Radiation-hardening components

Abstract

A radiation-curable composition comprising: a) 30-70% by weight of a radiation-polymerizable monomer (A) containing an N-vinylamide moiety; and b) 30-70% by weight of a number-average molecular weight (M) of 60,000 g / mol or less. n A radiation-curable composition comprising a thermoplastic polyurethane (B) having ) obtained from a polyol selected from the group consisting of polyester polyols, polyether polyols, polycaprolactone polyols, polycarbonate polyols and any combination thereof, and a radiation-sensitive polymerization initiator (C), wherein the weight % is based on 100% by weight of the radiation-polymerizable monomer (A) and the thermoplastic polyurethane (B).

Description

[Technical Field]

[0001] The present invention relates to a radiation-curable composition particularly suitable for use in three-dimensional printing, and to an article that can be obtained from the radiation-curable composition. [Background technology]

[0002] Three-dimensional printing technology is widely used for the production of three-dimensional articles and objects, starting from digital models. The materials used in the three-dimensional printing process, often referred to as resins, are typically subjected to either curing or fusing. Photocurable acrylics, for example, are typically used in curing-based three-dimensional printing technologies, while thermoplastic resins are generally used in fusing-based technologies. Both resin systems typically have various technical deficiencies. Three-dimensional articles obtained from photocurable acrylics usually suffer from insufficient mechanical properties, particularly toughness, due to excessive crosslinking density. With regard to the use of thermoplastic resins, which are typically used in sintering or heat-assisted extrusion processes, they usually result in articles characterized by insufficient resolution and poor surface finish properties.

[0003] A partial solution is described, for example, in International Publication No. 2022 / 136142 (Mc Grail et al.). Without disputing the technical advantages related to solutions known in the art, there is still a need for material that at least partially addresses the above-mentioned shortcomings. [Overview of the Initiative]

[0004] According to one aspect, the present disclosure relates to a radiation-curable composition, a) 30-70% by weight of a radiation-polymerizable monomer (A) containing an N-vinylamide moiety, b) A thermoplastic polyurethane (B) having a number average molecular weight (Mn) of 60,000 g / mol or less in an amount of 30 to 70% by weight, wherein the thermoplastic polyurethane (B) is obtained from a polyol selected from the group consisting of polyester polyols, polyether polyols, polycaprolactone polyols, polycarbonate polyols and any combination thereof, c) Radiosensitive polymerization initiator (C) and Includes, The present invention relates to a radiation-curable composition in which the weight percentage is based on 100% by weight of the radiation-polymerizable monomer (A) and the thermoplastic polyurethane (B).

[0005] In another aspect, the present disclosure relates to a method for producing the above-mentioned radiation-curable composition, the method being: a) A step of forming a mixed material by bringing the radiation polymerizable monomer (A) into the presence of the thermoplastic polyurethane (B), b) Optionally, a step of subjecting the mixture material to thermal energy, c) Optionally, a step of subjecting the mixture material to mechanical mixing. It is directed towards methods that include this.

[0006] In yet another aspect, the disclosure relates to the use of the above-mentioned radiation-curable compositions in three-dimensional printing processes, particularly in three-dimensional printing processes using vat (photo) polymerization technology. [Modes for carrying out the invention]

[0007] According to a first aspect, the present disclosure relates to a radiation-curable composition, a) 30-70% by weight of a radiation-polymerizable monomer (A) containing an N-vinylamide moiety, b) A thermoplastic polyurethane (B) having a number average molecular weight (Mn) of 60,000 g / mol or less in an amount of 30 to 70% by weight, wherein the thermoplastic polyurethane (B) is obtained from a polyol selected from the group consisting of polyester polyols, polyether polyols, polycaprolactone polyols, polycarbonate polyols and any combination thereof, c) Radiosensitive polymerization initiator (C) and Includes, The present invention relates to a radiation-curable composition in which the weight percentage is based on 100% by weight of the radiation-polymerizable monomer (A) and the thermoplastic polyurethane (B) when combined.

[0008] In the context of this disclosure, it has been found that the above-described radiation-curable compositions possess excellent solubility, excellent formulation stability, and favorable formulation flexibility, even at room temperature (i.e., about 23°C). Advantageously, the radiation-curable compositions of this disclosure, when stored for extended periods, are in the form of a homogeneous liquid formulation at room temperature, and maintain that homogeneous liquid formulation form, thereby allowing the thermoplastic polyurethane (B) to be (substantially) completely solubilized (or dissolved) in the radiation-curable composition. Even more advantageously, the thermoplastic polyurethane (B) is (substantially) completely solubilized (or dissolved) in the radiation-polymerizable monomer (A).

[0009] Even more surprisingly, the above radiation-curable compositions were found to be particularly suitable for forming cured polymer materials with excellent characteristics and performance attributes with respect to mechanical properties (especially tensile strength, elongation at break, and Young's modulus) and volume shrinkage.

[0010] Although not wishing to be bound by theory, these excellent features and attributes are considered to be due, in particular, to the use of a specific combination of (a) a radiation-polymerizable monomer (A) and (b) a thermoplastic polyurethane (B) as specifically described above, and the radiation-polymerizable monomer (A) and the thermoplastic polyurethane (B) are included in the radiation-curable composition within the specific ranges detailed above.

[0011] More specifically, surprisingly, a thermoplastic polyurethane (B) having a number-average molecular weight (Mn) of 60,000 g / mol or less, wherein the thermoplastic polyurethane (B) is obtained from (or derived from) a polyol selected from the group consisting of a polyester polyol, a polyether polyol, a polycaprolactone polyol or a polycarbonate polyol, has been found to contribute to providing a cured polymer material having an excellent balance of the mechanical properties detailed above. With respect to the radiation-polymerizable monomer (A) containing an N-vinylamide moiety, surprisingly, it has been found that the N-vinylamide moiety provides excellent dissolution properties with respect to the thermoplastic polyurethane (B) defined above. Although not wishing to be bound by theory, it is further considered that these excellent dissolution properties are promoted by the relatively high polarity, high dilution power and excellent ability to reduce viscosity increase resulting from the N-vinylamide moiety present in the radiation-polymerizable monomer (A).

[0012] Considering that it is somewhat technically self-contradictory or at least quite difficult to achieve both particularly high tensile strength and high elongation at break, these are particularly surprising and counterintuitive findings.

[0013] In the context of this disclosure, the applicant has faced the challenging task of formulating a radiation-curable composition that can combine at least two compounds having very different chemical properties, namely a thermoplastic material (B) and a radiation-polymerizable monomer (A) that formally act as reactive diluents and are generally recognized to provide poor compatibility with one another.

[0014] Therefore, the radiation-curable compositions of this disclosure are very suitable for use in three-dimensional printing processes, particularly in three-dimensional printing using vat (photo) polymerization technology.

[0015] Furthermore, in the context of this disclosure, the applicant has succeeded in combining the good mechanical properties provided by thermoplastic materials (and typically used in sintering or heat-assisted three-dimensional printing processes) with the ability to use liquid photopolymer resins (usually including photocurable acrylics) that, in this case, provide a variety of advantageous features when used in three-dimensional printing methods, such as processing speed, curing speed, high resolution, excellent reproducibility, and flexibility.

[0016] Furthermore, the above radiation-curable compositions were found to be recyclable. In particular, after proper radiation curing, the resulting cured polymer material was found to be at least partially (preferably completely) (re)dissolved in the radiation-polymerizable monomer (A) described herein for further (re)use. This is also a particularly surprising and counterintuitive finding, given that radiation-curable polymer materials are thermosetting and generally perceived to be difficult to recycle.

[0017] Therefore, the radiation-curable compositions of this disclosure are highly suitable for use in circular economy production and consumption models.

[0018] The radiation-curable composition of this disclosure comprises, as a first component, 100% by weight of a radiation-polymerizable monomer (A) and a thermoplastic polyurethane (B), with 30 to 70% by weight of the radiation-polymerizable monomer (A) containing an N-vinylamide moiety.

[0019] In one advantageous embodiment, the radiation-curable composition comprises 35-65% by weight, 40-60% by weight, or 45-55% by weight of the radiation-polymerizable monomer (A) based on 100% by weight of the radiation-polymerizable monomer (A) and a thermoplastic polyurethane (B).

[0020] The radiation-polymerizable monomer (A) for use herein is not particularly limited, as long as it contains an N-vinylamide moiety. Suitable radiation-polymerizable monomers (A) for use herein will be readily identifiable to those skilled in the art in light of this disclosure.

[0021] In a favorable embodiment, the radiopolymerizable monomer (A) for use herein is the following general formula (I): (L)CON(CH=CH2)(Q)(I) Having During the ceremony, L is a linear, branched, or cyclic hydrocarbon radical optionally substituted with an alkyl, hydroxyl, or alkoxy group, and / or optionally interrupted with an oxygen or nitrogen atom. Q is a linear, branched, or cyclic hydrocarbon radical optionally substituted with an alkyl, hydroxyl, or alkoxy group, and / or optionally interrupted with an oxygen or nitrogen atom, and Optionally, L and Q may be covalently bonded to form a linked or cyclic structure.

[0022] In another advantageous embodiment, the radiation-polymerizable monomer (A) for use herein contains (substantially) no additional (chemically) radiation-curable functional groups other than the vinyl group. In this advantageous embodiment, the radiation-polymerizable monomer (A) may be referred to as a monofunctional radiation-polymerizable monomer.

[0023] The monofunctional radiation-polymerizable monomer (A), detailed above, was surprisingly found to favorably influence the low volume shrinkage properties of the cured polymer material resulting from the curing of the radiation-curable composition according to this disclosure. While we do not wish to be bound by theory, it is thought that the use of monofunctional radiation-polymerizable monomer (A) favorably influences the crosslinking density of the cured polymer material, helping to maintain its level within an optimal range during the curing process, and in particular preventing the formation of excessively high crosslinking densities.

[0024] In a more advantageous embodiment, the radiation polymerizable monomer (A) for use herein is N-vinylpyrrolidone; N-vinylpiperidone; N-vinylcaprolactam; N-vinyl-3-methylpyrrolidone; N-vinyl-4-methylpyrrolidone; N-vinyl-5-methylpyrrolidone; N-vinyl-3-ethylpyrrolidone; N-vinyl-3-butylpyrrolidone; N-vinyl-3,3-dimethylpyrrolidone; N-vinyl-4,5-dimethylpyrrolidone; N-vinyl-5,5-dimethylpyrrolidone; N-vinyl- 5-methyl-5-ethylpyrrolidone; N-vinyl-3,4,5-trimethyl-3-ethylpyrrolidone; N-vinyl-6-methyl-2-piperidone; N-vinyl-6-ethyl-2-piperidone; N-vinyl-3,5-dimethyl-2-piperidone; N-vinyl-4,4-dimethyl-2-piperidone; N-vinyl-6-propyl-2-piperidone; N-vinyl-3-octylpiperidone; N-vinyl-7-methylcaprolactam; N-vinyl-7-ethylcaprolactam; N-vinyl-4-isopropylcaprolactam; N-vinyl-5-isopropylcaprolactam Lactam; N-vinyl-4-butylcaprolactam; N-vinyl-5-butylcaprolactam; N-vinyl-4-butylcaprolactam; N-vinyl-5-tert-butylcaprolactam; N-vinyl-4-octylcaprolactam; N-vinyl-5-tert-octylcaprolactam; N-vinyl-4-nonylcaprolactam; N-vinyl-5-tert-nonylcaprolactam; N-vinyl-3,7-dimethylcaprolactam; N-vinyl-3,5-dimethylcaprolactam; N-vinyl-4,6-dimethylcaprolactam; N-vinyl-3 ,5,7-trimethylcaprolactam; N-vinyl-2-methyl-4-isopropylcaprolactam; N-vinyl-5-isopropyl-7-methylcaprolactam; N-vinylformamide; N-vinylacetamide; N-vinylpropionamide; N-vinyl-N-methylacetamide; N-vinyl-N-methylpropionamide; N-vinyl-N-propylpropionamide; N-vinyloxazolidinone; N-vinyl-5-methyloxazolidinone; N-vinyl-4-methyloxazolidinone; N-vinyl-4,5-dimethyloxazolidinone;Selected from the group consisting of and any mixture thereof.

[0025] In a more advantageous embodiment, the radiation polymerizable monomer (A) is selected from the group consisting of N-vinylpyrrolidone; N-vinylpiperidone; N-vinylcaprolactam; N-vinyloxazolidinone; N-vinyl-5-methyloxazolidinone; N-vinylformamide; and any mixture thereof.

[0026] In a more advantageous embodiment, the radiation polymerizable monomer (A) is selected from the group consisting of N-vinylpyrrolidone; N-vinylcaprolactam; N-vinyl-5-methyloxazolidinone; N-vinylformamide; and any mixture thereof.

[0027] In a preferred embodiment, the radiation polymerizable monomer (A) for use herein is selected from the group consisting of N-vinylpyrrolidone; N-vinylcaprolactam; and any mixture thereof.

[0028] In a more preferred embodiment, the radiopolymerizable monomer (A) for use herein is selected to include N-vinylpyrrolidone.

[0029] In a particularly advantageous embodiment, the radiation polymerizable monomer (A) for use herein has a cyclic structure and is preferably of the following general formula (II): [ka] It has, During the ceremony, X is either oxygen or a carbon atom. R is an alkyl, hydroxyl, or alkoxy group, preferably R is an alkyl group, and n is an integer between 0 and 6, 0 and 5, 0 and 4, 0 and 3, or 0 and 2.

[0030] In the above general formula (II), the group X and the nitrogen atom N are typically linked by covalent bonds to form a linked or cyclic structure. Advantageously, such cyclic structures include hydrocarbon (main) chains containing 2 to 12, 2 to 10, 2 to 8, 2 to 6, or 2 to 4 carbon atoms. More advantageously, the cyclic structures include hydrocarbon (main) chains containing 12 or fewer, 10 or fewer, 8 or fewer, 6 or fewer, or 4 or fewer carbon atoms.

[0031] In the radiation polymerizable monomer (A) having the above general formula (II), n is typically 6 or less, 5 or less, 4 or less, 3 or less, or 2 or less.

[0032] In the context of this disclosure, it has been surprisingly found that radiation-polymerizable monomers (A) having a cyclic structure and typically possessing the above general formula (II) favorably influence the mechanical properties (particularly tensile strength) of cured polymer materials resulting from the curing of radiation-curable compositions. While we do not wish to be bound by theory, it is thought that the use of cyclic polymerizable monomers (A) favorably increases the overall glass transition temperature of the radiation-curable compositions according to this disclosure, which in turn is thought to have a beneficial effect on the mechanical properties of the cured polymer materials.

[0033] The radiation-curable composition of this disclosure comprises, as a second component, a thermoplastic polyurethane (B) having a number-average molecular weight (Mn) of 60,000 g / mol or less, wherein the thermoplastic polyurethane (B) is obtained from a polyol selected from the group consisting of polyester polyols, polyether polyols, polycaprolactone polyols, polycarbonate polyols, and any combination thereof.

[0034] In one advantageous embodiment, the radiation-curable composition is based on 100% by weight of a radiation-polymerizable monomer (A) and a thermoplastic polyurethane (B), comprising 35-65% by weight, 40-60% by weight, or 45-55% by weight of the thermoplastic polyurethane (B).

[0035] The thermoplastic polyurethane (B) for use herein is not particularly limited, as long as it satisfies the requirements detailed above regarding the number-average molecular weight (Mn) and chemical properties of the starting polyol. Suitable thermoplastic polyurethane (B) for use herein will be readily identifiable to those skilled in the art in light of this disclosure.

[0036] The number-average molecular weight (Mn) of thermoplastic polyurethane (B) is typically measured by conventional gel permeation chromatography (GPC) techniques well known to those skilled in the art.

[0037] In a favorable embodiment, the thermoplastic polyurethane (B) has a number average molecular weight (M) of 60,000 g / mol or less, 55,000 g / mol or less, 50,000 g / mol or less, 45,000 g / mol or less, 40,000 g / mol or less, 35,000 g / mol or less, 30,000 g / mol or less, 25,000 g / mol or less, or 20,000 g / mol or less. n ) has.

[0038] According to another advantageous embodiment, thermoplastic polyurethane (B) has a number average molecular weight (M) in the range of 10,000-60,000 g / mol, 10,000-55,000 g / mol, 15,000-50,000 g / mol, 15,000-45,000 g / mol, 20,000-45,000 g / mol, 20,000-40,000 g / mol, 25,000-40,000 g / mol, 30,000-40,000 g / mol, or 35,000-40,000 g / mol. n ) has.

[0039] In the context of this disclosure, it has been found that thermoplastic polyurethanes (B) that satisfy the above-detailed requirements regarding the number-average molecular weight (Mn) and chemical properties of the starting polyols provide excellent solubility in radiation-curable compositions, particularly in radiation-polymerizable monomers (A), even at room temperature (i.e., at a temperature of about 23°C). Thermoplastic materials that do not satisfy any of these above-detailed requirements have been found to provide at least insufficient solubility in radiation-curable compositions, particularly in radiation-polymerizable monomers (A), at room temperature. Although we do not wish to be bound by theory, a number-average molecular weight (Mn) of 60,000 g / mol or less is desirable. n The use of thermoplastic polyurethane (B) having ) is considered to provide optimal solubility properties with respect to at least a very specific type of radiation polymerizable monomer, represented by radiation polymerizable monomer (A) containing an N-vinylamide moiety.

[0040] In an advantageous embodiment, the thermoplastic polyurethane (B) for use herein is obtained from a polyol selected from the group consisting of polyester polyols, polyether polyols, polycarbonate polyols, and any combination thereof.

[0041] In a more advantageous embodiment, the thermoplastic polyurethane (B) is obtained from a polyol selected from the group of polyester polyols.

[0042] In the context of this disclosure, it has been surprisingly found that thermoplastic polyurethanes (B) obtained from polyols selected from the group of polyester polyols offer an optimal balance between (a) the solubility at room temperature of radiation-curable compositions, particularly of radiation-polymerizable monomers (A), and (b) the mechanical properties of cured polymer materials resulting from the curing of radiation-curable compositions.

[0043] Suitable thermoplastic polyurethanes (B) for use herein can be readily obtained by starting with at least one polyol selected from the group consisting of polyester polyols, polyether polyols, polycaprolactone polyols, polycarbonate polyols and any combination thereof, according to manufacturing techniques and processes well known to those skilled in the art.

[0044] A suitable thermoplastic polyurethane (B) can typically be obtained by polymerizing at least one polyol, at least one polyisocyanate, and optionally at least one chain extender as defined above, and by using well-known methods such as the one-shot method and the prepolymer method.

[0045] In a typical embodiment, thermoplastic polyurethane (B) is a) At least one polyol selected from the group consisting of polyester polyols, polyether polyols, polycaprolactone polyols, polycarbonate polyols, and any combination thereof; b) at least one type of polyisocyanate; and c) Optionally, at least one chain extender It is a reaction product.

[0046] Typically, at least one polyisocyanate for use herein is selected from the group consisting of aromatic polyisocyanates, aliphatic polyisocyanates, and any combination or mixture thereof.

[0047] Typically, at least one (optional) chain extender for use herein is selected from the group consisting of diols having hydrocarbon chains containing six or fewer carbon atoms; in particular ethylene glycol; diethylene glycol; propylene glycol; propylene glycol; 1,3-propylene glycol; dipropylene glycol; 1,4-butylene glycol; 1,5-pentanediol and 1,6-hexanediol; diamines having hydrocarbon chains containing six or fewer carbon atoms, in particular ethylenediamine, diaminopropane, diaminobutane and diaminopentane; and any combination or mixture thereof.

[0048] Alternatively, a suitable thermoplastic polyurethane (B) for use herein may be purchased from a chemical supplier. Commercially available thermoplastic polyurethanes (B) for use in this disclosure are known, for example, by trade names in the "ESTANE®" or "PEARLBOND®" series from Lubrizol Corporation.

[0049] In a favorable embodiment, the thermoplastic polyurethane (B) is substantially free of (chemically) radiation-curable functional groups. Surprisingly, such thermoplastic polyurethane (B) has been found to favorably influence the low volume shrinkage properties of the cured polymer material resulting from the curing of the radiation-curable composition according to the present disclosure. While we do not wish to be bound by theory, the use of thermoplastic polyurethane (B) which is substantially free of (chemically) radiation-curable functional groups is thought to favorably influence the crosslinking density of the cured polymer material, helping to maintain its level within an optimal range during the curing process, and in particular preventing the formation of excessively high crosslinking densities.

[0050] According to one particular embodiment, the radiation-curable composition according to this disclosure, a) 30-70% by weight of a radiation-polymerizable monomer (A) containing an N-vinylamide moiety, b) Number average molecular weight (M) of 30-70% by weight, less than or equal to 60,000 g / mol nA thermoplastic polyurethane (B) having ), wherein the thermoplastic polyurethane (B) is obtained from a polyol selected from the group consisting of polyester polyol, polyether polyol, polycaprolactone polyol, polycarbonate polyol and any combination thereof, c) Radiosensitive polymerization initiator (C) and It resides in, The aforementioned weight percentage is based on 100% by weight of the radiation-polymerizable monomer (A) and the thermoplastic polyurethane (B).

[0051] The radiation-curable compositions of this disclosure further comprise a radiation-sensitive polymerization initiator (C). Suitable radiation-sensitive polymerization initiators (C) for use herein are not particularly limited and will be readily identifiable to those skilled in the art in light of this disclosure. Any radiation-sensitive polymerization initiator generally known in the art may be used in the context of this disclosure.

[0052] Such initiators are desirable to assist in the curing of radiation-curable compositions. Advantageously, the radiation-sensitive polymerization initiators used herein are photopolymerization initiators and therefore absorb radiation, such as UV light radiation of a wavelength and intensity sufficient to generate free radical species and initiate the curing of the curable components of the radiation-curable composition.

[0053] Radiosensitive polymerization initiators (C) for use herein are commercially available from BASF under the trade names IRGACURE® and DAROCUR®. A specific example of a suitable radiosensitive polymerization initiator (C) is 1-hydroxycyclohexylphenyl ketone (available as BASF IRGACURE® IC-184). Other exemplary radiosensitive polymerization initiators (C) for use herein are described in detail, for example, in U.S. Patent Application Publication 2018 / 0100073 (Chopra et al.).

[0054] The radiosensitive polymerization initiator (C) may be present in any suitable or desired amount. In a typical embodiment of this disclosure, the total amount of radiosensitive polymerization initiator (C) contained in the radiocurable composition is in the range of 0.5 to 15% by weight, 1 to 10% by weight, or 1 to 5% by weight, based on the total weight of the radiocurable composition.

[0055] As is common practice in this art, the radiation-curable compositions of this disclosure may further include additional radiation-polymerizable compounds to modify certain properties or performance attributes and to meet the specific requirements of a targeted application.

[0056] According to one particular embodiment, the radiation-curable composition further comprises another radiation-polymerizable monomer (D) different from the radiation-polymerizable monomer (A). Suitable radiation-polymerizable monomers (D) for use herein are not particularly limited and will be readily identifiable by those skilled in the art in light of this disclosure.

[0057] The radiation-polymerizable monomer (D) for use herein may typically be selected from the group consisting of monomers containing one radiation-curable functional group, monomers containing two radiation-curable functional groups, monomers containing three radiation-curable functional groups, and any mixture thereof. In the context of this disclosure, the radiation-polymerizable monomer (D) may also be referred to as a reactive diluent.

[0058] In a favorable embodiment, the radiation-polymerizable monomer (D) is selected from the group consisting of monofunctional (meth)acrylate monomers, difunctional (meth)acrylate monomers, trifunctional (meth)acrylate monomers, and any mixture thereof. An example radiation-polymerizable monomer (D) for use herein is described, for example, in U.S. Patent Application Publication No. 2018 / 0100073 (Chopra et al.).

[0059] In another particular embodiment, the radiation-curable composition further comprises a radiation-polymerizable oligomer (E). Suitable radiation-polymerizable oligomers (E) for use herein are not particularly limited and will be readily identifiable to those skilled in the art in light of this disclosure.

[0060] The radiation-polymerizable oligomer (E) for use herein may typically be selected from the group consisting of oligomers containing one radiation-curable functional group, oligomers containing two radiation-curable functional groups, oligomers containing three radiation-curable functional groups, and any mixture thereof.

[0061] In advantageous embodiments, the radiation-polymerizable oligomer (E) is selected from the group consisting of urethane (meth)acrylate oligomers, polyester (meth)acrylate oligomers, epoxy (meth)acrylate oligomers, and any combination or mixture thereof. An example radiation-polymerizable oligomer (E) for use herein is described, for example, in U.S. Patent Application Publication No. 2018 / 0100073 (Chopra et al.).

[0062] If present, the radiation-polymerizable monomer (D) or radiation-polymerizable oligomer (E) described herein may be present in any appropriate or desired amount, depending on the target properties or applications of the radiation-curable composition.

[0063] As is common in the art, the radiation-curable compositions of this disclosure may further contain additional compounds as optional additives. These include, but are not limited to, dyes, fillers, modifiers, stabilizers, and adhesion promoters.

[0064] According to a typical embodiment of the radiation-curable composition of this disclosure, the thermoplastic polyurethane (B) for use herein is (substantially) completely solubilized in the radiation-curable composition, thereby forming a (homogenous) liquid at 23°C.

[0065] According to a more typical embodiment of this disclosure, the thermoplastic polyurethane (B) for use herein is (substantially) completely solubilized in a radiation-polymerizable monomer (A), thereby forming a (homogenous) liquid at 23°C.

[0066] Therefore, the radiation-curable compositions of this disclosure may not be suitable as dispersions or emulsions. In a typical embodiment, the radiation-curable composition is in the form of a single-phase homogeneous liquid.

[0067] In a typical embodiment, the radiation-curable compositions described herein are (substantially) non-aqueous.

[0068] In another typical embodiment of this disclosure, the radiation-curable composition is (substantially) 100% solid.

[0069] The radiation-curable compositions of this disclosure possess advantageous viscosity properties that make them particularly suitable for use in three-dimensional printing processes, especially in three-dimensional printing processes using vat (photo) polymerization technology.

[0070] In a typical embodiment, the radiation-curable compositions described herein have a viscosity of 300 Pa·s or less, 280 Pa·s or less, 250 Pa·s or less, 230 Pa·s or less, 200 Pa·s or less, 180 Pa·s or less, 150 Pa·s or less, 130 Pa·s or less, 100 Pa·s or less, 80 Pa·s or less, 60 Pa·s or less, 50 Pa·s or less, 40 Pa·s or less, 30 Pa·s or less, 25 Pa·s or less, or 20 Pa·s or less when measured at 60°C according to the test method described in the Experiments section.

[0071] In another typical embodiment, the radiation-curable compositions described herein have viscosities in the range of 5–300 Pa·s, 5–250 Pa·s, 10–200 Pa·s, 15–150 Pa·s, 15–100 Pa·s, 15–80 Pa·s, 20–60 Pa·s, 20–40 Pa·s, or 20–30 Pa·s when measured at 60°C according to the test methods described in the Experiments section.

[0072] As described above, the radiation-curable compositions of this disclosure are very suitable for use in a variety of technical applications.

[0073] In one advantageous embodiment, the radiation-curable compositions of the present disclosure are intended for use in three-dimensional printing processes, particularly in three-dimensional printing processes using vat (photo) polymerization technology.

[0074] In another advantageous embodiment, the radiation-curable compositions of this disclosure are intended for use in a coating process.

[0075] In yet another advantageous embodiment, the radiation-curable compositions of the present disclosure are intended for use in bonding or sealing processes.

[0076] In yet another advantageous embodiment, the radiation-curable compositions described herein are for the manufacture of adhesive or encapsulant compositions.

[0077] The radiation-curable compositions of this disclosure can be readily obtained according to manufacturing techniques and processes well known to those skilled in the art. Suitable techniques and processes for obtaining radiation-curable compositions are not particularly limited and will be readily identifiable to those skilled in the art in light of this disclosure.

[0078] In another aspect, the present disclosure relates to a method for producing the above-mentioned radiation-curable composition, the method being: a) A step of forming a mixed material by bringing the radiation polymerizable monomer (A) into the presence of the thermoplastic polyurethane (B), b) Optionally, a step of subjecting the mixture material to thermal energy, c) Optionally, a step of subjecting the mixture material to mechanical mixing. It is directed towards methods that include this.

[0079] In one particular embodiment, the step of bringing a radiation-polymerizable monomer (A) into the presence of a thermoplastic polyurethane (B) is carried out by adding the entirety of the thermoplastic polyurethane (B) to the entirety of the radiation-polymerizable monomer (A), or vice versa, in a suitable reactor.

[0080] In another specific embodiment, the step of bringing a radiation-polymerizable monomer (A) into the presence of a thermoplastic polyurethane (B) is carried out by successively adding a portion of the thermoplastic polyurethane (B) to all or a portion of the radiation-polymerizable monomer (A), or vice versa, into a suitable reactor.

[0081] In one beneficial embodiment, a mixture material formed by bringing a radiation-polymerizable monomer (A) into the presence of a thermoplastic polyurethane (B) is subjected to the application of thermal energy, particularly heat. This is particularly advantageous for improving the solubilization properties of the thermoplastic polyurethane (B) into a radiation-curable composition, especially into a chemically radiation-polymerizable monomer (A). In a typical embodiment, the mixture material is heat-treated at temperatures in the range of 70–90°C, 70–85°C, or 80–85°C.

[0082] In another beneficial embodiment, a mixture material formed by bringing a radiation-polymerizable monomer (A) into the presence of a thermoplastic polyurethane (B) undergoes mechanical mixing. This is equally advantageous for improving the solubilization properties of the thermoplastic polyurethane (B) into a radiation-curable composition, particularly into a chemically radiation-polymerizable monomer (A).

[0083] In a favorable embodiment, the method of the present disclosure provides a radiation-curable composition in which a thermoplastic polyurethane (B) is (substantially) completely solubilized in the radiation-curable composition, thereby forming a (homogeneous) liquid at 23°C.

[0084] In another advantageous embodiment, the method of the present disclosure provides a radiation-curable composition in which a thermoplastic polyurethane (B) is (substantially) completely solubilized in a chemically radiation-polymerizable monomer (A), thereby forming a (homogeneous) liquid at 23°C.

[0085] In a typical embodiment, the method of the present disclosure further includes the step of incorporating a radiosensitive polymerization initiator (C) into a mixture material.

[0086] In certain embodiments, the method of the present disclosure further includes the step of incorporating another radiation-polymerizable monomer (D) and optionally a radiation-polymerizable oligomer (E) into the mixture material, as described above.

[0087] In yet another aspect, the present disclosure relates to a method for producing a cured polymer material, a) A step of preparing the above-mentioned radiation-curable composition, b) A step of exposing the radiation-curable composition to chemical radiation It is directed towards methods that include this.

[0088] The chemical beam used for curing is preferably ultraviolet light, an electron beam, X-rays, radiation, or radiofrequency. Ultraviolet light with a wavelength of 180 to 400 nm is particularly preferred from an economic standpoint. Curing by irradiation may be followed by thermal curing in the presence of a suitable external (thermal) crosslinking agent.

[0089] In a typical embodiment, the above-mentioned radiation-curable composition is cured by ultraviolet irradiation in the presence of a photopolymerization initiator.

[0090] In yet another aspect, the present disclosure relates to a method for manufacturing a three-dimensional article, a) A step of preparing the above-mentioned radiation-curable composition, b) A step of exposing a radiation-curable composition to chemical radiation to form a cured surface, c) Repeat steps (a) and (b) thereby producing a (cured) three-dimensional article. This includes methods.

[0091] Advantageously, the method for producing a three-dimensional article includes a liquid bath (photo) polymerization process.

[0092] In yet another aspect, the present disclosure relates to a method for coating an object or substrate, a) A step of preparing the above-mentioned radiation-curable composition, b) A step of applying the composition to at least a portion of the surface of the object or the substrate, c) A step of curing the composition by exposing the coated surface to a chemical beam (in particular, UV, UV-LED or e-beam) This includes methods.

[0093] In yet another aspect of this disclosure, a method for recovering thermoplastic material for recycling, the method is: a) A step of preparing the above-mentioned radiation-curable composition, b) A step of exposing the radiation-curable composition to chemical radiation to form a cured polymer material, c) A step of mixing the cured polymer material with a radiation-polymerizable monomer (A) to form a mixed material, d) Optionally, a step of subjecting the mixture material to thermal energy, e) Optionally, a step of subjecting the mixture material to mechanical mixing, f) Optionally, a step of separating thermoplastic polyurethane (B) from the mixture material. A method is provided that includes this.

[0094] In yet another aspect, the present disclosure relates to a method for producing recycled radiation-curable polymer materials, a) A step of preparing the above-mentioned radiation-curable composition, b) A step of exposing the radiation-curable composition to chemical radiation to form a cured polymer material, c) A step of mixing the cured polymer material with a radiation-polymerizable monomer (A) to form a mixed material, d) Optionally, a step of subjecting the mixture material to thermal energy, e) Optionally, a step of subjecting the mixture material to mechanical mixing, f) Optionally, adding a radiation-sensitive polymerization initiator (C) to the mixture material, g) A step of exposing the mixture material to chemical radiation to form a recycled radiation-curable polymer material. This includes methods.

[0095] In yet another aspect of this disclosure, a cured polymer material produced by any one of the methods described herein is provided.

[0096] In one advantageous embodiment, the cured polymer material has a fracture elongation value greater than 50%, greater than 100%, greater than 150%, greater than 200%, greater than 250%, greater than 300%, greater than 350%, greater than 400%, greater than 450%, greater than 500%, greater than 550%, greater than 600%, greater than 650%, or greater than 700% when measured according to the test methods described in the Experiment section.

[0097] In another advantageous embodiment, the cured polymer material described above has a tensile strength value greater than 2 MPa, greater than 4 MPa, greater than 5 MPa, greater than 8 MPa, greater than 10 MPa, greater than 12 MPa, greater than 15 MPa, greater than 18 MPa, greater than 20 MPa, greater than 22 MPa, greater than 24 MPa, greater than 26 MPa, greater than 28 MPa, or greater than 30 MPa when measured according to the test methods described in the Experiment section.

[0098] In yet another advantageous embodiment, the cured polymer material has a Young's modulus value greater than 10 MPa, greater than 50 MPa, greater than 100 MPa, greater than 200 MPa, greater than 400 MPa, greater than 450 MPa, greater than 500 MPa, greater than 600 MPa, greater than 700 MPa, greater than 800 MPa, greater than 900 MPa, greater than 1000 MPa, greater than 1100 MPa, or greater than 1200 MPa, when measured according to the test methods described in the Experiments section.

[0099] In yet another advantageous embodiment, the cured polymer material has a volume shrinkage value of 10% or less, 9.5% or less, 9% or less, 8.5% or less, 8% or less, 7.5% or less, 7% or less, 6.5% or less, 6% or less, 5.5% or less, 5% or less, 4.5% or less, or 4% or less, as measured according to the test methods described in the Experiments section.

[0100] In a favorable embodiment, the cured polymer material is selected from the group consisting of cured three-dimensional articles, cured coatings, cured adhesive compositions, and cured sealing compositions.

[0101] In another aspect, the disclosure relates to the use of the above-mentioned radiation-curable compositions in three-dimensional printing processes, particularly in three-dimensional printing processes using vat (photo) polymerization technology.

[0102] In yet another aspect, the disclosure relates to the use of the above-mentioned radiation-curable composition for the manufacture of a coating or in a coating process.

[0103] In yet another aspect, the disclosure relates to the use of the above-mentioned radiation-curable composition for the manufacture of adhesive or encapsulant compositions, or in an adhesive or encapsulation process.

[0104] example The present disclosure will be further illustrated by the following examples, which are for illustrative purposes only and are not intended to limit the scope of the appended claims.

[0105] Throughout this disclosure and the Examples section, exemplary radiation-curable compositions and cured polymer materials obtained from such compositions are characterized using the following test and measurement methods.

[0106] Test method: A) Molecular weight The number-average molecular weight (Mn) is determined by conventional gel permeation chromatography (GPC) using Agilent's polystyrene standard EasyCal (molecular weight range: 370-110,500 g / mol). The sample is dissolved in tetrahydrofuran (THF) containing 0.5% toluene as a flow marker (1.0% wt / wt). The analysis is performed by liquid chromatography (Agilent HPLC 1100) equipped with PLGel GPC columns of six different pore sizes (300 × 7.5 mm × 5 μm). The components of the sample are separated by the GPC column based on their molecular size in solution and detected by a refractive index detector. The data are collected and processed using Agilent's ChemStation GPC data analysis software.

[0107] B) Viscosity The viscosity of various radiation-curable compositions was measured at 60°C using a cone-plate rheometer MCR102e (Anton Paar) according to the test method DIN EN ISO 3219. A fixed shear rate of 20 s⁻¹ was used.

[0108] C) Solubility The solubility of thermoplastic polyurethane (B) in various precursors of radiation-curable compositions is evaluated by visual observation at 23°C and 85°C. The test samples used for evaluation are prepared according to the following procedure. The radiation-polymerizable monomer (A) and thermoplastic polyurethane (B) are placed in a suitable container, and the resulting heterogeneous material is then heated at 85°C for 2 hours. The heated mixture is then mixed at 2000 rpm for 2 minutes using a speed mixer DAC.1 FVZ LR, and the resulting mixture is then heated again at 85°C until the thermoplastic polyurethane (B) is completely solubilized in the mixture. However, if the thermoplastic polyurethane (B) can be completely solubilized in the mixture, the heated mixture is further mixed at 2000 rpm for 2 minutes using the speed mixer. Visual evaluation of the solubility of thermoplastic polyurethane (B) in the resulting mixture is performed at 85°C or at 23°C after the mixture has been adequately allowed to return to room temperature.

[0109] D) Mechanical properties The elongation at break, tensile strength, and Young's modulus are measured at 23°C using a single-column universal tensile testing machine (Instron 4467 series) according to test method ASTM D-882-18. The test specimens used for measurement are prepared according to the following procedure. A mixture material containing a radiation-polymerizable monomer (A) and a thermoplastic polyurethane (B) is prepared according to the procedure described above for the solubility test. A radiation-sensitive polymerization initiator (C) is then incorporated into the mixture material, which is subsequently heated at 70°C for 1 hour. The heated mixture is then mixed at 2000 rpm using a speed mixer DAC.1 FVZ LR until the polymerization initiator (C) is completely solubilized in the mixture material. The resulting material is coated as a 0.127 mm thick film in a frame made of PET film, and then covered with another PET film placed on top. The laminated PET sheet is cured by passing it three times on each side at a speed of 50 fpm using a Fusion Aetek UV Hg lamp (400 W / inch output). The laminated PET sheet is cut into elongated strips with a length of 200 mm and a width of 12.7 mm. The top and bottom PET films are further removed to obtain a UV-curable free film test. The overall thickness of the UV-curable free film is approximately 0.127 mm.

[0110] E) Volume shrinkage The volume shrinkage of various cured polymer materials is measured according to the following procedure. The mixture is prepared according to the method described above. The liquid density (dm) of the mixture is determined by a density cup (Gardco 8.32 cc) according to the test method ASTM D1475-13. The solid density of the cured part is determined by the method described below: The mixture is heated at 70 °C and slowly poured into the mold to avoid air bubbles. The mixture is cured for 30 minutes under an autoshot UVA lamp. Then, the cured part is taken out of the mold, placed in the density cup, and the weight (W c+p ) is measured. Knowing the cup weight (W c ), the weight of the cured part (W p ) can be determined as W c+p - W c . The cup is filled with water with the part inside, and the total weight (W c+p+w ) is measured. The weight of the water (W w ) is W w = W c+p+w - W c - W p . Since the water density (d w ) is known, the volume of the water V w can be calculated as V w = W w / d w . Therefore, the volume of the solid part can be obtained as V p = V c - V w , where V c is the volume of the cup, which is 8.32 cm 3 . Knowing the weight and volume, the density (d c ) of the cured part is calculated as d c = W p / V p . The volume shrinkage is calculated as 100×(d c - d m ) / d m .

[0111] Raw materials: In this example, the following raw materials and starting products are used. Pearlbond (trademark) 5713 F1 has a number average molecular weight (M) of approximately 38,800 g / mol. n It is a polyester-type thermoplastic polyurethane (TPU) having ), and is commercially available from Lubrizol. Hereinafter referred to as TPU-5713. Pearlbond (trademark) 5717NT2 has a number average molecular weight (M) of approximately 20,410 g / mol. n It is a polyester-type thermoplastic polyurethane (TPU) having ), and is commercially available from Lubrizol. Hereinafter referred to as TPU-5717. Pearlbond™ UB410B has a number average molecular weight (M) of approximately 34,530 g / mol. n It is a polyester-type thermoplastic polyurethane (TPU) having ), and is commercially available from Lubrizol. Hereinafter referred to as TPU-UB410. Estane(registered trademark) 58215 has a number-average molecular weight (M) of approximately 73,575 g / mol. n It is a polyether-type thermoplastic polyurethane (TPU) having ), and is commercially available from Lubrizol. Hereinafter referred to as TPU-58215. Polyamide-6 is a polyamide-type thermoplastic material commercially available from Goodfellow under product code AM30-GL-000100. Hereinafter referred to as TP-PA6. N-vinylpyrrolidone is a radiation-polymerizable monomer and is commercially available from Sigma-Aldrich. Hereinafter referred to as NVP. N-vinylcaprolactam is a radiation-polymerizable monomer and is commercially available from Sigma-Aldrich. Hereinafter referred to as NVCL. N-vinylmethyloxazolidinone is a radiation-polymerizable monomer and is commercially available from BASF under the trade name VMOX®. Hereinafter, it will be referred to as VMOX. Isobornyl acrylate is a radiation-polymerizable cyclic acrylate monomer, commercially available from Allnex. Hereinafter referred to as IBOA. 2-Hydroxyethyl methacrylate is a radiation-polymerizable linear acrylate monomer, commercially available from Sigma-Aldrich. Hereinafter referred to as HEMA. Ebecryl® 118 is a radiation-polymerizable aromatic monofunctional acrylate monomer, known as a reactive diluent, and commercially available from Allnex. Hereinafter referred to as E-118. Genomer 1122 is a radiation-polymerizable monofunctional urethane acrylate monomer, known as a reactive diluent, and commercially available from Rahn AG. Hereinafter referred to as GE-1122. Sartomer SR256 is a radiation-polymerizable monofunctional acrylate monomer, known as a reactive diluent, and commercially available from Arkema. Hereafter, it will be referred to as SR256. Ebecryl® 130 is a radiation-polymerizable cyclic diacrylate monomer, commercially available from Allnex. Hereinafter referred to as E-130. PI-184 is a photopolymerization initiator and is commercially available from Aalchem. Ebecryl® 8413 is a urethane oligomer that is commercially available from Allnex. Hereinafter, it will be referred to as E-8413. Ebecryl® 4738 is an aliphatic urethane acrylate, commercially available from Allnex. Hereinafter referred to as E-4738.

[0112] example: Example 1: Formulations of exemplary precursors (Examples 1-7) and comparative examples (Examples C1-C16) of radiation-curable compositions. Exemplary precursors (Examples 1-7) and comparative examples (Examples C1-C16) of radiation-curable compositions are prepared according to the procedure described herein for solubility testing. Comparative examples C1-C3 have a number average molecular weight (M) greater than 60,000 g / mol. n Thermoplastic polyurethane having the ) is used. Comparative Examples C4 to C13 do not contain the N-vinylamide moiety and use radiation-polymerizable monomers that are representative of commonly used acrylate-based reactive diluents. Comparative Examples C14 to C16 use thermoplastic materials other than thermoplastic polyurethane. The corresponding formulations are shown in Tables 1 to 3 below. [Table 1] [Table 2] [Table 3]

[0113] Example 2: Characteristics and solubilization performance of exemplary precursors (Examples 1-7) and comparative examples (Examples C1-C16) of radiation-curable compositions. The characteristics and solubilization performance of exemplary precursors (Examples 1 to 7) and comparative examples (Examples C1 to C16) of radiation-curable compositions were evaluated at 23°C and 85°C according to the test methods described herein. The results are shown in Table 4 below. [Table 4]

[0114] As can be seen from the results shown in Table 4, the precursors of the radiation-curable compositions according to this disclosure (Examples 1 to 7) exhibit excellent solubility, excellent formulation stability, and favorable formulation flexibility even at 23°C. In contrast, the comparative compositions (Examples C1 to C16) are less advantageous. In particular, the comparative compositions are typically inadequate in terms of solubility, even at higher temperatures.

[0115] Example 3: Formulations of exemplary radiation-curable compositions (Examples 8-16) and comparative examples (Example C17). Exemplary radiation-curable compositions (Examples 8-16) and comparative examples (Example C17) are prepared according to the procedures described herein for mechanical property testing. Comparative example C17 uses a reference radiation-curable formulation recognized to have excellent mechanical properties. The corresponding formulations are shown in Table 5 below. [Table 5]

[0116] Example 4: Mechanical properties and viscosity characteristics of exemplary radiation-curable compositions (Examples 8-16) and comparative examples (Example C17). The mechanical properties of exemplary radiation-curable compositions (Examples 8-16) and comparative examples (Example C17) were determined at 23°C according to the test methods described herein. The viscosity properties were determined at 60°C according to the test methods described herein. The results are shown in Table 6 below. [Table 6]

[0117] As can be seen from the results shown in Table 6, the radiation-curable compositions according to this disclosure (Examples 8 to 16) possess an excellent balance of mechanical properties. In contrast, the composition of Comparative Example C17 is less advantageous. In particular, the comparative composition is typically inadequate in terms of Young's modulus.

[0118] Example 5: Volume shrinkage performance of exemplary radiation-curable compositions (Example 11) and comparative examples (Example C18). The volume shrinkage performance of exemplary radiation-curable compositions (Example 11) and comparative examples (Example C18) was determined according to the test methods described herein. Comparative Example C18 uses a benchmark radiation-curable formulation (a mixture of E-4738 and E130 in a 44 / 56 weight ratio) that is recognized to have excellent volume shrinkage properties. The formulation of Comparative Example C18 is obtained by adding 4 parts of a photopolymerization initiator (PI-184) to 100 parts of a radiation-curable formulation (E-4738 / E130 in a 44 / 56 ratio). The results are shown in Table 7 below. [Table 7]

[0119] As can be seen from the results shown in Table 7, the radiation-curable composition according to this disclosure (Example 11) exhibits excellent volume shrinkage performance. In contrast, the reference composition of Comparative Example C18 is less advantageous.

[0120] Example 6: Recyclability performance of exemplary radiation-curable compositions (Examples 18-19). The recyclability performance of an exemplary radiation-curable composition (Example 11) was determined by mixing the radiation-curable polymer material (hereinafter referred to herein as RCPM.11) resulting from the radiation curing of the radiation-curable composition (Example 11) with a radiation-polymerizable monomer NVP. The resulting mixtures (Examples 18-19) were then heated at 85°C for 2 hours. The heated mixtures were then mixed at 2000 rpm for 2 minutes using a speed mixer DAC.1 FVZ LR, and the resulting mixtures were then heated again at 85°C until the radiation-curable polymer material was completely solubilized in the mixture. The corresponding formulations (Examples 18-19) and the results of the recyclability performance tests are shown in Table 8 below. [Table 8]

[0121] As can be seen from the results shown in Table 8, the radiation-curable compositions according to this disclosure (Example 11) possess excellent recyclability properties. The corresponding formulations (Examples 18-19) can be exposed to chemical radiation to form new (recycled) radiation-curable polymer materials. The addition of further radiation-sensitive polymerization initiators (C) may be required.

Claims

1. A radiation-curable composition, a) 30 to 70% by weight of a radiation-polymerizable monomer (A) containing an N-vinylamide moiety, b) 30-70% by weight of a number-average molecular weight (M) of 60,000 g / mol or less. ｎ A thermoplastic polyurethane (B) having ), wherein the thermoplastic polyurethane (B) is obtained from a polyol selected from the group consisting of polyester polyol, polyether polyol, polycaprolactone polyol, polycarbonate polyol and any combination thereof, c) Radiosensitive polymerization initiator (C) and Includes, The aforementioned weight percentage is based on 100% by weight of the radiation-polymerizable monomer (A) and the thermoplastic polyurethane (B), wherein the radiation-curable composition is a radiation-curable composition.

2. The radiation polymerizable monomer (A) is defined by the following general formula (I): (L)CON(CH=CH ２ )(Q)(I) Having During the ceremony, L is a linear, branched, or cyclic hydrocarbon radical optionally substituted with an alkyl, hydroxyl, or alkoxy group, and / or optionally interrupted with an oxygen or nitrogen atom. Q is a linear, branched, or cyclic hydrocarbon radical optionally substituted with an alkyl, hydroxyl, or alkoxy group, and / or optionally interrupted with an oxygen or nitrogen atom, and Optionally, L and Q may be covalently bonded to form a linked or annular structure. The radiation-curable composition according to claim 1.

3. The radiation polymerizable monomer (A) is defined by the following general formula (II): 【Chemistry 1】 It has, During the ceremony, X is either oxygen or carbon, R is an alkyl, hydroxyl, or alkoxy group, and n is an integer between 0 and 6, 0 and 5, 0 and 4, 0 and 3, or 0 and 2. A radiation-curable composition according to any one of claims 1 or 2.

4. The radiation polymerizable monomer (A) is N-vinylpyrrolidone; N-vinylpiperidone; N-vinylcaprolactam; N-vinyl-3-methylpyrrolidone; N-vinyl-4-methylpyrrolidone; N-vinyl-5-methylpyrrolidone; N-vinyl-3-ethylpyrrolidone; N-vinyl-3-butylpyrrolidone; N-vinyl-3,3-dimethylpyrrolidone; N-vinyl-4,5-dimethylpyrrolidone; N-vinyl-5,5-dimethylpyrrolidone; N-vinyl-3,3,5-trimethylpyrrolidone; N-vinyl-5-methyl-5-ethylpyrrolidone; N-vinyl-3,4,5-trimethyl-3-ethylpyrrolidone; N-vinyl-6-methyl-2-piperidone; N-vinyl-6-ethyl-2-piperidone; N-vinyl-3,5-dimethyl-2-piperidone; N-vinyl-4,4-dimethyl-2-piperidone; N-vinyl-6-propyl-2-piperidone; N-vinyl-3-octylpiperidone; N-vinyl-7-methylcaprolactam; N-vinyl-7-ethylcaprolactam; N-vinyl-4-isopropylcaprolactam; N-vinyl-5-isopropylcaprolactam; N-vinyl-4-butylcaprolactam; N-vinyl-5-butylcaprolactam; N-vinyl-4-butylcaprolactam; N-vinyl-5-tert-butylcaprolactam; N-vinyl-4-octylcaprolactam; N-vinyl-5-tert-octylcaprolactam; N-vinyl-4-nonylcaprolactam; N-vinyl-5-tert-nonylcaprolactam; N-vinyl-3,7-dimethylcaprolactam; N-vinyl-3,5-dimethylcaprolactam; N-vinyl-4,6-dimethylcaprolactam; A radiation-curable composition according to any one of claims 1 to 3, selected from the group consisting of N-vinyl-3,5,7-trimethylcaprolactam; N-vinyl-2-methyl-4-isopropylcaprolactam; N-vinyl-5-isopropyl-7-methylcaprolactam; N-vinylformamide; N-vinylacetamide; N-vinylpropionamide; N-vinyl-N-methylacetamide; N-vinyl-N-methylpropionamide; N-vinyl-N-propylpropionamide; N-vinyloxazolidinone; N-vinyl-5-methyloxazolidinone; N-vinyl-4-methyloxazolidinone; N-vinyl-4,5-dimethyloxazolidinone; and any mixture thereof.

5. The radiation-curable composition according to any one of claims 1 to 4, wherein the radiation-polymerizable monomer (A) is selected from the group consisting of N-vinylpyrrolidone; N-vinylcaprolactam; N-vinyl-5-methyloxazolidinone; N-vinylformamide; and any mixture thereof.

6. a) 35-65% by weight, 40-60% by weight, or 45-55% by weight of the radiation polymerizable monomer (A), b) 35-65% by weight, 40-60% by weight, or 45-55% by weight of the thermoplastic polyurethane (B), c) Radiosensitive polymerization initiator (C) and Includes, The aforementioned weight percentage is based on 100% by weight of the radiation-polymerizable monomer (A) and the thermoplastic polyurethane (B). A radiation-curable composition according to any one of claims 1 to 5.

7. The thermoplastic polyurethane (B) has a number average molecular weight (M) of 60,000 g / mol or less, 55,000 g / mol or less, 50,000 g / mol or less, 45,000 g / mol or less, 40,000 g / mol or less, 35,000 g / mol or less, 30,000 g / mol or less, 25,000 g / mol or less, or 20,000 g / mol or less. ｎ A radiation-curable composition according to any one of claims 1 to 6, having the following characteristics:

8. The radiation-curable composition according to any one of claims 1 to 7, further comprising another radiation-curable monomer (D) different from the radiation-curable monomer (A) or a further radiation-curable oligomer (E).

9. A method for producing a radiation-curable composition according to any one of claims 1 to 8, wherein the method is: a) A step of forming a mixed material by bringing the radiation polymerizable monomer (A) into the presence of the thermoplastic polyurethane (B), b) Optionally, a step of subjecting the mixture material to thermal energy, c) Optionally, a step of subjecting the mixture material to mechanical mixing. Methods that include...

10. a) A step of preparing the radiation-curable composition according to any one of claims 1 to 8, b) A step of exposing the radiation-curable composition to chemical radiation A method for producing a cured polymer material, including [a specific component].

11. A cured polymer material produced by the method of claim 10, having a breaking elongation value greater than 50%, greater than 100%, greater than 150%, greater than 200%, greater than 250%, greater than 300%, greater than 350%, greater than 400%, greater than 450%, greater than 500%, greater than 550%, greater than 600%, greater than 650%, or greater than 700% when measured according to the test method described in the Experiment section.

12. The cured polymer material according to claim 11, having a tensile strength value greater than 2 MPa, greater than 4 MPa, greater than 5 MPa, greater than 8 MPa, greater than 10 MPa, greater than 12 MPa, greater than 15 MPa, greater than 18 MPa, greater than 20 MPa, greater than 22 MPa, greater than 24 MPa, greater than 26 MPa, greater than 28 MPa, or greater than 30 MPa when measured according to the test method described in the Experiment section.

13. A cured polymer material according to any one of claims 11 or 12, having a volume shrinkage value of 10% or less, 9.5% or less, 9% or less, 8.5% or less, 8% or less, 7.5% or less, 7% or less, 6.5% or less, 6% or less, 5.5% or less, 5% or less, 4.5% or less, or 4% or less, as measured according to the test method described in the Experiment section.

14. Use of the radiation-curable composition according to any one of claims 1 to 8 in a three-dimensional printing process, particularly in a three-dimensional printing process using a vat (photo) polymerization technique.

15. Use of the radiation-curable composition according to any one of claims 1 to 8 for the manufacture of a coating or in a coating process, for the manufacture of an adhesive or in an adhesive process, or for the manufacture of a sealant or in an sealing process.

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