Additives for build materials and related printed 3D articles

Abstract

In some embodiments, additives for three-dimensional printing materials or inks are described herein that can impart flame retardant properties and / or structural reinforcement to articles printed from the printing materials. In some embodiments, such additives include compounds of the present invention according to formula (I), where L and Z are ring substituents that contain at least one point of polymerizable unsaturation, and R 1 and R 2 is independently selected from the group consisting of alkylene and alkenylene; R 3 -R 6 each represents 1 to 4 optional ring substituents, 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.

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 / 159,133, filed March 10, 2021, the entirety of which is incorporated herein by reference. [Technical Field]

[0002] The present invention relates to additives for three-dimensional build materials, and in particular to additives that can impart flame retardant properties and / or structural reinforcement to articles printed from the build materials. [Background technology]

[0003] 3D printers use build materials, also known as inks, to form various 3D objects, articles, or parts according to computer-generated files. In some examples, the build materials are solid at ambient temperatures and turn into liquids at elevated jetting temperatures. In other examples, the build materials are liquids at ambient temperatures.

[0004] The build material can include a variety of chemical species. The choice of chemical species included in the build material can be selected 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 device. For example, ultraviolet (UV) curable acrylate formulations are generally capable of printing parts at high resolution in DLP systems. However, the resulting parts often lack desirable mechanical properties and are prone to fracture or other degradation pathways. Such degradation pathways impair the performance of the article and lead to premature failure. Summary of the Invention [Problem to be solved by the invention]

[0005] Additionally, some build materials and resulting articles printed therefrom may be unsuitable for high temperature applications and / or other applications requiring flame resistance. As a result, 3D printing technology may have limited application in fields requiring flame-retardant or flame-resistant materials and articles. [Means for solving the problem]

[0006] In view of the above, in some embodiments, described herein are additives for three-dimensional build materials or inks that can impart flame retardancy and / or structural reinforcement to articles printed from the build materials. In one aspect, the additives described herein are compounds of Formula I: [ka] where L and Z are ring substituents containing at least one point of polymerizable unsaturation, and R 1 and R 2 is independently selected from the group consisting of alkylene and alkenylene; R 3 ~R 6 each represent 1 to 4 optional ring substituents, each of the 1 to 4 ring substituents 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 or 1 to 5. Hydrogen is optionally substituted by the optional substituent R 3 ~R 6 It is understood that in the absence of occupies a position on the aryl ring of formula I.

[0007] In another aspect, a polymerizable liquid is provided that includes an additive of Formula I described herein. In some embodiments, the polymerizable liquid imparts flame retardant and / or flame resistant properties to an article printed from the liquid. The polymerizable liquid may also impart desirable mechanical properties to the article. In some embodiments, the polymerizable liquid includes at least one additive of Formula I and an acrylate component. In some embodiments, the polymerizable liquid includes multiple additives that fit the general structure of Formula I. Furthermore, the acrylate component can include an acrylate monomer, an acrylate oligomer, or a mixture thereof.

[0008] Also described herein is a method for printing a three-dimensional article. In some embodiments, the method includes providing a polymerizable liquid comprising at least one additive of Formula I described herein and an acrylate component. The polymerizable liquid is printed and cured to form the article. In some embodiments, the article is formed via a layer-by-layer process, where layer formation occurs via deposition and curing of layers of the polymerizable liquid. The acrylate component can include an acrylate monomer, an acrylate oligomer, or a mixture thereof.

[0009] As further described herein, the polymerizable liquid may further include a photoinitiator component, and curing of the polymerizable liquid may occur by irradiation of the liquid with light of an appropriate wavelength to initiate free radical polymerization.

[0010] These and other embodiments are further described in the detailed description that follows. [Brief explanation of the drawings]

[0011] [Figure 1] FIG. 1 illustrates a compound of formula I, according to some embodiments. DETAILED DESCRIPTION OF THE INVENTION

[0012] The embodiments described herein can be more readily understood by reference to the following detailed description and examples. However, the elements, devices, and methods described herein are not limited to the specific embodiments presented in the detailed description and examples. 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.

[0013] Furthermore, all ranges disclosed herein should be understood to encompass any and all subranges subsumed therein. For example, a stated range of "1.0 to 10.0" should be deemed to include any and all subranges beginning with a minimum value greater than or equal to 1.0 and ending with a maximum value less than or equal to 10.0, such as 1.0 to 5.3, or 4.7 to 10.0, or 3.6 to 7.9.

[0014] All ranges disclosed herein should also be considered to include the endpoints of the range, unless otherwise specified. For example, the range "between 5 and 10" should generally be considered to include the endpoints 5 and 10.

[0015] Furthermore, when the term "up to" is used in reference to an amount or quantity, it is understood that the amount is at least a detectable amount or quantity. For example, a substance present in an amount "up to" a particular amount can be present in an amount from a detectable amount up to and including the particular amount.

[0016] Terms such as "three-dimensional printing system," "three-dimensional printer," and "printing" 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 or that may become known in the art that use build materials or inks to fabricate three-dimensional objects.

[0017] In one embodiment, the additive described herein is a compound of Formula I: [ka] where L and Z are ring substituents containing at least one point of polymerizable unsaturation, and R 1 and R 2 is independently selected from the group consisting of alkylene and alkenylene; R 3 ~R 6 each represent 1 to 4 optional ring substituents, each of the 1 to 4 ring substituents 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 or 1 to 5. Hydrogen is optionally substituted by the optional substituent R 3 ~R 6 It is understood that in the absence of occupies a position on the aryl ring of formula I.

[0018] In certain implementations, the alkylene or alkenylene moiety R 1 and / or R 2 One or both of R can have a carbon chain length of 1 to 8 carbon atoms, e.g., 1 to 5 carbon atoms, 1 to 3 carbon atoms, or 4 to 5 carbon atoms. 1 and / or R 2 includes a C1-C10, C1-C8, or C1-C5 alkylene or alkenylene, with a "Cn" species (e.g., a "Cn" alkylene or alkenylene moiety) containing exactly "n" carbon atoms in the species (e.g., a "C5" species contains exactly 5 carbon atoms).

[0019] As used herein, an alkylene moiety is a straight-chain or branched saturated hydrocarbon moiety, such as an "ethylene" (-CHCH-) moiety. An alkenylene moiety is a straight-chain or branched hydrocarbon moiety containing one carbon-carbon double bond, such as a "propenylene" (-CHCH=CH-) moiety.

[0020] In some embodiments, L and Z comprise one or more moieties or functional groups independently selected from the group consisting of vinyl, vinyl ether, allyl, acrylate, and methacrylate. Further, in some embodiments, L and / or Z can comprise a cyclopolymerizable moiety or functional group. For example, L and / or Z can comprise a cyclopolymerizable moiety or functional group of the following formula: [ka] During the ceremony, [ka] is the point of attachment of the cyclopolymerizable moiety or functional group to the compound of formula I. In some embodiments, the compound of formula I has the structure shown in FIG.

[0021] In some embodiments, the compounds of Formula I can impart desirable mechanical properties to articles printed with build materials or polymerizable liquids comprising the compounds of Formula I. In some embodiments, for example, the compounds of Formula I can increase the heat deflection temperature (HDT) of articles printed from polymerizable liquids comprising the compounds. Additionally, the compounds of Formula I can impart flame resistance and / or fire retardancy to articles printed from polymerizable liquids comprising the compounds.

[0022] In another aspect, a polymerizable liquid is provided that includes an additive of Formula I described herein. In some embodiments, the polymerizable liquid imparts flame resistance and / or fire retardant properties to an article printed from the liquid. The polymerizable liquid may also impart desirable mechanical properties to the article. In some embodiments, the polymerizable liquid includes an additive of Formula I and an acrylate component. The acrylate component can include an acrylate monomer, an acrylate oligomer, or a mixture thereof.

[0023] The one or more additives of Formula I can be present in the polymerizable liquid in any desired amount. 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, and the chemical identity and / or amount of other species in the polymerizable liquid. In some embodiments, the one or more additives of Formula I are present in the polymerizable liquid in a total amount of 5 to 40 wt % or 10 to 30 wt %, based on the total weight of the polymerizable liquid.

[0024] As described herein, the polymerizable liquid can include an acrylate component in addition to the additive of Formula I. 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 known to those skilled in the art, a monomer is a single structural unit of a polymer or copolymer, not an oligomer or polymer. In contrast, an oligomer includes multiple 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 is 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. 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 mixtures thereof. In some embodiments, the acrylate component comprises a mono- or di-functional aliphatic urethane (meth)acrylate or a mono- or di-functional polyether urethane (meth)acrylate.

[0025] 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 comprises diacrylate 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.

[0026] Further non-limiting examples of species suitable for inclusion in the acrylate component include: isobornyl acrylate (IBOA), available commercially under the tradename SR 506A from SARTOMER; a difunctional acrylate available commercially under the tradename SR 833S from SARTOMER; a trifunctional acrylate monomer available commercially under the tradename SR 533 from SARTOMER; isobornyl methacrylate, available commercially under the tradename SR 423A from SARTOMER; an alkoxylated tetrahydrofurfuryl acrylate available commercially under the tradename SR 611 from SARTOMER; a monofunctional urethane acrylate available commercially under the tradename GENOMER 1122 from RAHN USA; an aliphatic urethane diacrylate available commercially under the tradename EBECRYL 8402 from ALLNEX; a difunctional aliphatic urethane (meth)acrylate available commercially under the tradename BR-952 from DYMAX; triethylene glycol diacrylate available commercially under the tradename SR 272 from SARTOMER; and SR 423A from SARTOMER. Triethylene glycol dimethacrylate is commercially available under the trade name 205. Other commercially available curable components may also be used. Additionally, in some cases, the mono- or di-functional acrylate comprises 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 comprises one or more acrylate derivatives, such as acryloylmorpholine.

[0027] In addition to the monofunctional and difunctional acrylate species components described above, it is also possible in some cases to include trifunctional or higher-functional acrylate species in the polymerizable liquids described herein. 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 build material with 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: 1,1-trimethylolpropane tri(meth)acrylate, ethoxylated or propoxylated 1,1,1-trimethylolpropane tri(meth)acrylate, ethoxylated or propoxylated glycerol tri(meth)acrylate, pentaerythritol monohydroxytri(meth)acrylate, dipentaerythritol monohydroxypenta(meth)acrylate, bis(trimethylolpropane) and tetra(meth)acrylate.

[0028] The acrylate component can be present in the polymerizable liquid in any amount 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.

[0029] The polymerizable liquids described herein can further include a photoinitiator component to initiate 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 polymerization of an additive of Formula I that contains one or more unsaturated points polymerizable via a free radical mechanism. Similarly, a photoinitiator can be used to polymerize an acrylate component. In some embodiments, the additive of Formula I can copolymerize with the acrylate component. In other embodiments, the additive of Formula I and the acrylate component are polymerized independently.

[0030] Any photoinitiator not inconsistent with the objectives of the present disclosure can be used. In some embodiments, the photoinitiator preferably comprises an alpha-cleavage (unimolecular decomposition process) photoinitiator or a hydrogen abstraction photosensitizer-tertiary amine synergist operable to absorb light at about 250 nm to about 420 nm or about 300 nm to about 385 nm to generate free radicals.

[0031] 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.

[0032] Further, in some examples, suitable photoinitiators include: benzoins, including benzoin ethers, such as benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether, benzoin phenyl ether, and benzoin acetate; acetophenones, including 2,2-dimethoxyacetophenone and 1,1-dichloroacetophenone; benzil ketals, such as benzil, benzil dimethyl ketal, and benzil diethyl ketal; anthraquinones, including 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, and 2-amylanthraquinone; trianthraquinones, including benzoin ethers, such as benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; Phenylphosphine, benzoylphosphine oxides, for example 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Lucirin TPO), benzophenone and benzophenones such as 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, for example 1-hydroxycyclohexyl phenyl ketone, phenyl 1-hydroxyisopropyl ketone and 4-isopropylphenyl 1-hydroxyisopropyl ketone.

[0033] Suitable photoinitiators may also include those operable for use with HeCd laser radiation sources, 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). Additionally, in some cases, suitable photoinitiators include those operable for use with Ar laser radiation sources, including benzil ketals, such as benzil dimethyl ketal. In some embodiments, the photoinitiator comprises an α-hydroxyphenyl ketone, benzil dimethyl ketal, or 2,4,6-trimethylbenzoyldiphenylphosphine oxide, or a mixture thereof.

[0034] Another class of suitable photoinitiators includes ionic dye-counterion compounds, which, in some instances, can absorb actinic radiation and generate free radicals for polymerization initiation. In some embodiments, polymerizable liquids containing ionic dye-counterion compounds can polymerize upon exposure to visible light within a tunable wavelength range of about 400 nm to about 700 nm. Ionic dye-counterion compounds and their mode of operation are disclosed in EP 0223587 and U.S. Pat. Nos. 4,751,102; 4,772,530; and 4,772,541.

[0035] The photoinitiator can be present in the polymerizable liquids described herein in any amount consistent with the objectives 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 ranging from about 0.1 wt. % to about 5 wt. %.

[0036] Additionally, in some embodiments, the polymerizable liquids described herein can further include one or more sensitizers. The sensitizers can be added to increase the effectiveness of one or more photoinitiators that may also be present. Any sensitizer not inconsistent with the objectives of the present disclosure can be used. In some cases, the sensitizer includes isopropylthioxanthone (ITX) or 2-chlorothioxanthone (CTX).

[0037] The sensitizer can be present in the polymerizable liquid in any amount consistent with the objectives of the present disclosure, hi some embodiments, the sensitizer is present in an amount ranging from about 0.1% to about 2% by weight, or from about 0.5% to about 1% by weight, based on the total weight of the polymerizable liquid.

[0038] In some embodiments, one or more UV absorbers and / or light stabilizers may be present in the polymerizable liquid. In some embodiments, for example, the one or more UV absorbers and / or light stabilizers may be present in an amount of 0.1 to 2 wt %, based on the total weight of the polymerizable liquid. In some embodiments, the UV absorbers and / or light stabilizers are commercially available from BASF, Florham Park, New Jersey, under the trade designation TINUVIN®.

[0039] Also described herein are methods for printing three-dimensional articles. In some embodiments, the methods include providing a polymerizable liquid comprising an additive of Formula I and an acrylate component. The polymerizable liquid is printed and cured to form the article. In some embodiments, the article is formed via a layer-by-layer process, where layer formation occurs via deposition and curing of layers of the polymerizable liquid. The acrylate component can include an acrylate monomer, an acrylate oligomer, or a mixture thereof.

[0040] As further described herein, the polymerizable liquid may further include a photoinitiator component, and curing of the polymerizable liquid may occur by irradiation of the liquid with light of an appropriate wavelength to initiate free radical polymerization.

[0041] In some embodiments, a 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. Additionally, in some cases, one or more layers of polymerizable liquid described herein have a thickness of about 10 μm to about 100 μm, about 10 μm to about 80 μm, about 10 μm to about 50 μm, about 20 μm to about 100 μm, about 20 μm to about 80 μm, or about 20 μm to about 40 μm. Other thicknesses are also possible.

[0042] It should further be understood that the methods of printing 3D articles described herein may include so-called "multi-jet" or "stereolithography" 3D printing methods. For example, in some examples, a multi-jet method of printing a 3D article includes selectively depositing layers of a polymerizable liquid described herein onto a substrate, such as a build pad of a 3D printing system. Furthermore, in some embodiments, the methods described herein further include supporting at least one of the layers of polymerizable liquid with a support material. Any support material not inconsistent with the objectives of the present disclosure may be used.

[0043] Stereolithography can also be used to form 3D articles from the polymerizable liquids described herein. For example, in some cases, a method for printing a 3D article includes holding a polymerizable liquid in a container and selectively applying energy to the polymerizable liquid in the container to solidify at least a portion of the polymerizable liquid, thereby forming a solidified layer that defines a cross-section of the 3D article. Furthermore, the methods described herein further include raising or lowering the solidified layer to provide a new or second layer of polymerizable liquid, and then selectively applying energy to the polymerizable liquid in the container again to solidify at least a portion of the new or second polymerizable liquid that defines a second cross-section of the 3D article. Furthermore, the first and second cross-sections of the 3D article can be bonded or adhered to each other in the z-direction (or a build direction corresponding to the above-mentioned rising or lowering direction) by applying energy to solidify the polymerizable liquid. Additionally, selectively applying energy to the polymerizable liquid within the container can include applying electromagnetic radiation, e.g., UV and / or visible radiation, having sufficient energy to initiate polymerization of the polymerizable material described herein. Additionally, in some cases, raising or lowering the solidified layer of polymerizable liquid is performed using an elevator platform disposed within the container of fluid modeling material. The methods described herein can also include planarizing the new layer of polymerizable liquid provided by raising or lowering the elevator platform. Such planarization can, in some cases, be performed with a wiper or roller.

[0044] 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 2500 to 3000 MPa. The tensile modulus values ​​provided herein can be determined according to ASTM D638. Additionally, 3D articles printed from the polymerizable liquids described herein can exhibit an HDT of at least 100°C, e.g., 100 to 130°C. HDT is measured using DMA at 0.455 MPa according to ASTM D648.

[0045] Some non-limiting exemplary embodiments of the invention described herein are provided below.

[0046] Embodiment 1. An additive of formula I: [ka] where L and Z are ring substituents containing at least one point of polymerizable unsaturation, and R 1 and R 2 is independently selected from the group consisting of alkylene and alkenylene; R 3 ~R 6 each represent 1 to 4 optional ring substituents, each of the 1 to 4 ring substituents 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.

[0047] Embodiment 2. R 1 and R 2 The additive of embodiment 1, wherein is alkylene.

[0048] Embodiment 3. The additive of embodiment 1 or 2, wherein L and Z each comprise a moiety independently selected from the group consisting of vinyl, allyl, vinyl ether, acrylate, and methacrylate.

[0049] Embodiment 4. The additive of any of embodiments 1-3, wherein L and Z each comprise a cyclopolymerizable functional group.

[0050] Embodiment 5. The cyclopolymerizable functional group has the formula: [ka] wherein: [ka] is the point of attachment of the cyclopolymerizable functional group to the compound of Formula I.

[0051] Embodiment 6. The additive of any of embodiments 1-5, wherein n is 2 or B.

[0052] Embodiment 7. The additive of embodiment 3, wherein L and Z each comprise an acrylate moiety.

[0053] Embodiment 8. The additive of embodiment 3, wherein L and Z each comprise a methacrylate moiety.

[0054] Embodiment 9. A polymerizable liquid comprising at least one polymerizable compound of Formula I: [ka] Contains the additive where L and Z are ring substituents containing at least one point of polymerizable unsaturation, and R 1 and R 2 is independently selected from the group consisting of alkylene and alkenylene; R 3 -R 6 each represent 1 to 4 optional ring substituents, each of the 1 to 4 ring substituents 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.

[0055] Embodiment 10. R 1 and R 210. The polymerizable liquid of embodiment 9, wherein is alkylene.

[0056] Embodiment 11. The polymerizable liquid of embodiment 9 or 10, wherein L and Z each comprise a moiety independently selected from the group consisting of vinyl, allyl, vinyl ether, acrylate, and methacrylate.

[0057] Embodiment 12. The polymerizable liquid of any of embodiments 9-10, wherein L and Z each comprise a cyclopolymerizable functional group.

[0058] Embodiment 13. The cyclopolymerizable functional group has the formula: [ka] wherein: [ka] is the point of attachment of the cyclopolymerizable moiety to the compound of Formula I.

[0059] Embodiment 14. The polymerizable liquid of any of embodiments 9-13, wherein n is 2 or 3.

[0060] Embodiment 15. The polymerizable liquid of embodiment 14, wherein L and Z each comprise an acrylate moiety.

[0061] Embodiment 16. The polymerizable liquid of embodiment 14, wherein L and Z each comprise a methacrylate moiety.

[0062] Embodiment 17. The polymerizable liquid of any of embodiments 9-16, wherein the additive is present in an amount of 5 to 40 weight percent, based on the total weight of the polymerizable liquid.

[0063] Embodiment 18. The polymerizable liquid of any of embodiments 9-16, wherein the additive is present in an amount of 10 to 30 weight percent, based on the total weight of the polymerizable liquid.

[0064] Embodiment 19. The polymerizable liquid of any of embodiments 9-18, further comprising an acrylate component.

[0065] Embodiment 20. The polymerizable liquid of embodiment 19, wherein the acrylate component comprises an acrylate monomer, an acrylate oligomer, or a mixture thereof.

[0066] Embodiment 21. The polymerizable liquid of embodiment 19 or 20, wherein the acrylate component is present in an amount of 30 to 70 weight percent, based on the total weight of the polymerizable liquid.

[0067] Embodiment 22. A method of printing a three-dimensional article, comprising: providing a polymerizable liquid; and Printing and curing a polymerizable liquid using light to form an article Including, The polymerizable liquid is an acrylate component; and At least one additive of formula I: [ka] Including, where L and Z are ring substituents containing at least one point of polymerizable unsaturation, and R 1 and R 2 is independently selected from the group consisting of alkylene and alkenylene; R 3 -R 6 each represent 1 to 4 optional ring substituents, 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.

[0068] Embodiment 23. The method of embodiment 22, wherein the at least one additive is present in an amount of 5 to 40 weight percent, based on the total weight of the polymerizable liquid.

[0069] Embodiment 24. The method of embodiment 22 or 23, wherein the acrylate component is present in an amount of 30 to 70 weight percent, based on the total weight of the polymerizable liquid.

[0070] Embodiment 25. The method of any of embodiments 22-24, wherein L and Z each comprise a moiety independently selected from the group consisting of vinyl, allyl, vinyl ether, acrylate, and methacrylate.

[0071] Embodiment 26. The method of any of embodiments 22-24, wherein L and Z each comprise a cyclopolymerizable functional group.

[0072] Embodiment 27. The cyclopolymerizable functional group has the formula: [ka] 27. The method of embodiment 26, wherein

[0073] Embodiment 28. The method of any of embodiments 22-24, wherein L and Z each comprise an acrylate moiety.

[0074] Embodiment 29. The method of any of embodiments 22-24, wherein L and Z each comprise a methacrylate moiety.

[0075] All patent documents mentioned herein are incorporated by reference in their entirety. In accomplishing various objectives of the present invention, various embodiments of the present invention have been described. It is to be recognized that these embodiments are merely illustrative of the principles of the present invention. Many modifications and adaptations thereof will be readily apparent to those skilled in the art without departing from the spirit and scope of the present invention.

Claims

1. Formula I: 【Chemistry 1】 An additive comprising: where L and Z are ring substituents containing at least one polymerizable unsaturated point, and R １ and R ２ is independently selected from the group consisting of alkylene and alkenylene; R ３ -R ６ each represent 1 to 4 optional ring substituents, each of the 1 to 4 ring substituents independently selected from the group consisting of alkyl, heteroalkyl, haloalkyl, halo, hydroxyl, alkoxy, and amine; and n is an integer from 1 to 7; L and Z each contain a cyclopolymerizable functional group. Additives.

2. The cyclopolymerizable functional group has the formula: 【Chemistry 2】 It is of During the ceremony, 【Transformation 3】 is the point of attachment of said cyclopolymerizable functional group to the compound of formula I The additive according to claim 1 , characterized in that

3. A polymerizable liquid, At least one additive of formula I: 【Chemistry 4】 Including, where L and Z are ring substituents containing at least one polymerizable unsaturated point, and R １ and R ２ is independently selected from the group consisting of alkylene and alkenylene; R ３ ~R ６ each represent 1 to 4 optional ring substituents, each of the 1 to 4 ring substituents independently selected from the group consisting of alkyl, heteroalkyl, haloalkyl, halo, hydroxyl, alkoxy, and amine; and n is an integer from 1 to 7; L and Z each contain a cyclopolymerizable functional group. Polymerizable liquid.

4. The cyclopolymerizable functional group has the formula: 【Transformation 5】 wherein: 【Transformation 6】 is the point of attachment of said cyclopolymerizable functional group to the compound of formula I The polymerizable liquid according to claim 3 .

5. 1. A method for printing a three-dimensional article, comprising: providing a polymerizable liquid; and printing and curing said polymerizable liquid with light to form said article. Including, The polymerizable liquid is an acrylate component; and At least one additive of formula I: 【Transformation 7】 Including, where L and Z are ring substituents containing at least one polymerizable unsaturated point, and R １ and R ２ is independently selected from the group consisting of alkylene and alkenylene; R ３ -R ６ each represent 1 to 4 optional ring substituents, each of the 1 to 4 ring substituents independently selected from the group consisting of alkyl, heteroalkyl, haloalkyl, halo, hydroxyl, alkoxy, and amine; and n is an integer from 1 to 7; L and Z each comprise a moiety independently selected from the group consisting of acrylate and methacrylate. method.

6. 6. The method of claim 5, wherein the at least one additive is present in an amount of 5 to 40% by weight, based on the total weight of the polymerizable liquid.

7. 6. The method of claim 5, wherein the acrylate component is present in an amount of 30 to 70 weight percent, based on the total weight of the polymerizable liquid.

8. 1. A method for printing a three-dimensional article, comprising: providing a polymerizable liquid; and printing and curing said polymerizable liquid with light to form said article. Including, The polymerizable liquid is an acrylate component; and At least one additive of formula I: 【Transformation 8】 Including, where L and Z are ring substituents containing at least one polymerizable unsaturated point, and R １ and R ２ is independently selected from the group consisting of alkylene and alkenylene; R ３ -R ６ each represent 1 to 4 optional ring substituents, each of the 1 to 4 ring substituents independently selected from the group consisting of alkyl, heteroalkyl, haloalkyl, halo, hydroxyl, alkoxy, and amine; and n is an integer from 1 to 7; L and Z each contain a cyclopolymerizable functional group. method.

9. The cyclopolymerizable functional group has the formula: 【Chemistry 9】 9. The method of claim 8, wherein

10. 6. The method of claim 5, wherein L and Z each comprise an acrylate moiety.

11. 6. The method of claim 5, wherein L and Z each comprise a methacrylate moiety.

Images