Photocurable polymers, photocurable polymer compositions and lithographic processes involving same - Patents.com

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] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Provisional Patent Application No. 62 / 743,756, filed October 10, 2018, the entire contents of which are incorporated herein by reference for all purposes.

[0002] The present invention relates to a polymer formulation for stereolithographic three-dimensional (3D) printing of articles, the formulation comprising a functionalized polymer. The present invention further relates to a lithographic method for forming a 3D object incorporating said polymer formulation. [Background technology]

[0003] Lithographic processes for the photofabrication of 3D objects from polymeric materials have recently gained popularity due to their relative speed and simplicity. Generally, lithographic processes involve the use of light, such as UV radiation, to locally harden a polymerizable formulation at specific locations. Localized hardening allows the fabrication of three-dimensional objects.

[0004] Lithographic processes generally use polymerizable formulations that are liquid in order 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 moderate mechanical properties and thermal stability.

[0005] Certain polymers used in lithographic processes exhibit good mechanical property profiles. These polymers need to melt above their melting temperature in order to be used in liquid polymerizable formulations. One of the challenges in identifying valuable polymers is that they need to remain thermally stable at the polymer melting temperature and be highly reactive in the printing process when a layer of the polymerizable formulation is irradiated.

[0006] Another challenge in identifying a polymerizable formulation worth using in a lithographic process is that it must be possible to produce 3D articles that exhibit good mechanical properties after photofabrication and that substantially retain these mechanical properties after exposure to high temperatures, e.g., above 150° C.

[0007] The polymerizable formulations of the present invention provide suitable solutions for high temperature 3D printing processes. Summary of the Invention

[0008] The present invention relates to a polymer (P) selected from poly(arylethersulfone) (PAES) and polyetherimide (PEI) polymers, the polymer (P) being represented by formula (M1) or (M2): TIFF0007607569000001.tif28170 (in the formula, R is H or CH3, - X is a bond or n is in the range of 1 to 20 (CH2) n is) and comprising at least one end group of The number average molecular weight (Mn) of the polymer (P) is less than 40,000 g / mol, less than 35,000 g / mol, less than 30,000 g / mol, less than 25,000 g / mol, less than 20,000 g / mol, less than 15,000 g / mol, or less than 10,000 g / mol, as measured by gel permeation chromatography (GPC) using methylene chloride as the mobile phase and polystyrene standards. The present invention relates to a polymer formulation (F) comprising a polymer.

[0009] This polymer formulation (F) can be used, for example, in photofabrication processes. In particular, the formulation (F) of the present invention can be incorporated into lithography processes in which light is used to cure functionalized polymers. The formulation (F) of the present invention can be transformed into a liquid state at temperatures below or above the Tg of the polymer (P) without visible changes, and then cured by irradiation with UV light to produce a high thermal property material with high Tg, high mechanical properties and high thermal stability. The formulation (F) of the present invention can be effectively used in 3D printing lithography processes.

[0010] The present invention also provides a method of manufacturing a three-dimensional (3D) article with an additive manufacturing system, comprising: - providing a polymer formulation (F) according to the invention, - printing a layer of a 3D object from a polymer formulation (F); The present invention relates to a method comprising the steps of:

[0011] According to another embodiment of the invention, the printing step comprises irradiating the polymer formulation (F) with UV light, which can be, for example, laser light.

[0012] The present invention also relates to a 3D article obtained, at least in part, by the method described above, and to the use of the polymer formulation (F) for the manufacture of a 3D object by stereolithography (SLA). [Brief description of the drawings]

[0013] [Figure 1] A schematic diagram of the 3D object to be printed. [Diagram 2] 1 is a photograph of an object printed from Comparative Formulation 1. [Diagram 3] 1 is a photograph of an object printed from invention formulation 2. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] The present invention relates to a polymer formulation (F) comprising at least one polymer (P) selected from the group consisting of poly(arylethersulfone) (PAES) polymers and polyetherimide (PEI) polymers, the polymer (P) being functionalized. More precisely, the polymer (P) has the formula (M1) or (M2): TIFF0007607569000002.tif28170 (in the formula, R is H or CH3, - X is a bond or n is in the range of 1 to 20, for example, 1 to 10 or 1 to 8 (CH2) n is) The polymer comprises at least one end group of

[0015] According to the invention, the number average molecular weight (Mn) of the polymer (P) is less than 40,000 g / mol, less than 35,000 g / mol, less than 30,000 g / mol, less than 25,000 g / mol, less than 20,000 g / mol, less than 15,000 g / mol, or less than 10,000 g / mol, as measured by gel permeation chromatography (GPC) using methylene chloride as the mobile phase and polystyrene standards. Preferably, the number average molecular weight (Mn) of the polymer (P) is less than 20,000 g / mol.

[0016] The formulations (F) comprising the functionalized polymers (P) of the present invention can be used in photofabrication processes. In particular, the polymers (P) and polymer formulations (F) of the present invention can be incorporated into lithographic processes in which light is used to cure the functionalized polymers.

[0017] The formulation (F) of the invention also comprises at least one solvent, at least one photoinitiator, - At least one blocker Includes.

[0018] The formulation (F) of the present invention is preferably liquid, for example at room temperature or above.

[0019] According to the present invention, photoinitiators are compounds that are especially added to the formulation to convert absorbed light energy, UV or visible light, into chemical energy in the form of initiating chemical species, e.g. free radicals or cations.

[0020] According to the present invention, a blocker is a compound that is added to capture unused radicals generated by the photoinitiator or to absorb part of the incident UV energy, which allows for improved dimensional accuracy of the parts produced.

[0021] The polymer (P) according to the invention is functionalized with functional groups, which are (meth)acrylate moieties (M1) and / or styrene (M2), introduced at at least one end of the polymer chain, for example at both ends of the polymer chain, and / or as a post-polymerization modification into the side chain of the polymer backbone.

[0022] More precisely, the polymer (P) described in the present invention is functionalized at at least one end of the polymer chain, as "terminal functionalization". The polymer (P) of the present invention can be functionalized at both ends of the polymer chain. The polymer (P) of the present invention can also be functionalized within the polymer backbone, as "internal functionalization". For example, with regard to internal functionalization, one or more of the repeating units of the polymer (P) that are not located at the end of the polymer chain can be functionalized with a functional group, which is a (meth)acrylate moiety.

[0023] The formulation (P) of the present invention may contain two or more polymers (P), for example two of three different polymers (P).

[0024] Poly(aryl ether sulfone) (PAES) According to one embodiment, P has the formula (L): Repeat unit (R PAES ) is a PAES having - Each R 1are independently selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium; - each i is an integer from 0 to 4 that is independently selected for each aromatic cycle; - T is 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 -(where each R a and R b are each independently a hydrogen atom or a C1-C12 alkyl, C1-C12 alkoxy, or C6-C18 aryl group; m is an integer of 1 to 6 -(CH2) m -and-(CF2) m -; a linear or branched, aliphatic divalent radical having 6 or fewer carbon atoms; and combinations thereof; R is H or CH3.

[0025] According to one embodiment, when P is a PAES, the polymer (P) of the invention has - Formula (L): At least one repeat unit (R PAES ), and / or - Formula (M): At least one end group of TIFF0007607569000005.tif28170 may include During the ceremony: - Each R 1are independently selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium; - each i is an integer from 0 to 4 that is independently selected for each aromatic cycle; - T is 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 -(where each R a and R b are each independently a hydrogen atom or a C1-C12 alkyl, C1-C12 alkoxy, or C6-C18 aryl group; m is an integer of 1 to 6 -(CH2) m -and-(CF2) m -; a linear or branched, aliphatic divalent radical having 6 or fewer carbon atoms; and combinations thereof; R is H or CH3.

[0026] According to another embodiment, the repeating unit (R PAES ) is represented by the formula (L'): TIFF0007607569000006.tif31170 (in the formula, R 1 and i are as described above. Follow.

[0027] According to one embodiment, the end groups of the polymer (P) have the formula (M'): TIFF0007607569000007.tif25170 (in the formula, R 1 , R and i are as defined above. Follow.

[0028] According to one embodiment, i is each R 1 In other words, according to this embodiment, - Repeating unit (R PAES ) is represented by the formula (L''): TIFF0007607569000008.tif27170 units, the end groups of the polymer (P) have the formula (M″): TIFF0007607569000009.tif27170 (wherein T is as defined above) Follow.

[0029] According to one embodiment, P is a PAES having at least 50 mole % (based on the total number of moles in the polymer) of repeat units of formula (L), (L') or (L'') and includes at least one end group of at least one of formula (M), (M') or (M'').

[0030] According to one embodiment 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 repeat units in the PAES (based on the total number of moles in the polymer) are repeat units (R PAES ) and comprising at least one end group of at least one of formula (M), (M') or (M'').

[0031] According to one embodiment of the present invention, P is a PAES, where T is selected from the group consisting of a bond, -SO2-, and -C(CH3)2-.

[0032] According to another embodiment of the invention, P is at least 50 mole % (based on the total number of moles in the polymer) of the formula: TIFF0007607569000010.tif96170 (in the formula, R 1 and i are as described above. The PAES has a repeat unit selected from the group consisting of:

[0033] 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 repeat units in the PAES (based on the total number of moles in the polymer) are repeat units (R PAES ).

[0034] According to one embodiment, P is a PAES where T is a bond. In other words, P is a functionalized poly(biphenyl ether sulfone) (PPSU).

[0035] 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 have the formula (LA): TIFF0007607569000011.tif31170 (wherein R1 and i are as defined above) Repeating units (R PPSU ) repeating units, - Formula (M1) or (M2): TIFF0007607569000012.tif28170 (in the formula, R is H or CH3, - X is a bond or n varies from 1 to 20, for example from 1 to 10, preferably equal to 1 or 2 (CH2) n is) and at least one end group of It is a PPSU containing.

[0036] The PPSU polymer of the present invention may be a homopolymer or a copolymer. If it is a copolymer, it may be a random, alternating or block copolymer.

[0037] According to one embodiment 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 repeat units in the PPSU are repeat units of formula (LA) (RPPSU ).

[0038] When poly(biphenyl ether sulfone) (PPSU) is a copolymer, it has repeating units (R PPSU ) is a repeating unit (R* PPSU ), for example repeat units of formula (LB) and / or formula (LC), and / or of formula (LD): TIFF0007607569000013.tif37170 (in the formula, R 1 and i are as described above. It can be made of repeating units such as:

[0039] Poly(biphenyl ether sulfone) (PPSU) can be prepared by any method known in the art. It can result, for example, from the condensation of 4,4'-dihydroxybiphenyl (biphenol) with 4,4'-dichlorodiphenyl sulfone in the presence of a base. The reaction of the monomer units 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 structure of the resulting poly(biphenyl ether sulfone) does not depend on the nature of the leaving group. PPSU is then modified after polymerization to introduce a functional group at at least one end of the polymer chain. The functional group can be represented by the formula CH2=CH-CH2-(CH2) n -, where n varies from 1 to 10. The alpha-olefin functional groups can also be introduced at both ends of the polymer chain and / or pendant to the polymer backbone.

[0040] According to one embodiment, P is a PAES where T is -C(CH3)2-. In other words, P is a functionalized polysulfone (PSU).

[0041] 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 have the formula (LB): TIFF0007607569000014.tif30170 (wherein R1 and i are as defined above) Repeating units (R PSU ) repeating units, - Formula (M1) or (M2): TIFF0007607569000015.tif30170 (in the formula, R is H or CH3, - X is a bond or n varies from 1 to 20, for example from 1 to 10, preferably equal to 1 or 2 (CH2) n is) and at least one end group of It is a PSU that includes.

[0042] The PSU polymer of the present invention can therefore be a homopolymer or a copolymer. If it is a copolymer, it can be a random, alternating or block copolymer.

[0043] According to one embodiment 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 repeat units in the PSU are repeat units of formula (LB) (R PSU ).

[0044] When the polysulfone (PSU) is a copolymer, it is a copolymer having a repeating unit (R PSU ) is a repeating unit (R* PSU ), for example, may be made up of repeat units of formula (LA), (LC) and / or (LD), all of which are described above.

[0045] According to one embodiment, P is a PAES where T is -SO2-. In other words, P is a functionalized polyethersulfone (PES).

[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 have the formula (LC): TIFF0007607569000016.tif30170 (wherein R1 and i are as defined above) Repeating units (R PES ) repeating units, - Formula (M1) or (M2): TIFF0007607569000017.tif30170 (in the formula, R is H or CH3, - X is a bond or n varies from 1 to 20, for example from 1 to 10, preferably equal to 1 or 2 (CH2) n is) and at least one end group of This is PES including.

[0047] The PES polymer of the present invention can therefore be a homopolymer or a copolymer. When it is a copolymer, it can be a random, alternating or block copolymer.

[0048] According to one embodiment 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 repeat units in the PES are repeat units of formula (LC) (R PES ).

[0049] When polyethersulfone (PES) is a copolymer, it has repeating units (R PESU ) is a repeating unit (R* PESU ), for example, may be made up of repeat units of formula (LA), formula (LB) and / or formula (LD), all of which are described above.

[0050] Poly(ether imide) (PEI) According to one embodiment, P comprises a repeating unit (R PEI ) is a PEI having a repeating unit (R PEI ) may optionally further comprise at least one amide group not included in the amic acid form of the imide group.

[0051] According to one embodiment, the repeating unit (R PEI ) are represented by the following formulae (I), (II), (III), (IV), (V) and mixtures thereof: TIFF0007607569000018.tif179170[In the formula, - Ar is a tetravalent aromatic moiety selected from the group consisting of substituted or unsubstituted, saturated, unsaturated or aromatic monocyclic and polycyclic groups having 5 to 50 carbon atoms; - Ar' is a trivalent aromatic moiety selected from the group consisting of substituted, unsubstituted, saturated, unsaturated, aromatic monocyclic and aromatic polycyclic radicals having 5 to 50 C atoms; - R, for example, (a) Aromatic hydrocarbon radicals having 6 to 20 carbon atoms and their halogenated derivatives; (b) a linear or branched alkylene radical having 2 to 20 carbon atoms; (c) a cycloalkylene radical having 3 to 20 carbon atoms, and (d) Formula (VI): TIFF0007607569000019.tif27170 (in the formula, - Y is an alkylene of 1 to 6 carbon atoms, such as -C(CH3)2 and -C n H 2n -(n is an integer from 1 to 6), perfluoroalkylene of 1 to 6 carbon atoms, such as -C(CF3)2 and -C n F 2n - (n is an integer from 1 to 6); is selected from the group consisting of cycloalkylene of 4 to 8 carbon atoms; alkylidene of 1 to 6 carbon atoms; cycloalkylidene of 4 to 8 carbon atoms; -O-; -S-; -C(O)-; -SO2-; -SO-, R″ is selected from the group consisting of hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkaline earth metal sulfonate, alkaline earth metal sulfonate, alkylsulfonate, alkaline earth metal phosphonate, alkaline earth metal phosphonate, alkylphosphonate, amine and quaternary ammonium; - i, for each R'', is independently zero or an integer ranging from 1 to 4. Divalent radical of selected from the group consisting of substituted and unsubstituted divalent organic radicals, provided that at least one of Ar, Ar' and R contains at least one ether group, and that the ether group is present in the backbone of the polymer chain. is selected from the group consisting of:

[0052] According to one embodiment, Ar has the formula: TIFF0007607569000020.tif47170[In the formula, X is a divalent moiety having a divalent bond at the 3,3', 3,4', 4,3'', or 4,4' positions, and is an alkylene of 1 to 6 carbon atoms, such as -C(CH) and -C n H 2n - (n is an integer from 1 to 6); perfluoroalkylene having 1 to 6 carbon atoms, such as -C(CF3)2 and -C n F 2n -(n is an integer from 1 to 6); cycloalkylene of 4 to 8 carbon atoms; alkylidene of 1 to 6 carbon atoms; cycloalkylidene of 4 to 8 carbon atoms; -O-; -S-; -C(O)-; -SO2-; -SO-, or X is a group of the formula -O-Ar"-O-, where Ar" is an aromatic moiety selected from the group consisting of substituted or unsubstituted, saturated, unsaturated or aromatic monocyclic and polycyclic groups having from 5 to 50 carbon atoms. is selected from the group consisting of:

[0053] According to one embodiment, Ar′ has the formula: TIFF0007607569000021.tif56170[In the formula, X is a divalent moiety having a divalent bond at the 3,3', 3,4', 4,3'', or 4,4' positions, and is an alkylene of 1 to 6 carbon atoms, such as -C(CH) and -C n H 2n - (n is an integer from 1 to 6); perfluoroalkylene having 1 to 6 carbon atoms, such as -C(CF3)2 and -C n F 2n -(n is an integer from 1 to 6); cycloalkylene of 4 to 8 carbon atoms; alkylidene of 1 to 6 carbon atoms; cycloalkylidene of 4 to 8 carbon atoms; -O-; -S-; -C(O)-; -SO2-; -SO-; or X is a group of the formula -O-Ar"-O-, where Ar" is an aromatic moiety selected from the group consisting of substituted or unsubstituted, saturated, unsaturated or aromatic monocyclic and polycyclic groups having from 5 to 50 carbon atoms. is selected from the group consisting of:

[0054] According to one embodiment of the present disclosure, at least 50 mol%, 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 repeat units in the PEI are repeat units (R PEI ).

[0055] According to one embodiment, P is at least 50 mole %, based on the total moles in the polymer, of formula (VII): TIFF0007607569000022.tif33170[In the formula, - R, for example, (a) Aromatic hydrocarbon radicals having 6 to 20 carbon atoms and their halogenated derivatives; (b) a linear or branched alkylene radical having 2 to 20 carbon atoms; (c) a cycloalkylene radical having 3 to 20 carbon atoms, and (d) Formula (VI): TIFF0007607569000023.tif27170 (in the formula, - Y is an alkylene of 1 to 6 carbon atoms, such as -C(CH3)2 and -C n H 2n - (n is an integer from 1 to 6); perfluoroalkylene having 1 to 6 carbon atoms, such as -C(CF3)2 and -C n F 2n - (n is an integer from 1 to 6); is selected from the group consisting of cycloalkylene of 4 to 8 carbon atoms; alkylidene of 1 to 6 carbon atoms; cycloalkylidene of 4 to 8 carbon atoms; -O-; -S-; -C(O)-; -SO2-; -SO-, R″ is selected from the group consisting of hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkaline earth metal sulfonate, alkaline earth metal sulfonate, alkylsulfonate, alkaline earth metal phosphonate, alkaline earth metal phosphonate, alkylphosphonate, amine and quaternary ammonium; - i is independently for each R" zero or an integer ranging from 1 to 4; provided that at least one of Ar, Ar' and R contains at least one ether group, and that the ether group is present in the polymer chain backbone. and selected from the group consisting of substituted and unsubstituted divalent organic radicals selected from the group consisting of divalent radicals of - T -O- or -O-Ar''-O- wherein the divalent bond of the -O- or -O-Ar''-O- group is in the 3,3', 3,4', 4,3', or 4,4' positions; where Ar″ can be either a substituted or unsubstituted, saturated, unsaturated or aromatic monocyclic and polycyclic group having 5 to 50 carbon atoms, such as a substituted or unsubstituted phenylene, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthalene group, or an aromatic moiety selected from the group consisting of a moiety containing two substituted or unsubstituted phenylenes. Repeating units (R PEI ) is PEI.

[0056] According to one embodiment of the present disclosure, Ar″ is of general formula (VI), as detailed above; for example, Ar″ is of formula (XIX): The file is TIFF0007607569000024.tif24170.

[0057] The polyetherimides (PEI) of the present invention are prepared by reacting a diamino compound of the formula H2N-R-NH2(XX), where R is as previously defined, with a diamino compound of the formula (XXI): TIFF0007607569000025.tif37170, where T is as previously defined. The compounds may be prepared by any of the methods known to those skilled in the art, including reaction of any of the compounds with an aromatic bis(ether anhydride).

[0058] Generally, the preparation can be carried out at temperatures ranging from 20° C. to 250° C. in solvents such as o-dichlorobenzene, m-cresol / toluene, N,N-dimethylacetamide.

[0059] Alternatively, these polyetherimides can be prepared by simultaneously mixing any dianhydride of formula (XXI) with any diamino compound of formula (XX) and melt polymerizing the mixture of these components while heating at an elevated temperature.

[0060] Examples of the aromatic bis(ether acid anhydride) of formula (XXI) include: 2,2-Bis[4-(2,3-dicarboxyphenoxy)phenyl]propane dianhydride; 4,4'-Bis(2,3-dicarboxyphenoxy)diphenyl ether dianhydride; 1,3-Bis(2,3-dicarboxyphenoxy)benzene dianhydride; 4,4'-Bis(2,3-dicarboxyphenoxy)diphenyl sulfide dianhydride; 1,4-Bis(2,3-dicarboxyphenoxy)benzene dianhydride; 4,4'-Bis(2,3-dicarboxyphenoxy)benzophenone dianhydride; 4,4'-Bis(2,3-dicarboxyphenoxy)diphenylsulfone dianhydride; 2,2-Bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride; 4,4'-Bis(3,4-dicarboxyphenoxy)diphenyl ether dianhydride; 4,4'-Bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride; 1,3-Bis(3,4-dicarboxyphenoxy)benzene dianhydride; 1,4-Bis(3,4-dicarboxyphenoxy)benzene dianhydride; 4,4'-Bis(3,4-dicarboxyphenoxy)benzophenone dianhydride; 4-(2,3-Dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl-2,2-propane dianhydride; and mixtures of such dianhydrides Examples include:

[0061] The organic diamine of formula (XX) is selected from the group consisting of m-phenylenediamine, p-phenylenediamine, 2,2-bis(p-aminophenyl)propane, 4,4'-diaminodiphenyl-methane, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, and mixtures thereof; preferably, the organic diamine of formula (XX) is selected from the group consisting of m-phenylenediamine and p-phenylenediamine, and mixtures thereof.

[0062] According to one embodiment, P represents at least 50 mole % of a group represented by formula (XXIII) or (XXIV), based on the total number of moles in the polymer: Repeat unit of TIFF0007607569000026.tif69170 (R PEI ) in their imide forms or their corresponding amic acid forms and mixtures thereof.

[0063] In a preferred embodiment of the invention, at least 50 mol%, 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 repeat units in the PEI are repeat units of formula (XXIII) or (XXIV) (R PEI ).

[0064] solvent The concentration of the solvent may be from 1 to 80% by weight, for example from 2 to 75% by weight, from 5 to 70% by weight, or from 10 to 65% by weight, based on the total weight of the formulation (F).

[0065] 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), dimethylsulfoxide (DMSO) and sulfolane.

[0066] Preferably, the solvent is a dipolar 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 dimethylsulfoxide (DMSO).

[0067] Photoinitiators According to the present invention, photoinitiators are compounds that are notably added to the formulation to convert absorbed light energy, UV or visible light, into chemical energy in the form of initiating chemical species, such as free radicals or cations. Based on the mechanism by which the initiating radicals are formed, photoinitiators are generally divided into two classes: - Type I photoinitiators undergo unimolecular bond cleavage upon irradiation to generate free radicals, - Type II photoinitiators undergo a bimolecular reaction in which the excited state of the photoinitiator interacts with a second molecule (a coinitiator) to generate free radicals.

[0068] The concentration of the photoinitiator in the formulation (F) may be from 0.05 to 10% by weight, for example from 0.1 to 5% by weight, from 0.2 to 4% by weight or from 0.5 to 3% by weight, based on the total weight of the formulation (F).

[0069] According to one embodiment of the present invention, the photoinitiator is - Acetophenone - Anisoin - Anthraquinone - 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'-morpholinobutyrophenone - 4,4'-Bis(diethylamino)benzophenone - 4,4'-Bis(dimethylamino)benzophenone - Camphorquinone - 2-Chlorothioxanthen-9-one - (Cumene)cyclopentadienyliron(II) hexafluorophosphate - Dibenzosuberenone - 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 blends) - 4'-Ethoxyacetophenone - 2-Ethyl anthraquinone - Ferrocene - 3'-hydroxyacetophenone, 4'-hydroxyacetophenone, 3-hydroxybenzophenone and 4-hydroxybenzophenone - 1-Hydroxycyclohexyl phenyl ketone - 2-Hydroxy-2-methylpropiophenone - 2-methylbenzophenone or 3-methylbenzophenone - Methyl benzoyl formate - 2-Methyl-4'-(methylthio)-2-morpholinopropiophenone - Phenanthrenequinone - 4'-Phenoxyacetophenone - Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide - Thioxanthen-9-one - Triarylsulfonium hexafluoroantimonate salts, mixed, 50% in propylene carbonate - triarylsulfonium hexafluorophosphate salts, mixed, 50% in propylene carbonate, and - A mixture of them is selected from the group consisting of:

[0070] 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.

[0071] blocker According to the present invention, a blocker is a compound that is added to the formulation to (i) scavenge a certain amount of radicals formed by the photoinitiator during irradiation by UV light, (ii) scavenge unused radicals that may be present after the UV irradiation source is switched off, and / or (iii) absorb a portion of the energy delivered to the system during UV irradiation.

[0072] The concentration of the blocker in the formulation (F) may be from 0.05 to 10% by weight, for example from 0.1 to 5% by weight, from 0.2 to 4% by weight or from 0.5 to 3% by weight, based on the total weight of the formulation (F).

[0073] According to one embodiment of the invention, the blocker comprises: - 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) (bisdisulfol disodium) - Hexyl 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoate (diethylamino hydroxybenzoyl hexyl benzoate) - Menthyl-o-aminobenzoate (menthyl anthranilate) - 2,2'-[6-(4-methoxyphenyl)-1,3,5-triazine-2,4-diyl]bis{5-[(2-ethylhexyl)oxy]phenol} (bemotrizinol) - 2,4-Dihydroxybenzophenone - 2,2',4,4'-Tetrahydroxybenzophenone - 4-Hydroxy-2-methoxy-5-(oxo-phenylmethyl)benzenesulfonic acid (sulisobenzone) - 2,2'-dihydroxy-4,4'-dimethoxybenzophenone - 5-Chloro-2-hydroxybenzophenone - (2-Hydroxy-4-methoxyphenyl)-(2-hydroxyphenyl)methanone (dioxybenzone) - 2,5-bis(5-tert-butyl-benzoxazol-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-trisilaheptan-4-yl)propyl]phenol (drometrizole trisiloxane) - Terephthalidenedicamphorsulfonic acid (Ecamsul) - 2-Ethylhexyl 2-cyano-3,3-diphenyl-2-propenoate (Octocrylene) - Diethylhexylbutamidotriazon (Iscotrizinol) - 2-Ethoxyethyl 3-(4-methoxyphenyl)propenoate (Cinoxate) - Isopentyl 4-methoxycinnamate (amyloxate) - 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 - A mixture of them is selected from the group consisting of:

[0074] Preferably, the blocker is selected from the group consisting of avobenzone and 2,5-bis(5-tert-butyl-benzoxazol-2-yl)thiophene.

[0075] Optional Ingredients The formulation of the present invention may contain at least one additive, for example selected from the group consisting of fillers such as silica, antioxidants, antimicrobial compounds and antistatic compounds. The additive may be, for example, a chemically inert species such as carbon black, silica (e.g., microsilica particles) and carbon nanotubes.

[0076] 3D object manufacturing process The present invention also provides a method of manufacturing a 3D article with an additive manufacturing system, comprising the steps of: - providing a polymer formulation (F) as described above, - printing layers of a 3D object from a polymer formulation (F); The present invention relates to a method comprising the steps of:

[0077] According to one embodiment, the printing step comprises irradiating with UV light the polymer formulation (F), for example a layer of such formulation (F) deposited on the printing surface, the layer preferably exhibiting a size ranging from 10 μm to 300 μm, for example from 50 μm to 150 μm.

[0078] The 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 of a layer of such a formulation (F). The irradiation is also preferably of sufficient intensity to cause adhesion of the layer of the polymer formulation (F).

[0079] According to another embodiment of the invention, a method of manufacturing a 3D article with an additive manufacturing system includes: - providing a polymer formulation (F) as described above, - forming layers of the 3D object from a polymer formulation (F); a) coating a layer of formulation (F) onto a surface; b) irradiating the layer with UV light; c) coating a layer of formulation (F) onto the previously irradiated layer; d) exposing the layer to UV light; and e) repeating steps c) and d) a sufficient number of times to produce a 3D article. The process of printing by Includes.

[0080] According to one embodiment, the polymer formulation (F) is at room temperature throughout the process. Alternatively, the formulation can be heated before and / or during printing, especially when the polymer concentration in the formulation is high. In this case, the temperature can be up to 130° C., up to 120° C. or up to 110° C. before and / or during printing.

[0081] Purpose The present invention also relates to the use of the polymer (P) according to the invention or of the polymer formulation (F) according to the invention for the manufacture of a 3D object / article.

[0082] All of the embodiments described above with respect to the polymer (P) and the polymer formulation (F) apply equally to the use for the manufacture of 3D objects / articles.

[0083] The present invention also relates to a 3D object or 3D article obtained, at least in part, from the manufacturing method of the present invention using the polymer (P) or the polymer formulation (F) described herein.

[0084] The 3D objects or articles obtained by such manufacturing methods can be used in a variety of end uses, including implantable devices, dental prostheses, brackets, and complex molded parts in the aerospace industry and underhood parts in the automotive industry, among others.

[0085] To the extent that the disclosure of any patents, patent applications, and publications incorporated herein by reference conflicts with the statements of this application to the extent that it may render a term unclear, this statement shall control.

[0086] The invention will now be described in more detail with reference to the following examples, the purpose of which is merely illustrative and not intended to limit the scope of the invention. EXAMPLES

[0087] Example 1 - Synthesis of PSU Polymer According to the Invention raw materials 4-(Dimethylamino)pyridine (DMAP) (Sigma-Aldrich, ≥99%), acryloyl chloride (Sigma-Aldrich, ≥97%), triethylamine (TEA) (Sigma-Aldrich, ≥99%), potassium carbonate (Fisher Chemical), toluene (Fisher Chemical), N,N-dimethylacetamide anhydrous (DMAc) (Acros Organics, 99.5%), sodium chloride (Fisher Chemical), magnesium sulfate (Spectrum), diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (97%, Sigma Aldrich), sodium bicarbonate (Spectrum), hydrochloric acid (Fisher Scientific), and chloroform anhydrous (Sigma-Aldrich, ≥99%) were used as received. Bis(4-chlorophenyl)sulfone (98%) and bisphenol A (≥99%) were purchased from Sigma-Aldrich and recrystallized from toluene. Nitrogen gas (99.999%) was purchased from Praxair. All raw materials were used as received unless otherwise stated.

[0088] Analysis method 1 H nuclear magnetic resonance (NMR) spectroscopy was performed on a Varian Unity 400 at 400 MHz at 23 °C. Deuterated chloroform (CDCl3) served as the solvent for all polymers.

[0089] Waters Acquity Advanced Permeation Chromatography (APC) was used to characterize the molecular weight (Mn) of the polymer against polystyrene standards at 35° C. An Acquity APC XT column was utilized at a flow rate of 1 mL / min with a sample concentration of 1 mg / mL.

[0090] Thermogravimetric analysis (TGA) was performed using a TA Instruments Q50 from 25 to 600 °C at 10 °C / min under constant N2 flow.

[0091] Differential scanning calorimetry (DSC) was performed using a TA instruments Q1000 DSC with an RCS90 cryocooling system and a 50 mL / min nitrogen sample cell purge. The instrument was calibrated using indium (Tm=156.60°C) and zinc (Tm=419.47°C) standards. An initial heating rate of 10°C / min was used, followed by a 100°C / min quench to remove thermal history. A second heating cycle at 10°C / min was used to calculate the temperature transition. Glass transition temperatures (Tg) were determined by inflection points with TA Universal Analysis software.

[0092] Photorheology is performed using a 20mm parallel plate geometry and Smart Swap TM Rheometer equipped with a TA Instruments DHR-2 UV curing accessory and an Omnicure S2000 light source installed with a broad spectrum bulb and a 320-500 nm filter allowing wavelengths in this window to pass through to the sample. Oscillatory analysis was performed on the polymer at 25 °C using 0.3% strain and 4 Hz. The samples were heated at 250 mW / cm for 200 seconds. 2 The mixture was subjected to vibration for 30 seconds before being exposed to UV light at an intensity of 1000 nm.

[0093] Storage (G') and loss (G") shear moduli were obtained and analyzed with the TA TRIOS software package, with the G' / G" crossover point determined as per the software. The plateau modulus (G_N^0) was determined by averaging the last 100 data points in the storage modulus curve.

[0094] Step 1 - Synthesis of Hydroxyl-Terminated PSU Polymer This example demonstrates the synthesis of a hydroxyl-terminated PSU polymer with controlled molecular weight according to Scheme 1 below. TIFF0007607569000027.tif37170

[0095] Polysulfone (PSU) polymers were synthesized using excess bisphenol A monomer (BPA) to control the molecular weight of the final polymer and to generate hydroxyl end groups.

[0096] An example of the synthesis of PSU with a target Mn of 6,000 g / mol PSU (ratio BPA:DCS=1.08:1) is as follows: Bisphenol A (11.11 g, 0.049 mol), 4,4'-dichlorophenylsulfone (12.98 g, 0.045 mol), potassium carbonate (8.07 g, 0.058 mol), anhydrous N,N-dimethylacetamide (160 mL), and toluene (80 mL) were weighed into a three-necked, round-bottom flask equipped with a Dean-Stark trap and a mechanical stir bar. The heterogeneous solution was purged with N2 for 10 min. The reaction was then heated at 160 °C for 4 h while monitoring water removal by the toluene / water azeotrope in the Dean-Stark trap. The reaction temperature was increased to 180 and toluene was removed over 12 h. The resulting solution was filtered to remove salts. Purification occurred by precipitation into 4 L of distilled water. The resulting white polymer was filtered and dried under vacuum at 210° C. overnight.

[0097] Step 2 - Synthesis of Acrylate-Terminated PSU Polymer This example demonstrates the synthesis of an acrylate-terminated PSU polymer with controlled molecular weight according to Scheme 2 below. TIFF0007607569000028.tif54170

[0098] Scheme 2 summarizes the general synthesis for acrylate-terminated PSU oligomers. PSU (5.00 g, 0.0009 mol) from step 1 and DMAP (0.0058 g, 0.000048 mol) were charged to a 100 mL round bottom flask. The reaction was purged with N2 for 10 min, followed by the addition of anhydrous CHCl3 (50 mL). Once homogeneous, the reaction was cooled to 0° C. Triethylamine (0.74 g, 0.0073 mol) was added via syringe, and once dissolved, acryloyl chloride (0.41 g, 0.0046 mol) was then added dropwise over 1 min. The reaction was allowed to warm to room temperature overnight. The solution was then washed twice with 2 M aqueous HCl to remove excess DMAP and convert excess TEA to salt form, then stirred over basic alumina (ca. 5 g) for 3 h. The solution was then filtered and then washed twice with saturated sodium bicarbonate solution and finally once with brine, and the resulting yellow solid was dried under vacuum at 40° C. for 18 h.

[0099] result 1H NMR spectroscopy confirmed the quantitative conversion of hydroxyl-terminated PSU to acrylate-terminated PSU. The observation and integration of acrylate protons at 6-7 ppm relative to the backbone resonances was a clear indication of quantitative termination.

[0100] Differential scanning calorimetry at 20 °C / min showed that the final polymer had a T g =167°C. Target Mn: 6,000 g / mol GPC Mn: 5,700 g / mol PDI:2.41 Titration Mn: 7,260 g / mol

[0101] Example 2 - Printing of PSU polymer Step 1 - Preparation of the formulation The ingredients and the weight percentage of each ingredient relative to the total weight of the formulation are shown in Table 1.

[0102] TIFF0007607569000029.tif52170

[0103] Process 2-Printing The formulation was transferred to a glass beaker and placed at the same height as the projector's focus. A ULTEM® build platform, fabricated by filament extrusion, was inserted into the resin beaker. The build platform was flush with the resin surface and then lowered 100 μm into the resin. The STL file of the test specimen was sliced ​​into 100 μm slices and converted to a monochrome bitmap image. The bitmap image, corresponding to the first layer of the part, was imaged at 15 W / cm 2 A 365 nm light source set at an intensity of 1000 nm was projected onto the resin surface for 8 seconds. The build platform was then lowered into the resin to be recoated with a fresh layer of resin. Subsequent layers were fabricated using an exposure time of 8 seconds / layer, followed by a recoating step. This process continued until a complete part was fabricated. The fabricated 3D part was extracted from the build platform and rinsed with NMP to remove any remaining uncured resin. The part was then wiped with Kim Wipes. TM The plate was wiped dry and transferred onto a glass slide for measurement.

[0104] result As shown in Figure 2, parts fabricated with Comparative Formulation 1 do not exhibit any of the planned porosity. The pores are either fully closed or partially closed. This can be attributed to over-curing. This formulation results in the fabrication of parts with poor feature resolution.

[0105] As shown in Figure 3, parts fabricated with invention formulation 2 exhibit all of the planned porosity. This can be attributed to the prevention of over-curing by the addition of the UV blocker, Avobenzone. This formulation results in the fabrication of parts with excellent feature resolution.

Claims

1. Based on the total weight of the formulation (F): 1 to 50% by weight of at least one polymer (P) selected from poly(aryl ether sulfone) (PAES) polymers, wherein the polymer (P) has the formula (M1) or (M2): (In the formula, - R 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 less than 40,000 g / mol as measured by gel permeation chromatography (GPC) using methylene chloride as the mobile phase and polystyrene standards; at least one solvent, at least one photoinitiator, at least one blocker, which is a compound different from said at least one photoinitiator; (F) a polymer formulation comprising:

2. P is a compound of formula (L): Repeating units (R ＰＡＥＳ ) is a PAES comprising - Each R １ are independently selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium; - each i is an integer from 0 to 4 that is independently selected for each aromatic cycle; - T is a bond, -CH ２ -;-O-;-SO ２ -;-S-;-C(O)-;-C(CH ３ ) ２ -;-C(CF ３ ) ２ -; -C(=CCl ２ )-;-C(CH ３ ) (CH ２ CH ２ COOH)-;-N=N-;-R ａ C=CR ｂ - (where each R ａ and R ｂ are each independently hydrogen or a C1-C12 alkyl, C1-C12 alkoxy, or C6-C18 aryl group; m is an integer from 1 to 6; ２ ) ｍ --and--(CF ２ ) ｍ -; linear or branched, aliphatic divalent radicals of 6 or less carbon atoms; and combinations thereof, 2. The formulation of claim 1.

3. T is a bond, -SO ２ - and -C(CH ３ ) ２ The formulation of claim 2, wherein said formulation is selected from the group consisting of:

4. 4. The formulation of claim 2 or 3, wherein the PAES polymer comprises at least 50 mole % (based on the total number of moles in the polymer) of repeat units of formula (L).

5. 4. The PAES polymer comprises at least 50 mole % (based on the total moles in the polymer) of the formula: (In the formula, R １ and i are as defined above. The formulation of any one of claims 2 to 4, comprising a repeating unit selected from the group consisting of:

6. 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), 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 - the blocker is selected from the group consisting of avobenzone and 2,5-bis(5-tert-butyl-benzoxazol-2-yl)thiophene; A formulation according to any one of claims 1 to 5.

7. 1. A method of manufacturing a 3D article with an additive manufacturing system, comprising: - providing a polymer formulation (F) according to any one of claims 1 to 6, - printing a layer of a 3D article from a polymer formulation (F); The method includes:

8. The method of claim 7 , wherein the step of printing comprises irradiating the polymer composition with UV light.

9. The method of claim 8 , wherein the UV light is laser light.

10. 3D article obtainable, at least in part, by the method according to any one of claims 7 to 9.

11. 7. Use of the polymer formulation (F) according to any one of claims 1 to 6 for the production of 3D objects by stereolithography.

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