trimethylolpropane triglycidyl ether, (3',4'-epoxycyclohexane)methyl-3,4-epoxycyclohexylcarboxylate, 1,2-epoxy-4(2-oxiranyl)-cyclohexane and 2,2-bis(hydroxymethyl)1-butanol condensation products, bisphenol A novolac epoxy resins (e.g. SU-8 resins) and / or oligomers of their derivatives, and / or prepolymers of their derivatives.

[0043] Component C may also consist of a composition comprising two, three or more different components C as described above.

[0044] The relative amounts of components A, B and C in the hybrid resin composition are the amount of photocurable component A is in the range of 5% by weight to 80% by weight, preferably 10% by weight to 60% by weight, more preferably 15% by weight to 55% by weight, and even more preferably 20% by weight to 45% by weight, based on the total weight of components A, B, and C; the amount of photocurable component B is in the range of 10% by weight to 90% by weight, preferably 20% by weight to 80% by weight, more preferably 25% by weight to 70% by weight, and even more preferably 30% by weight to 65% by weight, based on the total weight of components A, B, and C; The amount of thermosetting component C may be selected to be in the range of 1% to 50% by weight, preferably 2% to 40% by weight, more preferably 3% to 30% by weight, and even more preferably 5% to 25% by weight, based on the total weight of components A, B and C.

[0045] By way of example, preferred combinations of ranges for components A-C within the hybrid resin composition can be derived from the following table or from the non-limiting examples disclosed herein: [Table A]

[0046] The reactive diluent of the resin formulation, component A, is composed of one or more monofunctional substances composed of reactive groups. This means that such component can undergo polymerization reaction either via a radical curing mechanism or a cationic curing mechanism induced by light. Component A is preferably 750 gmol at processing temperature to obtain better processability of the resin formulation of the present invention in the additive manufacturing process. -1 and has a lower molecular weight than oligomeric component B, preferably less than 5 Pa.

[0047] In a preferred embodiment, the reactive diluent has a T g The polymer backbone has a crosslink density of 0.1 to 0.5, resulting in faster gelation and higher green strength for the photocured photopolymer. In a preferred embodiment, the monofunctional reactive diluent results in a lower crosslink density in the final photopolymer network. This results in higher toughness and more ductile behavior. In a preferred embodiment, the reactive species Y of component A includes radical polymerization groups such as, but not limited to, (meth)acrylates, (meth)acrylamides, vinyl esters, vinyl ethers, vinyl amides, N-vinyl compounds, vinyl carbonates, vinyl carbamates, maleimides, itaconates, fumarates, and styrene compounds.

[0048] In a further preferred embodiment, such reactive diluents undergo cyclopolymerization, resulting in higher green strength and higher T g By way of example, such cyclopolymerization reactive diluents are composed of two reactive groups that are susceptible to radical attack but do not undergo homopolymerization by themselves (e.g., 2-(allyloxymethyl)acrylic acid methyl ester).

[0049] Preferably, the resin composition is formulated in such a way that component B contains radical polymerizable groups such as (meth)acrylates, (meth)acrylamides, vinyl esters, vinyl ethers, vinyl amides, N-vinyl compounds, vinyl carbonates, vinyl carbamates, maleimides, itaconates, fumarates and styrene compounds. More preferably, component B has an average molecular weight of 1000 gmol -1 The photopolymerization initiators include mixtures of polyfunctional (meth)acrylates or (meth)acrylamides, and / or mixtures of mono- or polyfunctional (meth)acrylates and / or (meth)acrylamides, with the polyfunctional (meth)acrylates or (meth)acrylamides being greater than 1.3. Such (meth)acrylate or (meth)acrylamide oligomers are components having two or more radically polymerizable groups on the oligomer or at least an average number of reactive functionalities greater than 1.3. The high molecular weight oligomers are responsible for the formation of tough photopolymer networks, as such high molecular weight oligomers and reactive end groups provide toughness in the final photopolymer network through chain flexibility and chain entanglement.

[0050] In a more preferred embodiment, component B is complemented or replaced by a crosslinking component D (crosslinking agent CA), which is also photocurable and copolymerizes with components A and B via the corresponding curing mechanism, and has one or more chemical species selected from the group consisting of (meth)acrylates, (meth)acrylamides, vinyl esters, vinyl ethers, vinyl amides, N-vinyl compounds, vinyl carbonates, vinyl carbamates, maleimides, itaconates, fumarates, styrene compounds, epoxy compounds or cyclic ethers such as oxetanes, oxazolines, benzoxazines, cyanoacrylates, and derivatives thereof, and / or combinations thereof, and where necessary, component D is added for better processability and higher green strength. The multifunctional monomers constituting component D are possibly tri-, tetra-, penta- and / or hexa-functional CAs, and / or hyperbranched and / or dendritic CAs with even more functional sites. These are favorable for reasons of fast reaction rate and high crosslink density, improving heat resistance (e.g. higher T g ), but typically reduces toughness.

[0051] In a more preferred embodiment, component B is complemented or replaced by a crosslinking component D (crosslinking agent CA) so that the formulations related to the invention are composed of at least one di- and / or polyfunctional (meth)acrylate or a mixture of di- and / or polyfunctional (meth)acrylates. This component D can be composed of one or more radically polymerizable oligomers, thus polymerizable by light, and is therefore particularly preferred as part of the photocurable component matrix and as an additive to component B of the resin composition of the invention. The polyfunctional monomers constituting component D are possibly tri-, tetra-, penta- and / or hexafunctional (meth)acrylates, and / or even hyperbranched and / or dendritic (meth)acrylates with many more functional sites. These are favorable for the reasons of fast reaction rates and high crosslinking density, improving heat resistance (for example higher T g ), but typically at the expense of toughness.

[0052] Some preferred compounds of component D of the resin composition of the present invention are multifunctional (meth)acrylates and / or mixtures of multifunctional (meth)acrylates. These provide higher green strength for 3D printed parts to aid in the 3D fabrication of complex thin-walled structures. The crosslinking components are low molecular weight (500 gmol -1 Component B differs from component B in that it has either a functionality (less than 1) or a higher functionality (greater than 2), resulting in a higher crosslink density and therefore an overall higher green strength.

[0053] Such crosslinking components D are in particular 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate or 1,12-dodecanediol di-(meth)acrylate, 1,6-bis-[2-(meth)-acryloyloxyethoxycarbonylamino]-2,2,4-trimethylhexane, pentaerythri tetra(meth)acrylate, di-, tri- or tetraethylene glycol-di(meth)acrylate and / or trimethylolpropane tri(meth)acrylate.

[0054] Furthermore, preferred component D is comprised of anchoring groups such as aromatic or cycloaliphatic groups because they provide a cured resin with low tendency to polymerization shrinkage, high green strength, and high heat resistance. Some preferred crosslinking components D are 2-(2-biphenyloxy)-ethyl(meth)acrylate, bisphenol-A-di(meth)acrylate (adduct derived from (meth)acrylic acid and bisphenol A-diglycidyl ether), epoxy- or propoxylated bisphenol A-di(meth)acrylate (e.g. 2-[4-(2-(meth)acryloyloxyethoxyethoxy)phenyl]-2-[4-(2-(meth)acryloyloxyethoxy)phenyl]-propane) or 2,2-bis[4-(2-(meth)acryloyloxypropoxy)phenyl]propane, tricyclodecane dimethanol di(meth)acrylate, isophorone urethane di(meth)acrylate or tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate.

[0055] Preferably, the amount of monofunctional component A is in the range of 5% to 80% by weight, preferably 10% to 60% by weight, more preferably 15% to 55% by weight, and even more preferably 20% to 45% by weight, based on the total weight of components A, B, C, and D; the amount of photocurable component B is in the range of 10% by weight to 90% by weight, preferably 20% by weight to 80% by weight, more preferably 25% by weight to 70% by weight, and even more preferably 30% by weight to 65% by weight, based on the total weight of components A, B, C, and D; the amount of the primarily thermosetting component C ranges from 1% to 50% by weight, preferably from 2% to 40% by weight, more preferably from 3% to 30% by weight, and even more preferably from 5% to 25% by weight, based on the total weight of components A, B, C, and D; The amount of cross-linking component D is in the range of 3% by weight to 70% by weight, preferably 5% by weight to 60% by weight, more preferably 7% by weight to 50% by weight, and even more preferably 10% by weight to 40% by weight, based on the total weight of components B and D.

[0056] By way of example, preferred combinations of ranges for components A-D within the hybrid resin composition can be derived from the following table or from the non-limiting examples disclosed herein: [Table B]

[0057] According to a preferred embodiment of the invention, the resin composition of the invention comprises at least one photoinitiator suitable for radical polymerization upon photoexcitation, preferably within the wavelength spectrum of 150 nm to 1000 nm, more preferably 200 nm to 550 nm, in an amount of 0.01% to 10% by weight, preferably 0.1% to 7% by weight, more preferably 0.2% to 5% by weight, based on the total weight of components A, B and D. This means that the photoinitiator can be activated by light and is able to initiate the polymerization of the photocurable components of the formulation.

[0058] Photoinitiated polymerization (photopolymerization) is successful when the applied exposure light is of suitable wavelength and sufficient power for activation of the photoinitiator. Apart from the exposure light being suitable for the photoinitiator, all formulations (including, optionally, light absorbing monomers or additives) may not impede the interaction of the emitted light with the photoinitiator. Exposure light as applied herein includes any wavelength and ability to initiate polymerization. Preferred wavelengths of light are between 150 nm and 1000 nm, and even more preferably between 200 nm and 550 nm. Any suitable NIR, UV or visible light source may be used, including but not limited to laser or LED sources or broadband Hg lamps. The light source may emit a broadband or narrowband light spectrum, or a combination thereof. The light source may emit continuous or pulsed light during a single exposure period or repeated exposure periods. This may additionally be modified by the duration or intensity of the exposure. A suitable and high process temperature increases the reactivity of the system, thus improving the light-induced modeling process. Adjustment of the above parameters and variables provides an optimized protocol for carrying out the desired photopolymerization reaction, resulting in optimal 3D fabrication with L-AMT.

[0059] In a preferred embodiment, the light induced curing process is carried out using a NIR (near infrared) light source or a UV / Vis (ultraviolet-visible) light source and corresponding optics, with the NIR configuration being selected to enable 3D manufacturing via two-photon photopolymerization and the UV / Vis configuration being selected from the group consisting of Laser / DLP, LED / DLP, Laser / LCD and LED / LCD.

[0060] Preferred photoinitiators are Norrish Type I photoinitiators, either alone or in combination with one another, and may be selected from the group consisting of α-hydroxyketones, phenylglyoxylates, benzil dimethyl ketals, α-aminoketones, mono- or bisacylphosphines, -phosphine oxides, mono-, bis- or tetraacylsilanes, -germanes, -stannanes, metallocenes. Some preferred examples are 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, methylphenyl glyoxylate, 2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone, [1-(4-phenylsulfanylbenzoyl)heptylideneamino]benzoate, [1-[9-ethyl-6-(2-methylbenzoyl)carbazol-3-yl]ethylideneamino]acetate, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (TPO), ethyl-(2,4,6-trimethylbenzoyl)phenyl phosphinate (TPO-L), phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide ... oxide (BAPO), ethyl (3-benzoyl-2,4,6-trimethylbenzoyl)(phenyl)phosphinate, bis(4-methoxybenzoyl)diethylgermane (BMDG) and polymeric type I photoinitiators such as bis(cyclopentadienyl)bis[2,6-difluoro-3-(1-pyrryl)phenyl]titanium and / or Ominpol TP.

[0061] The preferred photoinitiator may also be a Norrish type II photoinitiator. Some preferred examples are benzophenones (e.g., benzophenone, 4-methylbenzophenone, 4,4'-bis(diethylamino)benzophenone, benzoin, diketones (e.g., 9,10-phenanthrenequinone, 1-phenyl-propane-1,2-dione, diacetyl or 4,4'-dichlorobenzil and / or their derivatives), and thioxanthones (e.g., chloropropoxythioxanthones, isopropylxanthones or 2,4-diethyl-9H-thioxathen-9-one). Such type II photoinitiators may be used in combination with co-initiators such as tertiary amines (e.g., aromatic tertiary amines such as N,N-dialkylanilines, -p-toluidine or -3,5-xylidine, pN,N-dialkylamino-phenylethanol, -benzoic acid derivatives, -benzaldehyde or triethanolamine).

[0062] In a further preferred embodiment, a combination of such Type I and / or Type II photoinitiators may be used.

[0063] Resin compositions of the type of the present invention can be processed in lithography-based 3D printing applications at high temperatures. The resin compositions of the present invention are heated and subsequently subjected to a layer-by-layer light-induced lamination process, in which the light-curable components of the resin compositions of the present invention are structured by light curing to obtain 3D objects by lithography-based additive manufacturing methods, which maintains toughness (e.g., as measured by elongation at break) and improves temperature resistance (e.g., T g The result is a material that has a desirable balance of the above-mentioned thermal and mechanical properties, such as thermal conductivity (measured by thermal expansion coefficient (Tc)) or vice versa.

[0064] In a preferred embodiment, hot lithography is used as a processing method that allows three-dimensional shaping of resins containing a high content of component B, its oligomers, or its prepolymers, which are usually characterized by high toughness (e.g., elongation at break of more than 10%) and, for conventional L-AMT, a relatively high viscosity of the resin formulation (more than 15 Pa·s at room temperature and 0.01-40 Pa·s, preferably 0.1-25 Pa·s, at processing temperatures). ... to obtain a high softening or melting temperature and high heat resistance (e.g., T of more than 100° C.) of the final material. g ) and a high content of component C, a stiff compound and / or its oligomers and / or its prepolymers, usually characterized by a relatively high resin formulation viscosity for conventional L-AMT (>15 Pa·s at room temperature and 0.01-40 Pa·s, preferably 0.1-25 Pa·s at processing temperatures). The resulting materials offer improved heat resistance while maintaining toughness, or vice versa. This is demonstrated by the (thermo)mechanical properties disclosed herein for 3D samples produced via L-AMT.

[0065] In some preferred embodiments, the thermosetting component C does not cure until subjected to heat, meaning a temperature of greater than 50° C., making the thermosetting system latent and essentially forming a resin formulation that is storage stable at room temperature, having a storage stability (e.g., as measured by a viscosity increase of less than 10%) of greater than 3 months, or even greater than 6 months, or even greater than 12 months, and the 3D object is produced by a process of hot lithography.

[0066] In a preferred embodiment, the heat curing step may be accomplished indirectly via active heating in an oven (e.g. electric, gas or solar oven) or via secondary exothermic reactions such as microwave irradiation, other light impulses (e.g. infrared) or thermal polymerization. Preferably, the heat curable component C is stable at ambient conditions and the processing conditions of the light curing step, so that the latent curing reaction requires induction.

[0067] In some preferred embodiments, at least one thermal initiator and / or catalyst may be used for the thermal curing of component C and / or its comonomers. Suitable catalysts may be preferably selected from the group consisting of tertiary amines (e.g. trialkylamines), especially DABCO and / or DMAP and / or triethylamine and / or other aliphatic and aromatic secondary and tertiary amines, alkali salts of organic alcohols, phosphines, triphenylphosphonates, imidazoles, especially substituted imidazoles such as 2-methyl-1-vinylimidazole, 2-phenylimidazole, 2-benzylimidazole and / or 2-ethyl-4-methylimidazole, organic acids, and / or peroxides, and / or dicyandiamide, preferably in an amount of 0.01% to 20% by weight, preferably in an amount of 0.1% to 15% by weight, more preferably in an amount of 0.2% to 10% by weight, based on the weight of component C.

[0068] For the maleimide compounds preferred as component C, such thermal initiators and / or catalysts are preferably tertiary amines (e.g., trialkylamines), in particular DABCO and / or DMAP, and / or triethylamine, and / or other aliphatic and aromatic secondary and tertiary amines, alkali salts of organic alcohols, trialkylphosphines, triphenylphosphine, etc., in an amount of preferably 0.01% to 20% by weight, preferably 0.1% to 15% by weight, more preferably 0.2% to 10% by weight, based on the weight of component C. They may be selected from the group consisting of phosphines, imidazoles, in particular substituted imidazoles such as 2-methyl-1-vinylimidazole, 2-phenylimidazole, 2-benzylimidazole and / or 2-ethyl-4-methylimidazole, organic acids and / or peroxides such as dibenzoyl peroxide, dilauroyl peroxide, dicumyl peroxide, tert-butyl perbenzoate and / or di-(tert-butyl)-peroxide and / or anionic catalysts such as 1,1,2,2-tetraphenyl-1,2-ethanediol. Optionally, in the case of citraconimide-based component C, up to 2% by weight of an auxiliary may be used, such as triallyl cyanurate or bismaleimide.

[0069] For the allyl compounds preferred as component C, such thermal initiators and / or catalysts, preferably in an amount of 0.01% to 20% by weight, preferably in an amount of 0.1% to 15% by weight, more preferably in an amount of 0.2% to 10% by weight, based on the weight of component C, may be selected from the group consisting of peroxides such as dibenzoyl peroxide, dilauroyl peroxide, dicumyl peroxide, tert-butyl perbenzoate, and / or di-(tert-butyl)-peroxide, and / or 1,1,2,2-tetraphenyl-1,2-ethanediol. Optionally, up to 10% by weight of coagents, such as bismaleimides, may be used.

[0070] For epoxy compounds preferred as component C, such thermal initiators and / or catalysts are preferably in an amount of 0.01% to 20% by weight, preferably in an amount of 0.1% to 15% by weight, more preferably in an amount of 0.2% to 10% by weight, based on the weight of component C, such as dicyandiamide, and / or tertiary amines (e.g., benzyldimethylamine), imidazoles, especially 2-methyl-1-vinylimidazole, 2-phenylimidazole, 2-benzylimidazole, and / or 2-ethyl-4-methylimidazole, etc. and / or accelerators such as ureas such as aryldimethylurea compounds (e.g. 3-(4-chlorophenyl)-1,1-dimethylurea, which is Diuron, Fenuron or Monuron), and / or carboxylic acid anhydrides (e.g. succinic anhydride, phthalic anhydride), and / or cobalt(III), nickel(II) or copper(II) acetylacetonates, and / or diacid dihydrazides, and / or boron trifluoride amine adducts.

[0071] In a further preferred embodiment, the resin composition of the present invention comprises one or more initiators for radical polymerization, in particular thermal initiators, suitable for thermal curing of component C. Some preferred examples are azo compounds, more preferably 2,2'azobis(isobutyronitrile) (AIBN) and / or azobis-(4-cyanovaleric acid), and / or peroxides, more preferably organic peroxides such as dibenzoyl peroxide, dilauroyl peroxide, dicumyl peroxide, tert-butyl perbenzoate and / or di-(tert-butyl)-peroxide, and / or 1,1,2,2-tetraphenyl-1,2-ethanediol, preferably in an amount of 0.01% to 5% by weight, preferably in an amount of 0.1% to 4% by weight, more preferably in an amount of 0.2% to 3% by weight, based on the total weight of components A to D.

[0072] In some preferred embodiments, the hybrid resin formulation further comprises a comonomer, and / or a cooligomer, and / or a coprepolymer that is copolymerizable with component C and its derivatives.

[0073] For the preferred maleimide compounds of component C, such comonomers, preferably in an amount of 0.5% to 50% by weight, preferably in an amount of 1% to 30% by weight, more preferably in an amount of 5% to 25% by weight, based on the weight of component C, may be preferably selected from the group consisting of alkenylphenols, alkenylphenyl ethers, alkenylphenol ethers, polyamines, aminophenols, amino acid hydrazines, cyanate esters, diallyl phthalates, triallyl isocyanurates, triallyl cyanurates, vinyl and / or styrene functional monomers, and / or oligomers, and / or prepolymers.

[0074] For the preferred allyl compounds of component C, such comonomers, preferably in an amount of 0.5% to 50% by weight, preferably in an amount of 1% to 30% by weight, more preferably in an amount of 5% to 25% by weight, based on the weight of component C, may be preferably selected from the group consisting of maleimide derivatives, citraconimide derivatives, polyamines, aminophenols, amino acid hydrazines, cyanate esters, vinyl and / or styrene functional monomers, and / or oligomers, and / or prepolymers.

[0075] For the preferred epoxy compounds of component C, such comonomers, preferably in an amount of 0.5% to 50% by weight, preferably in an amount of 1% to 30% by weight, more preferably in an amount of 5% to 25% by weight, based on the weight of component C, may be preferably selected from the group consisting of monomers and / or oligomers and / or prepolymers of polyfunctional alcohols or diols, such as polyester diols, polybutadiene diols, polycarbonate diols, and / or polyfunctional amines, such as Jeffamine, and / or polyfunctional anhydrides, such as pyromellitic dianhydride.

[0076] In some preferred embodiments, the resin composition of the present invention comprises at least one polymerization inhibitor, preferably selected from the group consisting of quinones, such as hydroquinone and / or benzoquinone, phenothiazine, diethylhydroxyamine, 4-tert-butylcatechol, butylated hydroxytoluene, pyrogallol, TEMPO, and / or 4-hydroxy-TEMPO, preferably in an amount of 0.001 wt % to 1 wt %, preferably in an amount of 0.005 wt % to 0.5 wt %, more preferably in an amount of 0.01 wt % to 0.1 wt %, based on the total weight of Components A to D.

[0077] In some preferred embodiments, the resin composition of the present invention comprises at least one light absorber such as a pigment or dye, preferably selected from the group consisting of inorganic particles such as titanium dioxide and / or carbon black, and / or organic UV light absorbers such as benzophenone derivatives, benzotriazole derivatives, triazine derivatives, thioxanthone, hindered amine light stabilizers such as Chimassorb, Tinuvin and / or Uvinul products, preferably in an amount of 0.001 wt % to 2 wt %, preferably in an amount of 0.01 wt % to 1 wt %, more preferably in an amount of 0.02 wt % to 0.5 wt %, based on the total weight of components A-D.

[0078] The above-mentioned photoinitiators, thermal initiators, catalysts, inhibitors, light absorbers and other additives may be polymeric and / or additionally functionalized with polymerizable functional groups and, as per the preferred embodiment of the present invention, may be polymerized with the photocurable components A, B, D and / or the thermosetting component C.

[0079] In some preferred embodiments, the resin composition of the present invention comprises an additional toughness modifier selected from the group consisting of thermoplastic resins. By way of example, such thermoplastic resins may be polypropylene, polyethylene, polyamide, polyethylene oxide and / or polypropylene oxide, reactive rubbers, especially butadiene-acrylonitrile copolymers, and / or natural polymers such as cellulose and / or gelatin, such components comprising one or more reactive groups susceptible to radical or ionic polymerization (e.g. (meth)acrylates, (meth)acrylamides, vinyl esters, vinyl ethers or cyclic ethers such as styrene compounds, epoxy compounds or oxetanes), and / or monomers comprising reactive groups with flexible linkers, especially aliphatic long chains and / or ethylene glycol spacers, and / or monomers with an elongation at break of more than 50% and a T of more than 0°C, preferably more than -30°C. g or is preferably terminated or functionalized, such as with a photocurable component B, which preferably forms a polymerized network, present in an amount of 0.5% to 30% by weight, preferably 2% to 15% by weight, more preferably 5% to 10% by weight, based on the total weight of components A to D.

[0080] In some preferred embodiments, the resin composition of the present invention further comprises an additive that produces good flame retardancy, low smoke toxicity or smoke formation. Such flame retardant or smoke suppressant additives are selected from the group of materials known in the polymer industry. By way of example, such flame retardant or smoke suppressant additives are inorganic fillers or inorganic flame retardants such as aluminum hydroxide, magnesium hydroxide, calcium hydroxide, antimony oxide, tin oxide, borax and / or zinc borate, red phosphorus, expanded graphite, organic additives such as nitrogen donors and / or phosphorus-containing substances (e.g. ammonium polyphosphate, melamine polyphosphate, organic phosphates, triphenylphosphine, phosphinates, 9,10-dihydro-9-oxa-10-phosphaphenanthran-10-oxide), halogenated organic flame retardants such as halogenated phosphates, halogenated diphenyl ethers, halogenated styrenes, halogenated epoxides, halogenated (meth)acrylates and / or halogenated paraffins, preferably in an amount of 0.5% to 50% by weight, preferably 1% to 30% by weight, more preferably 2% to 25% by weight, based on the total weight of components A to D. In another preferred embodiment, such organic flame retardant additives are functionalized with a polymerizable group such as a (meth)acrylate.

[0081] In some preferred embodiments, the resin composition of the present invention comprises organic and / or inorganic fillers, generally described as composites, preferably in an amount of 0.5% to 50% by weight, preferably 1% to 30% by weight, more preferably 2% to 25% by weight, based on the total weight of components A to D.

[0082] Preferred organic fillers can be, but are not limited to, core-shell particles, block copolymers, PTFE, high performance polymers, thermoplastics, especially polyamides, polycarbonates, polystyrene, polyoxymethylene, poly(etherimides), polyethersulfones or polysulfones, rubbers, and the like.

[0083] Preferred inorganic fillers may be metals, metal oxides and / or ceramics (e.g. SiO2, ZrO2, TiO2, ZnO or mixtures thereof with an average particle size of 1 to 100 μm, and / or preferred nano- or micro-fillers with an average particle size of 10 nm to 1000 nm), talc, clay, silica and / or silicates such as mica, glass powders (especially preferred nano- or micro-fillers with an average particle size of 0.01 to 100 μm), carbon black, graphene, graphite. The average particle size of the fillers may be determined by static light scattering using the Mie theory according to DIN / ISO 13320 for the determination of average particle size and particle size distribution. In a second embodiment, such organic or inorganic fillers may be spheres, platelets and / or fibers (e.g. nanofibers, whiskers and / or mixtures thereof, spherical, crushed and / or defined three-dimensional structures (especially graphite), and / or two-dimensional structures (especially graphene monolayers)).

[0084] Preferably, the filler may be modified on its surface (e.g., silanized with a radically polymerized silane such as 3-methacryloyloxypropyltrimethoxysilane). For surface modification of inorganic fillers such as ZrO2 or TiO2, functionalized acid phosphates (e.g., 10-methacryloyloxydecyldihydrogenphosphate) may be used. Such modifications control and / or influence phenomena such as aggregation, mixture stability, particle binding to the polymer matrix, etc.

[0085] The resin composition of the present invention may additionally comprise components such as stabilizers (such as UV stabilizers or anti-aging agents), antioxidants, colorants (such as dyes or pigments), antibacterial agents, antistatic agents, softeners or plasticizers or lubricants, wetting agents, matting agents, adhesion promoters, rheology modifiers, thixotropic agents, dispersants, fluorescent dyes, opacifiers, defoamers and / or UV absorbers, either alone or in combination with one another.

[0086] The resin compositions of the present invention may be cured to form any object including coatings, adhesives, sealants, inks, or preferably cured in a layer-by-layer manner to form 3D parts by a 3D printing process such as stereolithography, followed by post-curing by a secondary or multiple further thermal curing steps.

[0087] The mixture of components A-D disclosed herein may be mixed with the additional components described above in various ratios. The preferred ratios for mixing the formulations are: At least one monofunctional component A (photocurable reactive diluent) according to formula I: 5% to 80% by weight, preferably 10% to 60% by weight, more preferably 15% to 55% by weight, and even more preferably 20% to 45% by weight, based on the total weight of components A, B, C and D At least one component B (photocurable toughness modifier, preferably an oligomer): 10% to 90% by weight, preferably 20% to 80% by weight, more preferably 25% to 70% by weight, even more preferably 30% to 65% by weight, based on the total weight of components A, B, C and D At least one component C (thermosetting T g Raising agent): 1% to 50% by weight, preferably 2% to 40% by weight, more preferably 3% to 30% by weight, and even more preferably 5% to 25% by weight, based on the total weight of components A, B, C and D. At least one photoinitiator: 0.01 to 10% by weight, preferably 0.1 to 7% by weight, more preferably 0.2 to 5% by weight, based on the weight of components A, B and D Optionally, component D as a suitable comonomer which copolymerizes with components A and B and acts as a crosslinking agent (CA) to obtain good processability: 3% to 70% by weight, preferably 5% to 60% by weight, more preferably 7% to 50% by weight, even more preferably 10% to 40% by weight, based on the total weight of components B and D. Optionally, a suitable hardener for component C: may be 0.01% to 20% by weight, preferably 0.1% to 15% by weight, more preferably 0.2% to 10% by weight, based on component C.

[0088] The presence of a monofunctional reactive diluent (ingredient A) reduces the crosslink density, resulting in higher toughness (e.g., as measured by elongation at break), but also reduces the crosslinking temperature, preferably above 40° C., responsible for the formation of the polymer backbone. g , and even more preferably a T of more than 100° C. g The rigid polymer backbone, preferably generated by substituents such as aromatic or cyclic groups having the formula:

[0089] 500gmol -1 More than 1000 gmol, preferably -1 The presence of multifunctional photocurable component B as a toughness modifier, having a molecular weight above 100, is responsible for the formation of a polymer network with improved toughness (eg, increased elongation at break).

[0090] Components A and B are responsible for the photoinduced modeling process and are selected to provide sufficient green strength of the formulation and 3D modeling by hot lithography, preferably using lamination temperatures of 30-150° C. Optionally, the presence of crosslinking component D further improves the green strength of the formulation and 3D modeling by hot lithography, preferably using lamination temperatures of 30-150° C. The photopolymer formed after the photocuring process preferably has a T of more than 25° C. g and is characterized as a tough photopolymer exhibiting an elongation at break of greater than 10%.

[0091] The presence of the multifunctional thermosetting component C preferentially increases the T g Thus, improving the heat resistance (e.g., T) of the final photopolymer network while maintaining toughness (e.g., as measured by elongation at break). g Optionally, component C can also be photocurable by a different curing mechanism (e.g., cationic or radical curing) or at a different wavelength (e.g., radical curing at wavelengths above 390 nm and cationic curing at wavelengths below 380 nm).

[0092] Preferably, the resin composition at room temperature (20° C.) has a viscosity of more than 5 Pa·s. These viscosities result from a particularly high content of component B, whose high molecular weight leads to very high toughness of the materials formed from the resin composition of the present invention. High resin viscosity also results in a particularly high T g This also results from component C having a high softening or melting temperature, which tends to form a secondary network having

[0093] According to a further aspect, the present invention relates to a method for producing an object from the resin composition of the present invention, the resin composition being subjected to a light-induced modeling step followed by a heat-induced curing step. In a preferred embodiment, the light-induced modeling step is followed by a light-induced post-curing step. As will be clear to those skilled in the art, the light-induced curing process may be an additive manufacturing process, more preferably a 3D printing process with respective thermal post-processing steps, to obtain a final product with desired chemical, mechanical and thermal properties. The resin formulation of the present invention may therefore be used as a resin formulation for making 3D objects by additive manufacturing. The obtained 3D parts have an exceptional balance between glass transition temperature and heat resistance while exhibiting high toughness. Potential applications for such additively manufactured 3D objects derived from the materials may be jigs and fixtures, automotive parts (e.g., housings and interiors, parts in contact with fuel such as connectors), electronic connectors, parts for printed circuit boards, packaging and cooling architectures for electronics, chip attachment, robotic hands, battery storage enclosures, healthcare applications (e.g., parts exposed to high temperatures for sterilization), surgical instruments (e.g., retractors, dilators, dissection instruments), oral devices such as surgical guides for dental applications or other examples where mechanical durability and thermal stability at temperatures above 50°C are required.

[0094] According to a preferred embodiment of the method, the light-induced modeling process is performed using a NIR or UV / Vis light source and corresponding optics, the NIR configuration being selected to enable 3D manufacturing via two-photon photopolymerization and the UV / Vis configuration being selected from the group consisting of Laser / DLP, LED / DLP, Laser / LCD and LED / LCD.

[0095] Typically, formulations with viscosities below 1 Pa·s at ambient conditions or slightly elevated temperatures below 35° C. are required for conventional L-AMT, and temperatures above 35° C. are unlikely or not suitable. For resin viscosities above 1 Pa·s at temperatures above 35° C., L-AMT for high viscosity resins at elevated temperatures (e.g., hot lithography) is the printing process of choice.

[0096] In a preferred embodiment, the photoinduced modeling step is carried out at a high processing temperature of the resin composition, preferably between 35° C. and 120° C., more preferably between 40° C. and 100° C., even more preferably between 40° C. and 90° C. This is done for the purpose of providing processability to the high content of component B having a high molecular weight and component C having a high softening or melting temperature during the modeling step, thereby reducing the viscosity of the resin composition of the present invention.

[0097] In a preferred embodiment, a layer of the resin composition is formed on a carrier plate, for example by using a recoater blade. The resin composition preferably has a viscosity at the processing temperature of 0.01 to 70 Pa·s, preferably 0.1 to 30 Pa·s, and the formed layer preferably has a thickness of less than 2 mm, more preferably less than 1 mm, even more preferably less than 0.8 mm.

[0098] The light-induced modeling process is preferably carried out for building an object by 3D printing, the layers of which are alternately deposited by forming material layers of a defined thickness of the resin composition respectively between a transparent or at least partially transparent carrier, such as a plate, carrier film or tank, and a mechanically adjustable construction platform or an object at least partially formed on a construction platform, and the material layers thus defined are hardened in a position-selective manner, in particular by irradiation through the transparent or at least partially transparent carrier, resulting in a layer of the desired shape.

[0099] According to a preferred embodiment, the photoinduced modeling process is carried out using a first radiation source, which is irradiated to the resin composition through a transparent carrier plate, and the heating of the layer of the resin composition to be structured is carried out using a second radiation source, which is essentially opaque to the radiation of the second radiation source. In this way, the carrier plate is heated by the radiation of the second radiation source, which does not essentially enter the layer of the resin composition, and thus the resin composition indirectly heated via the carrier plate is structured by the radiation of the first radiation source. In particular, the thermosetting component C is not thermoset by said second radiation source.

[0100] In a preferred embodiment, a layer of the resin composition is formed on a carrier plate (e.g., by a recoater blade), the layer is cured by a first photocuring step, and the thickness of the formed layer is greater than 10 μm, preferably greater than 25 μm, more preferably 50 μm, even more preferably 80 μm, and less than 1000 μm, preferably less than 800 μm, more preferably less than 500 μm, and even more preferably less than 400 μm. The cured thickness is reduced to more than 1.1 times the layer height of the 3D printing process.

[0101] In a preferred embodiment, the object is manufactured from the resin composition of the present invention and the photoinduced modeling process is an additive manufacturing process and / or a 3D printing process, preferably based on stereolithography, digital light processing, material jetting or inkjet printing, more preferably based on hot lithography techniques.

[0102] After the photocuring step of the resin of the present invention has been carried out, a thermal curing step is carried out to obtain further curing. The heating step may be carried out within a temperature range of 100-300°C, preferably within a temperature range of 100-250°C, at a defined temperature and a defined heating rate (e.g. 10 K min -1 ) into one or more individual curing steps with time intervals defined by: Method A: 160℃ for 10 hours, Method B: 170°C for 0.5 hours and 150°C for 2 hours; Method C → 200°C for 0.5 hours and 160°C for 10 hours; Method D → 120°C for 2 hours and 150°C for 2 hours, It could be.

[0103] In a preferred embodiment, the heat-induced curing step is performed following a stereolithography 3D printing step, and the molded 3D object is cured at a temperature higher than the initial processing temperature of the stereolithography step, which is preferably above 100°C, more preferably above 120°C, even more preferably above 140°C, and at a temperature at which the molding material still exhibits sufficient thermal stability, such as preferably below 250°C, more preferably below 200°C, even more preferably below 180°C.

[0104] In a preferred embodiment, a thermally induced curing process is performed following a stereolithography 3D printing process, where the molded 3D object is cured at a temperature higher than the initial processing temperature of the stereolithography process, and heat is applied directly via active heating in an oven (e.g., electric, gas or solar oven) or indirectly via microwave irradiation, other light impulses (such as infrared) or secondary exothermic reactions such as thermal polymerization and / or combinations thereof.

[0105] In a preferred embodiment, i) an interpenetrating network, or ii) semi-interpenetrating networks, or iii) a sequential interpenetrating network, or iv) polymer blends; A hardened material is formed where

[0106] Subjecting the material of the present invention and / or the resin composition of the present invention to a light-induced shaping process followed by a heat-induced curing process results in an object having the following material properties: i) A tensile strength of 800 MPa or more, a tensile modulus 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 a storage modulus of 1 GPa 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 which the storage modulus of 1 GPa is 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 a storage modulus of 1 GPa 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, a deflection temperature under load of 70°C or more, or v) tensile modulus of elasticity of 2000 MPa or more, tensile strength of 55 MPa or more, elongation at break of 10% or more, deflection temperature under load of 85°C or more, It is preferably characterized in that it exhibits the following:

[0107] As used herein, the term "polymer" refers to a molecule composed of repeating structural units connected by covalent chemical bonds and characterized by a substantial number of repeating units (e.g., 10 or more repeating units, and often 50 or more repeating units, and often 100 or more repeating units) and high molecular weight (e.g., 5000 Da, 10000 Da, or 20000 Da or more). A polymer is generally the polymerization product of one or more monomer precursors. The term "polymer" includes homopolymers or polymers consisting essentially of a single repeating monomer subunit. The term "polymer" also includes copolymers formed when two or more different types of monomers are linked into the same polymer. Copolymers may include two or more monomer subunits and may include random copolymers, block copolymers, alternating copolymers, segmented copolymers, grafted copolymers, tapered copolymers, and other copolymers.

[0108] As used herein, the term "oligomer" refers to a molecule composed of repeating structural units connected by covalent chemical bonds, characterized by a smaller number of repeating units than those of a polymer (e.g., 10 or fewer repeating units) and a lower molecular weight than a polymer (e.g., less than 20,000 Da or 10,000 Da). An oligomer may be the polymerization product of one or more monomer precursors. In one embodiment, an oligomer or monomer cannot be considered a polymer in itself.

[0109] "Prepolymer" refers to a polymer or oligomer, those molecules that are capable of entering into further polymerization via reactive groups.

[0110] The oligomer and polymer mixture may additionally form crosslinks, thereby producing a polymer network.

[0111] Oligomeric and polymeric mixtures can be characterized and differentiated from other mixtures of oligomers and polymers by measuring their molecular weight and molecular weight distribution.

[0112] As used herein, terms such as "molecular weight" refer to number average molecular weight as measured by gel permeation chromatography (GPC) or size exclusion chromatography (SEC) in a suitable solvent (typically tetrahydrofuran) calibrated to polystyrene standards. EXAMPLES

[0113] Embodiments of the present disclosure will be described in further detail with reference to the following non-limiting examples, which are presented for illustrative purposes only and should not be construed as limiting the scope of the invention as defined in the appended claims.

[0114] All chemical reagents used herein were purchased from commercial sources and used without further purification.

[0115] The curable compositions according to the invention were prepared by mixing the respective compounds in a beaker using an Anchor Agitator from IKA or a Speed ​​Mixer DAC 150 FVZ from Hauschild Engineering at a temperature of 30-60° C. This was mixed until the resin was a homogenous blend.

[0116] Photorheological experiments were carried out on an Anton Paar MCR102 rheometer using LED coupling, which allows to mimic the illumination conditions of a commercial hot lithography printer, the Caligma 200. An OmniCure LX500 LED spot source with an LED wavelength of 400 nm was used, with a power intensity of approximately 45 mWcm. -2 All samples were measured in oscillatory mode (PP-10, frequency of 10 Hz, amplitude of 0.1%, temperature set to 30° C., measurement gap of 0.1 mm) and after an initial measurement step of 30 s, the samples were irradiated for 300 s.

[0117] Further rheological measurements of the exemplary materials were carried out on an MCR 102 rheometer. Experiments to evaluate the onset of thermal polymerization were carried out in oscillatory mode (PP-10, 1 Hz frequency, 0.5% amplitude, 2 K min -1 The temperature program was set at 100 to 200°C with a heating rate of 0.5 mm and a measurement gap of 0.5 mm. The resin viscosity was evaluated in rotation mode (PP-25, 50 s -1 Shear rate, 2K min -1 Each resin formulation was measured using a temperature program of 25 to 70°C with a heating rate of 1 mm and a measurement gap of 1 mm.

[0118] (Thermo)mechanical test specimens of the final materials described in this invention were produced from the exemplary resin compositions via hot lithography techniques on a development Caligma DLP printer (365 nm LED for CE1-6.3, E1-6.3, E13-E14 and E17-E19) and a commercial Caligma200 printer (405 nm diode laser for CE7, E7-E12, E15-E16 and E20-E23) from Cubicure GmbH. All printer parts in contact with the formulations (i.e. material tank, recoating unit, recoating blade and building platform) were heated to temperatures ranging from 30°C to 60°C depending on the adjusted printing temperature of each formulation. All 3D parts produced on the Caligma DLP were heated to temperatures ranging from 30°C to 60°C using a 300 W / mW cm2 laser with ... -2 The materials were printed with a light output intensity of 10000 mm s, a layer thickness of 100 μm (25 μm for E6.3) and exposure times of approximately 0.8 s (for CE4-5, E4-5, CE6.1-6.3, E6.1, E6.3, E13-14 and E17-19), approximately 1.6 s (for CE1-3 and E1-3) and approximately 2.4 s (for E6.2). On the top surface of the material tank, the pixel size was set to approximately 50 μm. All 3D parts printed with Caligma200 were printed with a 12000 mm s -1The structuring was performed with a laser scanning intensity of 1000 nm, a laser intensity of 170 mW and a laser thickness of 100 μm. The hatch distance was set to 15 μm in one direction. On the upper surface of the material tank, the laser spot had a diameter of about 20 μm (FWHM). The laser irradiation was repeated once per layer, which indicates the high reactivity of the respective resin formulation.

[0119] After each print job, the 3D printed samples were mechanically removed from the building platform using a blade and excess resin was removed using a wipe and / or via solvent cleaning with isopropanol. A UV post-cure step was performed at 100% intensity (approximately 150 mW cm -2 , broadband width of approximately 280–550 nm) was performed on all 3D printed samples on a Uvitron IntelliRay 600 for 2 × 5 min, flipping the samples between exposure cycles to ensure the photocuring step was complete. Thermal post-processing (second network formation step) was performed using the listed methods (heating rate of 10 K min -1 ) Temperature protocol: Method A → CE1-3, E1-3, CE6.2-6.3 and E6.2-6.3: 160°C for 10 hours Method B → CE4-5 and E4-5: 170°C for 0.5 hours and 150°C for 2 hours Method C → 0.5 hours at 200°C and 10 hours at 160°C for CE6.1 and E6.1 Method D → CE7 and E7-23: 120°C for 2 hours and 150°C for 2 hours; and was carried out in a Heratherm OMH60 oven from Thermo Scientific.

[0120] Tensile tests on the 3D printed samples were carried out using a Zwick / Roell ProLine Z010 TH materials testing machine. Tests were carried out according to DIN EN ISO 527 using 5A specimens. -1 The tensile modulus was measured within the range of 0.05 to 0.25% elongation at a strain rate of 10 mm. -1 The measurement is continued at a strain rate of .

[0121] Storage modulus plot and glass transition temperature T g The DMA measurement to evaluate the temperature was performed with a set temperature program (30℃ to 200℃) and 2K min. -1 The measurements were performed using a dynamic viscoelasticity analyzer (DMA 8000, Perkin Elmer) at a heating rate of 25 × 4 × 2 mm. 3 The sample having a box shape was measured in a three-point bending mode. The test conditions were set to a frequency of 1 Hz, a strain of 50 μm, and a preload force of 0 N. The glass transition temperature T was calculated from the maximum value (tan δ) of the loss factor plot. g Derive.

[0122] Heat deflection temperature (HDT) measurements were carried out according to the HDT / Vicat 3-300 standard. HDT(B) tests were carried out according to DIN EN ISO 75. For HDT(B), a load of 0.45 MPa was applied to the sample specimens (80 x 10 x 4 mm) on a flat surface. 3 The starting temperature for each measurement was set at 26°C, and the samples were subjected to the respective loading forces for 5 minutes each. -1 A temperature gradient of 1000 s was carried out.

[0123] Preliminary Exam: The low photoreactivity of the thermosetting component C was verified using LED coupling in the MCR102 rheometer. This makes it possible to mimic the irradiation conditions of the Caligma 200, a commercially available hot lithography printer. From FIG. 4, it can be seen that photocurable resins such as Comparative Example 3 (CE3) showed sufficient photocurability (gelation in less than 3 seconds) to support 3D printing in the Caligma printer, while thermosetting components C such as the allyl compounds TAIC or DAP show very low or no reactivity upon exposure (gelation in more than 10 seconds, outside the range of light output set on the Caligma DLP or Caligma 200 printer during 3D printing). This makes the aforementioned component C non-reactive via the light impulses set on the Caligma printer during the 3D printing process, which is the photocuring step.

[0124] Further, the exemplary thermosetting components C used within the examples of the present disclosure and combined with each of the thermal initiator or catalyst examples (triallyl isocyanurate (TAIC), diallyl phthalate (DAP) and oligomer of 1,3-bis(citraconimidomethyl)benzene (OBCI) with 0.5 phr of dicumyl peroxide, 4,4'-bismaleimidodiphenylmethane (BMIDPM) with 2 phr of 2-ethyl-4-methylimidazole, multifunctional epoxy resin bisphenol A diglycidyl ether (BADGE) with 5 phr of dicyandiamide) were characterized with respect to the initiation temperature for thermal polymerization. All samples were measured on an MCR102 rheometer in oscillatory mode within the temperature range of 100-200°C. The thermosetting component C is required to exhibit good storage stability at ambient conditions and further exhibit thermal stability at typical processing temperatures for hot lithographic printing, between 30 and 120°C. Preferably, the onset of thermal cure of the thermosetting component C is within a temperature window between 120 and 200°C. All evaluated examples of component C exhibit good storage stability at ambient conditions (at least over 3 months), which is also confirmed by the respective raw material suppliers. Furthermore, the thermal cure of each component C is confirmed within a temperature range of 120 to 200°C (see FIG. 5), which is beneficial for thermal post-processing of the 3D photopolymer parts of the present invention. The aryl-based component C (TAIC at about 145°C and DAP at about 165°C) and the imide-based component C (OBCI at about 140°C and BMIDPM at about 155°C) exhibit more favorable thermal onset temperatures in the range of 140 to 180°C, when compared to the epoxy-based component BADGE, which has an onset temperature slightly above 190°C. However, this initiation temperature of the epoxy-based components may be adjusted for the alternative state-of-the-art curing agents described in this disclosure to fall within the preferred temperature range of 140-180°C, which constitutes a method known to those skilled in the art.

[0125] Example 1 to Example 3 Examples 1-3, which are examples of resin compositions of the present invention, are composed of photocurable components A and B in combination with a thermosetting component C, and Comparative Examples 1-3 are photocurable resin compositions prepared by including components A and B (for CE3) and, optionally, crosslinking component D (for CE1-2) instead of thermosetting component C.

[0126] [Table 1]

[0127] Preparation of resin formulations: CE1: 18.9 g of monofunctional photocurable component A, isobornyl methacrylate, as RD, 44.1 g of photocurable component B, difunctional aliphatic urethane acrylate, Ebecryl 8811, as TNM, and 7 g of multifunctional crosslinking component D, bisphenol A-glycidyl dimethacrylate, as CA, were homogenized with 0.7 g (1 phr) of photoinitiator ethyl (2,4,6-trimethylbenzoyl)phenylphosphinate (TPO-L) and 0.35 g (0.5 phr) of thermal initiator dicumyl peroxide (DCP).

[0128] CE2: 18.9 g of monofunctional photocurable component A, isobornyl methacrylate, as RD, 44.1 g of photocurable component B, difunctional aliphatic urethane acrylate Ebecryl 8811, as TNM, and 7 g of multifunctional crosslinking component D, tris(2-hydroxyethyl)isocyanurate, as CA, were homogenized with 0.7 g (1 phr) of photoinitiator ethyl(2,4,6-trimethylbenzoyl)phenylphosphinate (TPO-L) and 0.35 g (0.5 phr) of thermal initiator dicumyl peroxide (DCP).

[0129] CE3: 21 g of monofunctional photocurable component A, isobornyl methacrylate, as RD, and 49 g of photocurable component B, Ebecryl 8811, a difunctional aliphatic urethane acrylate, as TNM, were homogenized with 0.7 g (1 phr) of photoinitiator ethyl (2,4,6-trimethylbenzoyl)phenylphosphinate (TPO-L) and 0.35 g (0.5 phr) of thermal initiator dicumyl peroxide (DCP).

[0130] E1: 18.9 g of monofunctional photocurable component A, isobornyl methacrylate, as RD, 44.1 g of photocurable component B, Ebecryl 8811, a difunctional aliphatic urethane acrylate, as TNM, and 7 g of thermally curable component C, diallyl phthalate, as TGE, were homogenized with 0.7 g (1 phr) of photoinitiator ethyl (2,4,6-trimethylbenzoyl)phenylphosphinate (TPO-L) and 0.35 g (0.5 phr) of thermal initiator dicumyl peroxide (DCP).

[0131] E2: 18.9 g of monofunctional photocurable component A, isobornyl methacrylate, as RD, 44.1 g of photocurable component B, Ebecryl 8811, a difunctional aliphatic urethane acrylate, as TNM, and 7 g of thermally curable component C, triallyl isocyanurate, as TGE, were homogenized with 0.7 g (1 phr) of photoinitiator ethyl (2,4,6-trimethylbenzoyl)phenylphosphinate (TPO-L) and 0.35 g (0.5 phr) of thermal initiator dicumyl peroxide (DCP).

[0132] E3: 19.95 g of monofunctional photocurable component A, isobornyl methacrylate, as RD, 46.55 g of photocurable component B, Ebecryl 8811, a difunctional aliphatic urethane acrylate, as TNM, and 3.5 g of thermally curable component C, triallyl isocyanurate, as TGE, were homogenized with 0.7 g (1 phr) of photoinitiator ethyl (2,4,6-trimethylbenzoyl)phenylphosphinate (TPO-L) and 0.35 g (0.5 phr) of thermal initiator dicumyl peroxide (DCP).

[0133] [Table 2]

[0134] Consideration When thermosetting component C is incorporated into a photocurable matrix as a TGE, it maintains toughness (e.g., elongation at break) or significantly exceeds the strength, modulus, and T of a comparable component (e.g., crosslinking component D) that also photocures but does not support the formation of a secondary network. gAn increase in elongation at break is expected. Example E1 exhibits significant improvements in strength (+23%), modulus (+10%) and thermal properties (+20%) when compared to Comparative Example CE3, which is composed only of components A and B, while only compromising elongation at break by about 19% (Table 2 and Figures 6a and 6b). Comparative Example CE1, however, exhibits significantly improved hardness, along with improved strength (+54%), modulus (+39%) and thermal properties (+30%) when compared to CE3, while significantly compromising elongation at break by 50%. It is clear that Example E1 exceeds Comparative Example CE1 by improving overall thermal properties without significantly sacrificing toughness as measured by elongation at break (+20% thermal properties and -19% toughness for E1 over +30% thermal properties and -50% toughness for CE1, see Figure 6b). While this is a first strong indicator of higher performance for the hybrid resin system, the comparison of DAP as component C in E1 and Bisphenol A-glycidyl dimethacrylate as component D in CE1 is not ideal since Bisphenol A-glycidyl dimethacrylate contains significantly more aromatic moieties between the crosslinks which is responsible for the higher overall strength and thermal performance compared to E1.

[0135] Example E2 suffers from a loss of elongation at break of about 40%, but results in significant improvements in strength (+42%), modulus (+23%) and thermal properties (+37%) when compared to comparative example CE3, which is composed only of components A and B (Table 2 and Figures 6c and 6d). When measuring comparative examples CE2 and CE3, rather similar hardness is recorded, along with improvements in strength (+38%) and modulus (+27%), but a very low improvement in thermal properties (only +16%) is recorded when compared to E2 for CE3. Further comparison of CE2 and CE3 also suffers from a loss of elongation at break of about 40%. It is clear that example E2 exceeds comparative example CE2 by improving overall thermal properties without significantly sacrificing toughness as measured by elongation at break (+37% thermal properties and -40% toughness for E2 over +16% thermal properties and -40% toughness for CE1, see Figure 6d).

[0136] When comparing the second example E2 with the comparative example CE2 directly, a more ideal comparison can be made since the thermosetting component C in E2, which is triallyl isocyanurate as the TGE, has a very similar molecular structure compared to the photocurable crosslinking component D in CE2, which is tris(2-hydroxyethyl) isocyanurate as the CA. As can be derived from the obtained data, E2 and CE2 show almost identical mechanical performance (less than 5% deviation for E2 vs. CE2), but E2 shows a significant improvement in thermal properties (+18% compared to CE2), which is very beneficial in terms of potential applications of the material system of the present invention (Table 2 and Figures 6c and 6d). In addition, as shown for E3, when the content of thermosetting component C is reduced by a factor of two, the impact on thermal performance is still evident (+18% compared to CE2). g is higher but the modulus with respect to temperature is reduced), while the elongation at break remains higher at +18% than CE2 (Table 2 and Figure 6c).

[0137] Example 4~Example 5 Examples 4-5, which are examples of resin compositions of the present invention, are composed of photocurable components A, B, and D in combination with a thermosetting component C, and Comparative Examples 4-5 make respective photocurable resin compositions containing components A, B, D, and an additional crosslinking component D which makes thermosetting component C for Examples 4-5.

[0138] [Table 3]

[0139] Preparation of resin formulations: CE4: 25 g of monofunctional photocurable component A, isobornyl methacrylate, as RD, 45 g of photocurable component B, difunctional aliphatic urethane acrylate, Ebecryl 8811, as TNM, and 30 g of multifunctional crosslinking component D, tris(2-hydroxyethyl)isocyanurate, as CA, were homogenized with 2 g (2 phr) of photoinitiator ethyl(2,4,6-trimethylbenzoyl)phenylphosphinate (TPO-L) and 0.5 g (0.5 phr) of thermal initiator dicumyl peroxide (DCP).

[0140] CE5: 25 g of monofunctional photocurable component A, isobornyl methacrylate, as RD, 45 g of photocurable component B, difunctional polyether urethane methacrylate, as TNM, and 30 g of multifunctional crosslinking component D, tris(2-hydroxyethyl)isocyanurate, as CA, were homogenized with 2 g (2 phr) of photoinitiator ethyl(2,4,6-trimethylbenzoyl)phenylphosphinate (TPO-L) and 0.5 g (0.5 phr) of thermal initiator dicumyl peroxide (DCP).

[0141] E4: 25 g of monofunctional photocurable component A, isobornyl methacrylate as RD, 45 g of photocurable component B, difunctional aliphatic urethane acrylate Ebecryl 8811 as TNM, 15 g of multifunctional crosslinking component D, tris(2-hydroxyethyl)isocyanurate as CA, and 15 g of thermal curable component C, triallyl isocyanurate as TGE, were homogenized with 2 g (2 phr) of photoinitiator ethyl(2,4,6-trimethylbenzoyl)phenylphosphinate (TPO-L) and 0.5 g (0.5 phr) of thermal initiator dicumyl peroxide (DCP).

[0142] E5: 25 g of monofunctional photocurable component A, which is isobornyl methacrylate as RD, 45 g of photocurable component B, which is difunctional polyether urethane methacrylate as TNM, 15 g of multifunctional crosslinking component D, which is tris(2-hydroxyethyl)isocyanurate as CA, and 15 g of thermal curable component C, which is triallyl isocyanurate as TGE, were homogenized with 2 g (2 phr) of photoinitiator ethyl(2,4,6-trimethylbenzoyl)phenylphosphinate (TPO-L) and 0.5 g (0.5 phr) of thermal initiator dicumyl peroxide (DCP).

[0143] [Table 4]

[0144] Consideration Examples E4 and E5 significantly exceeded their comparative counterparts CE4 and CE5 in terms of thermal performance (e.g., temperature and T g While the modulus vs. elongation - see Figures 7a and 7b) materials E4 and E5 show nearly identical mechanical performance when compared to CE4 and CE5 respectively (see tensile test results in Table 4). Both examples contain thermosetting component C, triallyl isocyanurate as the TGE, instead of photocurable component D, tris(2-hydroxyethyl)isocyanurate as the CA, and are represented in equal amounts in CE4 and CE5 respectively. In addition, thermosetting component C has been shown to have a relatively small detrimental effect on toughness as measured by elongation at break, but a significant impact on thermal performance by acting as a TGE, as evidenced in the comparative examples.

[0145] Example 6.1 to Example 6.3 Examples 6.1-6.3, which are examples of resin compositions of the present invention, are composed of photocurable components A and B in combination with a thermosetting component C, while Comparative Examples 6.1-6.2 are made from the same resin composition but post-processed via different methods (Method C for CE6.1 and Method A for CE6.2) to make respective photocurable resin compositions containing components A, B and crosslinking component D instead of thermosetting component C. Comparative Example 6.3 is made from a respective photocurable resin composition containing components A and B.

[0146] [Table 5]

[0147] Preparation of resin formulations: CE6.1 and CE6.2: 27 g of monofunctional photocurable component A, N-acryloylmorpholine as RD, 63 g of photocurable component B, Ebecryl 8811, a difunctional aliphatic urethane acrylate as TNM, and 10 g of multifunctional crosslinking component D, tris(2-hydroxyethyl)isocyanurate as CA, were homogenized with 1 g (1 phr) of photoinitiator ethyl(2,4,6-trimethylbenzoyl)phenylphosphinate (TPO-L) and 0.5 g (0.5 phr) of thermal initiator dicumyl peroxide (DCP).

[0148] CE6.3: 30 g of monofunctional photocurable component A, N-acryloylmorpholine as RD, and 70 g of photocurable component B, Ebecryl 8811, a difunctional aliphatic urethane acrylate as TNM, were homogenized with 1 g (1 phr) of ethyl (2,4,6-trimethylbenzoyl)phenylphosphinate (TPO-L) photoinitiator and 0.5 g (0.5 phr) of dicumyl peroxide (DCP) thermal initiator.

[0149] E6.1: 27 g of monofunctional photocurable component A, N-acryloylmorpholine as RD, 63 g of photocurable component B, Ebecryl 8811, a difunctional aliphatic urethane acrylate as TNM, and 10 g of thermosetting component C, multifunctional epoxy resin bisphenol A diglycidyl ether (BADGE), as TGE, were homogenized with 1 g (1 phr) of ethyl (2,4,6-trimethylbenzoyl)phenylphosphinate (TPO-L), a photoinitiator, 0.5 g (0.5 phr) of dicumyl peroxide (DCP), a thermal initiator, and 0.5 g (5 phr based on the weight of BADGE), a latent thermal hardener, dicyandiamide.

[0150] E6.2: 27 g of monofunctional photocurable component A, N-acryloylmorpholine as RD, 63 g of photocurable component B, Ebecryl 8811, a difunctional aliphatic urethane acrylate as TNM, and 10 g of thermally curable component C, oligomer of 1,3-bis(citraconimidomethyl)benzene (OBCI), as TGE, were homogenized with 1 g (1 phr) of photoinitiator ethyl (2,4,6-trimethylbenzoyl)phenylphosphinate (TPO-L) and 0.5 g (0.5 phr) of thermal initiator dicumyl peroxide (DCP).

[0151] E6.3: 27 g of monofunctional photocurable component A, N-acryloylmorpholine as RD, 63 g of photocurable component B, Ebecryl 8811, a difunctional aliphatic urethane acrylate as TNM, and 10 g of thermally curable component C, 4,4'-bismaleimidodiphenylmethane (BMIDPM), as TGE, were homogenized with 1 g (1 phr) of photoinitiator ethyl (2,4,6-trimethylbenzoyl)phenylphosphinate (TPO-L), 0.5 g (0.5 phr) of thermal initiator dicumyl peroxide (DCP), and 0.2 g (2 phr based on the weight of BMIDPM) of thermal catalyst 2-ethyl-4-methylimidazole.

[0152] [Table 6]

[0153] Consideration In Example 6.1, when a thermosetting component C, such as the multifunctional epoxy resin bisphenol A diglycidyl ether (BADGE), is incorporated as a TGE into a photocurable matrix of components A and B, the mechanical performance in terms of strength and modulus, as well as the T g Thermal properties in this respect are slightly decreased by approximately 5-15%, but toughness, as measured by elongation at break, is dramatically improved (approximately +50%) when compared directly with Comparative Example CE6.3, which does not contain crosslinking component D and is composed solely of photocurable components A and B (Table 6 and Figures 8a and 8b). The multifunctional epoxy resin in this case, bisphenol A diglycidyl ether (BADGE), exhibits the appropriate T g Although not present in a preferred amount to act as an enhancer, the toughness of the photopolymer is greatly improved by the resulting double network structure. g For E6.1, BADGE also exhibits poor thermal properties when compared to the allyl derivatives of Examples E1-5, although it is clear to one skilled in the art that by modifying the BADGE content or adapting the curing conditions (e.g., the content of the thermal curing agent dicyandiamide, additional accelerators such as amines, ureas or imidazoles), the thermal properties of photopolymers derived from E6.1 or similar formulations can be significantly improved.

[0154] Comparative Example CE6.1 is not an ideal comparison to E6.1 due to the high functionality of component D, tris(2-hydroxyethyl)isocyanurate, as CA. However, in this case (see FIG. 8b), it is clear that E6.1 is superior to CE6.1, since CE6.1 exhibits a slight improvement in mechanical and thermal performance (about 10-25% overall) but suffers a significant loss in toughness as measured by elongation at break (about 30%). Again, this proves to be a clear advantage for the inventive resin formulations disclosed herein.

[0155] Examples 6.2 and 6.3 are comprised of citraconimide-based and maleimide-based components C, TGEs classified as high temperature thermosets, respectively. Both examples show a high increase in thermal performance (higher T as measured by higher modulus vs. temperature plots and tan δ) when compared to Comparative Example CE6.3, which contains only components A and B. g , see Fig. 8c). For E6.2 with OBCI, a citraconimide-based oligomer, the toughness was almost maintained (less than 10% loss, see Table 6 and Fig. 8c) when compared to CE6.3, but the thermal properties were obviously improved (see Fig. 8d). For E6.3 with BMIDPM, a bismaleimide-based monomer, the thermal and mechanical properties were significantly improved (about 20-40%) (see Fig. 8e) due to the higher degree of crosslinking and the higher amount of fixed aromatic moieties inside the final photopolymer network structure, but here the toughness was significantly impaired (about 40%), indicating that in this case component C exceeded its preferred amount and the toughness could not be fully maintained, although the thermal properties were significantly improved. However, the elongation at break was maintained at more than 20%, which is due to the T above 100 °C. g This is an exceptional value for photopolymer networks having

[0156] Example 7: An example of a resin composition of the present invention, Example 7, is composed of photocurable components A, B and D in combination with a thermosetting component C, and Comparative Example 7 is a photocurable resin composition made with additional monofunctional component A in place of components A, B, D and thermosetting component C.

[0157] [Table 7]

[0158] Preparation of resin formulations: CE7: ​​27 g of monofunctional photocurable component A, N-acryloylmorpholine as RD, 46 g of photocurable component B, difunctional polyether urethane methacrylate as TNM, 16 g of photocurable component B, difunctional aliphatic urethane acrylate as TNM, and 11 g of multifunctional crosslinking component D, isophorone urethane dimethacrylate as CA, were homogenized with 1.5 g (1.5 phr) of photoinitiator phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (BAPO) and 0.5 g (0.5 phr) of thermal initiator dicumyl peroxide (DCP).

[0159] E7: 10 g of monofunctional photocurable component A, N-acryloylmorpholine as RD, 46 g of photocurable component B, difunctional polyether urethane methacrylate as TNM, 16 g of photocurable component B, difunctional aliphatic urethane acrylate as TNM, 11 g of multifunctional crosslinking component D, isophorone urethane dimethacrylate as CA, and 17 g of thermal curable component C, triallyl isocyanurate as TGE, were homogenized with 1.5 g (1.5 phr) of photoinitiator phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (BAPO) and 0.5 g (0.5 phr) of thermal initiator dicumyl peroxide (DCP).

[0160] [Table 8]

[0161] Consideration Example 7 shows that there is a high potential for substituting component A as the RD with thermosetting component C as the TGE to arrive at a photopolymer material with improved strength, modulus and high thermal performance (Table 8), but in this case the elongation at break is more dramatically sacrificed when component C is added to a resin formulation made from components A and B in other resin examples. Nevertheless, this example shows how the resin toolbox of the present invention offers great potential for improving the overall thermal performance of the final 3D part and maintaining toughness.

[0162] Example 8 to Example 23 Examples 8 to 23, which are examples of the resin composition of the present invention, are composed of a plurality of photocurable components A, B and, optionally, D in combination with a thermosetting component C.

[0163] [Table 9]

[0164] [Table 10]

[0165] Preparation of resin formulations: E8-23: 100 g of each resin formulation was prepared by mixing the components in Tables 9-10 in the respective weight ratios. All formulations were homogenized with 1.5 g (1.5 phr) of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (BAPO) as a photoinitiator and 0.5 g (0.5 phr) of dicumyl peroxide (DCP) as a thermal initiator.

[0166] [Table 11]

[0167] [Table 12]

[0168] Consideration Examples 8 to 23 are high T through hot lithography and thermal post-processing. g At the same time, the resin composition of the present invention is processed into a material having high elongation at break.

[0169] The results obtained by subjecting the resin composition of the present invention to a light-induced modeling process followed by a heat-induced curing process show the following material properties: i) A tensile modulus of elasticity of 1300 MPa or more, a tensile strength of 35 MPa or more, an elongation at break of 20% or more, and a deflection temperature under load of 70°C or more (E8, E11 to E16, E20 to E21), or ii) Tensile modulus of elasticity of 2000 MPa or more, tensile strength of 55 MPa or more, elongation at break of 10% or more, and deflection temperature under load of 85°C or more (E9-10, E17-19, E22-23); A material exhibiting

[0170] Examples E8-10 show how a resin composition containing a higher content of component B with higher functionality (in this case tetrafunctional) can yield a material with high mechanical and thermal properties but with reduced elongation at break. A similar effect is observed in examples E11-14 by implementing component B, a difunctional aliphatic urethane methacrylate, which has lower mechanical and thermal performance when compared to the tetrafunctional component B of E8-10.

[0171] In Examples E15 to E19, how much of component A mainly contributes to toughness, which is the elongation at break, and how much of component C mainly contributes to T g It becomes clear which is the main contributor to the thermal performance, which is . Examples E20-23 show the effect of increasing component D substituting for component B, resulting in higher (thermo)mechanical performance but lower toughness.

[0172] These non-limiting examples show how the resin toolbox of the present invention offers great potential for improving thermal performance and maintaining toughness throughout the final 3D part. [Brief description of the drawings]

[0173] [Figure 1] 1 shows a schematic diagram of a high temperature additive manufacturing apparatus used for photocuring a curable composition according to the present invention by a 3D printing process. [Diagram 2] FIG. 1 shows a schematic example of network formation via a first photocuring step with components A (RD) and B (TNM) and a subsequent thermal curing step with component C (TGE). [Diagram 3]FIG. 1 shows a schematic example of network formation via a first photocuring step with components A (RD), B (TNM) and D (CA) and a subsequent thermal curing step with component C (TGE). [Figure 4] 1 shows data collected from photorheology experiments (photocure step) using comparative resin CE3 and thermosetting component C (TGE, which is TAIC and DAP). [Diagram 5] 1 shows data collected from thermorheology experiments (mimicking a thermosetting process) with Component C (TGEs that are TAIC, DAP, OBCI, BMIDPM and BADGE). [Figure 6a] 1 shows data collected from DMA of photopolymer E1 that was printed (photocuring process) and post-cured (thermal curing process) in comparison with CE1 and CE3 (storage modulus plot top, tan δ plot - bottom). [Figure 6b] 1 shows the (thermo)mechanical performance of printed (photocuring process) and post-cured (thermal curing process) photopolymer E1 compared to CE3, comparing CE1 and CE3 in terms of their percentage deviation. [Figure 6c] 1 shows data collected from DMA of printed (photocure process) and post-cured (thermal cure process) photopolymers E2 and E3 compared to CE2 and CE3 (storage modulus plot top, tan δ plot - bottom). [Figure 6d] 1 shows the (thermo)mechanical performance of printed (photocuring process) and post-cured (thermal curing process) photopolymer E2 compared to CE2 and CE3, comparing CE2 and CE3 in terms of their percentage deviations. [Figure 7a] 1 shows data collected from DMA of printed (photocuring process) and post-cured (thermal curing process) photopolymer E4 compared to CE4 (storage modulus plot top, tan δ plot - bottom). [Figure 7b] 1 shows data collected from DMA of printed (photocuring process) and post-cured (thermal curing process) photopolymer E5 compared to CE5 (storage modulus plot top, tan δ plot - bottom). [Figure 8a]1 shows data collected from DMA of printed (photocuring process) and post-cured (thermal curing process) photopolymer E6.1 compared to CE6.1 and CE6.3 (storage modulus plot top, tan δ plot - bottom). [Figure 8b] Figure 1 shows the (thermo)mechanical performance of printed (photocuring process) and post-cured (thermal curing process) photopolymer E6.1 compared to CE6.1 and CE6.3, comparing CE6.1 and CE6.3 in terms of their percentage deviations. [Figure 8c] 1 shows data collected from DMA of printed (photocuring process) and post-cured (thermal curing process) photopolymers E6.2 and E6.3 compared to CE6.2 and CE6.3 (storage modulus plot top, tan δ plot - bottom). [Figure 8d] Figure 1 shows the (thermo)mechanical performance of printed (photocuring process) and post-cured (thermal curing process) photopolymer E6.2 compared to CE6.2 and CE6.3, comparing CE6.2 and CE6.3 in terms of their percentage deviations. [Figure 8e] Figure 1 shows the (thermo)mechanical performance of printed (photocuring process) and post-cured (thermal curing process) photopolymer E6.3 compared to CE6.2 and CE6.3, comparing CE6.2 and CE6.3 in terms of their percentage deviations.

[0174] In Fig. 1, reference number 1 denotes a material support on which material layers 11 are arranged. Spaced apart from the material support 1, a construction platform 8 is arranged, which is height adjustable in the z direction and tiltably mounted about an axis 4. Between the construction platform 8 and the material support 1, several material layers 11 are already built up. The material support 1 is translatable along the x direction perpendicular to the z material.

[0175] Further provided is a material introduction device 3 including a first recoater blade 5 and a second recoater blade 6. The first recoater blade 5 is height adjustable in the z-direction by a recoater motor 10, and the second recoater blade 6 has a spring 7 that holds the second recoater blade 6 adjacent to the material support 1 in the z-direction. Between the two recoater blades 5 and 6, a material container 2 is formed to which the resin composition of the present invention can be supplied by a conveyor 9.

[0176] In the method stage shown in Fig. 1, the material support 1 is in a second position. The build platform 8 is lowered in the direction of the material support 1, so that a novel material layer 11 of the resin composition of the invention can be formed by the material layer 11 and selectively irradiated by a radiation source (not shown) through the material support 1 from below and onto the material support 1, thereby being structured and solidified. The material layer 11 has been applied by a first recoater blade 5 during the movement of the material support 1 in the second position.

Claims

1. A hybrid resin composition for 3D printing of objects, comprising components A, B, and C, a) Component A is given by formula (I): X-Y formula (I) A monofunctional photocurable component comprising at least one reactant Y that is susceptible to radical polymerization and a side group X, wherein component A forms a polymer skeleton during photo-induced curing, and the skeleton is rated at temperatures above 25°C. ｇ It has, b) Component B is at least one monofunctional or polyfunctional photocurable component copolymerized with component A, and is 500 gmol －１ Having a number-average molecular weight greater than that of component B, the component B exhibits an elongation at break of more than 10% during photo-induced curing and a temperature above 0°C that is greater than that of a homopolymer of component B alone. ｇ Forms a polymer network having c) Component C is at least one monofunctional or polyfunctional thermosetting component, and the T of the homopolymer of component C alone above 100°C ｇ A second polymerization network having the following is formed: Based on the total weight of components A, B, and C, the amount of photocurable component A is in the range of 5% to 80% by weight, the amount of photocurable component B is in the range of 10% to 90% by weight, and the amount of thermosetting component C is in the range of 1% to 50% by weight. Component C is one or more compounds selected from the group consisting of allyl, vinyl, maleimide, citracomimide, benzoxazine, epoxy, phenol, cyanate ester, phthalonitrile and their oligomers or polymers, and / or their isomers, and / or combinations thereof, formula (II) 【Chemistry 1】 And in the formula, -n is an integer between 1 and 10, -R １ However, H, CH ３ or CH ２ This represents, -R ２ is methyl, ethyl, propyl, butyl, pentyl, hexyl, 2-ethylhexyl, octyl, decanyl, dodecanyl, acetic acid, propanoic acid, butanoic acid, pentanoic acid, undecanoic acid, dodecanoic acid, benzoic acid and the 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, one or more of the linear, branched or cyclic C ５ -C ４０ aliphatic residue or aromatic residue, independently, and one or more of these groups are one or more C １ -C ６ alkyl, C １ -C ６ alkoxy, C １ -C ６ thioether, halogen, -NO ２ , -SO ３ H, -CF ３ , -OH, -NH ２ , -SH, -CN, -trimethoxysilyl, -triethoxysilyl, optionally substituted by one or more ester, amide, urea, urethane, carbonate, ether, thioether groups, or maleimide and citraconimide compounds and / or polymers derived from the substance classification of their isomers, independently bonded via It comprises one or more chemical species selected from the group consisting of monomers, and / or oligomers, and / or prepolymers, of the maleimide and citracomide derivatives described above and their isomers, The aforementioned hybrid resin composition Based on the total weight of components A, B, and C, 5% to 80% by weight of component A, Based on the total weight of components A, B, and C, 10% to 90% by weight of component B, Based on the total weight of components A, B, and C, 1% to 50% by weight of component C, Includes, Component A is one or more compounds selected from the group consisting of monofunctional (meth)acrylates, (meth)acrylamides, vinyl esters and N-vinyl compounds, particularly 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, 2-(methacryloyloxy) cyclopentyl benzoate, 2-(methacryloyloxy) cyclohexyl benzoate, 2 - (methacryloyloxy)benzoate-2-isopropyl-5-methylcyclohexyl, 3- (methacryloyloxy)benzoate-2-isopropyl-5-methylcyclohexyl, 4- (methacryloyloxy)benzoate-2-isopropyl-5-methylcyclohexyl, 2- (methacryloyloxy)benzoate-3,3,5-trimethylcyclohexyl, 2- (acryloyloxy)benzoate-3,3,5-trimethylcyclohexyl, 2- (methacryloyloxy)benzoate decahydronaphthalene-2-yl, 2- (methacryloyloxy)benzoate-1,3,3-trimethyl-2-bicyclo[2.2.1]heptanyl, 2- (methacryloyloxy)benzoate-1,7,7-Trimethyl-2-bicyclo[2.2.1]heptanyl ester, 2-(methacryloyloxy)benzoate-bicyclo[2.2.1]heptan-2-ylmethyl ester, 2-(methacryloyloxy)benzoate-2-cyclohexylethyl ester, 2-(methacryloyloxy)benzoate benzyl ester, 4-(methacryloyloxy)benzoate benzoate, 3-(methacryloyloxy)benzoate-4-isopropylbenzyl ester, 2-(acryloyloxy)benzoate benzyl ester, 2-(methacryloyloxy)benzoate phenethyl ester, 4-(methacryloyloxy)-3-methoxybenzoate-3-methoxybenzyl ester, 2-(methacryloyloxy) It comprises one or more compounds selected from the group consisting of salicylates (meth)acrylates such as xy)-1-phenylethyl benzoate, 4-((methacryloyloxy)methyl)cycloheptyl benzoate and 2-(methacryloyloxy)cyclohexylmethyl benzoate, cholesteryl (meth)acrylate, biphenyl (meth)acrylate, phenylacrylamide, diacetone acrylamide, t-butylacrylamide, N-acryloylmorpholine, N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylformamide, vinyl cinnamate, vinylmethyloxazolidinone, and 2-(allyloxymethyl)methyl acrylate, Component B comprises one or more compounds selected from the group consisting of polyfunctional (meth)acrylates, particularly ethoxylated bisphenol A di(meth)acrylate, aliphatic urethane di(meth)acrylate, polyether urethane (meth)acrylate, hydrophobic urethane (meth)acrylate, polyester urethane (meth)acrylate, polyester di(meth)acrylate, modified epoxy di(meth)acrylate, and oligomeric polycarbonate di(meth)acrylate. Polyfunctional allyl compounds containing fixed substituents that contribute to the formation of a polymer skeleton or polymer network that provides the required high Tg, such as a group C that exhibits strong intermolecular forces and / or a high functional value (greater than 2) with respect to aromatic groups, and / or cyclic aliphatic groups, and / or heterocyclic groups, and / or reactive groups, particularly 1,3,5-trialyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,4,6-trialyloxy-1,3,5-triazine, trialyl borate, trialyl 1,3,5-benzenetricarboxylate, trialyl citrate, trialyl phosphate, tetraallyl pyromelitate, tetraallyloxyethane, diallylpropyl isocyanurate, diallyl isocyanurate, diallyl phthalate, 2,2-bis(4-allyloxy-3,5-dibromophenyl)propane, diallyl dicarbonate, diallyl carbonate, diallyl 1,4-Cyclohexanedicarboxylate, 2,2-Diallylbisphenol A diacetate ether, Diallyl terephthalate, Diallyl isophthalate, Diethyldiallyl malonate, 1,3-Diallylurea, 1,3-Diallyl-2-thiourea, 2,4-Diamino-6-Diallylamino-1,3,5-Triadin, Diallyl oxylate, Diallyl malonate, Diallyl tetrabromophthalate, 2,6-Dially-methacresol, N,N-Diallylaniline, Diallylcyanamide, N,N-Diallylmelamine, 2,2'-Diallylbisphenol A, N,N'-Diallylpiperazine, 2,2-Diallylpyrrolidine, Diallyl-carbamic acid The compound comprises one or more compounds selected from the group consisting of tert-butyl ester, diallyl ether bisphenol A, diallylphenyl phosphonate, 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. Characterized by, Hybrid resin composition.

2. Component B is partially substituted by crosslinking component D, which is at least one photocurable crosslinking agent (CA) copolymerized with component A and component B. The resin composition according to claim 1, characterized in that the amount of the crosslinking component D is 3% by weight to 70% by weight, based on the total weight of component B and component D in the resin composition.

3. Component C is required to have a high T ｇ The resin composition according to claim 1 or 2, characterized by comprising one or more compounds selected from the group consisting of polyfunctional epoxy compounds including fixed substituents that are responsible for forming a polymer backbone or polymer network that results in: 4,4'-methylenebis(N,N-diglycidylaniline), trimethylolpropane triglycidyl ether, (3',4'-epoxycyclohexane)methyl-3,4-epoxycyclohexylcarboxylate, condensation products of 1,2-epoxy-4(2-oxyranyl)-cyclohexane and 2,2-bis(hydroxymethyl)1-butanol, bisphenol A novolac epoxy resin, oligomers of derivatives thereof, and prepolymers of derivatives thereof.

4. Component D is i) Polyfunctional (meth)acrylates and / or mixtures of polyfunctional (meth)acrylates, ii) Aromatic group or cyclic aliphatic group, iii) Trifunctional, tetrafunctional, pentafunctional and / or hexafunctional (meth)acrylates, and / or hyperbranched and / or dendritic meta(acrylates) having even more functional sites, The resin composition according to claim 2 or 3, characterized by containing the following.

5. Component D is i) 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate and 1,12-dodecanediol di-(meth)acrylate, tri or tetraethylene glycol di(meth)acrylate, pentaerythritetra(meth)acrylate and trimethylolpropane tri(meth)acrylate, or ii) 2-(2-biphenyloxy)-ethyl (meth)acrylate, bisphenol-A-di(meth)acrylate (adducts derived from (meth)acrylic acid and bisphenol A-diglycidyl ether), ethoxylylated 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)acryloyloxypropoxy)phenyl]propane, tricyclodecanedimethanol di(meth)acrylate, isophorone urethane di(meth)acrylate and tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, A resin composition according to any one of claims 1 to 4, characterized by comprising one or more compounds selected from the group consisting of the following.

6. The resin composition according to any one of claims 1 to 5, characterized in that the hybrid resin compound further comprises a comonomer and / or cooligomer and / or coprepolymer that is copolymerizable with component C and its derivatives.

7. The resin composition according to any one of claims 1 to 6, characterized in that the resin composition contains at least one photoinitiator suitable for radical polymerization when photoexcited in a wavelength spectrum of 150 nm to 1000 nm, in an amount of 0.01% to 10% by weight, based on the total weight of components A, B, and D.

8. The resin composition according to any one of claims 1 to 7, characterized in that the resin composition comprises at least one thermal initiator and / or catalyst for the thermosetting of component C, wherein the catalyst is selected from the group consisting of tertiary amines, other aliphatic and aromatic secondary and tertiary amines, alkali salts of organic alcohols, phosphines, triphenylphosphonates, imidazoles, organic acids, and / or peroxides.

9. The resin composition according to any one of claims 1 to 8, characterized in that the resin composition comprises one or more initiators for radical polymerization.

10. The resin composition comprises a toughness modifier selected from the group consisting of thermoplastic resins, reactive rubbers, butadiene-acrylonitrile copolymers, and / or natural polymers. The toughness modifier is a monomer containing the reactive group having a flexible linker, such as (meth)acrylate, (meth)acrylamide, vinyl ester, vinyl ether or styrene compound, epoxy compound or oxetane, and / or elongation at break of more than 50% and T below 0°C. ｇ Photocurable component B, which forms a polymerization network having such a polymer network, is terminated or functionalized with one or more reactive groups that are susceptible to radical polymerization or ionic polymerization. The resin composition according to claims 1 to 9, characterized in that the toughness modifier is present in an amount of 0.5% to 30% by weight based on the total weight of components A, B, C, and D.

11. The resin composition according to any one of claims 1 to 10, characterized in that the resin composition comprises at least one or more components selected from the group consisting of polymerization initiators, polymerization inhibitors, solvents, fillers, antioxidants, pigments, dyes, surface modifiers, core-shell particles and / or mixtures thereof.

12. A resin composition according to any one of claims 7 to 11, characterized in that a photoinitiator, a thermal initiator, a catalyst, a curing agent, a polymerization initiator, a polymerization inhibitor, a solvent, a filler, an antioxidant, a pigment, a dye, a surface modifier, core-shell particles and / or mixtures thereof are polymeric and / or are further functionalized by polymerization functional groups that can be polymerized by component A, component B and component D and / or component C.

13. The resin composition according to any one of claims 1 to 12, characterized in that the resin composition has a viscosity of more than 2 Pa·s at 20°C.

14. The resin composition according to any one of claims 1 to 13, characterized in that the resin composition further comprises an inorganic flame retardant and / or an organic additive, a halogenated organic flame retardant, in an amount of 0.5% to 50% by weight, based on the total weight of components A, B, C, and D.

15. A method for manufacturing an object by 3D printing, wherein the resin composition according to any one of claims 1 to 14 is post-cured via a photo-induced molding step, optionally via secondary exposure, and subsequently subjected to a thermal induction curing step.

16. The method according to claim 15, characterized in that the photo-induced molding process is carried out at a processing temperature of the resin composition between 30°C and 150°C.

17. The method according to claim 15 or 16, characterized in that the photo-guided fabrication step is carried out using an NIR configuration or a UV / Vis configuration and a corresponding optical system, 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.

18. The aforementioned photo-induced fabrication process includes constructing the object layer by layer on a structural platform to obtain a stack of structural layers, wherein each structural layer is - A step of forming a non-structured layer of a predetermined thickness in the resin composition, - A step of selectively projecting light onto the unstructured layer according to a desired pattern, thereby curing the resin composition to obtain the structural layer, The method according to any one of claims 15 to 17, characterized in that it is obtained by

19. The method according to claim 18, characterized in that the unstructured layer of the resin composition has a viscosity of 0.01 to 70 Pa·s at a processing temperature of 30°C to 150°C.

20. The method according to any one of claims 15 to 19, characterized in that the thermal induction curing step is carried out at a temperature higher than the processing temperature of 30°C to 150°C of the photo-induced molding step.

21. The method according to any one of claims 15 to 19, characterized in that the thermal induction curing step includes heating the object in an oven and / or exposing the object to electromagnetic radiation and / or inducing a secondary exothermic reaction in the object.

22. An object comprising the resin composition according to any one of claims 1 to 14.

23. The aforementioned object is part of a mutual intrusion network, i) A network of mutual intrusions, or ii) Semi-mutual invasion network, or iii) Sequential mutual intrusion network, or iv) Polymer blend, The object according to claim 22, characterized by including

24. i) Tensile modulus of 800 MPa or higher, tensile strength of 25 MPa or higher, elongation at break of 20% or higher, glass transition temperature of 45°C or higher, and temperature value at storage modulus of 1 GPa of 30°C or higher, or ii) Tensile modulus of 1500 MPa or higher, tensile strength of 35 MPa or higher, elongation at break of 5% or higher, glass transition temperature of 90°C or higher, and temperature value of storage modulus of 1 GPa of 45°C or higher, or iii) Tensile modulus of 2000 MPa or higher, tensile strength of 50 MPa or higher, elongation at break of 5% or higher, glass transition temperature of 100°C or higher, and temperature value of storage modulus of 1 GPa of 60°C or higher, or iv) Tensile modulus of 1300 MPa or higher, tensile strength of 35 MPa or higher, elongation at break of 20% or higher, temperature of deflection under load of 70°C or higher, or v) Tensile modulus of 2000 MPa or higher, tensile strength of 55 MPa or higher, elongation at break of 10% or higher, temperature of deflection under load of 85°C or higher. The object according to claim 22 or 23, characterized by exhibiting the following characteristics.

Images