Inflammatory-resistant shaping materials and related printed 3D articles

Abstract

Described herein is a polymerizable liquid for 3D printing applications, which in some embodiments, imparts flame resistance and / or fire retardancy to an article printed from the liquid. The polymerizable liquid can also impart desirable mechanical properties to the article. In some embodiments, the polymerizable liquid includes a curable isocyanurate component in an amount of at least 5% by weight based on the total weight of the polymerizable liquid, and a brominated acrylate ester component. Further described herein is a method of printing a three-dimensional article using the polymerizable liquid.

Description

Cross - Reference to Related Applications

[0001] This application claims priority under 35 U.S.C. § 119 to U.S. Provisional Patent Application No. 63 / 159,225, filed on March 10, 2021, the entire disclosure of which is incorporated herein by reference.

Technical Field

[0002] The present invention relates to three - dimensional shaping materials, and more particularly to polymerizable liquids that impart flame - resistant or fire - retardant properties to articles printed from polymerizable liquids.

Background Art

[0003] 3D printers form various 3D objects, articles, or parts according to computer - generated files using shaping materials, also known as inks. In some examples, the shaping material is solid at ambient temperature and turns into a liquid at a high jetting temperature. In other examples, the shaping material is liquid at ambient temperature.

[0004] The shaping material can include various chemical species. The selection of the chemical species included in the shaping material can be made according to various considerations including, but not limited to, the desired chemical and / or mechanical properties of the printed article and the operating parameters of the 3D printing apparatus. For example, ultraviolet (UV) curable acrylate formulations can generally print parts with high resolution in a DLP system. However, in many cases, the resulting parts lack desirable mechanical properties and tend to break or follow other degradation paths. Such degradation paths impair the performance of the article and lead to early failure.

Summary of the Invention

Problems to be Solved by the Invention

[0005] Furthermore, some of the shaping materials and the articles resulting from printing from the shaping materials may be unsuitable for high-temperature applications and / or other applications that require flame resistance. As a result, 3D printing technology may have limited use in fields that require flame-retardant or flame-resistant materials and articles.

Means for Solving the Problems

[0006] In view of the above, in some embodiments, a polymerizable liquid for 3D printing applications is described herein, which imparts flame resistance and / or flame retardancy to articles printed from the liquid. The polymerizable liquid may also impart desired mechanical properties to the articles. In some embodiments, the polymerizable liquid comprises a curable isocyanurate component in an amount of at least 5% by mass based on the total weight of the polymerizable liquid and a brominated acrylate ester component. The brominated acrylate ester component can include one or more acrylate or methacrylate esters having bromine atoms bonded to aliphatic carbons.

[0007] In some embodiments, the polymerizable liquid further comprises an organic phosphate component comprising one or more organic phosphate compounds. In some embodiments, the polymerizable liquid further comprises an acrylate component. The acrylate component can include an acrylate monomer, an acrylate oligomer, or a mixture thereof.

[0008] Furthermore, in some embodiments, the polymerizable liquid further comprises an additive of formula I:

Chemical formula

[0009] Furthermore, a method of printing a three-dimensional article is described herein. In some embodiments, the method includes providing a polymerizable liquid comprising a curable isocyanurate component in an amount of at least 5% by mass based on the total weight of the polymerizable liquid and a brominated acrylate ester component. As detailed herein, the brominated acrylate ester component can include one or more acrylate or methacrylate esters having bromine atoms bonded to aliphatic carbons. In some embodiments, the polymerizable liquid can also contain one or more of an organic phosphate component, an acrylate component, and / or an additive of formula I described herein.

[0010] The polymerizable liquid is printed and cured to form an article. In some embodiments, the article is formed via a layer-by-layer process, and layer formation is performed via deposition and curing of layers of the polymerizable liquid.

[0011] As further described herein, the polymerizable liquid may further include a photoinitiator component, and curing of the polymerizable liquid can occur by irradiation of the liquid with light of a wavelength suitable for initiating free radical polymerization.

[0012] These and other embodiments are further described in the following detailed description.

Brief Description of the Drawings

[0013]

Figure 1

Best Mode for Carrying Out the Invention

[0014] The embodiments described in this specification can be more easily understood by referring to the following detailed description and examples. However, the elements, devices, and methods described in this specification are not limited to the specific embodiments presented in the detailed description and examples. It should be recognized that these embodiments are merely illustrative examples of the principles of the present invention. Many modifications and adaptations will be readily apparent to those skilled in the art without departing from the spirit and scope of the present invention.

[0015] Furthermore, all ranges disclosed in this specification are to be understood to encompass any and all sub-ranges subsumed therein. For example, a defined range of "1.0 to 10.0" should be considered to include any and all sub-ranges starting with a minimum value of 1.0 or more and ending with a maximum value of 10.0 or less, such as 1.0 to 5.3, or 4.7 to 10.0, or 3.6 to 7.9.

[0016] All ranges disclosed in this specification are also to be considered to include the endpoints of the range, unless otherwise specifically stated. For example, a range of "between 5 and 10" should generally be considered to include the endpoints 5 and 10.

[0017] Furthermore, when the term "maximum" is used in relation to an amount or quantity, it should be understood that the amount is at least a detectable amount or quantity. For example, a substance present in an amount of "maximum" a specified amount can be present in an amount from a detectable amount up to and including the specified amount and amounts greater than the specified amount.

[0018] Terms such as "three-dimensional printing system," "three-dimensional printer," "print," etc. generally describe various solid freeform manufacturing techniques for creating three-dimensional articles or objects by selective deposition, jetting, fused deposition modeling, multi-jet modeling, and other additive manufacturing techniques now known or later to be known in the art that use a shaping material or ink.

[0019] Definition As used herein, the term "alkyl" alone or in combination refers to a straight-chain or branched-chain saturated hydrocarbon group optionally substituted with one or more substituents. For example, alkyl is C1-C 30 or C1-C 18 and may be.

[0020] As used herein, the term "alkenyl" alone or in combination refers to a straight-chain or branched-chain hydrocarbon group having at least one carbon-carbon double bond and optionally substituted with one or more substituents.

[0021] As used herein, the term "alkynyl" alone or in combination refers to a straight-chain or branched-chain hydrocarbon group having at least one carbon-carbon triple bond and optionally substituted with one or more substituents.

[0022] As used herein, the term "aryl" alone or in combination refers to an aromatic monocyclic or polycyclic ring system optionally substituted with one or more ring substituents.

[0023] As used herein, the term "heteroaryl" alone or in combination refers to an aromatic monocyclic or polycyclic ring system in which one or more of the ring atoms are elements other than carbon, such as nitrogen, boron, oxygen and / or sulfur.

[0024] As used herein, the term "heterocyclic" alone or in combination refers to a monocyclic or polycyclic ring system in which one or more of the atoms of the ring system are elements other than carbon, such as boron, nitrogen, oxygen and / or sulfur or phosphorus, and the ring system is optionally substituted with one or more ring substituents. The heterocyclic ring system may include aromatic and / or non-aromatic rings, including rings having one or more unsaturation points.

[0025] As used herein, the term "heteroalkyl" refers to an alkyl moiety as defined above having one or more carbon atoms, e.g., one, two, or three carbon atoms, substituted with one or more heteroatoms, which may be the same or different, alone or in combination.

[0026] As used herein, the term "heteroalkenyl" refers to an alkenyl moiety as defined above having one or more carbon atoms, e.g., one, two, or three carbon atoms, substituted with one or more heteroatoms, which may be the same or different, alone or in combination.

[0027] As used herein, the term "cycloalkyl" refers to a non-aromatic, monocyclic or polycyclic ring system optionally substituted with one or more ring substituents, alone or in combination.

[0028] In one aspect, a polymerizable liquid for use in 3D printing applications is described herein. The polymerizable liquid can be used, for example, in DLP, SLA, and MJP printing applications in some embodiments. The polymerizable liquid, in some embodiments, comprises a curable isocyanurate component in an amount of at least 5% by weight based on the total weight of the polymerizable liquid and a brominated acrylate ester component.

[0029] Turning to specific components, the curable isocyanurate component can include any curable isocyanurate that is not inconsistent with the technical objectives described herein. In some embodiments, the curable isocyanurate includes one or a mixture of isocyanurate species.

[0030] The curable isocyanurate contains at least one moiety or functional group that is operable to participate in a polymerization process. In some embodiments, the isocyanurate can contain a plurality of polymerizable moieties or functional groups. For the purposes of reference herein, a "polymerizable moiety" includes a moiety that can be polymerized or cured to provide a printed 3D article or object. Such polymerization or curing can be carried out in any manner not inconsistent with the purposes of this disclosure. The polymerizable moiety or functional group can include, for example, those operable to undergo a polycondensation or reaction between an isocyanate and a hydroxyl, including non-radiation-induced polymerization mechanisms. In some embodiments, the curable isocyanurate can contain one or more reactive functional groups including, but not limited to, epoxy, amine, and thiol. Alternatively, one or more polymerizable functional groups can include one or more unsaturated sites suitable for free radical polymerization. The isocyanurate is, in some embodiments, isocyanurate acrylate or isocyanurate polyacrylate. In some embodiments, the isocyanurate polyacrylate has the formula II: [Chemical formula] wherein in the formula, R 1 ~R 3 are each independently selected from the group consisting of hydrogen and alkyl, and m, n, and p are each independently integers in the range of 1 to 10.

[0031] In some embodiments, the isocyanurate is an allyl isocyanurate such as polyallyl isocyanurate. Polyallyl isocyanurate is, in some embodiments, of the formula III: [Chemical formula] wherein in the formula, m, n, and p are independently integers in the range of 1 to 10.

[0032] In some embodiments, the curable isocyanurate is present in an amount of 30 to 80% by weight or 35 to 70% by weight, based on the total weight of the polymerizable liquid.

[0033] In addition to the curable isocyanurate component, the polymerizable liquid contains a brominated acrylate ester component. The brominated acrylate ester component can include one or more acrylate or methacrylate esters having bromine atoms bonded to aliphatic carbons. In some embodiments, the brominated acrylate ester component has the following formula:

Chemical formula

Chemical formula

[0034] The brominated acrylate ester component can be present in the polymerizable liquid in any amount that meets the technical objectives described herein of imparting flame resistance and / or flame retardancy to articles printed from the polymerizable liquid in a 3D printing apparatus. The amount of the brominated acrylate ester can be selected according to several considerations, including the desired flame resistance and mechanical properties of the article printed from the polymerizable liquid, as well as other species present in the polymerizable liquid, such as other flame-resistant species, but not limited thereto. In some embodiments, the brominated acrylate ester is present in an amount of 5 to 50% by weight, 10 to 40% by weight, or 15 to 35% by weight, based on the total weight of the polymerizable liquid.

[0035] In some embodiments, the polymerizable liquid further comprises an organic phosphate component in addition to the curable isocyanurate component and the brominated acrylate ester component, and the organic phosphate component comprises one or more organic phosphate compounds. Any organic phosphate that is consistent with imparting flame resistance or flame retardancy to the polymerizable liquid and articles printed from the polymerizable liquid can be used.

[0036] In some embodiments, the one or more organic phosphate compounds have the following formula:

Chemical formula

[0037] The organic phosphate compounds of the polymerizable liquid are, in some embodiments, not halogenated. The organic phosphate compounds are not halogenated, for example, with fluorine, chlorine or bromine. Alternatively, the organic phosphate compounds are halogenated with fluorine, chlorine, bromine, or combinations thereof. In some embodiments, for example, one or more of 1 ~R 3 in the organic phosphate formula are halogenated such as brominated.

[0038] The organic phosphate component can be present in any desired amount in the polymerizable liquid. In some embodiments, the organic phosphate component is present in an amount of 5 to 40% by weight or 10 to 30% by weight based on the total weight of the polymerizable liquid.

[0039] As described herein, the polymerizable liquid can further include an acrylate component in addition to the curable isocyanurate and brominated acrylate ester components. The acrylate component can include one or a mixture of photopolymerizable acrylate species. In some embodiments, for example, the acrylate component can include an acrylate monomer, an acrylate oligomer, or a mixture thereof. As is known to those skilled in the art, a monomer is a single structural unit of a polymer or copolymer and is not an oligomer or polymer. In contrast, an oligomer includes a plurality of chemically bonded monomers. In some embodiments, the acrylate component can include a monofunctional acrylate, a difunctional acrylate, or a mixture thereof. In some embodiments, for example, the acrylate component can include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, n-decyl (meth)acrylate, n-dodecyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2- or 3-ethoxypropyl (meth)acrylate, tetrahydrofurfuryl methacrylate, isobornyl (meth)acrylate, 2-(2-ethoxyethoxy)ethyl acrylate, cyclohexyl methacrylate, 2-phenoxyethyl acrylate, glycidyl acrylate, isodecyl acrylate, 2-phenoxyethyl (meth)acrylate, lauryl methacrylate, or a mixture thereof. In some embodiments, the acrylate component can include a monofunctional or difunctional aliphatic urethane (meth)acrylate, or a monofunctional or difunctional polyether urethane (meth)acrylate.

[0040] In some embodiments, the acrylate component can include one or more of allyl acrylate, allyl methacrylate, triethylene glycol di(meth)acrylate, tricyclodecane dimethanol diacrylate, and cyclohexane dimethanol diacrylate. Further, in some embodiments, the acrylate component includes diacrylates and / or dimethacrylate esters of aliphatic, alicyclic, or aromatic diols including 1,3- or 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, tripropylene glycol, ethoxylated or propoxylated neopentyl glycol, 1,4-dihydroxymethylcyclohexane, 2,2-bis(4-hydroxycyclohexyl)propane or bis(4-hydroxycyclohexyl)methane, hydroquinone, 4,4'-dihydroxybiphenyl, bisphenol A, bisphenol F, bisphenol S, ethoxylated or propoxylated bisphenol A, ethoxylated or propoxylated bisphenol F or ethoxylated or propoxylated bisphenol S.

[0041] Further non-limiting examples of suitable species to include in the acrylate component include the following: isobornyl acrylate (IBOA) commercially available under the trade name SR 506A from SARTOMER; a difunctional acrylate commercially available under the trade name SR 833S from SARTOMER; a trifunctional acrylate monomer commercially available under the trade name SR 533 from SARTOMER; isobornyl methacrylate commercially available under the trade name SR 423A from SARTOMER; alkoxylated tetrahydrofurfuryl acrylate commercially available under the trade name SR 611 from SARTOMER; a monofunctional urethane acrylate commercially available under the trade name GENOMER 1122 from RAHN USA; an aliphatic urethane diacrylate commercially available under the trade name EBECRYL 8402 from ALLNEX; a difunctional aliphatic urethane (meth)acrylate commercially available under the trade name BR-952 from DYMAX; triethylene glycol diacrylate commercially available under the trade name SR 272 from SARTOMER; and triethylene glycol dimethacrylate commercially available under the trade name SR 205 from SARTOMER. Other commercially available curable components may be used. Further, in some cases, monofunctional or difunctional acrylates include an aliphatic polyester urethane acrylate oligomer, a urethane (meth)acrylate resin, and / or an acrylate amine oligomer resin such as EBECRYL 7100. In some embodiments, the acrylate component includes one or more acrylate derivatives such as acryloyl morpholine.

[0042] In addition to the monofunctional and difunctional acrylate species components described above, it may also be possible to include trifunctional or higher functional acrylate species in the polymerizable liquid described herein in some cases. For example, in some cases, one or more tri(meth)acrylates can be used. However, it should be understood that the functionality (i.e., mono-, di-, tri-, or higher functionality) and molecular weight of the acrylate species described herein can be selected to provide a shaping material having a viscosity suitable for use in a desired 3D printing system. Non-limiting examples of trifunctional or higher (meth)acrylates that may be suitable for use in some embodiments described herein include the following: 1,1-trimethylolpropane tri(meth)acrylate, ethoxylated or propoxylated 1,1,1-trimethylolpropane tri(meth)acrylate, ethoxylated or propoxylated glycerol tri(meth)acrylate, pentaerythritol monohydroxy tri(meth)acrylate, dipentaerythritol monohydroxy penta(meth)acrylate, bis(trimethylolpropane) and tetra(meth)acrylate.

[0043] The acrylate component can be present in the polymerizable liquid in any amount that is consistent with the purposes described herein. In some embodiments, the acrylate component is present in an amount of up to about 80% by weight. For example, the acrylate component can be present in an amount of 30 - 70% by weight, or 40 - 60% by weight, based on the total weight of the polymerizable liquid.

[0044] As described herein, the polymerizable liquid further comprises an additive of Formula I:

Chemical formula

[0045] In certain embodiments, the alkylene or alkenylene moiety R 1 and / or R 2 can each have a carbon chain length of from 1 to 8 carbon atoms, such as from 1 to 5 carbon atoms, from 1 to 3 carbon atoms, or from 4 to 5 carbon atoms. In some embodiments, R 1 and / or R 2 comprises C1-C10, C1-C8, or C1-C5 alkylene or alkenylene, and the "Cn" species (e.g., alkylene or alkenylene) contains exactly "n" carbon atoms in the species (e.g., the "C5" species contains exactly 5 carbon atoms).

[0046] As used herein, an alkylene moiety is a straight or branched saturated hydrocarbon moiety such as an "ethylene" (-CH2CH2-) moiety. An alkenylene moiety is a straight or branched hydrocarbon moiety containing one carbon-carbon double bond such as a "propenylene" (-CH2CH=CH-) moiety.

[0047] In some embodiments, L and Z independently comprise one or more moieties or functional groups selected from the group consisting of vinyl, vinyl ether, allyl, acrylate, and methacrylate. Further, in some embodiments, L and / or Z can comprise a cyclo-polymerizable moiety or functional group. For example, L and / or Z may comprise a cyclo-polymerizable moiety or functional group of the following formula:

Chemical formula

[0048] One or more additives of formula I can be present in any desired amount in the polymerizable liquid. The amount of the additive of formula I in the polymerizable liquid can be selected according to several considerations including, but not limited to, the desired mechanical properties and / or flame resistance of the article printed from the polymerizable liquid, as well as the chemical identity and / or amount of other species in the polymerizable liquid. In some embodiments, one or more additives of formula I are present in the polymerizable liquid in a total amount of 5 to 40% by mass or 10 to 30% by mass based on the total weight of the polymerizable liquid.

[0049] As detailed in the following examples, the isocyanurate component, brominated acrylate ester component, organic phosphate component, acrylate component and / or additive of formula I can be present in any combination and / or in any amount.

[0050] The polymerizable liquid described herein can, in some embodiments, further comprise a photoinitiator component for initiating the polymerization of one or more components of the liquid upon exposure to light of an appropriate wavelength. In some embodiments, the photoinitiator component can initiate the polymerization of an isocyanurate containing one or more moieties polymerizable via a free radical mechanism such as isocyanurate acrylate. Similarly, the acrylate component can be polymerized using a photoinitiator. In some embodiments, the curable isocyanurate can copolymerize with the acrylate component. In other embodiments, the curable isocyanurate and the acrylate component are polymerized independently.

[0051] Any photoinitiator that does not conflict with the objectives of the present disclosure can be used. In some embodiments, the photoinitiator is preferably an alpha-cleavage (unimolecular decomposition process) photoinitiator or a hydrogen abstraction photosensitizer-tertiary amine synergist that is operable to absorb light in the range of about 250 nm to about 420 nm or about 300 nm to about 385 nm to generate free radicals.

[0052] Examples of alpha-cleavage photoinitiators are Irgacure 184 (CAS 947-19-3), Irgacure 369 (CAS 119313-12-1), and Irgacure 819 (CAS 162881-26-7). An example of a photosensitizer-amine combination is Darocur BP (CAS 119-61-9) with diethylaminoethyl methacrylate.

[0053] Furthermore, in some examples, suitable photoinitiators include: benzoin, benzoin ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether, benzoin phenyl ether and benzoin acetate, benzoins; acetophenones including 2,2-dimethoxyacetophenone and 1,1-dichloroacetophenone; benzyl ketals such as benzyl, benzyl dimethyl ketal and benzyl diethyl ketal; anthraquinones including 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone and 2-amylanthraquinone; triphenylphosphine; benzoylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Lucirin TPO); benzophenones such as benzophenone and 4,4'-bis(N,N'-dimethylamino)benzophenone; thioxanthone and xanthone; acridine derivatives, phenazine derivatives, quinoxaline derivatives or 1-phenyl-1,2-propanedione, 2-O-benzoyloxime, 1-aminophenyl ketones or 1-hydroxyphenyl ketones such as 1-hydroxycyclohexyl phenyl ketone, phenyl 1-hydroxyisopropyl ketone and 4-isopropylphenyl 1-hydroxyisopropyl ketone.

[0054] Suitable photoinitiators may also include those operable for use with a HeCd laser radiation source, including acetophenones, 2,2-dialkoxybenzophenones and 1-hydroxyphenyl ketones such as 1-hydroxycyclohexyl phenyl ketone or 2-hydroxyisopropyl phenyl ketone (= 2-hydroxy-2,2-dimethylacetophenone). Further, in some cases, suitable photoinitiators include those operable for use with an Ar laser radiation source, including benzyl ketals such as benzyl dimethyl ketal. In some embodiments, the photoinitiator includes α-hydroxyphenyl ketone, benzyl dimethyl ketal or 2,4,6-trimethylbenzoyldiphenylphosphine oxide or mixtures thereof.

[0055] Another class of suitable photoinitiators includes, in some instances, ion dye-counterion compounds that can absorb actinic radiation and generate free radicals for polymerization initiation. In some embodiments, a polymerizable liquid containing an ion dye-counterion compound can polymerize when exposed to visible light within an adjustable wavelength range of from about 400 nm to about 700 nm. Ion dye-counterion compounds and their modes of operation are disclosed in European Patent Application Publication No. 0223587 and U.S. Patent Nos. 4,751,102; 4,772,530; and 4,772,541.

[0056] The photoinitiator can be present in the polymerizable liquid described herein in any amount that is not inconsistent with the purposes of the present disclosure. In some embodiments, the photoinitiator is present in an amount up to about 5 wt% based on the total weight of the polymerizable liquid. In some cases, the photoinitiator is present in an amount in the range of from about 0.1 wt% to about 5 wt%.

[0057] Furthermore, in some embodiments, the polymerizable liquids described herein can further include one or more sensitizers. The sensitizer can be added to increase the effectiveness of one or more photoinitiators that may also be present. Any sensitizer that is not inconsistent with the purposes of the present disclosure can be used. In some cases, the sensitizer includes isopropylthioxanthone (ITX) or 2-chlorothioxanthone (CTX).

[0058] The sensitizer can be present in the polymerizable liquid in any amount that is not inconsistent with the purposes of the present disclosure. In some embodiments, the sensitizer is present in an amount in the range of from about 0.1 wt% to about 2 wt% or from about 0.5 wt% to about 1 wt% based on the total weight of the polymerizable liquid.

[0059] In some embodiments, one or more UV absorbers and / or light stabilizers may be present in the polymerizable liquid. In some embodiments, for example, one or more UV absorbers and / or light stabilizers can be present in an amount of 0.1 to 2% by weight, based on the total weight of the polymerizable liquid. In some embodiments, the UV absorbers and / or light stabilizers are commercially available under the TINUVIN® product designation from BASF in Florham Park, New Jersey.

[0060] In another aspect, a method of printing a 3D article or object is described herein. The method of printing a 3D article or object can include forming the 3D article layer by layer from a plurality of layers of the polymerizable liquid described herein. Any of the polymerizable liquids or components described herein can be used in the fabrication of articles by additive manufacturing.

[0061] In some embodiments, the method includes providing a polymerizable liquid that includes a curable isocyanurate component in an amount of at least 20% by weight, based on the total weight of the polymerizable liquid, and an organophosphate component that includes one or more organophosphate compounds. The polymerizable liquid is printed and cured to form an article. In some embodiments, the polymerizable liquid also includes an acrylate component. The acrylate component can include an acrylate monomer, an acrylate oligomer, or a mixture thereof.

[0062] As further described herein, the polymerizable liquid may further include a photoinitiator component, and curing of the polymerizable liquid can occur by irradiation of the liquid with light of a wavelength suitable to initiate free radical polymerization.

[0063] In some embodiments, the layer of polymerizable liquid can be deposited according to an image of the 3D article in a computer-readable format during the formation of the three-dimensional article. The polymerizable liquid can be deposited according to preselected computer-aided design (CAD) parameters. Further, optionally, one or more layers of the polymerizable liquid described herein can have a thickness of from about 10 μm to about 100 μm, from about 10 μm to about 80 μm, from about 10 μm to about 50 μm, from about 20 μm to about 100 μm, from about 20 μm to about 80 μm, or from about 20 μm to about 40 μm. Other thicknesses are possible.

[0064] Furthermore, it should be understood that the method of printing a 3D article described herein may include so-called "multi-jet" or "stereolithography" 3D printing methods. For example, in some examples, the multi-jet method of printing a 3D article includes selectively depositing a layer of the polymerizable liquid described herein on a substrate such as a build pad of a 3D printing system. Further, in some embodiments, the method described herein further includes supporting at least one of the layers of polymerizable liquid with a support material. Any support material that does not conflict with the objectives of the present disclosure can be used.

[0065] It is also possible to form a 3D article from the polymerizable liquid described herein using stereolithography. For example, in some cases, the method of printing a 3D article includes the steps of holding a polymerizable liquid in a container and selectively applying energy to at least a portion of the polymerizable liquid in the container to solidify it, thereby forming a solidified layer that defines a cross-section of the 3D article. Further, the method described herein further includes the step of raising or lowering the solidified layer to provide a new or second layer of the polymerizable liquid, and then selectively applying energy again to the polymerizable liquid in the container to solidify at least a portion of the new or second polymerizable liquid that defines a second cross-section of the 3D article. Further, the first and second cross-sections of the 3D article can be joined or adhered to each other in the z-direction (or the shaping direction corresponding to the upward or downward direction described above) by the application of energy to solidify the polymerizable liquid. Further, the step of selectively applying energy to the polymerizable liquid in the container can include the step of applying electromagnetic radiation, such as UV and / or visible radiation, having sufficient energy to initiate the polymerization of the polymerizable material described herein. Further, in some cases, the step of raising or lowering the solidified layer of the polymerizable liquid is performed using an elevator platform disposed within the container of the fluid shaping material. The method described herein can also include the step of flattening the new layer of the polymerizable liquid provided by raising or lowering the elevator platform. Such flattening can, in some cases, be performed by a wiper or roller.

[0066] Articles printed according to the methods described herein can exhibit one or more desirable mechanical properties. 3D articles printed from the polymerizable liquids described herein can, in some embodiments, exhibit a tensile modulus of 2700 to 3200 MPa. The values for tensile strength and tensile modulus provided herein can be determined according to ASTM D638. Further, 3D articles printed from the polymerizable liquids described herein can exhibit an HDT of at least 100 °C, such as 100 to 130 °C. The HDT is measured using DMA at 0.455 MPa according to ASTM D648.

[0067] Articles printed according to the methods described herein can also exhibit desirable flame resistance and / or flame retardant properties. In some embodiments, articles printed according to the methods described herein exhibit a v0 rating under flammability UL 94V. The thickness of the test samples achieving the v0 rating can, in some embodiments, be less than 2 mm or less than 1 mm, such as 0.8 mm or 0.4 mm.

[0068] These foregoing embodiments are further illustrated in the following non-limiting examples.

Examples

[0069] Table 1 provides formulations of polymerizable liquids according to some embodiments described herein.

Table 1

[0070] The properties of articles formed from the polymerizable liquids of Samples 1 - 6 are provided in Table II. The flammability tests were conducted according to UL 94V using samples with a thickness of 0.8 mm.

Table 2

[0071] Some additional non-limiting, exemplary embodiments are further described below.

[0072] Embodiment 1. The polymerizable liquid includes the following: A curable isocyanurate component in an amount of at least 5% by mass based on the total weight of the polymerizable liquid; and A brominated acrylate ester component.

[0073] Embodiment 2. The polymerizable liquid of Embodiment 1, wherein the curable isocyanurate component is polymerizable via free radical polymerization.

[0074] Embodiment 3. The polymerizable liquid of Embodiment 2, wherein the curable isocyanurate component includes isocyanurate polyacrylate, polyallyl isocyanurate, or a mixture thereof.

[0075] Embodiment 4. The isocyanurate polyacrylate has the formula II:

Chemical formula

[0076] Embodiment 5. The polyallyl isocyanurate has the formula III:

Chemical formula

[0077] Embodiment 6. The brominated acrylate ester component includes one or more compounds of the following formula:

Chemical formula

[0078] Embodiment 7. The polymerizable liquid according to Embodiment 6, wherein the brominated acrylate ester component contains trinole acrylate.

[0079] Embodiment 8. The polymerizable liquid according to any one of Embodiments 1 to 7, wherein the brominated acrylate ester component is present in an amount of 10 to 40% by mass based on the total weight of the polymerizable liquid.

[0080] Embodiment 9. The polymerizable liquid according to any one of Embodiments 1 to 8, wherein the polymerizable liquid further contains an organic phosphate component containing one or more organic phosphate compounds.

[0081] Embodiment 10. The polymerizable liquid according to Embodiment 9, wherein the organic phosphate component is present in an amount of 5 to 40% by mass based on the total weight of the polymerizable liquid.

[0082] Embodiment 11. One or more organic phosphate compounds have the following formula:

Chemical formula

[0083] Embodiment 12. The polymerizable liquid according to Embodiment 9 or 10, wherein one or more organic phosphate compounds contain bis(organophosphate).

[0084] Embodiment 13. A polymerizable liquid according to any one of Embodiments 1 to 12, wherein the curable isocyanurate component is present in an amount of 30 to 70 mass percent based on the total weight of the polymerizable liquid.

[0085] Embodiment 14. A polymerizable liquid according to any one of Embodiments 1 to 13, further comprising an acrylate component.

[0086] Embodiment 15. The polymerizable liquid of Embodiment 14, wherein the acrylate component is present in an amount of 30 to 70 mass% based on the total weight of the polymerizable liquid.

[0087] Embodiment 16. The polymerizable liquid of Embodiment 14 or 15, wherein the acrylate component comprises a mixture of an acrylate monomer and an acrylate oligomer.

[0088] Embodiment 17. Formula I:

Chemical formula

[0089] Embodiment 18. The polymerizable liquid of Embodiment 17, wherein R 1 and R 2 are alkylene.

[0090] Embodiment 19. The polymerizable liquid according to Embodiment 17 or 18, wherein L and Z each independently contain a moiety selected from the group consisting of vinyl, allyl, vinyl ether, acrylate, and methacrylate.

[0091] Embodiment 20. The polymerizable liquid according to Embodiment 17 or 18, wherein L and Z each contain a cyclo-polymerizable functional group.

[0092] Embodiment 21. The cyclo-polymerizable functional group has the formula:

Chemical formula

Chemical formula

[0093] Embodiment 22. The polymerizable liquid according to any one of Embodiments 17 to 21, wherein n is 2 or 3.

[0094] Embodiment 23. The polymerizable liquid according to any one of Embodiments 17 to 22, wherein L and Z each contain an acrylate moiety.

[0095] Embodiment 24. The polymerizable liquid according to any one of Embodiments 17 to 22, wherein L and Z each contain a methacrylate moiety.

[0096] Embodiment 25. Further comprising at least one of an organic phosphoric acid component, an acrylate component, and an additive of Formula I:

Chemical formula

[0097] Embodiment 26. A polymerizable liquid according to any one of Embodiments 1 to 25, further comprising a photoinitiator component.

[0098] Embodiment 27. The polymerizable liquid of Embodiment 26, wherein the photoinitiator component is present in an amount of 0.1 to 5 mass percent based on the total weight of the polymerizable liquid.

[0099] Embodiment 28. A step of providing a polymerizable liquid according to any one of Embodiments 1 to 27; and A step of printing and curing the polymerizable liquid using light to form an article A method of printing a three-dimensional article, comprising.

[0100] Embodiment 29. The method of Embodiment 28, wherein the polymerizable liquid is provided in a layer-by-layer process.

[0101] Embodiment 30. The method of Embodiment 28, wherein the polymerizable liquid further comprises a photoinitiator component, and the step of curing the polymerizable liquid proceeds via free radical polymerization.

[0102] Embodiment 31. The method of Embodiment 28, wherein the article has a v0 rating according to UL 94V.

[0103] All patent documents referred to herein are incorporated by reference in their entirety. In achieving the various objects of the present invention, various embodiments of the present invention have been described. It should be recognized that these embodiments are merely illustrative of the principles of the present invention. Many modifications and adaptations will be readily apparent to those skilled in the art without departing from the spirit and scope of the present invention.

Claims

Claim 1 A polymerizable liquid, Based on the total weight of the polymerizable liquid, a curable isocyanurate component in an amount of at least 5% by mass; and A brominated acrylate ester component Comprising, The curable isocyanurate component is characterized by comprising a mixture of isocyanurate polyacrylate and polyallyl isocyanurate Polymerizable liquid. Claim 2 The polymerizable liquid according to claim 1, wherein the curable isocyanurate component is polymerizable via free radical polymerization. Claim 3 The isocyanurate polyacrylate is of formula II: 【Chemical 1】 And, In the formula, R １ to R ３ are each independently selected from the group consisting of hydrogen and alkyl, and m, n, and p are each independently integers in the range of 1 to 10. The polymerizable liquid according to claim 1, characterized in that. Claim 4 The polyallyl isocyanurate is of formula III: 【Chemical Formula 2】 And, Wherein m, n and p are independently integers from 1 to 10, The polymerizable liquid according to claim 1, characterized in that. Claim 5 The brominated acrylate ester component comprises one or more compounds of the following formula: [Chemical Formula 3] Including, wherein, R １ is selected from the group consisting of hydrogen and methyl, and R ２ is selected from the group consisting of brominated alkyl and brominated alkenyl The polymerizable liquid according to claim 1, characterized in that. Claim 6 The polymerizable liquid according to claim 5, wherein the brominated acrylate ester component comprises trinole acrylate. Claim 7 The polymerizable liquid according to claim 1, wherein the brominated acrylate ester component is present in an amount of 10 - 40% by mass based on the total weight of the polymerizable liquid. Claim 8 The polymerizable liquid according to claim 1, further comprising an organic phosphate component comprising one or more organic phosphate compounds. Claim 9 The polymerizable liquid according to claim 8, wherein the organic phosphate component is present in an amount of 5 - 40% by mass based on the total weight of the polymerizable liquid. Claim 10 The one or more organic phosphate compounds are of the following formula: 【Chemical Formula 4】 And, wherein, R １ to R ３ are independently selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, heteroalkyl, heteroalkenyl, heterocyclyl, aryl and heteroaryl The polymerizable liquid according to claim 8, characterized in that. Claim 11 The polymerizable liquid according to claim 8, wherein the one or more organic phosphate compounds comprise bis(organophosphate). Claim 12 The polymerizable liquid according to claim 1, wherein the curable isocyanurate component is present in an amount of 30 - 70 mass percent based on the total weight of the polymerizable liquid. Claim 13 The polymerizable liquid according to claim 1, further comprising an acrylate component. Claim 14 The polymerizable liquid according to claim 13, wherein the acrylate component is present in an amount of 30 to 70% by mass based on the total weight of the polymerizable liquid.

15. The polymerizable liquid according to claim 13, wherein the acrylate component comprises a mixture of an acrylate monomer and an acrylate oligomer.

16. Additive of formula I: 【Chemical Formula 5】 further comprising In the formula, L and Z are ring substituents containing at least one polymerizable unsaturated point, and R １ and R ２ are independently selected from the group consisting of alkylene and alkenylene, and R ３ to R ６ each represent 1 to 4 optional ring substituents, and each of the 1 to 4 ring substituents is independently selected from the group consisting of alkyl, heteroalkyl, haloalkyl, halo, hydroxyl, alkoxy, amine, amide, and ether, and n is an integer from 1 to 7. The polymerizable liquid according to claim 1, characterized in that.

17. R １ and R ２ The polymerizable liquid according to claim 16, wherein is alkylene.

18. The polymerizable liquid according to claim 16, wherein L and Z each independently comprise a moiety selected from the group consisting of vinyl, allyl, vinyl ether, acrylate, and methacrylate.

19. The polymerizable liquid according to claim 16, wherein L and Z each comprise a cyclo-polymerizable functional group.

20. The cyclo-polymerizable functional group is of the following formula: 【Chemical Formula 6】 wherein in the formula 【Chemical Formula 7】 is the point of attachment of the cyclo-polymerizable functional group to the compound of formula I, The polymerizable liquid according to claim 19, characterized in that.

21. The polymerizable liquid according to claim 16, wherein n is 2 or 3.

22. The polymerizable liquid according to claim 16, wherein L and Z each comprise an acrylate moiety.

23. The polymerizable liquid according to claim 16, wherein L and Z each comprise a methacrylate moiety.

24. Organic phosphoric acid component, acrylate component, and additive of formula I: 【Chemical 8】 further comprising at least one of In the formula, L and Z are ring substituents containing at least one polymerizable unsaturated point, and R １ and R ２ are independently selected from the group consisting of alkylene and alkenylene, and R ３ to R ６ each represent 1 to 4 optional ring substituents, and each of the 1 to 4 ring substituents is independently selected from the group consisting of alkyl, heteroalkyl, haloalkyl, halo, hydroxyl, alkoxy, amine, amide, and ether, and n is an integer from 1 to 7. The polymerizable liquid according to claim 1, characterized in that.

25. The polymerizable liquid according to claim 1, further comprising a photoinitiator component.

26. The polymerizable liquid according to claim 25, wherein the photoinitiator component is present in an amount of 0.1 to 5 mass percent based on the total weight of the polymerizable liquid.

27. Providing a polymerizable liquid according to any one of claims 1 to 26; and Printing and curing the polymerizable liquid with light to form an article A method of printing a three-dimensional article, characterized by comprising.

28. The method according to claim 27, wherein the polymerizable liquid is provided in a layer-by-layer process.

29. The method according to claim 27, characterized in that the polymerizable liquid further contains a photoinitiator component, and the step of curing the polymerizable liquid proceeds through free radical polymerization.

30. The method according to claim 27, characterized in that the article has a v0 rating according to UL 94V.

31. A polymerizable liquid, a curable isocyanurate component in an amount of at least 5% by weight based on the total weight of the polymerizable liquid; and a brominated acrylate ester component wherein the curable isocyanurate component includes polyallyl isocyanurate, the polyallyl isocyanurate is of formula III: 【Chemical Formula 9】 wherein m, n and p are independently integers from 1 to 10, characterized in that it is a polymerizable liquid.

32. A polymerizable liquid, a curable isocyanurate component in an amount of at least 5% by weight based on the total weight of the polymerizable liquid; and a brominated acrylate ester component wherein the brominated acrylate ester component includes one or more compounds of the following formula: 【Chemical Formula 10】 wherein R 1 is selected from the group consisting of hydrogen and methyl, and R 2 is selected from the group consisting of brominated alkyl and brominated alkenyl, characterized in that it is a polymerizable liquid.

33. An additive of formula I: 【Chemical 11】 further comprising wherein L and Z are ring substituents containing at least one polymerizable unsaturated point, R 1 and R 2 are independently selected from the group consisting of alkylene and alkenylene, and R 3 to R 6 each represent 1 to 4 optional ring substituents, and each of the 1 to 4 ring substituents is independently selected from the group consisting of alkyl, heteroalkyl, haloalkyl, halo, hydroxyl, alkoxy, amine, amide, and ether, and n is an integer from 1 to 7, L and Z each independently include a moiety selected from the group consisting of vinyl, allyl, vinyl ether, acrylate, methacrylate, and cyclo-polymerizable functional groups characterized in that it is the polymerizable liquid according to claim 1.

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