Liquid, hybrid UV / vis radiation curable resin compositions for additive fabrication

Abstract

To provide liquid radiation curable compositions which are suitable for hybrid (i.e. cationic and free-radical) polymerization when processed via additive fabrication equipment utilizing sources of actinic radiation with peak spectral intensities in the UV / vis region.SOLUTION: According to one aspect, the compositions possess a first photoinitiator that is an iodonium salt of a non-fluorinated borate anion. According to another aspect, the composition is substantially devoid of a Norrish Type I and / or Type II photoinitiator. Also disclosed are methods of creating three-dimensional parts via additive fabrication processes utilizing sources of actinic radiation with peak spectral intensities in the UV / vis region employing liquid radiation curable compositions suitable for hybrid polymerization, and the parts cured therefrom.SELECTED DRAWING: None

Description

Detailed Description of the Invention

[0001] [Technical field] The present invention relates to liquid compositions for additive manufacturing processes that are hybrid curable in the UV or visible spectrum.

[0002] [CROSS-REFERENCE TO RELATED APPLICATIONS]

[0001] This application claims priority to U.S. Provisional Patent Application No. 62 / 893,969, filed August 30, 2019, the entire contents of which are incorporated herein by reference as if fully set forth herein.

[0003] [background]

[0002] Additive manufacturing processes for producing three-dimensional objects are well known. Additive manufacturing processes utilize computer-aided design (CAD) data of an object to build three-dimensional parts. These three-dimensional parts may be formed from liquid resin, powder, or other materials.

[0004] A well-known, non-limiting example of an additive manufacturing process is stereolithography (SL). Stereolithography is a process for rapidly producing models, prototypes, patterns, and production parts for specific applications. SL uses CAD data of an object, which is converted into a thin cross-section of a three-dimensional object. The data is loaded into a computer, which controls a laser to trace the cross-section pattern with a liquid radiation-curable resin composition contained in a vat and solidify a thin layer of resin corresponding to the cross-section. The solidified layer is recoated with resin, and the laser traces another cross-section, curing another layer of resin on top of the previous layer. The process is repeated, layer by layer, until the three-dimensional object is complete. When first formed, the three-dimensional object is generally not fully cured and is called a "green model." Although not required, the green model may undergo post-curing to enhance the mechanical properties of the finished part. An example of the SL process is described, for example, in U.S. Pat. No. 4,575,330.

[0005]

[0004] Lasers have traditionally served as the radiation source of choice in additive manufacturing processes such as stereolithography. The use of gas lasers to cure liquid radiation-curable resin compositions is well known. Laser energy delivery in stereolithography systems can be continuous wave (CW) or Q-switched pulsed. CW lasers provide continuous laser energy and can be used in rapid scanning processes. Historically, several types of lasers have been used in stereolithography, traditionally with peak spectral output in the wavelength range of 193 nm to 355 nm, although other wavelengths exist. Light emitted from lasers is monochromatic, i.e., a significant percentage of the total spectral output is present within a very narrow wavelength range. Among laser-based additive manufacturing systems in the industry, those operating with a peak spectral output of 355 nm have become the most prevalent.

[0006] However, laser-based systems, especially those operating with peak spectral output at or near 355 nm, are not without drawbacks. The significant power output of such laser-based systems can generate excessive heat at the point of irradiation, which can be harmful to the resin. Furthermore, the use of lasers at any wavelength requires point-by-point scanning over the resin surface, a process that can be particularly time-consuming when the cross-sectional pattern to be cured is large or complex. Also, 355 nm laser-based systems are expensive and associated with high maintenance costs and energy consumption.

[0007] To combat some of the drawbacks associated with laser-based systems, other additive manufacturing systems have begun to utilize image projection technology as the actinic radiation source. One example of this is liquid crystal display (LCD), a technology well known in other industries, such as television and computer monitor manufacturing. Another non-limiting example is that developed by Texas Instruments called Digital Light Processing (DLP®). DLP systems use tiny mirrors, known as digital micromirror devices (DMDs), representing pixels controlled by and fixed to microchips to selectively transmit light from an input source and project that light in a desired output pattern or mask. DLP technology was developed for use in image projection systems as an alternative display system to LCD-based technology. Because the boundaries of the cured and created three-dimensional object are ultimately defined by the boundaries of the projected light, the exceptional image sharpness, brightness, and uniformity associated with DLP systems make them extremely useful for additive manufacturing, where image resolution and precision are critical. Furthermore, image projection systems such as LCDs and DLPs offer theoretical speed advantages in that entire cross-sectional layers can be exposed and cured simultaneously. Furthermore, while the curing time required in laser-based systems is directly proportional to the complexity of the cross-section being scanned, image projection systems are said to be cross-section independent, meaning that the exposure time of a given layer does not change with increasing shape complexity of any given layer. This makes image projection systems particularly well suited for producing parts with complex and detailed geometries by additive manufacturing.

[0008]

[0007] DLPs and LCDs do not provide an alternative method of generating light itself, but rather a way to process light emitted from an existing light source into a more desirable pattern. Therefore, a combined input light source is still needed. The light input to an image projection system can be from any source, including a traditional lamp or even a laser, but more commonly the input light is collimated from one or more light-emitting diodes (LEDs).

[0009]

[0008] LEDs are semiconductor devices that generate light using the phenomenon of electroluminescence. Currently, LED light sources for additive manufacturing systems emit light at wavelengths between 300 and 475 nm, with common peak spectral outputs at 365 nm, 375 nm, 395 nm, 401 nm, 405 nm, and 420 nm. For a more detailed discussion of LED light sources, see the text "Light-Emitting Diodes," by E. Fred Schubert, 2nd Edition, published by Cambridge University Press, © E. Fred Schubert 2006. LEDs theoretically offer the advantage of operating at near-peak efficiency for longer sustained periods than other light sources. Furthermore, LEDs are typically more energy efficient and less expensive to maintain than laser-based optical systems, resulting in lower initial and ongoing costs of ownership.

[0010]

[0009] Thus, various additive manufacturing systems use one of the following non-limiting optical configurations: (1) laser only, (2) laser / DLP, (3) LED only, (4) LED / DLP, or (5) LED / LCD. Systems that do not utilize DLP technology may also incorporate other collimating or focusing lenses / mirrors to selectively direct light onto the liquid resin.

[0011] In recent years, newer additive manufacturing systems (regardless of optical configuration) have begun to more frequently use light sources that emit radiation at wavelengths greater than the traditional 355 nm output. Other systems have shifted away from monochromatic light sources, instead opting for light sources that emit light with broader spectral power distributions. Thus, these newer systems, incorporating laser / DLP-based, LED-based, LED / DLP-based, or LED / LCD-based optical configurations, have begun to operate with peak spectral outputs at longer wavelengths and broader spectral distributions than previously common. The wavelengths used therein have shifted away from 355 nm toward the visible spectrum, with some even having peak spectral outputs within the visible range. These longer wavelengths (i.e., 375 nm to 500 nm) have traditionally been referred to as "UV / vis."

[0012] Some commonly cited, non-limiting reasons for the current trend toward increased use of optical systems in the UV / vis region are: (1) the reduction in the cost (both initial and maintenance costs) of light sources operating in the UV / vis range, and (2) the fact that UV / vis light sources, which emit lower energy radiation than sources emitting deeper in the UV region, are, all else being equal, less damaging to human tissue. This makes UV / vis light sources less harmful upon accidental exposure than those operating deeper in the UV region. As additive manufacturing continues to grow in popularity among consumer, "prosumer," and industrial market segments, the need for additive modeling systems that use lower cost, less hazardous actinic radiation sources to cure liquid photopolymers will become increasingly important.

[0013] However, the advantages of utilizing UV / vis light sources / optics are not without significant trade-offs. To date, the greatest drawback has been the relatively great difficulty in developing photopolymers suitable for systems utilizing UV / vis optics. One of the main reasons for this is that, in addition to the natural phenomenon that light of longer wavelengths has lower energy, the intensity of commercial light sources also typically decreases with increasing wavelength of peak spectral output. Thus, traditional 355 nm laser-based light systems can deliver 1500 W / cm at the resin surface. 2 While commercial systems operating at about 400 nm are known to deliver an irradiance of only about 1 / 1000 of that value at the resin surface, the irradiance delivered by the UV / vis optics in existing 365 nm or 405 nm DLP-based commercial additive manufacturing systems is only about 0.1 W / cm in some of the more economical desktop units. 2 or even 0.0002 W / cm 2 These relatively reduced radiation energies / intensities make it more difficult to induce photopolymerization reactions in radiation-curable resins using such UV / vis optics unless exposure times are extremely long. This in turn significantly increases part build times, thereby negating the theoretical speed advantage of photomasking display systems. Furthermore, there are fewer photoinitiating systems, particularly cationic photoinitiating systems, on the market to promote photopolymerization at these longer UV / vis wavelengths.

[0014]

[0013] As a result of the above challenges, the number of photopolymers made available for modern optical systems operating in the UV / vis region is limited compared to the variety of options available for systems operating deeper in the UV region, such as 355 nm laser-based systems.

[0015]

[0014] Radical-polymerizable resins for systems using UV / vis optics are known to exist. Such resins generally consist of one or more (meth)acrylate compounds (or other free-radically polymerizable organic compounds) along with a free-radical photoinitiator for radical generation. U.S. Pat. No. 5,418,112 describes one such radical-cure system. Although radical-polymerizable resins can easily cure under the relatively lower energy and intensity provided by UV / vis optics, they are not suitable for all additive manufacturing applications. First, (meth)acrylate-based resins considered suitable for additive manufacturing processes have traditionally produced cured parts with insufficient mechanical properties for incorporation into many end uses. Thus, parts that are not robust enough for non-prototyping applications are typically produced. Additionally, such resins typically exhibit deformation problems, such as producing warped or misshapen parts, due to residual strain caused by differential shrinkage during curing. These problems are exacerbated on larger platform additive manufacturing machines, where the cumulative effects of differential shrinkage amplify part warpage or misshapenness as the cured object grows. These distortion problems can be partially corrected with software that accounts for known shrinkage rates by modifying the CAD files that create the solid 3D part. However, software corrections are insufficient to fully compensate for distortions in parts with intricate, complex geometries or that require tight dimensional tolerances over long distances.

[0016] Another well-known type of resin suitable for use in additive manufacturing systems is a "hybrid" curable resin, i.e., one that includes (1) an epoxy, oxetane, or other type of cationically polymerizable compound; (2) one or more cationic photoinitiators; (3) an acrylate resin or other type of free-radically polymerizable compound; and (4) one or more free-radical photoinitiators. Examples of such hybrid cure systems are described, for example, in U.S. Pat. No. 5,434,196. Such resins have long been known to produce cured parts produced by additive manufacturing processes that have superior mechanical properties compared to all-acrylate resins. Furthermore, hybrid cure systems are superior to all-acrylate systems in that they are less susceptible to the differential shrinkage problems that have long plagued all-acrylate systems.

[0017] However, because the ring-opening process of cationic polymerization generally occurs slower and requires more activation energy than free-radical polymerization, ensuring that such formulations for additive manufacturing applications properly cure, or successfully "build" three-dimensional objects, is inherently more difficult. And even if at least partial curing occurs after a hybrid curable resin is exposed to actinic radiation, green models produced therefrom have insufficient mechanical strength (or "green strength") for use in many additive manufacturing applications, as measured, for example, by elastic modulus or fracture strength. These problems are significantly exacerbated by UV / vis optics, which emit radiation of lower energy and intensity than conventional systems.

[0018]

[0017] Due to these limitations, to date, only a few hybrid liquid radiation-curable resins for additive manufacturing are known that are suitable for use in more modern additive manufacturing systems that use UV / vis optics. Some are described in U.S. Patent Nos. 9,708,442 and 10,604,659 (each assigned to DSM IP Assets BV), but given the wide range of changes in additive manufacturing systems that use UV / vis optics, further solutions would be welcome.

[0019]

[0018] It would therefore be desirable to provide a liquid radiation-curable resin (hybrid curable or otherwise) for additive manufacturing that is suitable for additive manufacturing systems using UV / vis optics and that also (1) cures sufficiently rapidly and (2) is capable of imparting sufficient mechanical strength and resistance to shrinkage distortion to three-dimensional parts cured therefrom. Additionally or alternatively, it would be desirable to provide a hybrid-curable liquid radiation resin composition suitable for use in additive manufacturing systems using UV / vis optics that is capable of producing three-dimensional parts having superior accuracy and / or mechanical properties comparable to, at least, existing hybrid-curable materials designed for traditional laser-based 355 nm systems.

[0020] [Brief Overview]

[0019] Several embodiments of the present invention are described herein. According to a first aspect, the present invention comprises a radiation-curable composition comprising a cationically curable component and a free-radically curable component, said composition further comprising at least a first photoinitiator which is an iodonium salt of a non-fluorinated borate anion. According to another embodiment of the first aspect, the non-fluorinated borate anion of the iodonium salt is represented by the formula [ka] wherein R1 to R4 are independently selected from the group consisting of alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, and heteroaryl, and further wherein (i) one or more substitutable carbon atoms of the alkyl, alkenyl, or alkynyl are optionally substituted with hydroxy, carboxy, alkoxy, alkanoyl, hydroxyalkyl, carboxyalkyl, alkoxyalkyl, or alkanoylalkyl, or (ii) one or more substitutable carbon atoms of the cycloalkyl, heterocycloalkyl, aryl, or heteroaryl are optionally substituted with alkyl, hydroxy, carboxy, alkoxy, alkanoyl, hydroxyalkyl, carboxyalkyl, alkoxyalkyl, or alkanoylalkyl. It has.

[0021] According to yet further embodiments, the composition is substantially devoid of certain types of free radical photoinitiators, such as phosphorus-containing photoinitiators, Norrish Type I photoinitiators, and / or Norrish Type II photoinitiators.

[0022] According to yet a further embodiment, the composition further comprises a photosensitizer and / or a reducing agent, preferably a polyfunctional vinyl ether compound containing electron-donating substituents attached to the vinyl groups, e.g., at least two vinyl groups per molecule.

[0023]

[0022] A second aspect of the invention as claimed describes a method of forming a three-dimensional article using any of the compositions according to the first aspect by an additive manufacturing system utilizing UV / vis optical systems.

[0024] A third aspect of the invention claimed is a three-dimensional part formed according to the second aspect of the invention using the liquid radiation curable composition of the first aspect of the invention.

[0025] [Detailed explanation]

[0024] Throughout this specification, "UV / vis" is defined as the 375 nanometer (nm) to 500 nanometer (nm) region of the electromagnetic spectrum.

[0026]

[0025] Thus, throughout this specification, "UV / vis optics" is defined as any electrical, mechanical, or electromechanical system that generates and directs / displays actinic radiation operating with a peak spectral intensity between 375 nm and 500 nm. Specific, non-limiting examples of UV / vis optics include lasers, LEDs, one or more LEDs coupled to a DLP display system, one or more LEDs coupled to an LCD display system, a laser coupled to a DLP display system, and a laser coupled to an LCD display system.

[0027]

[0026] Furthermore, as used herein, "substantially devoid" is intended to indicate that a particular composition or component (as specified by context) has virtually no amount by weight of a particular substance, for example, less than 0.1 wt.%, or less than 0.05 wt.%, or preferably less than 0.01 wt.%, or about 0.00 wt.% of a particular substance.

[0028]

[0027] A first embodiment of the present invention is a radiation-curable composition comprising a cationically curable component and a free-radically curable component, the composition further comprising at least a first photoinitiator which is an iodonium salt of a non-fluorinated borate anion.

[0029]

[0028] The composition according to the first aspect therefore contains a cationically curable component, a free-radically polymerizable component, and a photoinitiator. In a preferred embodiment, the composition includes both a free-radical photoinitiator and a cationic photoinitiator. The composition may further include one or more photosensitizers, reducing agents, and / or additives.

[0030] [Cationic curing component] According to an embodiment, the liquid radiation-curable resin for additive manufacturing of the present invention comprises at least one cationically polymerizable component, i.e., a component that undergoes polymerization initiated by cations or in the presence of an acid generator. The cationically polymerizable component may be a monomer, oligomer, and / or polymer and may contain an aliphatic moiety, an aromatic moiety, a cycloaliphatic moiety, an arylaliphatic moiety, a heterocyclic moiety, and any combination thereof. Preferably, the cationically polymerizable component comprises at least one cycloaliphatic compound. Suitable cyclic ether compounds may contain a cyclic ether group as a side group or as a group forming part of an alicyclic or heterocyclic ring system.

[0031] The cationically polymerizable component is selected from the group consisting of cyclic ether compounds, cyclic acetal compounds, cyclic thioether compounds, spiro-orthoester compounds, cyclic lactone compounds, and any combination thereof.

[0032] Suitable cationically polymerizable components include cyclic ether compounds such as epoxy compounds and oxetanes, cyclic lactone compounds, cyclic acetal compounds, cyclic thioether compounds, and spiro-orthoester compounds. Specific examples of cationically polymerizable components include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, epoxy novolac resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3,4- Epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)-cyclohexane-1,4-dioxane, bis(3,4-epoxycyclohexylmethyl)adipate, vinylcyclohexene oxide, 4-vinylepoxycyclohexane, vinylcyclohexene dioxide, limonene oxide, limonene dioxide, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate , 3,4-epoxy-6-methylcyclohexyl-3',4'-epoxy-6'-methylcyclohexanecarboxylate, ε-caprolactone-modified 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, trimethylcaprolactone-modified 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, β-methyl-δ-valerolactone-modified 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane dicyclopentadiene diepoxide, di(3,4-epoxycyclohexylmethyl)ether of ethylene glycol, ethylenebis(3,3'-epoxycyclohexane), dicyclohexyl-3,3'-epoxide, bis(3,4-epoxycyclohexyl) having the linkages -O-, -S-, -SO-, -SO2-, -C(CH3)2-, -CBr2-, -C(CBr3)2-, -C(CF3)2-, -C(CCl3)2- or -CH(C6H5)-, dicyclopentadiene diepoxide, di(3,4-epoxycyclohexylmethyl)ether of ethylene glycol, ethylenebis(3,4-epoxycyclohexanecarboxylate), epoxy hexahydrodioctyl phthalate, epoxy hexahydro-di-2-ethylhexyl phthalate, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, diglycidyl esters of aliphatic long-chain dibasic acids, monoglycidyl ethers of aliphatic higher alcohols, monoglycidyl ethers of phenol, cresol, butylphenol, or polyether alcohols (obtained by addition of alkylene oxide to these compounds), glycidyl esters of higher fatty acids, epoxidized soybean oil, epoxy butyl stearic acid, epoxy octyl stearic acid, epoxidized linseed oil, epoxidized polybutadiene, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(3-hydroxypropyl)oxymethyloxetane, 3-ethyl-3-(4-hydroxybutyl)oxymethyloxetane, 3-ethyl-3-(5-hydroxypentyl)oxymethyloxetane, 3-ethyl-3-phenoxymethyloxetane, bis((1-ethyl(3-oxetanyl))methyl)ether 3-ethyl-3-((2-ethylhexyloxy)methyl)oxetane, 3-ethyl-((triethoxysilylpropoxymethyl)oxetane, 3-(meth)-allyloxymethyl-3-ethyloxetane, 3-hydroxymethyl-3-ethyloxetane, (3-ethyl-3-oxetanylmethoxy)methylbenzene, 4-fluoro-[1-(3-ethyl-3-oxetanylmethoxy)methyl]benzene, 4-methoxy-[1-(3-ethyl-3-oxetanylmethoxy)methyl]benzene, Examples of the hydroxyethyl ether include 1-(3-ethyl-3-oxetanylmethoxy)ethyl]phenyl ether, isobutoxymethyl (3-ethyl-3-oxetanylmethyl) ether, 2-ethylhexyl (3-ethyl-3-oxetanylmethyl) ether, ethyl diethylene glycol (3-ethyl-3-oxetanylmethyl) ether, dicyclopentadiene (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl (3-ethyl-3-oxetanylmethyl) ether, tetrahydrofurfuyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxyethyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxypropyl (3-ethyl-3-oxetanylmethyl) ether, and any combination thereof.

[0033] The cationically polymerizable component may also optionally contain polyfunctional materials, including dendritic polymers having epoxy or oxetane functional groups, such as dendrimers, linear dendritic polymers, dendrigraft polymers, hyperbranched polymers, star-branched polymers, and hypergraft polymers. The dendritic polymers may contain one type of polymerizable functional group or various types of polymerizable functional groups, such as epoxy and oxetane functional groups.

[0034] In embodiments, the compositions of the present invention also include one or more mono- or polyglycidyl ethers of aliphatic alcohols, aliphatic polyols, polyester polyols, or polyether polyols. Examples of preferred components include 1,4-butanediol diglycidyl ether, glycidyl ethers of polyoxyethylene and polyoxypropylene glycols and triols having a molecular weight of about 200 to about 10,000, and glycidyl ethers of polytetramethylene glycol or poly(oxyethylene-oxybutylene) random or block copolymers. In a specific embodiment, the cationically polymerizable component comprises a polyfunctional glycidyl ether lacking a cyclohexane ring in the molecule. In another specific embodiment, the cationically polymerizable component comprises neopentyl glycol diglycidyl ether. In another specific embodiment, the cationically polymerizable component comprises 1,4 cyclohexanedimethanol diglycidyl ether.

[0035] An example of a commercially available preferred polyfunctional glycidyl ether is Erisys TM GE 22 (Erisys TM Products are manufactured by Emerald Performance Materials TM (Available from Heloxy) TM 48. Heloxy TM 67. Heloxy TM 68. Heloxy TM 107(Heloxy TMModifiers are available from Momentive Specialty Chemicals, and Grilonit® F713. Examples of preferred commercially available monofunctional glycidyl ethers are Heloxy TM 71. Heloxy TM 505, Heloxy TM 7. Heloxy TM 8, and Heloxy TM The number is 61.

[0036] In embodiments, the epoxide is 3,4-epoxycyclohexylmethyl-3',4-epoxycyclohexanecarboxylate (available from Daicel Chemical as CELLOXIDE TM 2021P or CYRACURE from Dow Chemical TM UVR-6105), hydrogenated bisphenol A-epichlorohydrin-based epoxy resin (EPON from Momentive) TM 1510), 1,4-cyclohexanedimethanol diglycidyl ether (available from Momentive as HELOXY TM 107), hydrogenated bisphenol A diglycidyl ether (EPON from Momentive) TM 825), a mixture of dicyclohexyl diepoxide and nanosilica (NANOPOX TM available as CI 14491, CI 14492, CI 14493, CI 14494, CI 14495, CI 14496, CI 14497, CI 1449 ...

[0037] In a specific embodiment, the cationically polymerizable component is a cycloaliphatic epoxy, such as that represented by the following Formula I: [ka] (wherein R is a carbon atom, an ester-containing C1-C 10 Aliphatic chain, or C1-C 10 alkyl chain) and cycloaliphatic epoxies having two or more epoxy groups according to

[0038] In another specific embodiment, the cationically polymerizable component comprises an epoxy having an aromatic or aliphatic glycidyl ether group having two (difunctional) or three or more (multifunctional) epoxy groups.

[0039]

[0038] The above-mentioned cationically polymerizable compounds can be used alone or in combination of two or more thereof. In an embodiment of the present invention, the cationically polymerizable component further comprises at least two different epoxy components.

[0040] In another embodiment of the present invention, the cationically polymerizable component also includes an oxetane component. In a specific embodiment, the cationically polymerizable component includes an oxetane, for example, an oxetane containing one, two, or more than two oxetane groups. In another embodiment, the oxetane used is monofunctional and further comprises a hydroxyl group. According to an embodiment, the oxetane has the following structure: [ka] It has.

[0041] When utilized in the composition, the oxetane component is suitably present in an amount of from about 5 to about 50 wt % of the resin composition. In another embodiment, the oxetane component is present in an amount of from about 10 to about 25 wt % of the resin composition, and in yet another embodiment, the oxetane component is present in an amount of from 20 to about 30 wt % of the resin composition.

[0042]

[0041] The liquid radiation-curable resin for additive manufacturing can therefore comprise a suitable amount of cationically curable component, for example, in certain embodiments, an amount of about 10 to about 80% by weight of the resin composition, in further embodiments about 20 to about 70 wt% of the resin composition, in further embodiments about 25 to about 65 wt% of the resin composition, in even more preferred embodiments about 30 to about 80 wt% of the resin composition, and more preferably about 50 to about 85 wt%.

[0043] [Free radical curing component] According to an embodiment of the present invention, the liquid radiation-curable resin for additive manufacturing of the present invention comprises at least one free-radical-curable component, i.e., a component that undergoes free-radical initiated polymerization. The free-radical polymerizable component may be a monomer, oligomer, and / or polymer, which may be a monofunctional or polyfunctional material, i.e., having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10... 20... 30... 40... 50... 100 or more functional groups capable of polymerization by free-radical initiation, and may contain aliphatic, aromatic, cycloaliphatic, arylaliphatic, heterocyclic, or any combination thereof. Examples of polyfunctional materials include dendritic polymers, such as dendrimers, linear dendritic polymers, dendrigraft polymers, hyperbranched polymers, star-branched polymers, and hypergraft polymers; see, for example, U.S. Patent Application Publication No. 2009 / 0093564 A1. Dendritic polymers can contain one type of polymerizable functional group or various types of polymerizable functional groups, such as acrylate and methacrylate functional groups.

[0044]

[0043] Examples of free radically curable or polymerizable components include acrylates and methacrylates, such as isobornyl (meth)acrylate, bornyl (meth)acrylate, tricyclodecanyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, 4-butylcyclohexyl (meth)acrylate, acryloylmorpholine, (meth)acrylic acid, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl ... propyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, amyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, caprolactone acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, isooctyl Cetyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, tridecyl (meth)acrylate, undecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, butoxyethyl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate ) acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, methoxyethylene glycol (meth)acrylate, ethoxyethyl (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, diacetone (meth)acrylamide, beta-carboxyethyl (meth)acrylate, phthalic acid (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate,Examples include butylcarbamylethyl (meth)acrylate, n-isopropyl (meth)acrylamide fluorinated (meth)acrylate, and 7-amino-3,7-dimethyloctyl (meth)acrylate.

[0045] Examples of polyfunctional free radical polymerizable components include those having a (meth)acryloyl group, such as trimethylolpropane tri(meth)acrylate, pentaerythritol (meth)acrylate, ethylene glycol di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, dicyclopentadiene dimethanol di(meth)acrylate, [2-[1,1-dimethyl-2-[(1-oxoallyl)oxy]ethyl]-5-ethyl-1,3-dioxan-5-yl]methyl acrylate; 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane di(meth)acrylate; Acrylates; dipentaerythritol monohydroxypenta(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, propoxylated neopentyl glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polybutanediol di(meth)acrylate, tripropylene glycol di(meth)acrylate, glycerol tri(meth)acrylate, mono- and di(meth)acrylate phosphates, C7 to C 20Alkyl di(meth)acrylates, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tricyclodecanediyldimethyl di(meth)acrylate, and alkoxylated (e.g., ethoxylated and / or propoxylated) versions of any of the foregoing monomers, as well as bis(meth)acrylates. Examples include di(meth)acrylates of diols which are addition products of ethylene oxide or propylene oxide to phenol A, di(meth)acrylates of diols which are addition products of ethylene oxide or propylene oxide to hydrogenated bisphenol A, epoxy (meth)acrylates which are (meth)acrylate addition products of diglycidyl ethers to bisphenol A, diacrylates of polyoxyalkylated bisphenol A, and addition products of triethylene glycol divinyl ether and hydroxyethyl acrylate.

[0046]

[0045] According to an embodiment, the radically polymerizable component is a multifunctional (meth)acrylate, which may contain all methacryloyl groups, all acryloyl groups, or any combination of methacryloyl and acryloyl groups. In embodiments, the free radically polymerizable component is selected from the group consisting of bisphenol A diglycidyl ether di(meth)acrylate, ethoxylated or propoxylated bisphenol A or bisphenol F di(meth)acrylate, dicyclopentadiene dimethanol di(meth)acrylate, [2-[1,1-dimethyl-2-[(1-oxoallyl)oxy]ethyl]-5-ethyl-1,3-dioxan-5-yl]methyl acrylate, dipentaerythritol monohydroxypenta(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, and propoxylated neopentyl glycol di(meth)acrylate, and any combination thereof.

[0047] In an embodiment, the multifunctional (meth)acrylate has three or more functional groups. According to another embodiment, the multifunctional (meth)acrylate has four or more functional groups. In yet another embodiment, the multifunctional (meth)acrylate has five or more functional groups. In another preferred embodiment, the radically polymerizable component consists exclusively of a single multifunctional (meth)acrylate component. In a further embodiment, the exclusively radically polymerizable component is tetrafunctional, in a further embodiment, the exclusively radically polymerizable component is pentafunctional, and in a further embodiment, the exclusively radically polymerizable component is hexafunctional.

[0048] In another embodiment, the free-radically polymerizable component contains an aromatic (meth)acrylate. The aromatic acrylate may be derived from, by way of non-limiting example, bisphenol A, bisphenol S, or bisphenol F. In certain embodiments, the aromatic is selected from the group consisting of bisphenol A diglycidyl ether diacrylate, dicyclopentadiene dimethanol diacrylate, [2-[1,1-dimethyl-2-[(1-oxoallyl)oxy]ethyl]-5-ethyl-1,3-dioxan-5-yl]methyl acrylate, dipentaerythritol monohydroxypentaacrylate, propoxylated trimethylolpropane triacrylate, and propoxylated neopentyl glycol diacrylate, and any combination thereof. In an embodiment, the aromatic (meth)acrylate is difunctional.

[0049]

[0048] In a specific embodiment, the liquid radiation curable resin for additive manufacturing of the present invention comprises one or more of bisphenol A diglycidyl ether di(meth)acrylate, dicyclopentadiene dimethanol di(meth)acrylate, dipentaerythritol monohydroxypenta(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, and / or propoxylated neopentyl glycol di(meth)acrylate, more specifically one or more of bisphenol A diglycidyl ether diacrylate, dicyclopentadiene dimethanol diacrylate, dipentaerythritol pentaacrylate, propoxylated trimethylolpropane triacrylate, and / or propoxylated neopentyl glycol diacrylate.

[0050] The above-described radically polymerizable compounds can be used alone or in combination of two or more thereof. The liquid radiation-curable resin for additive manufacturing can include the free-radically polymerizable component in any suitable amount, for example, in certain embodiments, up to about 50 wt % of the resin composition, in certain embodiments, about 2 to about 40 wt % of the resin composition, in other embodiments, about 5 to about 30 wt %, in further embodiments, about 10 to about 20 wt % of the resin composition, and in even more preferred embodiments, about 8 to about 50 wt %, and more preferably, about 15 to about 25 wt % of the resin composition.

[0051] [Photoinitiator] In an embodiment according to the present invention, the composition comprises at least one photoinitiator. A photoinitiator is a compound that is chemically altered by the action of light (or a synergistic effect between the action of light and the electronic excitation of a sensitizing dye) to generate at least one of a radical, an acid, and a base, which then effect a polymerization reaction in one or more of the polymerizable substances present in the corresponding composition. According to an embodiment of the first aspect of the present invention, the composition comprises a photoinitiator useful for effecting polymerization in a free-radically curable component, a cationically curable component, or both such components.

[0052] Photoinitiators that can bring about polymerization of free-radical curable components (when exposed to light of an appropriate wavelength and / or intensity) are free-radical photoinitiators. Photoinitiators that can bring about polymerization of cationically curable components (when exposed to light of an appropriate wavelength and / or intensity) are cationic photoinitiators. While certain photoinitiators can function as both free-radical and cationic photoinitiators, typically at least two different photoinitiators are used for this purpose. According to embodiments, the liquid radiation-curable resin composition comprises a photoinitiating system containing at least one photoinitiator with cationic initiation functionality and at least one photoinitiator with free-radical initiation functionality. In another embodiment, the photoinitiating system can comprise a photoinitiator containing both free-radical initiation functionality and cationic initiation functionality on the same molecule.

[0053] In an embodiment, the liquid radiation-curable resin for additive manufacturing of the present invention includes a free radical photoinitiator. Typically, free radical photoinitiators include those that form radicals by either a Norrish Type I or Type II mechanism. Such mechanisms are well known in the art to which the present invention applies and are described, for example, in Parikh, A., Parikh, H., & Parikh, K. (2006). Norrish Type I and II Reaction (Cleavage). In Name Reactions in Organic Synthesis (pp. 325-329). Foundation Books. Such photoinitiators include those that form radicals by cleavage, known as "Norrish Type I," and those that form radicals by hydrogen abstraction, known as "Norrish Type II." Norrish Type II photoinitiators require a hydrogen donor to serve as a source of free radicals. Because initiation is based on a bimolecular reaction, Norrish Type II photoinitiators are generally slower than Norrish Type I photoinitiators, which are based on the unimolecular formation of radicals. On the other hand, Norrish Type II photoinitiators have better light absorption characteristics in the near-UV spectral region. Photolysis of aromatic ketones such as benzophenone, thioxanthone, benzil, and quinone in the presence of a hydrogen donor such as an alcohol, amine, or thiol results in the formation of a radical (ketyl radical) derived from the carbonyl compound and another radical derived from the hydrogen donor. Photopolymerization of vinyl monomers is usually initiated by the radical derived from the hydrogen donor. Ketyl radicals are usually not reactive with vinyl monomers due to steric hindrance and delocalization of the unpaired electron.

[0054] The present inventors have discovered that not all compounds suitable for use in promoting free radical polymerization, particularly for promoting the polymerization of radiation-curable compositions in additive manufacturing processes utilizing UV / vis light sources, can be characterized in either of the two categories described above. To the inventors' surprise, some photoinitiators are effective in promoting free radical polymerization (and potentially cationic polymerization) despite not utilizing the Norrish Type I or Type II mechanism. Specific examples of this include certain iodonium salts, preferably iodonium salts with non-fluorinated borate anions. As used herein, "non-fluorinated" means not containing fluorine atoms. In addition to being non-fluorinated, the anions of the iodonium salt compounds are preferably also non-halogenated. As used herein, "non-halogenated" means not containing any halogen atoms.

[0055]

[0054] To successfully formulate a liquid radiation-curable resin for additive manufacturing, it is, of course, necessary to review the wavelength sensitivity of the photoinitiator present in the resin composition to determine whether it will be activated by the radiation source selected to provide the curing light.

[0056] However, in embodiments, the composition has the following structure: [ka] wherein R1-R4 are independently selected from the group consisting of alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, and heteroaryl, and further wherein (i) one or more substitutable carbon atoms of the alkyl, alkenyl, or alkynyl are optionally substituted with hydroxy, carboxy, alkoxy, alkanoyl, hydroxyalkyl, carboxyalkyl, alkoxyalkyl, or alkanoylalkyl, or (ii) one or more substitutable carbon atoms of the cycloalkyl, heterocycloalkyl, aryl, or heteroaryl are optionally substituted with alkyl, hydroxy, carboxy, alkoxy, alkanoyl, hydroxyalkyl, carboxyalkyl, alkoxyalkyl, or alkanoylalkyl. of an iodonium salt photoinitiator.

[0057] In embodiments, R1-R4 are independently selected from aryl radicals optionally substituted at one or more substitutable carbon atoms with alkyl or alkoxy. More specifically, R1-R4 can be phenyl groups optionally and independently substituted with alkyl or alkoxy groups, where the alkyl portion of the alkyl or alkoxy group contains 1 to 10 carbon atoms.

[0058] In embodiments, the non-fluorinated borate anion of the iodonium salt has the following structure: [ka] It is a tetraphenylborate according to the formula:

[0059] The cation of the iodonium salt of the non-fluorinated borate anion described above can be of any suitable type. In embodiments, the iodonium salt has a diaryliodonium cation. In embodiments, the cation is a diphenyliodonium salt having two phenyl radicals optionally substituted with alkyl or alkoxy groups, where the alkyl portion of the alkyl or alkoxy group has 1 to 10 carbon atoms.

[0060] In embodiments, the photoinitiator has the following structure: [ka] The iodonium salt cations include one or both of the following:

[0061] In embodiments, the photoinitiator comprises bis 4-cumyl iodonium tetraphenylborate or bis 4-tert-butyl iodonium tetraphenylborate. Such compounds are commercially available from Hampford Research as FP5041 and FP5028, respectively.

[0062] The inventors have discovered that free radical and / or cationic polymerization can be maximized when a radiation-curable composition is exposed to an additive fabrication system utilizing a UV / optical light source when the photoinitiator comprises, consists of, or consists essentially of one or more of the above-described iodonium salt photoinitiators. The inventors have further surprisingly discovered that the further addition of other, more well-known free radical photoinitiators does not improve (and may even inhibit) polymerization efficacy. Thus, in embodiments, a composition according to the first aspect is substantially devoid of any Norrish Type I photoinitiator. In other embodiments, the composition is additionally or alternatively devoid of any Norrish Type II photoinitiator. In embodiments, the composition contains an amount by weight of Norrish Type I and / or Norrish Type II photoinitiators that is less than about 0.1 wt. %, or less than about 0.05 wt. %, or less than about 0.01 wt. %, or about 0.00 wt. %.

[0063]

[0063] According to an embodiment, the liquid radiation-curable resin for additive manufacturing includes at least one free radical photoinitiator, such as one selected from the group consisting of benzoylphosphine oxide, aryl ketones, benzophenones, hydroxylated ketones, 1-hydroxyphenyl ketones, ketals, metallocenes, and any combination thereof.

[0064]

[0064] Nevertheless, in some embodiments, the composition may have an additional free radical photoinitiator. In embodiments, the liquid radiation curable resin for additive manufacturing may further comprise, for example, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 2,4,6-trimethylbenzoylphenyl, ethoxyphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone-1,2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone, 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, 4-benzoyl-4′-methyldiphenyl sulfide, 4,4′-bis(diethylamino)benzophenone, and 4,4′-bis(N,N′-dimethylamino)benzophenone (Michler's ketone), benzophenone, 4 4,4'-bis(diethylamino)benzophenone, or benzil dimethyl ketal, bis(eta-5-2-4-cyclopentadien-1-yl)bis[2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl]titanium, and any combination thereof.

[0065] For light sources emitting in the wavelength range of 300 to 475 nm, particularly those emitting at 365 nm, 390 nm, or 395 nm, examples of potentially suitable free radical photoinitiators absorbing in this region include benzoylphosphine oxides, such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Lucirin TPO from BASF) and 2,4,6-trimethylbenzoylphenyl,ethoxyphosphine oxide (Lucirin TPO-L from BASF), bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (Irgacure 819 or BAPO from Ciba), 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone-1 (Irgacure 819 from Ciba), and 2,4,6-trimethylbenzoylphenyl,ethoxyphosphine oxide (Lucirin TPO-L from BASF). 907), 2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone (Irgacure 369 from Ciba), 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one (Irgacure 379 from Ciba), 4-benzoyl-4'-methyldiphenyl sulfide (Chivacure BMS from Chitec), 4,4'-bis(diethylamino)benzophenone (Chivacure EMK from Chitec), and 4,4'-bis(N,N'-dimethylamino)benzophenone (Michler's ketone). Mixtures thereof are also suitable.

[0066]

[0066] According to an embodiment of the present invention, the free radical photoinitiator may further comprise an acylphosphine oxide photoinitiator. Acylphosphine oxide photoinitiators are disclosed, for example, in U.S. Patent Nos. 4,324,744, 4,737,593, 5,942,290, 5,534,559, 6,020,528, 6,486,228, and 6,486,226. Acylphosphine oxide photoinitiators include bisacylphosphine oxide (BAPO) and monoacylphosphine oxide (MAPO). Generally, acylphosphine oxide photoinitiators are preferred for use with UV / vis optics because they have good delocalization of the phosphinoyl radical upon irradiation, but when iodonium salt photoinitiators of non-fluorinated borate anions are used, such phosphorus-containing photoinitiators are not necessarily required and may not promote cure very well or even at all. Thus, in embodiments, the composition is substantially devoid of free radical phosphorus-containing photoinitiators or contains less than about 0.1 wt.%, preferably less than about 0.05 wt.%, or preferably less than about 0.01 wt.%, or about 0.00 wt.% of free radical phosphorus-containing photoinitiators by weight.

[0067]

[0067] The liquid radiation-curable resin for additive manufacturing can include any suitable amount of the free radical photoinitiator described herein, for example, in certain embodiments, up to about 10 wt% of the resin composition, in certain embodiments, from about 0.1 to about 10 wt% of the resin composition, and in further embodiments, from about 1 to about 6 wt% of the resin composition.

[0068] According to some embodiments, the liquid radiation-curable resin composition includes a cationic photoinitiator. The cationic photoinitiator initiates cationic ring-opening polymerization upon irradiation with light. In preferred embodiments, the cationic photoinitiator comprises, consists of, or consists essentially of an iodonium salt-based cationic photoinitiator.

[0069]

[0069] In embodiments, any suitable iodonium-based cationic photoinitiator can be used, for example, those having a cation selected from the group consisting of diaryliodonium salts, triaryliodonium salts, aromatic iodonium salts, and any combination thereof.

[0070] In another embodiment, the cation of the cationic photoinitiator is selected from the group consisting of aromatic diazonium salts, aromatic sulfonium salts, aromatic iodonium salts, metallocene-based compounds, aromatic phosphonium salts, acylsulfonium salts, and any combination thereof. In another embodiment, the cation is a polymeric sulfonium salt, such as that described in U.S. Pat. No. 5,380,923 or U.S. Pat. No. 5,047,568, or other aromatic heteroatom-containing cations and naphthyl-sulfonium salts, such as those described in U.S. Pat. No. 7,611,817, U.S. Pat. No. 7,230,122, U.S. Patent Application Publication No. 2011 / 0039205, U.S. Patent Application Publication No. 2009 / 0182172, U.S. Pat. No. 7,678,528, EP 2,308,865, WO 2010,046,240, or EP 2,218,715. In another embodiment, the cationic photoinitiator is selected from the group consisting of triarylsulfonium salts, diaryliodonium salts, and metallocene-based compounds, and any combination thereof. Onium salts, such as iodonium and sulfonium salts, and ferrocenium salts, have the advantage of generally being more thermally stable.

[0071] In certain embodiments, the cationic photoinitiator is BF - , AsF6 - , SbF6 - , PF6 - , [B(CF3)4] - , B(C6F5)4 - , B[C6H3-3,5(CF3)2]4 - , B(C6H4CF3)4 - , B(C6H3F2)4 - , B[C6F4-4(CF3)]4 - , Ga(C6F5)4- , [(C6F5)3B-C3H3N2-B(C6F5)3] - , [(C6F5)3B-NH2-B(C6F5)3] - , tetrakis(3,5-difluoro-4-alkyloxyphenyl)borate, tetrakis(2,3,5,6-tetrafluoro-4-alkyloxyphenyl)borate, perfluoroalkyl sulfonate, tris[(perfluoroalkyl)sulfonyl]methide, bis[(perfluoroalkyl)sulfonyl]imide, perfluoroalkyl phosphate, tris(perfluoroalkyl)trifluorophosphate, bis(perfluoroalkyl)tetrafluorophosphate, tris(pentafluoroethyl)trifluorophosphate, and (CHB 11 Br6) - , (CH6B 11 Cl6) - and other halogenated carborane anions.

[0072]

[0072] Surveys on other onium salt initiators and / or metallocene salts can be found in "UV Curing, Science and Technology" (edited by S.P. Pappas, Technology Marketing Corp., 642 Westover Road, Stamford, Conn., USA), "Chemistry & Technology of UV & EB Formulation for Coatings, Inks & Paints", Vol. 3 (edited by P.K. Toldring), or J.P. Fouassier, J. Lavelee, "Photoinitiators for polymer synthesis" Wiley 2012 ISBN978-3-527-33210-6.

[0073] In embodiments, the cationic photoinitiator comprises at least SbF6 - , PF6 - , B(C6F5)4 - , [B(CF3)4] -, tetrakis(3,5-difluoro-4-methoxyphenyl)borate, perfluoroalkyl sulfonate, perfluoroalkyl phosphate, tris[(perfluoroalkyl)sulfonyl]methide, and [(C2F5)3PF3] - and a cation selected from the group consisting of aromatic sulfonium salts, aromatic iodonium salts, and metallocene-based compounds.

[0074] Examples of known cationic photoinitiators include 4-[4-(3-chlorobenzoyl)phenylthio]phenylbis(4-fluorophenyl)sulfonium hexafluoroantimonate, 4-[4-(3-chlorobenzoyl)phenylthio]phenylbis(4-fluorophenyl)sulfonium tetrakis(pentafluorophenyl)borate, 4-[4-(3-chlorobenzoyl)phenylthio]phenylbis(4-fluorophenyl)sulfonium tetrakis(3,5-difluoro-4-methyloxyphenyl)borate, 4-[4-(3-chlorobenzoyl)phenylthio]phenylbis(4-fluorophenyl)sulfonium tetrakis(2,3,5,6-tetrafluoro-4-methyloxyphenyl)borate, tris(4-(4-acetylphenyl)thiophenyl)sulfonium tetrakis(pentafluorophenyl)borate (Irgacure® PAG from BASF), 290), tris(4-(4-acetylphenyl)thiophenyl)sulfonium tris[(trifluoromethyl)sulfonyl]methide (Irgacure® GSID 26-1 from BASF), tris(4-(4-acetylphenyl)thiophenyl)sulfonium hexafluorophosphate (Irgacure® 270 from BASF), and HS-1 available from San-Apro Ltd.

[0075] Known cationic photoinitiators include bis[4-diphenylsulfonium phenyl]sulfide bishexafluoroantimonate; thiophenoxyphenylsulfonium hexafluoroantimonate (available as Chivacure 1176 from Chitec), tris(4-(4-acetylphenyl)thiophenyl)sulfonium tetrakis(pentafluorophenyl)borate (Irgacure® PAG 290 from BASF), tris(4-(4-acetylphenyl)thiophenyl)sulfonium tris[(trifluoromethyl)sulfonyl]methide (Irgacure® GSID 26-1 from BASF), and tris(4-(4-acetylphenyl)thiophenyl)sulfonium hexafluorophosphate (Irgacure® 270 from BASF), [4-(1-methylethyl)phenyl](4-methylphenyl)iodonium tetrakis(pentafluorophenyl)borate (Rhodorsil® from Rhodia). 2074), (4-octyloxyphenyl)phenyliodonium hexafluoroantimonate (available from Hampford as OPPI FP 5386), 4-[4-(2-chlorobenzoyl)phenylthio]phenylbis(4-fluorophenyl)sulfonium hexafluoroantimonate (available from Adeka as SP-172), SP-300 from Adeka, and (PF 6-m (C n F 2n+1 ) m ) - wherein m is an integer from 1 to 5, and n is an integer from 1 to 4 (available as monovalent sulfonium salts CPI-200K or CPI-200S from San-Apro Ltd., TK-1 available from San-Apro Ltd., or HS-1 available from San-Apro Ltd.), either alone or in admixture.

[0076] In an embodiment of the present invention, the liquid radiation-curable resin for additive manufacturing includes an aromatic triarylsulfonium salt cationic photoinitiator. The use of aromatic triarylsulfonium salts in additive manufacturing applications is known. See U.S. Patent Application Publication No. 20120251841 (DSM IP Assets, BV) and U.S. Patent No. 6,368,769 (Asahi Denki Kogyo), which discuss aromatic triarylsulfonium salts with tetraarylborate anions, including tetrakis(pentafluorophenyl)borate, and the use of such compounds in stereolithography applications. Triarylsulfonium salts are disclosed, for example, in J Photopolymer Science & Tech (2000), 13(1), 117-118 and J Poly Science, Part A (2008), 46(11), 3820-29. Complex metal halide anions, such as BF4, are also known. - , AsF6 - , PF6 - , and SbF6 - Triarylsulfonium salts Ar3S with + MXn - is disclosed in J Polymr Sci, Part A (1996), 34(16), 3231-3253.

[0077] An example of a triarylsulfonium tetrakis(pentafluorophenyl)borate cationic photoinitiator is tris(4-(4-acetylphenyl)thiophenyl)sulfonium tetrakis(pentafluorophenyl)borate, which is commercially known as IRGACURE® PAG-290 and is available from Ciba / BASF.

[0078] In another embodiment, the cationic photoinitiator is SbF - , PF6 - , BF4 - , (CF3CF2)3PF3 -, (C6F5)4B - , ((CF3)2C6H3)4B - , (C6F5)4Ga - , ((CF3)2C6H3)4Ga - , trifluoromethanesulfonate, nonafluorobutanesulfonate, methanesulfonate, butanesulfonate, benzenesulfonate, or p-toluenesulfonate. Such photoinitiators are described, for example, in U.S. Pat. No. 8,617,787.

[0079] Another cationic photoinitiator is an aromatic triarylsulfonium cationic photoinitiator having an anion that is a fluoroalkyl-substituted fluorophosphate. Commercially available examples of aromatic triarylsulfonium cationic photoinitiators having a fluoroalkyl-substituted fluorophosphate anion are the CPI-200 series (e.g., CPI-200K® or CPI-210S®) or 300 series available from San-Apro Limited.

[0080] The liquid radiation-curable resin composition can include any suitable amount of cationic photoinitiator, for example, in certain embodiments, up to about 15 wt. % of the resin composition, in certain embodiments, up to about 5 wt. % of the resin composition, in further embodiments, from about 2 wt. % to about 10 wt. % of the resin composition, and in other embodiments, from about 0.1 wt. % to about 5 wt. % of the resin composition. In further embodiments, the amount of cationic photoinitiator is from about 0.2 wt. % to about 4 wt. % of the total resin composition, and in other embodiments, from about 0.5 wt. % to about 3 wt. %.

[0081] [Photosensitizer] In some embodiments, depending on the wavelength of light used to cure the liquid radiation-curable resin, it may be desirable for the liquid radiation-curable resin composition to contain a photosensitizer. The term "photosensitizer" is used to refer to any substance that either increases the rate of photoinitiated polymerization or shifts the wavelength at which polymerization occurs. See the text by G. Odian, Principles of Polymerization, 3rd Edition, 1991, p. 222. Substances that operate by the latter definition and that are used in conjunction with photoinitiators that cannot otherwise absorb light of a particular wavelength are said to operate by an "indirect excitation" mechanism with their associated photoinitiators. Applicants have utilized this mechanism to formulate compositions of the present invention that are suitable for curing with UV / vis optics.

[0082]

[0082] A variety of compounds can be used as photosensitizers, including heterocyclic and fused-ring aromatic hydrocarbons, organic dyes, and aromatic ketones. Examples of photosensitizers include those selected from the group consisting of methanone, xanthenone, pyrenemethanol, anthracene, pyrene, perylene, quinone, xanthone, thioxanthone, benzoyl ester, benzophenone, and any combination thereof. Specific examples of photosensitizers include [4-[(4-methylphenyl)thio]phenyl]phenyl-methanone, isopropyl-9H-thioxanthen-9-one, 1-pyrenemethanol, 9-(hydroxymethyl)anthracene, 9,10-diethoxyanthracene, 9,10-dimethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutyloxyanthracene, 9-anthracenemethanol acetate, 2-ethyl-9,10-dimethoxyanthracene, 2-methyl-9,10-dimethoxyanthracene, 2-t-butyl-9,10- Dimethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene and 2-methyl-9,10-diethoxyanthracene, anthracene, anthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, thioxanthone and xanthone, isopropyl thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 1-chloro-4-propoxythioxanthone, methyl benzoyl formate (Darocur from BASF) MBF), methyl-2-benzoylbenzoate (Chivacure OMB from Chitec), 4-benzoyl-4'-methyldiphenyl sulfide (Chivacure BMS from Chitec), 4,4'-bis(diethylamino)benzophenone (Chivacure EMK from Chitec), and any combination thereof.

[0083]

[0083] The novel mixtures may also contain various photoinitiators with different sensitivities to radiation of emission lines of different wavelengths in order to obtain better utilization of UV light sources. The use of known photoinitiators with different sensitivities to radiation of emission lines is well known in the art of additive manufacturing and may be selected, for example, according to the radiation sources of 351 nm, 355 nm, 365 nm, 385 nm, and 405 nm. In this connection, it is advantageous to select the various photoinitiators and use them in such concentrations so that equal light absorption occurs with the emission lines used.

[0084] In embodiments, the photosensitizer is a fluorone, such as 5,7-diiodo-3-butoxy-6-fluorone, 5,7-diiodo-3-hydroxy-6-fluorone, 9-cyano-5,7-diiodo-3-hydroxy-6-fluorone, or the photosensitizer is [ka] , and any combination thereof.

[0085]

[0085] When a photosensitizer is used, other photoinitiators that absorb at shorter wavelengths can be used. Examples of such photoinitiators include benzophenones such as benzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, and dimethoxybenzophenone, as well as 1-hydroxyphenyl ketones such as 1-hydroxycyclohexylphenyl ketone, phenyl(1-hydroxyisopropyl)ketone, 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-1-propanone, and 4-isopropylphenyl(1-hydroxyisopropyl)ketone, benzil dimethyl ketal, and oligo-[2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone] (Esacure KIP 150 from Lamberti).

[0086] It may be noted that some cationic photoinitiators have low absorption at preferred actinic wavelengths. For example, in embodiments, target additive manufacturing applications utilize UV / optical systems with peak intensity at approximately 400 nm. For example, iodonium salts such as Rhodorsil 2074 available from Rhodia Silicones, Irgacure 250 iodonium, (4-methylphenyl) [4-(2-methylpropyl) phenyl]-hexafluorophosphate (1-) available from Ciba, and UV9380c available from GE Silicones have poor direct absorption at preferred wavelengths and therefore require excessive concentrations or sensitizers. Therefore, triplet sensitizers such as thioxanthone and Michler's ketone may be used to absorb actinic energy and then efficiently transfer that energy to the iodonium initiator. However, some thioxanthones and Michler's ketones tend to produce an orange or red color, raising safety concerns, and although they have significant actinic absorption at 430 nm, they are not very effective at sensitizing photoreaction at curing light wavelengths of about 400 nm.

[0087]

[0087] However, in embodiments, chloropropylthioxanthone (CPTX) is a suitable sensitizer for iodonium initiators, particularly for use in stereolithography, because it does not have significant light absorption above 500 nm and produces articles with little color.

[0088] To reduce the concentration of sensitizer used in the formulation and prevent adverse effects on the final physical properties of the composition that can result from relatively high concentrations of sensitizer, it is preferable to use a sensitizer with a high extinction coefficient at 400 nm. For example, benzophenone can act as a triplet sensitizer in some cases, but at the laser wavelength of, for example, a frequency-tripled YAG laser (Coherent AVIA model #355-1800) operating at approximately 355 nm, its extinction coefficient is on the order of 108 liters / mole cm. On the other hand, CPTX, at the same laser wavelength of approximately 400 nm and using the same laser, has an extinction coefficient of 2585 liters / mole cm, approximately X times that of benzophenone. This suggests that CPTX may require a concentration 1 / X lower in the formulation to provide equivalent light absorption. Thus, it is preferred, but not required, that the sensitizer have an extinction coefficient of 300 Liters / mole·cm or greater, for example, greater than 1000 Liters / mole·cm, preferably greater than 2000 Liters / mole·cm, at curing light wavelengths greater than 380 nm.

[0089] Although CPTX can be used to improve the activity of cationic photoinitiators, the sensitizers used in combination with the cationic photoinitiators described above are not necessarily limited to CPTX. Various compounds, including heterocyclic and fused-ring aromatic hydrocarbons, organic dyes, and aromatic ketones, can be used as photosensitizers. Examples of sensitizers include those disclosed by J. V. Crivello in Advances in Polymer Science, 62, 1 (1984), and J. V. Crivello & K. Dietliker, "Photoinitiators for Cationic Polymerization" in Chemistry & Technology of UV & EB Formulation for Coatings, Inks & Paints. Volume III, Photoinitiators for Free Radical and Cationic Polymerization by K. Dietliker; [P.K. Toldring, ed.], SITA Technology Ltd, London, 1991. Specific examples include polycyclic aromatic hydrocarbons and derivatives thereof, such as anthracene, pyrene, perylene and derivatives thereof, substituted thioxanthones, α-hydroxyalkylphenones, 4-benzoyl-4′-methyldiphenyl sulfide, acridine orange, and benzoflavin.

[0090] In an embodiment, the liquid radiation curable composition for additive manufacturing according to the first aspect of the present invention has the following structure: [ka] (Wherein, R is C1 to C 20 containing an aliphatic chain of The compound contains a photosensitizer having a structure according to

[0091] In embodiments, the photosensitizer used is an anthracene-based photoinitiator. Commercially available such photosensitizers include Anthracure, available from Kawasaki Chemical. TM Includes UVS-1101 and UVS-1331.

[0092] The photosensitizer is present in any suitable amount from about 0.5 wt.% to about 10 wt.%, more preferably from 0.5 wt.% to 3 wt.%.

[0093]

[0093] Liquid radiation-curable resins for additive manufacturing can include other cationic photoinitiators or photosensitizers in any suitable amount, for example, in certain embodiments, 0.1 to 10 wt% of the resin composition, in certain embodiments, about 1 to about 8 wt% of the resin composition, and in further embodiments, about 2 to about 6 wt% of the resin composition. In embodiments, the above ranges are particularly suitable for use with epoxy monomers. In another embodiment, the photosensitizer can be used in an amount of about 0.05 wt% to about 2 wt% of the total composition into which it is incorporated.

[0094] [Reducing agent] As used herein, a reducing agent is a component that loses, or "donates," one or more electrons to a cationic photoinitiator component in a redox chemical reaction during polymerization of a liquid radiation-based composition for additive manufacturing according to the present invention. Even if such components may not have the ability to readily donate electrons until they form free radicals or decompose into free radicals after dissociation, or otherwise become excited states upon exposure to UV / vis wavelength actinic radiation, they are still considered reducing agents for purposes of the present invention. Thus, they may alternatively be referred to herein as "activated reducing agents."

[0095] Photoinitiated cationic polymerization of monomers such as epoxides and vinyl ethers plays a necessary role in hybrid-cure additive manufacturing applications. Because of the additive use in various applications, wavelength flexibility of photoinitiation becomes a fundamental factor in determining the cure performance of a particular formulation when targeting specific spectral sensitivity. Therefore, photoinitiating systems for cationic polymerization that are sensitive to longer wavelengths, such as those emitted by modern UV / vis optics, are becoming increasingly important. Many existing photoinitiating systems for cationic polymerization are based on the use of specific onium salts, such as diphenyliodonium, triphenylsulfonium, and alkoxypyridinium salts. However, these salts do not absorb significantly (if at all) in the UV / vis spectrum unless additional chromophores are incorporated into the salt structure. Therefore, finding alternative methods to synthetically extend the sensitivity range of readily available onium salts to UV / vis wavelengths is important, especially in light of the fact that commercially available photoinitiators already designed to absorb in the UV / vis spectrum are unsuitable for incorporation into hybrid-cure systems for additive manufacturing for other reasons.

[0096] This is known to be achieved using a combination of sensitizers through a mechanism called indirect excitation. Furthermore, onium salts act as electron acceptors in redox reactions involving free radicals, electron donor compounds in charge-transfer complexes, and long-lived electronically excited states of the sensitizer, respectively. Among these approaches, so-called "free-radical-promoted" cationic polymerization appears to be a more effective and flexible method for generating cationic species capable of initiating the cationic polymerization of monomers. The overall mechanism involves the oxidation of photochemically formed radicals by onium salts (On+) with an appropriate reduction potential: R·+ON+ → R+ (1)

[0097] Latent reducing agents said to promote free-radical promoted cationic polymerization generally include some of the free-radical photoinitiators mentioned above, such as acylphosphine oxides, along with amines, benzoin and its derivatives, o-phataldehyde, polysilanes, and compounds having electron-donating substituents attached to the vinyl group, such as vinyl ethers or vinyl halides, to name a few.

[0098] Amines are believed to be efficient hydrogen donors and will readily form free radicals capable of reducing associated cationic photoinitiators by a chain transfer mechanism. Therefore, in certain embodiments, they can act as suitable reducing agents. However, care must be taken when including such compounds in hybrid radiation-curable compositions for additive manufacturing, as the nitrogen atoms they contain are known to tend to inhibit cationic polymerization reactions in other ways.

[0099] Several systems exist for generating oxidizing radicals in the presence of a UV / vis light source. For example, radicals formed by irradiation of a system containing a xanthene dye and an aromatic amine can serve as reducing agents for diphenyliodonium salts. Similarly, decacarbonyldimanganese-organohalide combinations, when used with onium salts, are efficient reducing agents for cationic polymerization at UV / vis wavelengths. Furthermore, commercially available titanocene-type photoinitiators, such as Irgacure 784, can be used as a source of reducing agent generated by irradiation with visible light.

[0100] Preferably, the reducing agent comprises, consists of, or consists essentially of a component having an electron-donating substituent attached to a vinyl group. Such a component can further provide a mechanism for improving cationic curing of liquid radiation-curable compositions for additive modeling systems using UV / vis optics. Such compounds, such as vinyl ethers, are avoided in many modern commercially available hybrid curable compositions exposed to additive modeling systems using traditional UV-based radiation sources due to (1) their tendency to generate excessive heat due to their rapid exothermic polymerization; and (2) their tendency to induce copolymerization and concomitant non-uniform polymers, thereby resulting in three-dimensional parts with inconsistent and poor physical properties. Nevertheless, their inclusion in compositions tailored for systems utilizing lower-energy / intensity UV / vis optics becomes desirable when used with other required components according to the present invention. Specifically, the inclusion of an additional component having an electron-donating substituent attached to a vinyl group synergistically improves polymerization.

[0101]

[0101] One preferred example of a component having an electron-donating substituent attached to a vinyl group is a vinyl ether. Vinyl ethers can be formed from a variety of starting materials, such as ethers, esters, or biscarbamates, or vinyl ether-terminated (poly)urethanes or carbonates. Some non-limiting examples of each include the following:

[0102] Vinyl ether monomers from ethers: Specific examples of polyfunctional vinyl ethers include divinyl ethers such as ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, isobutyl vinyl ether, butylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, cyclohexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, and bisphenol F alkylene oxide divinyl ether; and polyfunctional vinyl ethers such as trimethylolethane trivinyl ether, trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, glycerol trivinyl ether, pentaerythritol tetravinyl ether, and pentaerythritol divinyl ether. Examples of the vinyl vinyl ether include dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, ethylene oxide addition products of trimethylolpropane trivinyl ether, propylene oxide addition products of trimethylolpropane trivinyl ether, ethylene oxide addition products of ditrimethylolpropane tetravinyl ether, propylene oxide addition products of ditrimethylolpropane tetravinyl ether, ethylene oxide addition products of pentaerythritol tetravinyl ether, propylene oxide addition products of pentaerythritol tetravinyl ether, ethylene oxide addition products of dipentaerythritol hexavinyl ether, and propylene oxide addition products of dipentaerythritol hexavinyl ether.

[0103] Vinyl ether monomers from esters or biscarbamates: specific examples of polyfunctional vinyl ethers such as divinyl adipate, divinyl terephthalate, divinylcyclohexyl dicaroxylate, bis[4-(vinyloxy)butyl]adipate (VEctomer® 4060), bis[4-(vinyloxy)butyl]succinate (VEctomer® 4030), bis[4-(vinyloxy)butyl]isophthalte (VEctomer® 4010), bis[4-(vinyloxymethyl)cyclohexylmethyl]glutarate (VEctomer® 4020), tris[4-(vinyloxy)butyl] butyl]trimellitate (VEctomer® 5015), bis[4-(vinyloxymethyl)cyclohexylmethyl]isophthalate (VEctomer® 4040), bis[4-(vinyloxy)butyl](4-methyl-1,3-phenylene)biscarbamate (VEctomer® 4220), and bis[4-(vinyloxy)butyl](methylenedi-4,1-phenylene)biscarbamate (VEctomer® 4210).

[0104]

[0104] Vinyl ether-terminated urethane or carbonate: Specific examples of polyfunctional vinyl ethers, such as polyurethanes or polycarbonates end-capped with hydroxyvinyl ethers having at least a hydroxyl group and at least a vinyl ether group in the molecule, such as 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxyisopropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 2-hydroxybutyl vinyl ether, 3-hydroxyisobutyl vinyl ether, 2-hydroxyisobutyl vinyl ether, 1-methyl-3-hydroxypropyl vinyl ether, 1-methyl-2-hydroxypropyl vinyl ether, 1-hydroxymethylpropyl vinyl ether, 4-hydroxycyclohexyl vinyl ether, 1,6-hexanediol monovinyl ether, 1,4-cyclohexanedimethanol monovinyl ether, 1,3-cyclohexanedimethanol monovinyl ether, 1,2-cyclohexane Dimethanol monovinyl ether, p-xylene glycol monovinyl ether, m-xylene glycol monovinyl ether, o-xylene glycol monovinyl ether, diethylene glycol monovinyl ether, triethylene glycol monovinyl ether, tetraethylene glycol monovinyl ether, pentaethylene glycol monovinyl ether, oligoethylene glycol monovinyl ether, polyethylene glycol monovinyl ether, dipropylene glycol monovinyl ether, tripropylene glycol monovinyl ether, tetrapropylene glycol monovinyl ether, derivatives thereof, for example, pentapropylene glycol monovinyl ether, oligopropylene glycol monovinyl ether, and polypropylene glycol monovinyl ether.

[0105] In preferred embodiments, the component having an electron-donating substituent attached to the vinyl group is one or more of the following: vinyl ether, vinyl ester, vinyl thioether, n-vinyl carbazole, n-vinyl pyrrolidone, n-vinyl caprolactam, allyl ether, and vinyl carbonate.

[0106] In another preferred embodiment, the component having an electron-donating substituent attached to a vinyl group is polyfunctional. As used herein, "polyfunctional" means that the vinyl ether has at least two vinyl groups per molecule.

[0107]

[0107] One or more of the above-described components having an electron-donating substituent attached to a vinyl group can be used in the compositions of the present invention in any suitable amount, selected alone or in combination from one or more of the types listed herein. In a preferred embodiment, the component having an electron-donating substituent attached to a vinyl group is present in an amount of from about 1 wt.% to about 25 wt.%, more preferably from about 5 wt.% to about 20 wt.%, and more preferably from about 5 wt.% to about 12 wt.%, based on the total weight of the composition. In another embodiment, the component having an electron-donating substituent attached to a vinyl group is present in an amount of from 1 wt.% to 15 wt.%, more preferably from 1 wt.% to 10 wt.%, and more preferably from 3 wt.% to about 8 wt.%.

[0108] [Additives] Stabilizers are often added to resin compositions to further prevent viscosity increase, for example, during use in solid imaging processes. Useful stabilizers include those described in U.S. Pat. No. 5,665,792. The presence of a stabilizer is optional. In a specific embodiment, the liquid radiation-curable resin composition for additive manufacturing includes 0.1 wt % to 3% of a stabilizer.

[0109] Other possible additives include organic and inorganic fillers, dyes, pigments, antioxidants, wetting agents, cell collapsers, chain transfer agents, leveling agents, defoamers, surfactants, etc. Such additives are known and, as will be appreciated by those skilled in the art, can generally be used as desired for a particular application.

[0110]

[0110] The liquid radiation-curable resin composition for additive manufacturing of the present invention may further contain one or more additives selected from the group consisting of bubble disintegrators, antioxidants, surfactants, acid scavengers, pigments, dyes, thickeners, flame retardants, silane coupling agents, ultraviolet absorbers, resin particles, core-shell particle impact modifiers, soluble polymers, and block polymers.

[0111] Furthermore, many known liquid radiation-curable resin compositions for additive manufacturing use hydroxy-functional compounds to improve the properties of parts produced from the resin composition. If present, any hydroxy group can be used for specific purposes. If present, the hydroxyl-containing material preferably contains one or more primary or secondary aliphatic hydroxyls. The hydroxyl groups can be internal or terminal. Monomers, oligomers, or polymers can be used. The hydroxyl equivalent weight, i.e., the number average molecular weight divided by the number of hydroxyl groups, preferably ranges from 31 to 5,000. If present, the resin composition preferably contains at most 10 wt %, more preferably at most 5 wt %, and most preferably at most 2 wt %, of one or more non-free-radically polymerizable hydroxy-functional compounds, based on the total weight of the resin composition.

[0112] A second aspect of the invention as claimed is a method of forming a three-dimensional article by an additive fabrication system utilizing UV / vis optics, the method comprising: (1) providing a liquid radiation curable composition for additive manufacturing according to the first aspect of the present invention; (2) depositing a first liquid layer of a liquid radiation curable resin; (3) exposing the first liquid layer to actinic radiation in an imagewise manner with a UV / vis optical arrangement to form an imaged cross section, thereby forming a first cured layer; (4) forming a new layer of liquid radiation curable resin in contact with the first cured layer; (5) exposing the new layer to actinic radiation in an imagewise manner to form additional imaged cross sections; (6) repeating steps (4) and (5) a sufficient number of times to construct a three-dimensional article. wherein the UV / vis optics emits radiation with a peak spectral intensity from about 375 nm to about 500 nm, more preferably from about 380 nm to about 450 nm, more preferably from about 390 nm to about 425 nm, more preferably from about 395 nm to about 410 nm.

[0113] The liquid radiation-curable composition provided in the second aspect of the present invention described above should be suitable for curing by an additive manufacturing system utilizing UV / vis optics. Such compositions are described in the first aspect of the present invention. In depositing the first liquid layer or forming a new layer of liquid radiation-curable resin, the layer may be of any suitable thickness and shape, depending on the additive manufacturing process being utilized. For example, the layer may be selectively dispensed by jetting, or may be added by dipping an already cured layer into a vat of resin to produce a layer of substantially uniform thickness, as is typical in most stereolithography processes. In another non-limiting embodiment, the layer may alternatively be transferred by a foil, film, or carrier of a predetermined thickness using a cartridge or dispenser.

[0114]

[0114] In the above, "exposure" refers to irradiation with actinic radiation. As already mentioned, the liquid radiation compositions for additive manufacturing of the present invention described herein are particularly suitable for providing hybrid cure with UV / vis optics. In embodiments, the UV / vis optics utilize one or more LEDs as the light source. In embodiments, the light source is a laser. In embodiments, the LED or laser light source is coupled to a DLP or LCD image projection system. In embodiments where the image projection system includes an LCD display, the light source may be configured to emit actinic radiation exclusively above 400 nm to minimize the deleterious effects that UV wavelengths have on the LCD components.

[0115]

[0115] A third aspect of the claimed invention is a three-dimensional part formed according to the second aspect of the invention using the liquid radiation curable composition of the first aspect of the invention.

[0116] The following examples further illustrate the present invention but, of course, should not be construed as in any way limiting its scope.

[0117] [Example] These examples illustrate embodiments of the liquid radiation curable resin for additive manufacturing of the present invention. Table 1 lists the various components of the liquid radiation curable resin for additive manufacturing used in the examples.

[0118] [Table 1]

[0119] [Test method]

[0118] Real-time Fourier transform infrared (FTIR) spectroscopy was used to measure the polymerization rate (cure rate) of each example. A cadmium mercury telluride (MCT) detector was used to increase data acquisition frequency and resolution. An attenuated total reflectance (ATR) setting was used instead of transmission mode. All polymerization rate measurements were carried out using a Thermo Scientific Nicolet 8700 model. The following table shows the experimental conditions set for the measurements. Under these conditions, a total of 41 spectra were acquired for 200 seconds for each measurement.

[0120] [Table 2]

[0121] For UV / Vis light control, a Digital Light Lab LED spot lamp (wavelength 385 nm, intensity 5 mW) and controller (AccuCure Photo Rheometer) were used. Calibration continuous mode was selected. Light intensity and duration (exposure time) were selected before measurement.

[0122] Two to three drops of the selected sample for measurement were placed in the center of the ATR crystal setup. Next, a 3 mil (±0.4 mil) drawdown bird bar was used to coat the top of the ATR crystal with an approximately 3 mil film (±0.4 mil). Immediately after applying the 3 mil coating, an LED lamp was held on top of the ATR setup, with the hole positioned in the center of the holder. Next, a real-time FTIR scan was initiated. Once one spectrum was obtained, the light source was turned on to initiate polymerization. Based on the program entered above, each spectrum was acquired every 5 seconds for a total of 200 seconds. A total of 41 spectra were acquired for each experiment.

[0123]

[0121] The polymerization conversion rate versus time was calculated based on the specific IR peak changes representing each functional group. Examples of IR peak changes are shown in the diagram above. To calculate the conversion rate of each relevant functional group, the peak height or peak area was calculated according to the following table, as appropriate:

[0124] [Table 3]

[0125] For the raw data obtained, it was important to remove the first one or two data points because the experimental cure rate procedure has an unknown short time lag between turning on the FTIR detector and turning on the light source used to cure the sample. To account for any uncertainty associated with the amount of statistical noise introduced by these preliminary data points, three sets of curve fits were generated for each data set. In each case, the model equation to which the data sets were fitted was Conv = a(1 - e(- b * (time-c))). For this, the raw data were fitted using Microsoft Excel version 14.0.7116.5000 (32-bit) with the addition of data analysis.

[0126] In the first case, the entire data set (including the first two data points) was fitted. In the second case, the entire data set minus the first data point was fitted. In the third case, the entire data set minus the first and second data points was fitted. In both cases, the curve fit coefficient r 2 The curve fit combination with the first data point greater than 1% conversion and an r greater than 0.90 was created. 2 The data set resulting in the curve fit equation was used for further calculation of the cure rate at 95% of the plateau conversion. 2 If the σ was less than 0.90, the data were rerun again.

[0127] As discussed above, the data is calculated using the equation Conv = a(1-e(-b * The fit was made to (time-c)), where "Conv" is the percent conversion as measured by FTIR peak ratio, time is the duration of exposure, "a" is the plateau conversion, "b" is the resulting cure rate coefficient used to calculate the cure rate, and "c" is the resulting cure induction time. Once the data was fitted, the software created an experimentally derived equation with the numerical parameters "a," "b," and "c" determined from the experimental data and the fit. For cationically curable materials (i.e., epoxies and oxetanes), "c" is meaningless since there is no cure induction time. Therefore, in these cases, "c" was ignored. The variable "a" is used as the plateau conversion under the cure conditions used and represents the entire asymptotic range over which the components are converted. The variable "b" is used in the equation T 95 = ln(.05 / b) to obtain the 95% plateau conversion of "a" (T 95 ) was used to calculate the time to conversion. Reported below in Table 3 are the calculated conversions at 100 seconds for three different polymerizable components (epoxy, oxetane, and acrylate).

[0128] [Examples 1 to 13]

[0125] First, the base resins for additive manufacturing were prepared by combining the oxetane component, cycloaliphatic epoxide component, polyol component, glycidyl ether epoxide component, and acrylate component according to methods well known in the art. Details of the so-called "control package" are provided in Table 2 below. The complete compositions of Formulations 1-13, along with conversion test results using a 5 mW, 385 nm UV / vis light source, are provided in Table 3.

[0129] [Table 4]

[0130] [Table 5]

[0131] [Discussion of results] The data in Table 3 demonstrate the suitability of various embodiments according to the present invention for promoting hybrid cure under UV / vis exposure conditions. In particular, when comparing Formulation 1 with Formulations 10-12, the addition of Norrish Type I or Type II photoinitiators did not significantly improve cure performance. In fact, the presence of phosphine-containing photoinitiators (BAPO and TPO; see Examples 10-11) actually reduced cure performance.

[0132] Additional Exemplary Embodiments A first additional exemplary embodiment is: a. A first photoacid generator having an iodonium salt cation and a borate-containing anion lacking a fluorine atom, preferably wherein the cation has the following structure: [ka] (bis-4-cumyl iodonium tetraphenylborate; CAS 1158840-74-4), or [ka] (Bis(4-tert-butylphenyl)iodonium tetraphenylborate CAS131725-16-1) and preferably the cation has one of the following structures: [ka] a first photoacid generator having the formula: b. a second photoacid generator, preferably an iodonium salt; c. an electron donating substituent attached to the vinyl group, such as a vinyl ether; d. optionally, a photosensitizer; e. a polymerizable component; f. optionally, an additive component including one or more stabilizers; wherein the composition is preferably substantially devoid of free radical photoinitiators having phosphorus atoms, or substantially devoid of Norrish Type I photoinitiators, or substantially devoid of Norrish Type II photoinitiators.

[0133]

[0128] A first aspect of a second additional exemplary embodiment is a radiation-curable composition comprising a free radically polymerizable component, a cationically polymerizable component, a free radical photoinitiator component, and a cationic photoinitiator component, wherein the free radical photoinitiator component is substantially devoid of Norrish Type I photoinitiator or contains less than 0.1 wt.%, or less than 0.05 wt.%, or less than 0.01 wt.% Norrish Type I photoinitiator.

[0134]

[0129] Another aspect of the second additional exemplary embodiment is a radiation-curable composition according to the first aspect of the second additional exemplary embodiment, wherein the free-radical photoinitiator component is substantially devoid of Norrish Type II photoinitiators or contains less than 0.1 wt.%, or less than 0.05 wt.%, or less than 0.01 wt.% Norrish Type II photoinitiators.

[0135]

[0130] Another aspect of the second additional exemplary embodiment is a radiation-curable composition according to any of the previous aspects of the second additional exemplary embodiment, wherein the composition is substantially devoid of Norrish Type I photoinitiators or contains less than 0.1 wt.%, or less than 0.05 wt.%, or less than 0.01 wt.% Norrish Type I photoinitiators.

[0136]

[0131] Another aspect of the second additional exemplary embodiment is a radiation-curable composition according to any of the previous aspects of the second additional exemplary embodiment, wherein the free-radical photoinitiator component comprises, consists essentially of, or consists of one or more iodonium salt-based photoinitiators.

[0137]

[0132] Another aspect of the second additional exemplary embodiment is a radiation-curable composition according to the previous aspect of the second additional exemplary embodiment, wherein the iodonium salt-based photoinitiator includes a borate-containing anion.

[0138]

[0133] Another aspect of the second additional exemplary embodiment is a radiation-curable composition according to either of the previous two aspects of the second additional exemplary embodiment, wherein the iodonium salt-based photoinitiator includes a tetraphenylborate anion.

[0139]

[0134] Another aspect of the second additional exemplary embodiment is a radiation-curable composition according to any of the previous aspects of the second additional exemplary embodiment, wherein the cationic photoinitiator component comprises, consists of, or consists essentially of one or more iodonium salt-based cationic photoinitiators.

[0140]

[0135] Another aspect of the second additional exemplary embodiment is a radiation-curable composition according to any of the previous aspects of the second additional exemplary embodiment, wherein the free-radically polymerizable component comprises, consists of, or consists essentially of one or more (meth)acrylate-functional compounds.

[0141]

[0136] Another aspect of the second additional exemplary embodiment is a radiation-curable composition according to any of the previous aspects of the second additional exemplary embodiment, wherein the cationically polymerizable component comprises, consists of, or consists essentially of one or more epoxy- and / or oxetane-functional compounds.

[0142]

[0137] Another aspect of the second additional exemplary embodiment is a radiation-curable composition according to any of the previous aspects of the second additional exemplary embodiment, wherein the cationically polymerizable component comprises, consists of, or consists essentially of one or more cycloaliphatic epoxides, glycidyl ether epoxides, and / or oxetanes.

[0143]

[0138] Another aspect of the second additional exemplary embodiment is a radiation-curable composition according to any of the previous aspects of the second additional exemplary embodiment, further comprising a photosensitizer.

[0144]

[0139] Another aspect of the second additional exemplary embodiment is a radiation-curable composition according to any of the previous aspects of the second additional exemplary embodiment, further comprising a multifunctional vinyl ether compound.

[0145]

[0140] Another aspect of the second additional exemplary embodiment is a radiation-curable composition according to the previous aspect of the second additional exemplary embodiment, wherein the multifunctional vinyl ether compound has at least two vinyl groups.

[0146]

[0141] Another aspect of the second additional exemplary embodiment is a radiation curable composition according to any of the previous aspects of the second additional exemplary embodiment, further comprising one or more additives.

[0147] Another aspect of the second additional exemplary embodiment is a radiation-curable composition according to any of the previous aspects of the second additional exemplary embodiment, wherein, by weight of the total composition: the free radically polymerizable component is present at 5 wt.% to 50 wt.%; The cationically polymerizable component is present at 20 wt.% to 90 wt.%; the free radical photoinitiator component is present at 0.025 wt.% to 5 wt.%; The cationic photoinitiator component is present at 0.5 to 8 wt. %; The additive is present at 0-40 wt.% The weights of all ingredients equal 100%.

[0148]

[0143] Unless otherwise specified, the term wt. % refers to the amount by weight of a particular component relative to the total radiation-curable liquid composition for additive manufacturing into which that component is incorporated.

[0149]

[0144] In the context of describing the present invention (particularly in the context of the claims which follow), the use of the terms "a," "an," and "the," and similar referents, should be construed to encompass both the singular and the plural, unless otherwise stated herein or otherwise clearly contradicted by context. The terms "comprising," "having," "including," and "containing" should be construed as open-ended terms (i.e., meaning "including, but not limited to"), unless otherwise stated. The recitation of ranges of values ​​herein, unless otherwise stated herein, is intended to serve merely as a shorthand method of referring individually to each separate value falling within that range, and each separate value is incorporated herein as if it were individually set forth herein. All methods described herein can be performed in any suitable order, unless otherwise stated herein or otherwise clearly contradicted by context. The use of any and all examples or exemplary language (e.g., "such as") provided herein is intended merely to better clarify the invention and does not impose a limitation on the scope of the invention unless otherwise claimed. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the invention.

[0150] Preferred embodiments of this invention are described herein, including the best mode known to the inventors for carrying out the invention. Variations of these preferred embodiments will become apparent to those skilled in the art upon reading the foregoing description. The inventors anticipate that skilled artisans will employ such variations as appropriate, and the inventors intend that the invention be practiced otherwise than as specifically described herein. Accordingly, this invention includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is encompassed by the invention unless otherwise described herein or otherwise clearly contradicted by context.

[0151]

[0146] Although the present invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to those skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope of the invention as claimed.

Claims

1. 1. A radiation-curable composition comprising a cationically curable component and a free-radically curable component, the composition further comprising at least a first photoinitiator that is an iodonium salt of a non-fluorinated borate anion.

2. 2. The radiation curable composition of claim 1, wherein the iodonium salt of a non-fluorinated borate anion is an iodonium salt of a non-halogenated borate anion.

3. The non-fluorinated borate anion of the iodonium salt has the formula: 【Chemical 1】 (In the formula, R １ ~R ４ are independently selected from the group consisting of alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, and heteroaryl, and further wherein (i) one or more substitutable carbon atoms of said alkyl, alkenyl, or alkynyl are optionally substituted with hydroxy, carboxy, alkoxy, alkanoyl, hydroxyalkyl, carboxyalkyl, alkoxyalkyl, or alkanoylalkyl, or (ii) one or more substitutable carbon atoms of said cycloalkyl, heterocycloalkyl, aryl, or heteroaryl are optionally substituted with alkyl, hydroxy, carboxy, alkoxy, alkanoyl, hydroxyalkyl, carboxyalkyl, alkoxyalkyl, or alkanoylalkyl.

10. The radiation curable composition of claim 1, having

4. R １ ~R ４ 4. The radiation curable composition of claim 3, wherein is independently selected from aryl radicals optionally substituted at one or more substitutable carbon atoms with alkyl or alkoxy.

5. R １ ~R ４ 5. The radiation curable composition of claim 4, wherein each is phenyl optionally independently substituted with alkyl or alkoxy, the alkyl portion of said alkyl or alkoxy having 1 to 10 carbon atoms.

6. The non-fluorinated borate anion of the iodonium salt has the formula: 【Chemistry 2】 6. The radiation curable composition of claim 5, wherein the anion is a tetraphenylborate anion having the formula:

7. The radiation curable composition of any one of claims 1 to 6, wherein the iodonium salt of a non-fluorinated borate anion has a diaryliodonium cation.

8. 8. The radiation-curable composition of claim 7, wherein the diaryliodonium cation of the iodonium salt is a diphenyliodonium salt having two phenyl radicals optionally substituted with alkyl or alkoxy, the alkyl moiety of the alkyl or alkoxy having 1 to 10 carbon atoms.

9. The diphenyliodonium cation of the iodonium salt has the structure: 【Chemistry 3】 9. The radiation-curable composition according to claim 8, wherein the iodonium cation is a bis-4-cumyl iodonium cation or a bis-4-tert-butyl iodonium cation having the formula:

10. The radiation curable composition of any one of claims 1 to 9, wherein the first photoinitiator is bis 4-cumyl iodonium tetraphenylborate or bis 4-tert-butyl iodonium tetraphenylborate.

11. 11. The radiation curable composition of any one of claims 1 to 10, wherein the composition is substantially devoid of free radical phosphorus-containing photoinitiators or contains free radical phosphorus-containing photoinitiators in an amount by weight of less than about 0.1 wt.%, preferably less than about 0.05 wt.%, or preferably less than about 0.01 wt.%, or about 0.00 wt.%.

12. 12. The radiation curable composition of any one of claims 1 to 11, wherein the composition is substantially devoid of Norrish Type I and / or Norrish Type II photoinitiators, or contains Norrish Type I and / or Norrish Type II photoinitiators in an amount by weight of less than about 0.1 wt%, or less than about 0.05 wt%, or less than about 0.01 wt%, or about 0.00 wt%.

13. The radiation curable composition of any one of claims 1 to 12, wherein the cationically curable component comprises both a cycloaliphatic epoxy compound and an oxetane compound.

14. The composition has a peak spectral output between 375 and 405 nm and a peak spectral output of 2 mW / cm ２ 14. The radiation curable composition of claim 13, wherein the cycloaliphatic epoxy compound achieves at least about 35%, or at least about 40%, or at least about 45% conversion, and the oxetane compound achieves at least about 40%, or at least about 45%, or at least about 50% conversion, when exposed for 10 seconds to UV / vis optics emitting radiation having an irradiance at the surface of the composition of

15. The radiation curable composition of any one of claims 1 to 14, wherein the first photoinitiator is present in the composition in an amount of from about 0.1 wt % to about 1 wt %.

16. 16. The radiation curable composition of any one of claims 1 to 15, further comprising a second iodonium salt cationic photoinitiator, wherein the second iodonium salt cationic photoinitiator is present in the composition in an amount of from about 0.5 wt % to about 8 wt %.

17. The radiation curable composition of any one of claims 1 to 16, further comprising a photosensitizer.

18. 18. The radiation curable composition of any one of claims 1 to 17, further comprising a reducing agent, said reducing agent having an electron donating substituent attached to the vinyl group.

19. 20. The radiation curable composition of claim 18, wherein the reducing agent comprises, consists of, or consists essentially of a vinyl ether compound, preferably wherein the vinyl ether compound has at least two vinyl groups.

20. 20. The radiation curable composition of any one of claims 17 to 19, wherein the photosensitizer is present in the composition in an amount by weight of about 0.05 to about 0.8 wt %, and the reducing agent is present in the composition in an amount by weight of about 1 wt % to about 10 wt %.

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