Photocurable polymer composition

Abstract

The present invention relates to a polymer formulation for three-dimensional (3D) printing of articles by stereolithography, the formulation comprising a functionalized polymer. The present invention further relates to a lithographic method for forming a 3D object incorporating the aforementioned polymer formulation.

Description

[Technical Field]

[0001] Related applications This application claims priority to U.S. Provisional Patent Application No. 63 / 007,454 filed on 9 April 2020 and European Patent Application Publication No. 20185769.5 filed on 14 July 2020, the entire contents of each of these applications being incorporated herein by reference for any purpose.

[0002] The present invention relates to a polymer formulation for three-dimensional (3D) printing of articles by stereolithography, comprising a functionalized polymer and a crosslinking agent. The present invention further relates to a lithography method for forming a 3D object incorporating the aforementioned polymer formulation. [Background technology]

[0003] Polymer compositions are commonly used to manufacture articles for the automotive and aerospace industries, such as engine parts, and articles for the healthcare industry, such as implantable devices and dental prostheses. These articles must exhibit good mechanical properties after manufacture, but they must also maintain a sufficient percentage of these properties over time, especially at their operating temperatures (sometimes exceeding 150°C).

[0004] Lithography processes for the photofabrication of 3D articles from polymer materials have recently gained popularity due to their relative speed and simplicity. Generally, lithography processes involve the use of light, such as UV irradiation, to locally cure polymerizable formulations at specific locations. Local curing enables the fabrication of three-dimensional articles.

[0005] Lithography processes commonly use polymerizable formulations that are liquid to obtain parts with good resolution. Polymerizable formulations that are liquid at room temperature are easier to use in printing processes, but they generally result in articles with average mechanical properties and thermal stability.

[0006] Polymeric materials used in a lithography process need to be in a liquid state under printing conditions. For certain polymeric materials such as high-performance polymers, this means that they need to be heated above the glass transition temperature (Tg) or the melting temperature (Tm). They also need to have functional groups that are photopolymerizable or crosslinkable, i.e., functional groups that react during the printing process when irradiating a layer of the polymerization formulation. One of the challenges in applying lithography methods to high-performance polymers is that the material needs to maintain thermal stability at high temperatures while avoiding thermal polymerization of the photopolymerizable functional groups.

[0007] Another challenge is the identification of effective photopolymerizable groups and the synthetic methods for adding them to the materials to be printed to make the polymeric materials photopolymerizable.

[0008] Another challenge in the identification of valuable polymerization formulations used in the lithography process is that it must be possible to manufacture 3D articles that exhibit good mechanical properties after photolithography and substantially retain these mechanical properties after exposure to high temperatures, for example above 150 °C.

[0009] The polymerization formulation of the present invention provides a solution well-suited for 3D printing processes that can be carried out, for example, at room temperature or higher temperatures.

[0010] International Publication No. WO 2020 / 074332 A1 (Solvay) relates to a polymer formulation (F) containing a low molecular weight polymer containing a photopolymerizable end group. Due to their low molecular weight, i.e., short chain length, these polymers have a high concentration of photopolymerizable groups and exhibit good printing suitability.

[0011] The paper "Solvent-stable UV-cured acrylic polysulfone membranes" (2016) by Mehmood Mian Farrukh et al. concerns the effect of the presence of acrylic resin on polysulfone-based membranes prepared by UV curing of polymer dope followed by a non-solvent-induced phase separation process.

[0012] The paper "Synthesis, preparation and characterization of UV-cured methacrylated polysulfone-based membranes" (2015) by M. Sangermano et al. describes a two-step method for fabricating networked polysulfone membranes, including non-solvent-induced phase separation (NIPS) and a UV curing process.

[0013] These two papers do not describe the poly(aryl ether sulfone) (PAES) polymer (P) of the present invention, nor the use of a polyfunctional photocrosslinker that forms a high molecular weight network with the polymer (P) after printing and curing due to the presence of photocurable groups on the polymer (P).

[0014] The polymerizable formulation of the present invention provides a suitable solution for high-temperature 3D printing processes and enables the production of 3D printed articles from high molecular weight polymer formulations having a low concentration of photopolymerizable groups in order to achieve good printability and to obtain 3D printed parts with excellent mechanical properties. [Overview of the Initiative]

[0015] The present invention relates to a polymer formulation (F) comprising a polymer (P), which is a poly(aryl ether sulfone) (PAES) polymer having at least one photopolymerizable terminal group, preferably two photopolymerizable terminal groups, in combination with a polyfunctional photocrosslinking agent.

[0016] This polymer formulation (F) can be used, for example, in photofabrication processes. In particular, formulation (F) of the present invention can be incorporated into lithography processes in which light is used to cure functionalized polymers. Formulation (F) of the present invention can be converted to a liquid state at a temperature below or above the Tg of polymer (P) without any visible change, and then cured by irradiation with UV light to produce a highly thermally property material having a high Tg, high mechanical properties, and high thermal stability. Formulation (F) of the present invention can be effectively used in 3D printing lithography processes.

[0017] The present invention also relates to a method for manufacturing a three-dimensional (3D) article using an additive manufacturing system, - A step of providing a polymer compound (F) according to the present invention, - A process of printing layers of a 3D object from a polymer compound (F) and Regarding methods including

[0018] According to another embodiment of the present invention, the printing step includes irradiating the polymer formulation (F) with UV light or visible light. The UV light may be, for example, laser light.

[0019] The present invention also relates to the use of polymer formulations (F) for the manufacture of 3D articles and 3D objects by stereolithography (SLA), at least in part, by the methods described above. [Modes for carrying out the invention]

[0020] The present invention relates to a formulation (F) comprising a PAES polymer (P) which can be used, for example, in a lithography process for the photofabrication of three-dimensional (3D) articles.

[0021] Stereolithography is an additive manufacturing (AM) process that works by focusing light, such as ultraviolet (UV) or visible light, onto a liquid bath of crosslinkable photopolymer resin. Complex 3D structures can then be constructed layer by layer.

[0022] The polymers (P) described herein, in combination with crosslinking agents, can be 3D printed to manufacture articles, for example, using stereolithography (SLA), inkjet technology, direct ink writing (DIW), or digital light processing (DLP).

[0023] The present invention relates to a polymer formulation (F) comprising a poly(aryl ether sulfone) (PAES) polymer (P), wherein the polymer (P) is functionalized. More precisely, the polymer (P) comprises at least one terminal group of formula (M1) or (M2): [ka] (In the formula, - R 2 is H or CH3, - X is a bond or (CH2) n n is in the range of 1 to 20, for example, 1 to 10 or 1 to 8, and is preferably 1 or 2).

[0024] The polymer (P) preferably has two terminal groups of formula (M1) or (M2), more preferably two terminal groups of formula (M1), and even more preferably R 2 Formula (M1) contains two terminal groups where H is present.

[0025] According to the present invention, the number-average molecular weight (Mn) of the polymer (P) is at least 12,000 g / mol, at least 13,000 g / mol, at least 14,000 g / mol, at least 15,000 g / mol, at least 17,000 g / mol, or at least 20,000 g / mol, when measured by gel permeation chromatography (GPC) using methylene chloride and a polystyrene standard as the mobile phase. Preferably, the number-average molecular weight (Mn) of the polymer (P) is less than 50,000 g / mol or less than 40,000 g / mol.

[0026] A formulation (F) containing the functionalized polymer (P) of the present invention can be used in a photofabrication process. In particular, the polymer (P) and polymer formulation (F) of the present invention can be incorporated into a lithography process in which light is used to cure the functionalized polymer.

[0027] The crosslinking ability of the formulation of the present invention can be evaluated by photorheology. When the formulation (F) of the present invention is printed, it changes from liquid to solid when irradiated with light such as UV light or visible light. The change can be measured with a rotational rheometer. The transition from liquid resin to solid manifests as an increase in the storage modulus G' and the loss modulus G''. The crossover between G' and G'' approximates the gelation point, which signifies the conversion from liquid to gel during network formation. The gelation point is an important engineering parameter for achieving high-quality printed structures. By measuring the G' of the formulation, the stiffness of the printed part can be evaluated, and therefore the ability of the printed resin to support the next layer can be evaluated. The crossover between G' and G'' provides an index of the crosslinking rate and the liquid-solid transition time.

[0028] In addition to the photopolymerizable (or crosslinkable) polymer (P), the formulation (F) of the present invention is: - At least one polyfunctional acrylate, - At least one solvent, - At least one optional photoinitiator, - At least one optional blocker and This also includes.

[0029] The formulation (F) of the present invention is preferably a liquid. For example, formulation (F) is a liquid at room temperature or above.

[0030] The polyfunctional acrylate is added to the formulation (F) as a crosslinking agent. That is, due to the presence of photocurable material on the polymer (P), it forms a high molecular weight network with the polymer (P) after printing and curing.

[0031] According to the present invention, a photoinitiator is a compound added to a formulation to convert absorbed light energy, UV or visible light, into chemical energy in the form of an initiating chemical species, such as a free radical or a cation.

[0032] According to the present invention, the blocker is a compound added to capture unused radicals generated by the photoinitiator or to absorb a portion of the incident UV energy. This compound enables improved dimensional accuracy of the manufactured parts.

[0033] The polymer (P) described in the present invention is functionalized with a functional group which is a (meth)acrylate moiety (M1) and / or styrene (M2). The functional group is introduced as a post-polymerization modification, for example, as "end-functionalization" at at least one end of the polymer chain, such as both ends of the polymer chain.

[0034] The formulation (F) of the present invention may contain two or more polymers (P), for example, two or three different polymers (P).

[0035] Poly(aryl ether sulfone) (PAES) P is preferably given by the following formula (L): [ka] (In the formula, - Each R 1 Each aromatic ring is independently selected from the group consisting of halogens, alkyls, alkenyls, alkynyls, aryls, ethers, thioethers, carboxylic acids, esters, amides, imides, alkali or alkaline earth metal sulfonates, alkyl sulfonates, alkali or alkaline earth metal phosphonates, alkyl phosphonates, amines, and quaternary ammonium compounds; - Each i is independent for each aromatic ring and is either zero or an integer between 1 and 4; - T is selected from the group consisting of a bond, -CH2-, -O-, -SO2-, -S-, -C(O)-, -C(CH3)2-, -C(CF3)2-, -C(=CCl2)-, -C(CH3)(CH2CH2COOH)-, -N=N-; - R a C=CR b -(each R a and R b is, independently of one another, hydrogen, a C1-C12 alkyl group, a C1-C12 alkoxy group, a C6-C18 aryl group); m is an integer from 1 to 6 of -(CH2) m - and -(CF2) m -; a straight-chain or branched aliphatic divalent group having 6 or fewer carbon atoms; and combinations thereof) of repeating units (R PAES ) is a PAES.

[0036] In some embodiments, the polymer (P) of the present invention is - at least a repeating unit (R PAES ):

Chemical formula

Chemical formula

[0037] In some embodiments, the repeating unit (R PAES ) follows the following formula (L'): [ka] (In the formula, R 1 (and i are as described above).

[0038] In some embodiments, the terminal groups of polymer (P) follow the formula (M'): [ka] (In the formula, R 1 , R 2 (and i are as described above).

[0039] According to one embodiment, i is each R 1 It is zero for this. In other words, according to this embodiment, - Repeating unit (R PAES ) is given by the following formula (L''): [ka] It is a unit of, - The terminal group of polymer (P) is given by the following formula (M''): [ka] in accordance with T and R in the formula 2 This is as stated above.

[0040] In some embodiments, P is PAES having repeating units of formula (L), (L'), or (L'') in at least 50 mol% (based on the total number of moles in the polymer), and containing at least one terminal group of formula (M), (M'), or (M'').

[0041] In some embodiments, at least 60 mol%, at least 70 mol%, at least 80 mol%, at least 90 mol%, at least 95 mol%, at least 99 mol%, or all of the repeating units in the polymer (P) (based on the total number of moles in the polymer) are repeating units (R) of formula (L), (L'), or (L''). PAES ) and P includes at least one terminal group of at least one of formulas (M), (M'), or (M''), for example, two terminal groups of formulas (M), (M'), or (M'').

[0042] According to one embodiment of the present invention, P is a PAES in which T is selected from the group consisting of bond, -SO2-, and -C(CH3)2-.

[0043] According to another embodiment of the present invention, P is at least 50 mol% (based on the total number of moles in the polymer) of the formula: [ka] (In the formula, R 1 (and i are as described above) This is a PAES having repeating units selected from the group consisting of the following.

[0044] According to this embodiment, at least 60 mol%, at least 70 mol%, at least 80 mol%, at least 90 mol%, at least 95 mol%, at least 99 mol%, or all of the repeating units in the polymer (P) (based on the total number of moles in the polymer) are repeating units (R) of formulas (LA), (LB), and / or (LC). PAES ) and P includes at least one terminal group of at least one of formulas (M), (M'), or (M''), for example, two terminal groups of formulas (M), (M'), or (M'').

[0045] According to one embodiment, P is a PAES in which T is a bond. In other words, P is a functionalized poly(biphenyl ether sulfone) (PPSU).

[0046] According to one embodiment, P is - At least 50 mol% (mol% is based on the total number of moles in the polymer) of the repeating units of formula (LA) (R PPSU ) and: [ka] (In the formula, R 1 (and i is as described above), - Formula (M1) or (M2): [ka] (In the formula, - R 2 is H or CH3, - X is a bond, or n varies from 1 to 20, for example, 1 to 10 or 1 to 8, preferably equal to 1 or 2 (CH2) n (is) at least one terminal group and This is a PPSU that includes this.

[0047] The polymer (P) of the present invention may be a homopolymer or a copolymer. If it is a copolymer, it may be random, alternating, or block copolymer.

[0048] In some embodiments of the present invention, at least 60 mol%, at least 70 mol%, at least 80 mol%, at least 90 mol%, at least 95 mol%, at least 99 mol%, or all of the repeating units in the polymer (P) are repeating units (R) of formula (LA). PPSU ) and P includes at least one terminal group of at least one of formulas (M), (M'), or (M''), for example, two terminal groups of formulas (M), (M'), or (M'').

[0049] If the polymer (P) is a poly(biphenyl ether sulfone) (PPSU) copolymer, then it is a repeating unit (R PPSU ) is a different repeating unit (R* PPSU ), for example, the repeating units of formula (LB) and / or formula (LC), and / or formula (LD), both listed above: [ka] (In the formula, R 1 (and i are as described above) It can be composed of the following.

[0050] Poly(biphenyl ethersulfone) (PPSU) polymers can be prepared by any method known in the art. For example, they can be obtained by the condensation of 4,4'-dihydroxybiphenyl (biphenol) and 4,4'-dichlorodiphenyl sulfone in the presence of a base. The monomer unit reaction occurs by nucleophilic aromatic substitution with the elimination of one unit of hydrogen halide as a leaving group. However, it should be noted that the resulting poly(biphenyl ethersulfone) structure does not depend on the nature of the leaving group. PPSU is then modified postpolymerically to introduce a functional group at at least one end of the polymer chain. The functional group is an acrylate, alkyl acrylate, or styrene.

[0051] According to one embodiment, P is a PAES in which T is -C(CH3)2-. In other words, P is a functionalized polysulfone (PSU).

[0052] According to one embodiment, P is - At least 50 mol% of the repeating units are repeating units of formula (LB) (R PSU ) and (mol% is based on the total number of moles in the polymer): [ka] (In the formula, R 1 (and i is as described above) and; - Formula (M1) or (M2): [ka] (In the formula, - R 2 is H or CH3, - X is a bond, or n varies from 1 to 20, for example, 1 to 10 or 1 to 8, preferably equal to 1 or 2 (CH2) n (is) at least one terminal group and This is a PSU that includes this.

[0053] In some embodiments of the present invention, at least 60 mol%, at least 70 mol%, at least 80 mol%, at least 90 mol%, at least 95 mol%, at least 99 mol%, or all of the repeating units in the polymer (P) are repeating units of formula (LB) (R PSU ) and P includes at least one terminal group of at least one of formulas (M), (M'), or (M''), for example, two terminal groups of formulas (M), (M'), or (M'').

[0054] If the polymer (P) is a polysulfone (PSU) copolymer, then it is a repeating unit (R PSU ) is a different repeating unit (R* PSU), for example, may consist entirely of repeating units of the formulas (LA), (LC), and / or (LD) listed above.

[0055] According to one embodiment, P is a PAES in which T is -SO2-. In other words, P is a functionalized polyethersulfone (PES).

[0056] According to one embodiment, P is - At least 50 mol% of the repeating units are repeating units of formula (LC) (R PES ) and (mol% is based on the total number of moles in the polymer): [ka] (In the formula, R 1 (and i is as described above), - Formula (M1) or (M2): [ka] (In the formula, - R 2 is H or CH3, - X is a bond, or n varies from 1 to 20, for example, 1 to 10 or 1 to 8, preferably equal to 1 or 2 (CH2) n (is) at least one terminal group and This is a PES that includes this.

[0057] According to one embodiment of the present invention, at least 60 moles, at least 70 moles, at least 80 moles, at least 90 mole%, at least 95 moles, at least 99 mole%, or all of the repeating units in the polymer (P) are repeating units (R) of formula (LC). PES ) and P includes at least one terminal group of at least one of formulas (M), (M'), or (M''), for example, two terminal groups of formulas (M), (M'), or (M'').

[0058] If the polymer (P) is a polyethersulfone (PES) copolymer, then it is a repeating unit (R PESU ) is a different repeating unit (R* PESU ), for example, may consist entirely of repeating units of the formulas (LA), (LB), and / or (LD) listed above.

[0059] Polyfunctional acrylates According to the present invention, the polyfunctional acrylate is a compound that is particularly added to the formulation (F) as a crosslinking agent, that is, to form a high molecular weight network with the polymer (P) after printing and curing due to the presence of photocurable groups on the polymer (P).

[0060] In some embodiments, the polyfunctional acrylate used in formulation (F) of the present invention is selected from the group consisting of trimethylolpropane triacrylate (TMPTA), trimethylolpropane ethoxytriacrylate, trimethylolpropane propoxytriacrylate, pentaerythritol triacrylate (PETA), glycerylpropoxytriacrylate (GPTA), di(trimethylolpropane)tetraacrylate, glycerolpropoxylate triacrylate, pentaerythritol tetraacrylate, 1,3,5-triacryloylhexahydro-1,3,5-triazine, trimethylolpropane ethoxylate triacrylate, trimethylolpropane ethoxylate triacrylate, trimethylolpropane trimethacrylate, tris[2-(acryloyloxy)ethyl]isocyanurate, and mixtures thereof.

[0061] In some embodiments, the polyfunctional acrylate used in formulation (F) of the present invention is of biological origin, for example, derived from castor oil.

[0062] The polyfunctional acrylate used in formulation (F) of the present invention is preferably of formula (I): [ka] (In the formula, - R 3 is either H or an alkyl group having 1 to 5 carbon atoms, preferably H or CH3. - R 4 Equation (II): [ka] Accordingly, n in the formula varies between 0 and 10, preferably between 0 and 3.

[0063] The polyfunctional acrylate crosslinking agent used in formulation (F) of the present invention more preferably conforms to formula (III): [ka]

[0064] The concentration of the polyfunctional acrylate in formulation (F) may be at least 0.05% by weight, for example 0.05 to 30% by weight, for example 0.1% to 25% by weight, 0.2% to 20% by weight, or 0.5% to 15% by weight, based on the total weight of formulation (F).

[0065] solvent The concentration of the solvent may be 1 to 80% by weight, for example, 2 to 75%, 5 to 70%, or 10 to 65% by weight, based on the total weight of the compound (F).

[0066] According to one embodiment of the present invention, the solvent is selected from the group consisting of N-methylpyrrolidone (NMP), N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAC), 1,3-dimethyl-2-imidazolidinone, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), and sulfolane.

[0067] Preferably, the solvent is a bipolar aprotic solvent. Preferably, the solvent is selected from the group consisting of N-methylpyrrolidone (NMP), dimethylacetamide (DMAc or DMA), N-cyclohexyl-2-pyrrolidone (CHP), and dimethyl sulfoxide (DMSO).

[0068] Photoinitiator In some embodiments, formulation (F) further comprises a photoinitiator. A photoinitiator is a compound added to the formulation to convert absorbed light energy, UV or visible light, into chemical energy in the form of an initiating chemical species, such as a free radical or a cation. Based on the mechanism by which the initiating radical is formed, photoinitiators are generally divided into two classes: - Type I photoinitiators generate free radicals upon irradiation through single-molecule bond cleavage. - Type II photoinitiators generate free radicals through a bimolecule reaction in which the excited photoinitiator interacts with a second molecule (co-initiator).

[0069] The concentration of the photoinitiator in formulation (F) may be 0.05 to 10% by weight, for example, 0.1 to 5%, 0.2 to 4%, or 0.5 to 3% by weight, based on the total weight of formulation (F).

[0070] According to one embodiment of the present invention, the photoinitiator is - Acetophenone - Anisoin - Anthraquinon - Anthraquinone-2-sulfonic acid, sodium salt monohydrate - (Benzene)tricarbonylchromium - Benzyl - Benzoin - Benzoin ethyl ether, benzoin isobutyl ether, benzoin methyl ether, and benzophenone - 3,3',4,4'-benzophenonetetracarboxylic dianhydride - 4-benzoylbiphenyl - 2-benzyl-2-(dimethylamino)-4'-morpholinbutyrophenone - 4,4'-bis(diethylamino)benzophenone - 4,4'-bis(dimethylamino)benzophenone - Camphor quinone - 2-Chlorothioxanthene-9-one - (Cumene)cyclopentadienyl iron(II) hexafluorophosphate - Dibenzosverenone - 2,2-diethoxyacetophenone - 4,4'-dihydroxybenzophenone - 2,2-dimethoxy-2-phenylacetophenone - 4-(dimethylamino)benzophenone - 4,4'-dimethylbenzyl - 2,5-dimethylbenzophenone - 3,4-dimethylbenzophenone - Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, 2-hydroxy-2-methylpropiophenone and blends (e.g., 50 / 50 blend) - 4'-Ethoxyacetophenone - 2-ethylanthraquinone - Ferrocene - 3'-hydroxyacetophenone, 4'-hydroxyacetophenone, 3-hydroxybenzophenone, and 4-hydroxybenzophenone - 1-Hydroxycyclohexylphenyl ketone - 2-hydroxy-2-methylpropiophenone - 2-methylbenzophenone or 3-methylbenzophenone - Methylbenzoylformate - 2-methyl-4'-(methylthio)-2-morpholinopropiophenone - Phenanthrenquinone - 4'-Phenoxyacetophenone - Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide - Thioxanthen-9-one - Triarylsulfonium hexafluoroantimonate salt, mixed, 50% in propylene carbonate - Triarylsulfonium hexafluorophosphate salt, mixed, 50% in propylene carbonate, and - those mixtures It is selected from the group consisting of the following.

[0071] Preferably, the photoinitiator is selected from the group consisting of 2,2-dimethoxy-2-phenylacetophenone (DMPA), diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide.

[0072] blocker In some embodiments, formulation (F) further contains a blocker, which is a compound added to the formulation to (i) capture a predetermined amount of radicals formed by the photoinitiator while irradiated with UV light, (ii) capture any unused radicals that may be present after the UV irradiation source is switched off, and / or (iii) absorb some of the energy carried into the system during UV irradiation.

[0073] The concentration of the blocker in formulation (F) may be 0.05 to 10% by weight, for example, 0.1 to 5%, 0.2 to 4%, or 0.5 to 3% by weight, based on the total weight of formulation (F).

[0074] According to one embodiment of the present invention, the blocker is - 2-Hydroxy-4-methoxybenzophenone (oxybenzene) - 1-(4-methoxyphenyl)-3-(4-tert-butylphenyl)propane-1,3-dione (avobenzone) - Disodium 2,2'-(1,4-phenylene)bis(6-sulfo-1H-benzimidazole-4-sulfonate) (bisdisurisol disodium) - Hexyl 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoate (diethylaminohydroxybenzoylhexylbenzoate) - Menthyl-o-aminobenzoate (menthyl anthranilate) - 2,2'-[6-(4-methoxyphenyl)-1,3,5-triazine-2,4-diyl]bis{5-[(2-ethylhexyl)oxy]phenol}(bemotoridinol) - 2,4-dihydroxybenzophenone - 2,2',4,4'-tetrahydroxybenzophenone - 4-Hydroxy-2-methoxy-5-(oxophenylmethyl)benzenesulfonic acid (surisobenzone) - 2,2'-dihydroxy-4,4'-dimethoxybenzophenone - 5-Chloro-2-hydroxybenzophenone - (2-hydroxy-4-methoxyphenyl)-(2-hydroxyphenyl)methanone (dioxybenzone) - 2,5-bis(5-tert-butyl-benzoxazole-2-yl)thiophene - Sodium 2,2'-dihydroxy-4,4'-dimethoxybenzophenone-5,5'-disulfonate - (2-hydroxy-4-methoxyphenyl)(4-methylphenyl)methanone (mexenone) - (2-hydroxy-4-octoxy-phenyl)-phenyl-methanone (octabenzone) - 2-(1,2,3-benzotriazol-2-yl)-4-methyl-6-[2-methyl-3-(2,2,4,6,6-pentamethyl-3,5-dioxa-2,4,6-tricilaheptan-4-yl)propyl]phenol (drometrizole trisiloxane) - Terephthalylidene dicamphor sulfonic acid (Ecamsul) - 2-Ethylhexyl 2-cyano-3,3-diphenyl-2-propenoate (octocrylene) - Diethylhexylbutamide triazone (iscotridinol) - 2-Ethoxyethyl 3-(4-methoxyphenyl)propenoate (cinoxate) - Isopentyl 4-methoxycinnamate (amiloxate) - 2,2'-Methanediylbis[6-(2H-benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol](bisoctrizole) - 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol - 2,2'-Methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol] - 2-Hydroxy-4-(octyloxy)benzophenone - 2-ethyl-,2-[4-(4,6-diphenyl-1,3,5-triazin-2-yl)-3-hydroxyphenoxy]ethyl ester - 2-tert-butyl-6-(5-chloro-2H-benzotriazol-2-yl)-4-methylphenol - 2-(2-hydroxy-5-methylphenyl)benzotriazole - 2,4-dinitrophenylhydrazine - N-(4-ethoxycarbonylphenyl)-N'-methyl-N'-phenylformamidine - Hexadecyl 3,5-bis-tert-butyl-4-hydroxybenzoate - 2-ethyl-2'-ethoxy-oxalanilide, and - those mixtures It is selected from the group consisting of the following.

[0075] Preferably, the blocker is selected from the group consisting of avobenzone and 2,5-bis(5-tert-butylbenzoxazole-2-yl)thiophene.

[0076] Selective components The formulation (F) of the present invention may include, for example, at least one additive selected from the group consisting of fillers such as silica, antioxidants, antimicrobial compounds, and antistatic compounds. The additive may be a chemically inert chemical species such as carbon black, silica (e.g., microsilica particles), and carbon nanotubes.

[0077] 3D item manufacturing process The present invention also relates to a method for manufacturing 3D articles using an additive manufacturing system, - A step of providing a polymer compound (F) as described above, - A process for printing layers of a 3D object from a polymer compound (F), - Optionally, a step of curing the 3D article at a temperature in the range of 50 to 450°C, preferably 100 to 300°C, and even more preferably 120 to 180°C. Regarding methods including

[0078] According to one embodiment, the printing step includes irradiating a polymer formulation (F), for example, a layer of such formulation (F) deposited on a printing surface, with UV light. The layer preferably has a size in the range of 5 μm to 300 μm, for example, 20 μm to 150 μm.

[0079] UV light can be, for example, laser light. The irradiation is preferably of sufficient intensity to cause substantial curing of the polymer formulation (F), for example, a layer of such formulation (F). The irradiation is also preferably of sufficient intensity to cause adhesion of the layer of polymer formulation (F).

[0080] According to another embodiment of the present invention, a method for manufacturing a 3D article using an additive manufacturing system is: - A step of providing a polymer compound (F) as described above, - Layers of the 3D object are made from polymer compound (F), a) Coating the surface with a layer of compound (F), b) Irradiating the layer with UV light, c) Coating the layer of compound (F) onto the previously irradiated layer. d) Irradiating the layer with UV light, and e) Repeat steps c) and d) a sufficient number of times to manufacture a 3D object. The printing process Includes.

[0081] According to one embodiment, the polymer formulation (F) is at room temperature during the process. Alternatively, the formulation may be heated before and / or during printing, in particular if the polymer concentration in the formulation is high. In this case, the temperature may be heated to a maximum of 130°C, a maximum of 120°C, or a maximum of 110°C before and / or during printing.

[0082] Purpose The present invention also relates to the use of the polymer (P) or polymer formulation (F) of the present invention for the manufacture of 3D objects / articles.

[0083] All embodiments described above with respect to polymers (P) and polymer formulations (F) are equally applicable to use for the manufacture of 3D objects / articles.

[0084] The present invention also relates to a 3D object or 3D article obtained, at least in part, from a manufacturing method of the present invention, using a polymer (P) or polymer compound (F) described herein.

[0085] In some embodiments, the 3D article of the present invention contains at least 1 ppm, for example, at least 2 ppm, at least 5 ppm, or at least 10 ppm of residual acrylate or residual styrene, as detected by photoacoustic FTIR measurement.

[0086] 3D objects or articles obtained by such manufacturing methods can be used in a variety of end uses. In particular, these include implantable devices, dental prosthetics, brackets, complex fabricated parts in the aerospace industry, and under-hood parts in the automotive industry.

[0087] If any disclosure of a patent, patent application, or publication incorporated herein by reference conflicts with the description of this application to such an extent that it could obscure the terminology, the description herein shall prevail.

[0088] The present invention will be described in more detail here in relation to the following embodiments, but the purpose is merely illustrative and not to limit the scope of the invention. [Examples]

[0089] raw materials N,N-dimethylacetamide (DMAc) (anhydrous, 99.8%), potassium carbonate (K2CO3) (anhydrous, >99.0%), Celite® 545 filter agent, and sodium bicarbonate (NaHCO3) were purchased from Sigma-Aldrich and used as received. Bisphenol A (BPA, >99%), trimethylolpropane triacrylate (TPM, containing 600 ppm monomethyl etherhydroquinone as an inhibitor), acryloyl chloride (>97%, containing 400 ppm phenothiazine as a stabilizer), and 4,4'-dichlorophenyl sulfone (DCPS) were purchased from Aldrich and used as received. Hydrochloric acid, chloroform (HPLC grade), toluene, sodium chloride, methanol, and tetrahydrofuran were purchased from Fisher Chemical and used as received. Diphenyl (2,4,6-trimethylbenzoyl)phosphine oxide (>98%) was purchased from TCI and used as received. Chloroform-d (CDCl3) (99.8% atomic D) was purchased from Cambridge Isotope Labs and used as received. N-methylpyrrolidone (NMP, BioSolv) and N,N-dimethylformamide (spectroscopic grade) were purchased from Spectrum and used as received. Triethylamine was purchased from Acros Organics, stirred overnight on calcium hydride (Sigma-Aldrich, 95%), and then distilled at 90°C before use.

[0090] Example 1 - Synthesis of polysulfone polymer Three types of acrylate-terminated PSU polymers (comparative and present invention) were prepared by a two-step procedure as shown in Table 1. In Step 1, phenol-terminated PSU polymers were prepared and characterized as shown in Scheme 1 below. In Step 2, the phenol-terminated PSU polymers were converted to the corresponding acrylate-terminated PSU polymers as shown in Scheme 2 below. Subsequently, the polymers were characterized by DSC and TGA as detailed below. The results are shown in Table 2 below.

[0091] [Table 1]

[0092] Scheme 1 (Synthesis of PSU polymer - Step 1) [ka] Scheme 2 (Synthesis of PSU polymer - Step 2) [ka]

[0093] Step 1: Preparation of phenol-terminated PSU polymer with Mn = 20,000 g / mol Nitrogen adapter, Dean Stark trap with condenser, and Teflon TMIn a three-necked round-bottom flask fitted with a glass mechanical stirring rod with a paddle, BPA (52.74 g, 0.2310 mol), DCPS (64.89 g, 0.2260 mol), and potassium carbonate (38.32 g, 0.2772 mol) were dispersed in anhydrous N,N-dimethylacetamide (400 mL) and toluene (200 mL). The heterogeneous solution was purged with N2 for 20 minutes, then heated to 160°C, where the reaction was refluxed for 5 hours. The resulting toluene / water azeotrope was then removed, and the polymerization was further heated at 180°C for 12 hours, cooled to room temperature, and the resulting solution was filtered through Celite® to remove salts formed during polymerization. To protonate the phenol chain ends, the solution was then neutralized with a 1 M HCl solution in THF, and the final 20,000 Mn PSU polymer was isolated by precipitation in 4 L MeOH. The resulting white powder was vacuum-dried at 200°C for 18 hours. The molecular weight was determined using GPC.

[0094] Step 2: Preparation of acrylate-terminated PSU polymer with Mn = 20,000 g / mol The phenol-terminated PSU polymer (60.00 g, 0.003 mol) obtained in step 1 was weighed into a round-bottom flask containing chloroform (200 mL) and an electromagnetic stirring bar. Next, N2 was blown into the resulting solution for 20 minutes, and triethylamine (5.735 mL, 0.041 mol) was added dropwise, at which point the solution was cooled to 0°C using an ice bath. Acryloyl chloride (2.078 mL, 0.026 mol) was added dropwise to the stirred solution. After the addition was complete, the reaction was stirred at 0°C for 20 minutes, then heated to 23°C, and stirred for a further 12 hours. The final product was washed with a 2M aqueous HCl solution, the layers were separated, the organic layer was stirred on basic alumina for 1 hour, and then washed three times each with 1M NaOH, sodium bicarbonate solution, and again with saline solution. After drying on MgSO4 for 2 hours, a white powder was obtained by precipitation in MeOH, and then isolated by vacuum drying overnight at 50°C. The terminal group transformation of the phenol chain ends was, 1This was confirmed by observing peak shifts using 1H NMR. This was done by positioning three peaks characteristic of acrylate at 6.00, 6.31, and 6.59 ppm. In this case, the four benzyl protons used to track the previous terminal group are shifted, leaving only two protons visible, so these two are used instead of the four previously used. Since these two protons are also partially located below the aromatic peak of the main chain, the integral becomes high, and the integral value of the acrylate peak becomes pseudo-low.

[0095] Characterization of PSU polymers GPC 20 mg of PSU was dissolved in 20 mL of chloroform to prepare a 1 mg / mL sample. The solution was filtered through a 450 nm PTFE filter and placed in a quartz cuvette with a 1 cm path length. Dynamic light scattering (DLS) using a Malvern Zetasizer Nano ZS confirmed the dissolution of single chains in chloroform without aggregation. The sample was then eluted at a flow rate of 1 mL / min using an Acquity APC XT column in a Waters Acquity Advanced Polymer chromatography system. Mn was determined from the refractive index by comparison with a polystyrene standard at 35°C.

[0096] DSC By differential scanning calorimetry using TA instruments Q1000, the glass transition temperature (T) was determined for heating / cooling / heating cycles of 20 / 5 / 20°C / min, respectively. g ) revealed. g This was obtained from the inflection point of the second heating cycle.

[0097] TGA Thermogravimetric analysis was performed using a TA Instruments Q50 with N2-filled gas, under a temperature gradient of 10°C / min from 25°C to 800°C.

[0098] [Table 2]

[0099] Example 2 - Formulation prepared for photorheology Several formulations were prepared according to Table 3 below. 0.36 g of PSU polymer was weighed into two drum vials together with 0.84 g of NMP. The solutions were mixed in a VWR mini vortexer until a homogeneous solution was obtained. 9 mg of diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (photoinitiator) and TMP (polyfunctional acrylate) were added to the solution, the vials were covered with aluminum foil, and mixed overnight on a VWR standard analog shaker table. The samples were used within 24 hours.

[0100] [Table 3]

[0101] Photorheology experiments: A series of photorheology experiments were conducted to determine the suitability of specific formulations for printability. For the solution to be treatable by vat photopolymerization, the elastic modulus must exceed 30,000 Pa, and G ’ / G ” A crossover time of less than 2 seconds is desirable. Photorheology experiments were performed at 25°C using a TA Instruments DHR-2. These measurements were performed using an Omnicure S2000 high-pressure mercury light source with a 320–500 nm filter, and a Smart Swap with a 20 mm disposable aluminum parallel plate and a 20 mm quartz parallel plate lower geometry with a 1000 μm gap. TM The measurement was performed using geometry. UV intensity was measured using a Silverline radiometer with a 20mm attachment. Measurement parameters were: sampling frequency 1Hz, strain 0.1%, and UV light intensity 250mW / cm². 2 The settings were adjusted. The samples were exposed to UV light for 15 seconds, 30 seconds after the start of the experiment. The data was analyzed using TA Instruments TRIOS software to determine the storage modulus (G ’ ), loss modulus of elasticity (G ”), and the crossover time were identified.

[0102] Table 4 shows how the molecular weight (Mn) of the polymer affects printability based on photorheology when the formulation contains only the polymer and a photoinitiator. Polymers with a molecular weight of less than 12,000 g / mol exhibit a storage modulus that makes them printable, while the polymer in Comparative Example 3, with a molecular weight of 20,000 g / mol, has a storage modulus that is too low to be printable.

[0103] [Table 4]

[0104] Table 5 shows that the addition of trifunctional acrylates makes it possible to obtain a sufficiently high modulus of elasticity for photorheology-based part printing of acrylate-functionalized polysulfone polymers with Mn = 20,000 g / mol. This also demonstrates a significant improvement in crossover time.

[0105] [Table 5]

[0106] Example 3 - Formulation used in vat photopolymerization The formulation of the present invention was prepared by dissolving polymer P3 (27.552 g, 23.85 wt%), TMP (6.888 g, 5.96 wt%), and diphenyl (2,4,6-trimethylbenzoyl)phosphine oxide photoinitiator (0.706 g, 0.612 wt%) in NMP (80.36 g, 69.57%).

[0107] The parts were manufactured using a laser-based VP (Voltage Valve) device.

[0108] Laser-based VP device: A 405nm UV laser and optical train were extracted from a Formlabs 1+ and used to deliver UV irradiation to the resin surface. An aluminum tank was used to hold the resin during the printing process. A stainless steel build stage with a glass build platform was used as the stage for manufacturing parts. A stainless steel rotary topcoat system was used to coat the resin on the build platform.

[0109] Printing method 65 ml of the mixture was transferred to an aluminum tank, and the build platform was positioned at the projector's focal plane. After a short immersion period, the build platform was positioned to a depth of one layer thickness from the resin surface. Next, a rotary topcoat blade was used to smooth the resin surface from the meniscus-free state. The pattern corresponding to the layer to be manufactured was rasterized onto the resin surface with a predetermined number of passes, laser power, and scanning speed. These processes were repeated until the part was completed.

[0110] Using PreForm 2.3.3, an STL file was sliced ​​into 120-micron layers. A customized Python program was used to control the equipment and printing process.

[0111] A hexagonal open grid with a column wall thickness of 750 microns, side wall size of 2 mm, height of 24 mm, width of 17 mm, and length of 28 mm was constructed in Netfabb, and then extruded to a height of 24 mm to form the reference geometry.

[0112] Print result Print parameters: • Layer thickness = 120 microns ·Intensity=20mW • Scanning speed = 1550 mm / s • Number of passes per layer = 1

[0113] Feature resolution: A hexagonal wall was visible at the height of the part. The average wall thickness was approximately 2 mm.

[0114] The addition of TMP increased the elastic modulus of the cured gel, resulting in faster formation of a self-supporting structure compared to formulations without TMP.

Claims

1. A polymer blend (F), comprising, based on the total weight of said polymer blend (F): from 1 to 50% by weight, based on the total weight of F, of at least one poly(arylethersulfone) (PAES) polymer (P) of formula (M1) or (M2): 【Chemistry 1】 (In the formula, - R ２ is H or CH ３ and X is a bond or n is in the range of 1 to 20 (CH ２ ) ｎ (It is) and A polymer (P) having a number average molecular weight (Mn) of greater than 12,000 g / mol, as measured by gel permeation chromatography (GPC) using methylene chloride as the mobile phase and polystyrene standards; at least one multifunctional acrylate, at least one solvent, optionally at least one photoinitiator, - optionally with at least one blocker Including, The polymer (P) has the formula (L): 【Chemistry 2】 [In the formula, each R 1 is, independently for each aromatic ring, selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkylsulfonate, alkali or alkaline earth metal phosphonate, alkylphosphonate, amine, and quaternary ammonium; each i, independently for each aromatic ring, is zero or an integer from 1 to 4; - T is a bond, -CH 2 -; -O-; -SO 2 -; -S-; -C(O)-; -C(CH3)2-; -C(CF3)2-; -C(=CCl2)-; -C(CH3)(CH2CH2COOH)-; -N=N-; -RaC=CRb-, where each Ra and Rb is independently hydrogen, a C1 to C12 alkyl group, a C1 to C12 alkoxy group, a C6 to C18 aryl group, -(CH2)m- and -(CF2)m-, where m is an integer from 1 to 6, a linear or branched aliphatic divalent group of 6 or less carbon atoms, or a combination thereof. is a PAES containing a repeat unit (R PAES ), The multifunctional acrylate has the following formula (I): 【Chemistry 4】 (In the formula, R 3 is H or alkyl having 1 to 5 carbon atoms; R 4 is of formula (II): 【Chemistry 5】 where n varies between 0 and 10. or the multifunctional acrylate is selected from the group consisting of trimethylolpropane propoxy triacrylate, pentaerythritol triacrylate (PETA), glyceryl propoxy triacrylate (GPTA), di(trimethylolpropane) tetraacrylate, glycerol propoxylate triacrylate, pentaerythritol tetraacrylate, 1,3,5-triacryloylhexahydro-1,3,5-triazine, trimethylolpropane ethoxylate triacrylate, trimethylolpropane trimethacrylate, tris[2-(acryloyloxy)ethyl]isocyanurate, and mixtures thereof; Polymer blend (F).

2. T is a bond, -SO ２ - and -C(CH ３ ) ２ The polymer blend (F) according to claim 1, which is selected from the group consisting of:

3. 3. The polymer blend (F) according to claim 1 or 2, wherein the PAES polymer comprises at least 50 mol % (based on the total number of moles in the polymer) of repeat units of formula (L).

4. The PAES polymer comprises at least 50 mole % (based on the total moles in the polymer) of a carboxylic acid having the following formula: １ and i are as defined above): 【Chemistry 3】 The polymer blend (F) according to any one of claims 1 to 3, comprising a repeating unit selected from the group consisting of:

5. The polymer blend (F) according to any one of claims 1 to 4, comprising at least 0.05 wt.-% of a multifunctional acrylate, based on the total weight of said polymer blend (F).

6. The repeating unit (R PAES ) has the formula (L″): is the unit of The end group of the polymer (P) has the formula (M″): The polymer compound (F) according to any one of claims 1 to 5.

7. 7. The polymer formulation (F) according to any one of claims 1 to 6, wherein the multifunctional acrylate is selected from the group consisting of trimethylolpropane propoxy triacrylate, pentaerythritol triacrylate (PETA), glyceryl propoxy triacrylate (GPTA), di(trimethylolpropane) tetraacrylate, glycerol propoxylate triacrylate, pentaerythritol tetraacrylate, 1,3,5-triacryloylhexahydro-1,3,5-triazine, trimethylolpropane ethoxylate triacrylate, trimethylolpropane trimethacrylate, tris[2-(acryloyloxy)ethyl]isocyanurate, and mixtures thereof.

8. The multifunctional acrylate has the following formula (III): 【Chemistry 6】 The polymer blend (F) according to any one of claims 1 to 6,

9. the solvent is selected from the group consisting of N-methylpyrrolidone (NMP), N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAC), 1,3-dimethyl-2-imidazolidinone (DMI), tetrahydrofuran (THF), dimethylsulfoxide (DMSO) and sulfolane; the photoinitiator is selected from the group consisting of 2,2-dimethoxy-2-phenylacetophenone (DMPA), diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, and / or - said blocker is selected from the group consisting of avobenzone and 2,5-bis(5-tert-butyl-benzoxazol-2-yl)thiophene; A polymer blend (F) according to any one of claims 1 to 8.

10. The polymer blend (F) according to any one of claims 1 to 9, wherein the number average molecular weight (Mn) of the polymer (P) is at least 12,000 g / mol.

11. 1. A method of manufacturing a 3D article with an additive manufacturing system, comprising: - providing a polymer blend (F) according to any one of claims 1 to 10, - printing a layer of a 3D article from said polymer formulation (F), - optionally curing said 3D article at a temperature in the range of 50 to 450°C; The method includes:

12. 12. The method of claim 11 , wherein the step of printing a layer of the 3D article from the polymer formulation (F) comprises irradiating the polymer formulation (F) with light.

13. Use of the polymer formulation (F) according to any one of claims 1 to 10, alone or in combination with other components, for the production of 3D objects by stereolithography (SLA), direct ink writing (DIW), digital light processing (DLP) or inkjet processes.

14. Use of the polymer blend (F) according to any one of claims 1 to 10, alone or in combination with other components, for coating an article.

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