Actinically curable compositions and methods for manufacturing thermoformed products thereof

Abstract

A photoactuable curable composition comprising: a polymerizable resin comprising one or more polymerizable components; about 2 wt% to about 20 wt% of a non-polymerizable silicon-based additive based on the total weight of the polymerizable components; optionally, less than 10 wt% of a reactive additive based on the total weight of the non-polymerizable silicon-based additive; and a photoinitiator. A method of manufacturing a three-dimensional (3D) printed object comprising curing the photoactuable curable composition in a 3D printing process to form the 3D printed object. A method of manufacturing a thermoformed product comprising: heating a thermoplastic material to provide a plastic thermoplastic material; pressing the plastic thermoplastic material against a mold comprising a 3D printed object formed from a photoactuable curable composition.

Description

Technical Field

[0001] This disclosure relates to curable chemical compositions. Specifically, this disclosure relates to an actinically-curable composition that can be used in 3D printing applications. Background Technology

[0002] Plastic articles can be produced using thermoforming processes. In thermoforming, plastic is heated to a pliable molding temperature and then molded into the desired shape through a mold. The plastic can be cooled to form a thermoformed plastic article, which is then demolded from the mold. However, removing the thermoformed plastic article from the mold can be difficult. If removing the thermoformed plastic article from the mold is too difficult, it may warp, crack, deform, or otherwise be damaged by the force required to remove it. The mold may also be damaged, which is also undesirable. Therefore, there is a need for materials used to manufacture molds used in thermoforming processes that have improved demolding properties. Summary of the Invention

[0003] Embodiments of this disclosure address this need by providing photocurable compositions comprising non-polymerizable silicon-based additives. These photocurable compositions can be used in 3D printing processes to form 3D printed articles. These 3D printed articles can be used as molds in thermoforming processes. The inclusion of non-polymerizable silicon-based additives in the photocurable compositions yields 3D printed articles with low surface energy and minimal surface texture. These characteristics improve the demolding performance of the 3D printed articles when used as molds in thermoforming processes. Improved demolding performance reduces the force required to separate the thermoformed plastic article from the mold, lowering the likelihood of damage to both the thermoformed article and the mold when removing it from the mold.

[0004] According to one or more embodiments described herein, a photocurable composition comprises: a polymerizable resin containing one or more polymerizable components, about 2% to about 20% by weight of a nonpolymerizable silicone-based additive based on the total weight of the polymerizable components, optionally less than 10% by weight of a reactive additive based on the total weight of the nonpolymerizable silicone-based additive, and a photoinitiator.

[0005] According to one or more embodiments described herein, a photocurable composition comprises: a polymerizable resin containing one or more polymerizable components; at least about 4.5% by weight, preferably at least about 5% by weight, at least about 5.5% by weight, most preferably at least about 6% by weight to about 20% by weight of a nonpolymerizable silicone-based additive, based on the total weight of the polymerizable components, wherein the nonpolymerizable silicone-based additive is free of any urethane groups; optionally, less than 10% by weight of a reactive additive based on the total weight of the nonpolymerizable silicone-based additive; and a photoinitiator, wherein the composition is substantially solvent-free.

[0006] According to one or more embodiments described herein, a photocurable composition comprises: a polymerizable resin containing one or more polymerizable components; at least about 8.5% by weight, preferably at least about 9% by weight, more preferably at least about 9.5% by weight, and most preferably at least about 10% by weight to about 20% by weight of the total polymerizable components, wherein the non-polymerizable silicone-based additive is free of any urethane groups; optionally, less than 10% by weight of a reactive additive based on the total weight of the non-polymerizable silicone-based additive; and a photoinitiator.

[0007] According to one or more embodiments described herein, a method for manufacturing a three-dimensional (3D) printed object includes curing a photocurable composition in a 3D printing process to form the 3D printed object. The photocurable composition may comprise: a polymerizable resin containing one or more polymerizable components; about 2% to about 20% by weight of a nonpolymerizable silicone-based additive based on the total weight of the polymerizable components; and a photoinitiator.

[0008] According to one or more embodiments described herein, a method of manufacturing a thermoformed product includes: heating a thermoplastic material to provide a malleable thermoplastic material; pressing the malleable thermoplastic material against a mold comprising a 3D-printed object formed from a photocurable composition. The photocurable composition may comprise: a polymerizable resin containing one or more polymerizable components; about 2% to about 20% by weight of a nonpolymerizable silicone-based additive based on the total weight of the polymerizable components; and a photoinitiator.

[0009] This summary is provided to introduce some of the selections of concepts that will be further described in the detailed embodiments. This summary is not intended to identify key or essential features of the claimed subject matter, nor is it intended to limit the scope of the claimed subject matter.

[0010] Additional features and advantages of the embodiments will be set forth in the following detailed description. Those skilled in the art will (in part) understand the additional features and advantages of the embodiments from the specification or by practicing the embodiments (including the following detailed description, drawings, and claims). Detailed Implementation

[0011] As described above, molds used in thermoforming processes require favorable release properties. Embodiments of this disclosure meet this requirement by providing a photocurable composition comprising a non-polymerizable silicon-based additive. This photocurable composition can be used to form 3D printed articles. When used as a mold in a thermoforming process, the 3D printed articles exhibit favorable release properties.

[0012] definition

[0013] In this application, the term "comprising one / a" means "comprising one or more / a combination of".

[0014] The term "photocurable" means that a photocurable composition can polymerize when exposed to photochemical radiation (e.g., ultraviolet light).

[0015] The term "cationically polymerizable resin" refers to a resin that forms a polymer in the presence of a cation.

[0016] The term "free radical polymerizable resin" refers to a resin that can polymerize when exposed to free radicals.

[0017] The terms "(meth)acrylate", "(meth)acrylate group" and "(meth)acrylate functional group" refer to (meth)acryloyloxy group of the formula (-OC(=O)-CR=CH2), where R is hydrogen or methyl. It should be understood that the term "(meth)acrylate" encompasses the terms methacrylate and acrylate.

[0018] The term "oligomer" refers to a molecule having a molecular weight distribution and typically having one or more polymerizable functional groups. Oligomers can be the reaction products of two or more monomers, with a number-average molecular weight typically greater than or equal to 500 g / mol, preferably from 500 g / mol to 30,000 g / mol, more preferably from 1,000 g / mol to 8,000 g / mol. Oligomers may not always have a single molecular weight. It is known that commercially available products containing certain oligomers may contain impurities or other chemicals.

[0019] The term "monomer" refers to a molecule having one or more polymerizable functional groups. Monomers have a single molecular weight, typically below 1000 g / mol, preferably from 100 to 950 g / mol. It is known in the art that commercial products of particular monomers may contain impurities or other chemicals.

[0020] The term "photoinitiator" refers to a compound that undergoes a photoreaction upon absorbing light, producing a reactive substance. This reactive substance then initiates the curing (polymerization) of the reactive component in a curable composition. Generally, this polymerization (curing) involves the reaction of such carbon-carbon double bonds when the compound present in the reactive component contains such bonds.

[0021] The term "weight %" refers to a percentage by weight. Unless otherwise stated, the weight percentage in a compound or composition is relative to the weight of the compound or composition, respectively.

[0022] Implementation

[0023] The photocurable composition of the present invention comprises a polymerizable resin, a non-polymerizable silicone-based additive, and a photoinitiator. The photocurable composition may also contain reactive additives.

[0024] Polymerizable resins

[0025] The photocurable composition comprises a polymerizable resin. The polymerizable resin may comprise a free radical polymerizable resin. The polymerizable resin may comprise a cationic polymerizable resin. In some embodiments, the polymerizable resin may comprise both a free radical polymerizable resin and a cationic polymerizable resin.

[0026] The free radical polymerizable resin may contain (meth)acrylate groups, allyl groups, thiols, and amines, as well as other free radical polymerizable groups. The polymerizable resin may contain at least one (meth)acrylate monomer. The polymerizable resin may contain at least one (meth)acrylate oligomer, which, if present, is also a polymerizable component. In some embodiments, the polymerizable resin may contain at least one (meth)acrylate monomer and at least one (meth)acrylate oligomer.

[0027] The polymerizable resin may contain at least one (meth)acrylate monomer, which, if present, is also a polymerizable component. In one or more embodiments, the polymerizable resin may contain a mixture of (meth)acrylate monomers with different functionalities. For example, the polymerizable component may contain a mixture of (meth)acrylate monomers containing one acrylate or methacrylate group per molecule (referred to herein as "mono(meth)acrylate functionalized compounds") and (meth)acrylate functionalized monomers containing two or more, preferably two or three acrylate and / or methacrylate groups per molecule (referred to herein as "poly(meth)acrylate functionalized compounds"). Mono(meth)acrylate functionalized monomers can advantageously act as reactive diluents and reduce the viscosity of the composition.

[0028] Examples of suitable mono(meth)acrylate functionalized monomers include, but are not limited to: mono(meth)acrylates of aliphatic alcohols [wherein the aliphatic alcohol may be linear, branched, or alicyclic, and may be a monohydric, dihydric, or polyhydric alcohol, provided that only one hydroxyl group is (meth)acrylated]; mono(meth)acrylates of aromatic alcohols (e.g., phenols, including alkylated phenols); mono(meth)acrylates of alkylaryl alcohols (e.g., benzyl alcohol); oligomers and polymeric diols (e.g., diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol, and polypropylene glycol). Mono(meth)acrylates; mono(meth)acrylates of monoalkyl ethers of glycols and oligomeric glycols; mono(meth)acrylates of alkoxylated (e.g., ethoxylated and / or propoxylated) aliphatic alcohols [wherein the aliphatic alcohol may be linear, branched or alicyclic, and may be a monohydric alcohol, dihydric alcohol or polyhydric alcohol, provided that only one hydroxyl group of the alkoxylated aliphatic alcohol is (meth)acrylated]; mono(meth)acrylates of alkoxylated (e.g., ethoxylated and / or propoxylated) aromatic alcohols (e.g., alkoxylated phenols); caprolactone mono(meth)acrylates, etc.

[0029] The following compounds are specific examples of mono(meth)acrylate functionalized monomers suitable for polymerizable resins: methyl methacrylate; ethyl methacrylate; n-propyl methacrylate; n-butyl methacrylate; isobutyl methacrylate; n-hexyl methacrylate; 2-ethylhexyl methacrylate; n-octyl methacrylate; isooctyl methacrylate; n-decyl methacrylate; n-dodecyl methacrylate; tridecyl methacrylate; tetradecyl methacrylate; hexadecyl methacrylate; 2-hydroxyethyl methacrylate; 2- and 3-hydroxypropyl methacrylate; 2-methoxyethyl methacrylate; 2-ethoxyethyl methacrylate; 2- and 3-ethoxypropyl methacrylate; tetrahydrofurfuryl methacrylate; alkoxylated tetrahydrofurfuryl methacrylate; 2-(2-ethoxy)acrylate Ethoxyethyl acrylate; Cyclohexyl acrylate; Glycidyl acrylate; Isodecyl acrylate; Lauryl acrylate; 2-phenoxyethyl acrylate; Alkoxylated phenol (meth)acrylate; Alkoxylated nonylphenol (meth)acrylate; Cyclic trimethylolpropane acetal (meth)acrylate; Isoborneol acrylate; Tricyclodecane methanol acrylate; Tert-butylcyclohexanol acrylate; Trimethylcyclohexanol acrylate; Diethylene glycol monomethyl ether (meth)acrylate; Diethylene glycol monoethyl ether (meth)acrylate; Diethylene glycol monobutyl ether (meth)acrylate; Triethylene glycol monoethyl ether (meth)acrylate; Ethoxylated lauryl (meth)acrylate; Methoxylated polyethylene glycol (meth)acrylate; Hydroxyethyl butyl carbamate (meth)acrylate; 3-(2-hydroxyalkyl)oxazolidinone (meth)acrylate; and combinations thereof.

[0030] The polymerizable resin may contain poly(meth)acrylate functionalized monomers. The poly(meth)acrylate functionalized monomers may have 2 to 6 (meth)acrylate groups, particularly 2 to 6 acrylate groups.

[0031] Examples of suitable poly(meth)acrylate functionalized monomers include acrylates and methacrylates of polyols. Examples of suitable polyols include polyether glycols, polyester glycols, polycarbonate glycols, polyorganosiloxane glycols (e.g., polydimethylsiloxane glycol), polydienediols (including fully or partially hydrogenated polydienediols, such as polybutadiene glycol), and nonpolymerized aliphatic glycols. Such polyols can be fully or partially esterified (with (meth)acrylic acid, (meth)acrylic anhydride, (meth)acryloyl chloride, etc.) provided that each molecule contains at least two (meth)acrylate functional groups.

[0032] Exemplary poly(meth)acrylate functionalized monomers may include: bisphenol A di(meth)acrylate; hydrogenated bisphenol A di(meth)acrylate; ethylene glycol di(meth)acrylate; diethylene glycol di(meth)acrylate; triethylene glycol di(meth)acrylate; tetraethylene glycol di(meth)acrylate; polyethylene glycol di(meth)acrylate; propylene glycol di(meth)acrylate; dipropylene glycol di(meth)acrylate; tripropylene glycol di(meth)acrylate; tetrapropylene glycol di(meth)acrylate; polypropylene glycol di(meth)acrylate; polytetramethylene glycol di(meth)acrylate; ) acrylates; 1,2-butanediol di(meth)acrylate; 2,3-butanediol di(meth)acrylate; 1,3-butanediol di(meth)acrylate; 1,4-butanediol di(meth)acrylate; 1,5-pentanediol di(meth)acrylate; 1,6-hexanediol di(meth)acrylate; 1,8-octanediol di(meth)acrylate; 1,9-nonanediol di(meth)acrylate; 1,10-nonanediol di(meth)acrylate; 1,12-dodecanediol di(meth)acrylate; neopentanediol di(meth)acrylate; 2-methyl-2 4-Pentanediol di(meth)acrylate; Polybutadiene di(meth)acrylate; Cyclohexane-1,4-diethanol di(meth)acrylate; Tricyclodecanediethanol di(meth)acrylate; Metallic di(meth)acrylates; Modified metallic di(meth)acrylates; Glyceryl di(meth)acrylate; Glyceryl tri(meth)acrylate; Trimethylolethane tri(meth)acrylate; Trimethylolethane di(meth)acrylate; Trimethylolpropane tri(meth)acrylate; Trimethylolpropane di(meth)acrylate; Pentaerythritol di(meth)acrylate; Pentaerythritol Tri(meth)acrylate; pentaerythritol tetra(meth)acrylate; di(trimethylolpropane)diacrylate; di(trimethylolpropane)triacrylate; di(trimethylolpropane)tetraacrylate; sorbitol penta(meth)acrylate; di(pentaerythritol)tetraacrylate; di(pentaerythritol)pentaacrylate; di(pentaerythritol)hexa(meth)acrylate; tri(2-hydroxyethyl)isocyanurate tri(meth)acrylate; neopentyl glycol hydroxyneopentate di(meth)acrylate; and their alkoxylated (e.g., ethoxylated and / or propoxylated) derivatives; and combinations thereof.

[0033] The polymerizable resin may contain at least one (meth)acrylate oligomer, which, if present, is also a polymerizable component. In one or more embodiments, the polymerizable resin may contain a mixture of (meth)acrylate oligomers. The (meth)acrylate oligomers may be selected to enhance properties such as flexibility, strength, and / or modulus of the cured polymer, which is prepared by curing the photocurable composition described herein.

[0034] (Meth)acrylate oligomers may have 1 to 18 (meth)acrylate groups, particularly 2 to 6 (meth)acrylate groups, and even more particularly 2 to 6 acrylate groups. The number average molecular weight of (meth)acrylate oligomers may be equal to or greater than 600 g / mol, particularly 800 to 15,000 g / mol, and even more particularly 1,000 to 5,000 g / mol.

[0035] In particular, the polymerizable resin may comprise (meth)acrylate oligomers selected from the group consisting of: epoxy (meth)acrylate, polyester (meth)acrylate, polyether (meth)acrylate, urethane (meth)acrylate, (meth)acrylated poly(meth)acrylate, and mixtures thereof.

[0036] Non-limiting examples of epoxy (meth)acrylates are reaction products of epoxides (e.g., glycidyl ethers, glycidyl esters, alicyclic epoxides, or epoxides obtained by epoxidation of mono- and / or polyunsaturated compounds) with (meth)acrylic agents (e.g., (meth)acrylic acid, (meth)acrylic anhydride, (meth)acryloyl chloride, or combinations thereof). The epoxide may be selected from: 1,2,3,4-diepoxybutane; 1,2,4,5-diepoxypentane; 1,2,5,6-diepoxyhexane; 1,2,7,8-diepoxyoctane; 1,2,9,10-diepoxydecane; 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 phenolic resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3,4-cyclohexane Oxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-1,4-dioxane, bis(3,4-epoxycyclohexylmethyl) adipic acid, vinylcyclohexene oxide, 4-vinylepoxycyclohexane, bis(3,4-epoxy-6-methylcyclohexylmethyl) adipic acid, 3,4-epoxy-6-methylcyclohexyl-3',4'-epoxy-6'-methylcyclohexane carboxylate, methylene bis(3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol di(3,4-epoxycyclohexane) 4-Epoxycyclohexylmethyl ether, ethylene bis(3,4-epoxycyclohexane carboxylate), ethylene glycol diglycidyl ether, 1,2- or 1,3-propanediol diglycidyl ether, 1,2-, 1,3- or 1,4-butanediol diglycidyl ether, 1,5-pentanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,7-hexanediol diglycidyl ether, 1,8-octanediol diglycidyl ether, 1,9-nonanediol diglycidyl ether, 1,10-decanediol diglycidyl ether, 1,12-dodecanediol diglycidyl ether, 2-methyl-1,3- Propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 2,2-diethyl-1,3-propanediol diglycidyl ether, 3-methyl-1,5-pentanediol diglycidyl ether, 3,3-dimethyl-1,5-pentanediol diglycidyl ether, 2,4-diethyl-1,5-pentanediol diglycidyl ether, 3,3-butylethyl-1,5-pentanediol diglycidyl ether, di, tri, or tetra(ethylene glycol) diglycidyl ether, di, tri, or tetra(1,2-propanediol) diglycidyl ether, di, tri, or tetra(1,3-propanediol) diglycidyl ether, di, tri, or tetra(1,3-propanediol) diglycidyl ether, di, tri, or tetra(1,4-Butanediol) diglycidyl ether, poly(ethylene glycol) diglycidyl ether, poly(propylene glycol) diglycidyl ether, poly(trimethylene glycol) diglycidyl ether, poly(tetramethylene glycol) diglycidyl ether, poly(ethylene glycol-co-propylene glycol) diglycidyl ether, glycerol triglycidyl ether, polyglycerol polyglycidyl ether, trimethylolpropane triglycidyl ether, trimethylolpropane triglycidyl ether, trimethylolpropane triglycidyl ether Glycidyl ether, di(trimethylolpropane)tetraglycidyl ether, pentaerythritol tetraglycidyl ether, cyclohexane dicarboxylic acid diglycidyl ester, cyclohexane diglycidyl ether, cyclohexane-1,4-diethanol diglycidyl ether, tricyclodecane diethanol diglycidyl ether, isosorbide diglycidyl ether, catechol diglycidyl ether, resorcinol diglycidyl ether, cashew nut shell phenol diglycidyl ether, phloroglucinol triglycidyl ether Pyrogallol triglycidyl ether, tris(hydroxyphenyl)methane triglycidyl ether, tris(hydroxyphenyl)ethane triglycidyl ether, diglycidyl phthalate, diglycidyl terephthalate, diglycidyl isophthalate, polyglycidyl ethers of polyether polyols obtained by adding one or more epoxides to aliphatic polyols (e.g., ethylene glycol, propylene glycol, and glycerol), diglycidyl esters of aliphatic long-chain (C6-C22) dicarboxylic acids, monoglycidyl ethers of aliphatic higher alcohols, monoglycidyl ethers of phenol, cresol, butylphenol, or polyether alcohols obtained by adding epoxides to these compounds, glycidyl esters of higher fatty acids, epoxidized vegetable oils (e.g., epoxidized soybean oil and epoxidized linseed oil), epoxidized butyl stearic acid, epoxidized octyl stearic acid, epoxidized polybutadiene, triglycidyl isocyanurate, etc.

[0037] Non-limiting examples of polyester (meth)acrylates are the reaction products of hydroxyl-terminated polyester polyols with (meth)acrylic agents (e.g., (meth)acrylic acid, (meth)acrylic anhydride, (meth)acryloyl chloride, or combinations thereof). Reactions can be carried out such that a significant concentration of hydroxyl groups remains in the polyester (meth)acrylate, or that all or substantially all of the hydroxyl groups of the polyester polyol are (meth)acrylated. Polyester polyols can be prepared by polycondensation of a polyhydroxy functional component (particularly a diol) and a polycarboxylic acid functional compound (particularly a dicarboxylic acid or anhydride). To prepare polyester (meth)acrylates, the hydroxyl groups of the polyester polyol are partially or completely esterified by reacting with a (meth)acrylic agent. Polyester (meth)acrylates can also be synthesized by reacting a hydroxyl-containing (meth)acrylate, such as a hydroxyalkyl (meth)acrylate (e.g., hydroxyethyl acrylate), with a polycarboxylic acid. The polyhydroxy functional component and the polycarboxylic acid functional component can each have a linear, branched, alicyclic, or aromatic structure, and can be used alone or as a mixture.

[0038] Non-limiting examples of polyether (meth)acrylates are the products of condensation reactions of polyether alcohols (which are polyether polyols) with (meth)acrylic agents (e.g., (meth)acrylic acid, (meth)acrylic anhydride, (meth)acryloyl chloride, or combinations thereof). Suitable polyether alcohols can be straight-chain or branched substances containing ether bonds and terminal hydroxyl groups. Polyether alcohols can be prepared by ring-opening polymerization of epoxides and other oxygen-containing heterocyclic compounds (e.g., ethylene oxide, 1,2-epoxypropane, butene oxide, tetrahydrofuran, or combinations thereof) with initiator molecules. Suitable initiator molecules include water, hydroxyl-functionalized materials, polyester polyols, and amines. Polyether alcohols can also be obtained by condensation of glycols (e.g., ethylene glycol).

[0039] Non-limiting examples of urethane (meth)acrylates are condensation reaction products of at least one polyisocyanate (e.g., diisocyanate, triisocyanate), at least one polyol (e.g., polyether polyol or polyester polyol), and a hydroxyl-functionalized (meth)acrylate (e.g., 2-hydroxyethyl (meth)acrylate or 3-hydroxypropyl (meth)acrylate) to provide terminal (meth)acrylate groups. For example, urethane (meth)acrylates may contain two, three, four, or more (meth)acrylate groups per molecule. The order of addition of the components in the preparation of urethane (meth)acrylates is well known in the art. For example, a hydroxyl-functionalized (meth)acrylate may first react with a polyisocyanate to obtain an isocyanate-functionalized (meth)acrylate, and then react with a polyol. In another embodiment, a polyisocyanate may first react with a polyol to obtain an isocyanate-functionalized polyol, and then react with a hydroxyl-functionalized (meth)acrylate. Alternatively, all components may be combined and reacted simultaneously.

[0040] Non-limiting examples of (meth)acrylated poly(meth)acrylates are substances having an oligomeric (meth)acrylate backbone functionalized with one or more (meth)acrylate groups, which may be located at the end of the oligomer or side-attached to the acrylic backbone. The (meth)acrylate backbone may be a homopolymer, random copolymer, or block copolymer comprising repeating units of (meth)acrylate monomers. The (meth)acrylate monomers may be any monomeric (meth)acrylate, such as C1-C6 alkyl (meth)acrylates, and functionalized (meth)acrylates, such as (meth)acrylates with hydroxyl, carboxylic acid, and / or epoxy groups. (Meth)acrylate esterified poly(meth)acrylate can be prepared using any procedure known in the art, for example by oligomerizing (meth)acrylate monomers (in which at least a portion of the monomers are functionalized with hydroxyl, carboxylic acid and / or epoxy groups (e.g. hydroxyalkyl (meth)acrylate, (meth)acrylic acid, glycidyl (meth)acrylate)) to obtain functionalized poly(meth)acrylate, and then reacting it with one or more (meth)acrylate-containing reactants to introduce the desired (meth)acrylate functional groups.

[0041] The polymerizable resin may include cationic polymerizable resins. Cationic polymerizable resins may be selected from epoxides, oxetanes, vinyl ethers, vinylamides, oxetanes, cycloacetals, cyclolactones, thiohexacyclopropanes, thiohexacyclobutanes, spiroacetic acid esters, alcohols (including polyols), olefinic unsaturated compounds other than (meth)acrylates, their derivatives, and mixtures thereof.

[0042] Epoxides can include aromatic epoxides, alicyclic epoxides, oxetanes, and mixtures thereof, which, if present, are polymerizable components. Suitable epoxy functionalizing compounds capable of cationic polymerization include glycidyl ethers, particularly mono-, di-, tri-, and polyglycidyl ether compounds, as well as alicyclic ether compounds, including those containing carboxylic acid residues (e.g., alkyl carboxylic acid residues, alkylcycloalkyl carboxylic acid residues, and dialkyldicarboxylic acid residues). For example, epoxy functionalizing compounds can be 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 phenolic resins, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate, 2-(3,4- Epoxycyclohexyl-5,5-spiro-3,4-epoxycyclohexane-1,4-dioxane, bis(3,4-epoxycyclohexylmethyl) adipic acid ester, vinylcyclohexene oxide, limonene dioxide, bis(3,4-epoxy-6-methylcyclohexylmethyl) adipic acid ester, 3,4-epoxy-6-methylcyclohexyl-3',4'-epoxy-6'-methylcyclohexane carboxylic acid ester, methylene bis(3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol Di(3,4-epoxycyclohexylmethyl) ether of alcohols, ethylene bis(3,4-epoxycyclohexane carboxylate), epoxy hexahydrodioctyl phthalate, epoxy hexahydrodi-2-ethylhexyl phthalate, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, by adding one or more epoxides to esters Polyether polyols obtained from aliphatic polyols (such as ethylene glycol, propylene glycol, and glycerol) include polyglycidyl ethers of polyether polyols, diglycidyl esters of aliphatic long-chain dicarboxylic acids, monoglycidyl ethers of aliphatic higher alcohols, monoglycidyl ethers of phenol, cresol, and butylphenol, or polyether alcohols obtained by adding epoxides to these compounds, glycidyl esters of higher fatty acids, epoxidized soybean oil, epoxidized butyl stearic acid, epoxidized octyl stearic acid, epoxidized linseed oil, epoxidized polybutadiene, etc.

[0043] Additional suitable olefinic unsaturated compounds capable of cationic polymerization include vinyl ethers, such as ethylene glycol divinyl ether, triethylene glycol divinyl ether, and trimethylolpropane trivinyl ether; aliphatic vinyl monomers such as vinylcyclohexane; olefins such as isobutylene; dienes such as butadiene; vinyl alkyl ethers; vinyl aromatic monomers such as styrene and alkylstyrene; unsaturated polymers such as polybutadiene; derivatives of the above organic substances, etc., at least some of which can also be polymerized via a free radical mechanism.

[0044] The polymerizable resin content is from about 70% to about 95% by weight, based on the total weight of the photocurable composition. For example, the photocurable composition may contain polymerizable resin in amounts of about 70% to about 95% by weight, about 75% to about 95% by weight, about 80% to about 95% by weight, about 85% to about 95% by weight, about 90% to about 95% by weight, about 70% to about 90% by weight, about 70% to about 85% by weight, about 70% to about 80% by weight, about 70% to about 75% by weight, or any range or combination of ranges formed by these endpoints.

[0045] Non-polymerizable silicon-based additives

[0046] The photocurable composition comprises a non-polymerizable silicon-based additive. The additive is "silicon-based" when it comprises a polymer containing repeating siloxane units (-O-R2Si-O-SiR2-, where R is an organic group). The additive is "non-polymerizable" when its functional groups do not participate in the curing process, such that the additive is not covalently bonded to the polymer network during curing of the photocurable composition.

[0047] The non-polymerizable silicone-based additive may contain at least one functionalized siloxane. The functionalized siloxane may contain a functional group selected from the group consisting of polyethers, polyesters, (poly)alkyl groups, (poly)aralkyl groups, and combinations thereof. In one or more embodiments, the functional group is a polyether.

[0048] Unbound by theory, functional groups can be selected to improve the compatibility of non-polymerizable silicone-based additives with polymerizable resins. For example, siloxanes functionalized with one or more of polyethers, polyesters, (poly)alkyl, and (poly)aralkyl groups exhibit better compatibility with (meth)acrylate monomers and (meth)acrylate oligomers contained in polymerizable resins compared to unfunctionalized siloxanes. Using functionalized siloxanes containing functional groups selected from polyethers, polyesters, (poly)alkyl, (poly)aralkyl, and combinations thereof as non-polymerizable silicone-based additives can prevent phase separation between the non-polymerizable silicone-based additives and polymerizable resins in photocurable compositions. Phase separation between non-polymerizable silicone-based additives and polymerizable resins is undesirable when using photocurable compositions in 3D printing applications.

[0049] The siloxane used in the non-polymerizable silicone-based additive is not particularly limited. In one or more embodiments, the non-polymerizable silicone-based additive comprises a functionalized polydimethylsiloxane. The chemical formula of polydimethylsiloxane (PDMS) may be CH3[Si(CH3)2O]. n Si(CH3)3, in which nThis refers to the number of repeating monomer [Si(CH3)2O] units. Polydimethylsiloxane can be functionalized at any suitable location. For example, polydimethylsiloxane can be functionalized on any monomer unit at or between end groups. Polydimethylsiloxane can be functionalized by functional groups selected from polyethers, polyesters, (poly)alkyl, (poly)aralkyl, and combinations thereof. In one or more embodiments, the non-polymerizable silicone-based additive comprises a polyether-functionalized polydimethylsiloxane. For example, the non-polymerizable silicone-based additive may comprise a commercially available polyether-functionalized polydimethylsiloxane, such as BYK-333 or BYK-3760.

[0050] In embodiments of the present invention, the non-polymerizable silicon-based additive does not have any urethane groups.

[0051] In embodiments of the present invention, the non-polymerizable silicon-based additive is not a block copolymer.

[0052] In an embodiment of the present invention, the non-polymerizable silicon-based additive contains less than 0.1% by weight of cyclic siloxane.

[0053] In embodiments of the present invention, the KOH value (measured according to DIN 53240-2) of the non-polymerizable silicon-based additive is less than 20 mg KOH / g, less than 15 mg KOH / g, less than 10 mg KOH / g, less than 5 mg KOH / g, less than 1 mg KOH / g, less than 0.5 mg KOH / g, less than 0.1 mg KOH / g, and preferably 0 mg KOH / g.

[0054] Based on the total weight of the polymerizable components, the photocurable composition may contain about 2% to about 20% by weight of a nonpolymerizable silicone-based additive. The polymerizable components include components of the polymerizable resin and any other reactive components (excluding "reactive additives" mentioned below) that may be present in the photocurable composition and participate in polymerization. For example, based on the total weight of the polymerizable components, the photocurable composition may contain nonpolymerizable silicone-based additives in amounts of about 2% to about 20% by weight, about 4% to about 20% by weight, about 4.5% to about 20% by weight, about 5% to about 20% by weight, about 5.5% to about 20% by weight, about 6% to about 20% by weight, about 8% to about 20% by weight, about 8.5% to about 20% by weight, about 9% to about 20% by weight, about 9.5% to about 20% by weight, about 10% by weight, etc. % to about 20 wt%, about 12 wt% to about 20 wt%, about 14 wt% to about 20 wt%, about 16 wt% to about 20 wt%, about 18 wt% to about 20 wt%, about 2 wt% to about 18 wt%, about 2 wt% to about 16 wt%, about 2 wt% to about 14 wt%, about 2 wt% to about 12 wt%, about 2 wt% to about 10 wt%, about 2 wt% to about 8 wt%, about 2 wt% to about 6 wt%, about 2 wt% to about 4 wt%, or any range or combination of ranges formed by these endpoints.

[0055] Unbound by theory, including non-polymerizable silicon-based additives in photocurable compositions can improve the demolding properties of 3D printed articles formed from such compositions. For example, 3D printed articles formed from photocurable compositions containing non-polymerizable silicon-based additives can have low surface energy and minimal surface texture. These characteristics improve the demolding properties of 3D printed articles when used as molds in thermoforming processes.

[0056] Reactive additives

[0057] The photocurable composition may contain reactive additives. Reactive additives are optional components. In some embodiments, the photocurable composition does not contain reactive additives. In such embodiments, the photocurable composition does not contain reactive additives.

[0058] Reactive additives are polymerizable additives other than polymerizable resins or materials falling within the range of said polymerizable resins. An additive is “polymerizable” when its functional groups participate in the curing process, such that the additive is covalently bonded to a polymer network during curing of the photocurable composition. While reactive additives described herein may contain (meth)acrylate groups, they are distinct from the polymerizable components described above (as part of a polymerizable resin) and are not included in the “total weight of the polymerizable component” when determining the weight percentage of non-polymerizable silicone-based additives (e.g., 2 to 20 wt%) or photoinitiators.

[0059] In one or more embodiments, the reactive additive may be a surfactant having a polymerizable group. The polymerizable group may be a cationic polymerizable group or a free radical polymerizable group. The reactive additive may contain at least one polymerizable group selected from the group consisting of: epoxy group, oxetyl group, vinyl ether group, olefinic unsaturated group, or alcohol group. "Surfactant" refers to a compound having an oil-compatible lipophilic portion and a water-compatible hydrophilic portion.

[0060] The reactive additive may comprise a silicone-based additive having polymerizable groups. In one or more embodiments, the reactive additive may comprise at least one functionalized siloxane. In one or more embodiments, the reactive additive may be a silicone-based surfactant. In some embodiments, the reactive additive may comprise a perfluoroalkyl chain having polymerizable groups. In such embodiments, the reactive additive may be a fluoropolymer surfactant.

[0061] Specific examples include anionic surfactants (such as dialkyl sulfosuccinates, alkylnaphthalene sulfonates, or fatty acid salts), nonionic surfactants (such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, ethynyl glycol, or polyoxyethylene / polyoxypropylene block copolymers), and cationic surfactants (such as alkylamine salts or quaternary ammonium salts). Organofluorine compounds can be used as known surfactants. These organofluorine compounds are preferably hydrophobic. Examples of organofluorine compounds include fluorinated surfactants, oily fluorinated compounds (e.g., fluorinated oils), and solid fluorinated compound resins (e.g., tetrafluoroethylene resins).

[0062] The reactive additive may be selected from surfactants having polymerizable groups, silicone-based additives having polymerizable groups, and perfluoroalkyl chains having polymerizable groups.

[0063] The reactive additive may be included in the photocurable composition in an amount less than 10% by weight of the non-polymerizable silicone-based additive. For example, the reactive additive may be included in the photocurable composition in an amount less than 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, or even 1% by weight of the non-polymerizable silicone-based additive. In one or more embodiments, the photocurable composition contains 0% by weight of the reactive additive based on the total weight of the non-polymerizable silicone-based additive. In such embodiments, the reactive additive is not intentionally added to the photocurable composition.

[0064] Photoinitiator

[0065] The photocurable composition may contain a photoinitiator. Photoinitiators are generally classified into two categories based on their mode of action: radical photoinitiators and cationic photoinitiators. Cationic photoinitiators are typically salts, such as iodonium salts and sulfonium salts. When these salts are exposed to UV light, they undergo homolytic bond cleavage, generating radicals. These radicals react with a proton donor to generate Brønsted acids or Lewis acids. The generated acids then initiate polymerization. Radical photoinitiators can employ two different modes of action and are classified into Norrish type I photoinitiators and Norrish type II photoinitiators based on their mode of action. In some embodiments, the photocurable composition contains a radical photoinitiator, such as a Norrish type I or Norrish type II photoinitiator.

[0066] As used herein, the term "activity" in relation to Norish type I and Norish type II activity refers to Norish photoinitiation and similar reactions. For example, a photoinitiator with Norish type I activity is characterized by generating two radical fragments of the original photoinitiator through a cleavage reaction upon exposure to UV light. For initiators with Norish type II activity, exposure to UV light leads to the abstraction of atoms (e.g., hydrogen) to generate radicals.

[0067] Non-limiting types of free radical photoinitiators suitable for use in the curable compositions of this disclosure include, for example, benzoin, benzoin ether, acetophenone, α-hydroxyacetophenone, benzyl, benzyl ketal, anthraquinone, phosphine oxide, acylphosphine oxide, α-hydroxy ketone, phenylglyoxylate, α-amino ketone, benzophenone, thioxanone, xanthonone, acridine derivatives, phenazine derivatives, quinoxaline derivatives, triazine compounds, benzoylcarbamate, aromatic oximes, metallocenes, acylsilyl or acylgermanyl compounds, camphorquinone, polymeric derivatives thereof, and mixtures thereof.

[0068] Examples of suitable free radical photoinitiators include, but are not limited to: 2-methylanthraquinone, 2-ethylanthraquinone, 2-chloroanthraquinone, 2-benzanthraquinone, 2-tert-butylanthraquinone, 1,2-benzo-9,10-anthraquinone, benzyl, benzoin derivatives, benzoin ethers, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, α-methylbenzoin, α-phenylbenzoin, Michler's ketone ketone), acetophenones (such as 2,2-dialkoxybenzophenone and 1-hydroxyphenyl ketone), benzophenone, 4,4'-bis(diethylamino)benzophenone, acetophenone, 2,2-diethoxyacetophenone, diethoxyacetophenone, 2-isopropylthioxanthone, thioxanthone, diethylthioxanthone, 1,5-acetylnaphthalene, benzoinone, α-hydroxy ketone, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, benzyl dimethyl ketal, 2,2-dimethoxy-1,2-diphenyl ethyl ketone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinoacetone-1- 2-Hydroxy-2-methyl-1-phenyl-propanone, oligo-α-hydroxy ketone, benzoylphosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl(2,4,6-trimethylbenzoyl)phenylphosphinate, anisolein, anthraquinone, sodium anthraquinone-2-sulfonic acid monohydrate, (benzene)tricarbonylchromium, benzoyl, benzoin isobutyl ether, benzophenone / 1-hydroxycyclohexylphenyl ketone (50 / 50 mixture), 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 4-benzoylbiphenyl, 2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenyl ketone, 4,4'-bis(diethylamino) Benzyl ketone, 4,4'-bis(dimethylamino)benzophenone, camphorquinone, 2-chlorothiazol-9-one, dibenzocycloheptenone, 4,4'-dihydroxybenzophenone, 2,2-dimethoxy-2-phenylacetophenone, 4-(dimethylamino)benzophenone, 4,4'-dimethylbenzoin, 2,5-dimethylbenzophenone, 3,4-dimethylbenzophenone, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide / 2-hydroxy-2-methylphenylacetone (50 / 50 mixture), 4'-ethoxyacetophenone, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, phenylbis(2,4,6)-dimethylbenzoyl) ... -trimethylbenzoyl)phosphine oxide, ferrocene, 3'-hydroxyacetophenone, 4'-hydroxyacetophenone, 3-hydroxybenzophenone, 4-hydroxybenzophenone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methylphenylacetone, 2-methylbenzophenone, 3-methylbenzophenone, methyl benzoylformate, 2-methyl-4'-(methylthio)-2-morpholinylphenylacetone, phenanthrenequinone, 4'-phenoxyacetophenone, (isopropylbenzene)cyclopentadienyl iron(II) hexafluorophosphate, 9,10-diethoxy and 9,10-dibutoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, thioxanthone-9-one and combinations thereof.

[0069] Specifically, suitable photoinitiators include benzophenone (e.g., SpeedCure BP, SpeedCure 7005, SpeedCure 7006), thioxanthone (e.g., SpeedCure 7010, SpeedCure ITX), α-hydroxyacetophenone, and acylphosphine oxide (e.g., SpeedCure BPO, SpeedCure TPO, SpeedCure TPO-L); each of which is available from Sartomer Americas.

[0070] The photocurable composition may contain about 0.1% to about 10% by weight of a photoinitiator based on the total weight of the polymerizable components. For example, the photocurable composition may contain a photoinitiator in amounts of about 0.1 wt% to about 10 wt%, about 0.5 wt% to about 10 wt%, about 1 wt% to about 10 wt%, about 2 wt% to about 10 wt%, about 3 wt% to about 10 wt%, about 4 wt% to about 10 wt%, about 5 wt% to about 10 wt%, about 6 wt% to about 10 wt%, about 7 wt% to about 10 wt%, about 8 wt% to about 10 wt%, about 9 wt% to about 10 wt%, about 0.1 wt% to about 9 wt%, about 0.1 wt% to about 8 wt%, about 0.1 wt% to about 7 wt%, about 0.1 wt% to about 6 wt%, about 0.1 wt% to about 5 wt%, about 0.1 wt% to about 4 wt%, about 0.1 wt% to about 3 wt%, about 0.1 wt% to about 2 wt%, about 0.1 wt% to about 1 wt%, about 0.1 wt% to about 0.5 wt%, or any range or combination of ranges formed by these endpoints, based on the total weight of the polymerizable components.

[0071] Additional components

[0072] In addition to the components described above, the photocurable composition may also contain one or more additives. The photocurable compositions disclosed herein may contain one or more additives to replace or supplement the components described above. Such additives include, but are not limited to: antioxidants, ultraviolet absorbers, light stabilizers, defoamers, flow or leveling agents, colorants, pigments, dispersants (wetting agents), slip additives, fillers (excluding inorganic nanoparticles or added in addition to inorganic nanoparticles), thixotropic agents, matting agents, accelerators, adhesion promoters (e.g., acidic adhesion promoters), thermoplastics and other types of polymers (excluding the block copolymers described above or added in addition to the block copolymers described above), waxes, or other various additives, including any additives commonly used in the fields of coatings, sealants, adhesives, molding, or inks. In one or more embodiments, the photocurable composition may contain one or more additives selected from the group consisting of: ultraviolet absorbers, pigments, stabilizers, and defoamers.

[0073] Photocured composition

[0074] This invention comprises a photocurable composition comprising a photocurable product of a photocurable composition. The photocurable composition can be cured by exposing it to photochemical radiation (and optionally heating). Photochemical radiation may include UV, near-UV, visible light, infrared and / or near-infrared radiation, or electron beam radiation.

[0075] The photocurable composition can form a solid three-dimensional article after photocuring. The water contact angle of the solid three-dimensional article can be greater than or equal to 45°, 50° or 55°, and less than or equal to 105°, 100° or 95°.

[0076] The water contact angle generally refers to the angle between a water surface and a solid surface at their contact point. More specifically, the water contact angle is the angle between the tangent at the water-vapor interface and the tangent at the solid-water interface at their intersection. The water contact angle can be used to quantify the wettability of photocured compositions.

[0077] The determination of the water contact angle is well known in the art. The water contact angle is the angle between a liquid surface and a solid surface at their point of contact. More specifically, it is the angle between the tangents on the surfaces at the solid-liquid interface at their intersection. The water contact angle can be determined using essentially the same measurement procedure as described in ASTM D5946.

[0078] The viscosity of photocurable compositions at 25°C can be greater than or equal to 80 centipoise (cp) and less than or equal to 200,000 cp, for example, viscosities greater than or equal to 100 cp, greater than or equal to 150 cp, greater than or equal to 200 cp, greater than or equal to 250 cp, or greater than or equal to 300 cp, and less than or equal to 100,000 cp, less than or equal to 75,000 cp, less than or equal to 50,000 cp, less than or equal to 25,000 cp, less than or equal to 10,000 cp, or less than or equal to 1,000 cp. Viscosity is measured at room temperature or 60°C using a Brookfield DV-III+ viscometer and an SC-27 rotor (the viscometer will not be operable at room temperature if the viscosity is high enough). Each sample is measured at the revolutions per minute (rpm) required to reach 50% of the torque range. Viscosity is measured in centipoise (cP) after the temperature is reached and the sample has stabilized (typically after 10 minutes).

[0079] In embodiments, the photocurable composition is substantially solvent-free, preferably containing less than 5% by weight of solvent, more preferably less than 2% by weight of solvent, more preferably less than 1% by weight of solvent, more preferably less than 0.5% by weight of solvent, even more preferably less than 0.1% by weight of solvent, and most preferably solvent-free. For the avoidance of doubt, the term "solvent" as used herein does not include the non-polymerizable silicone-based additives described herein.

[0080] Applications of 3D printing technology

[0081] The photocurable compositions disclosed herein can be used as 3D printing compositions in 3D printing processes. Therefore, the photocurable compositions can be used to construct 3D printed objects, which may comprise photocurable compositions, photocured compositions, or combinations thereof.

[0082] A method of manufacturing a 3D printed object may include providing a photocurable composition and curing the photocurable composition in a 3D printing process to form a 3D printed object. The photocurable composition may be any of the photocurable compositions described above. In one or more embodiments, the photocurable composition may comprise: a polymerizable resin containing one or more polymerizable components; about 2% to about 20% by weight of a non-polymerizable silicone-based additive based on the total weight of the polymerizable components; and a photoinitiator.

[0083] 3D printing (also known as additive manufacturing) is a process that creates 3D digital models by stacking building materials. 3D printed objects are constructed by using computer-aided design (CAD) data of the object and sequentially building two-dimensional (2D) layers or sheets corresponding to the cross-sections of the 3D object. Radiation can take the form of electromagnetic waves or electron beams. The most common energy sources used are ultraviolet, visible, or infrared radiation.

[0084] 3D printing processes can include printing 3D objects layer by layer or continuously. For example, a multilayer photocurable composition according to this disclosure can be applied to a substrate surface; the multilayers can be cured simultaneously (e.g., by exposure to a single dose of radiation), or each layer can be cured sequentially before applying another layer of photocurable composition. In some embodiments, each layer can be cured sequentially before applying another layer, and then the multilayers can be cured simultaneously.

[0085] Non-limiting examples of suitable 3D printing processes may include VAT polymerization, digital light printing (DLP), stereolithography (SLA), inkjet printing, multi-nozzle printing, piezoelectric printing, photopolymerization extrusion, liquid crystal display (LCD) printing, volumetric printing, and gel deposition printing, and combinations thereof. The construction method can be "layer-by-layer" or continuous. The liquid can be deposited in a vat or, for example, by inkjet or gel deposition.

[0086] The photocurable compositions disclosed herein are particularly suitable for 3D printing resin formulations, i.e., compositions intended for use in manufacturing three-dimensional articles using 3D printing technology. Such three-dimensional articles may be free-standing / self-supporting and may comprise, consist primarily of, or consist of the compositions according to this disclosure, regardless of whether the photocurable composition has been cured. 3D printed objects may also be composite materials comprising at least one component consisting primarily of or composed of the aforementioned cured compositions, and at least one additional component comprising one or more materials other than the aforementioned cured compositions (e.g., metallic components, thermoplastic components, inorganic fillers, or fiber reinforcements). The photocurable compositions of this disclosure may be used in a 3D printing operation with another material serving as a support or carrier for the article formed from the photocurable compositions of this disclosure.

[0087] The photocurable compositions disclosed herein can be used in various types of three-dimensional manufacturing or printing practices, including methods for constructing three-dimensional objects in a step-by-step or layer-by-layer manner. In such methods, layer formation can be achieved by solidification (curing) of the photocurable compositions upon exposure to radiation (e.g., visible light, UV, or other photochemical radiation). For example, new layers can be formed on the top or bottom surface of a grown object. The photocurable compositions disclosed herein can also be advantageously used in methods for producing three-dimensional objects by additive manufacturing, wherein the method is carried out continuously. For example, the object can be generated from a liquid interface. Such suitable methods are sometimes referred to in the art as "continuous liquid interface (or interface phase) product (or printing)" ("CLIP") methods. For example, such methods are described in WO 2014 / 126830; WO 2014 / 126834; WO 2014 / 126837; and Tumbleston et al., “Continuous Liquid Interface Production of 3D Objects”, Science, Vol. 347, No. 6228, pp. 1349-1352 (March 20, 2015), the entire contents of which are incorporated herein by reference for all purposes.

[0088] When stereolithography is performed above an oxygen-permeable construction window, an article using a photocurable composition according to this disclosure can be produced in a CLIP process by creating an oxygen-containing "dead zone" (an uncured thin layer of the curable composition) between the window and the surface of the cured article during its production process. In this process, a curable composition is used where curing (polymerization) is inhibited by the presence of molecular oxygen; for example, such inhibition is commonly seen in curable compositions capable of curing via a free radical mechanism. The desired dead zone thickness can be maintained by selecting various control parameters, such as photon flux and the optical and curing properties of the curable composition. The CLIP process is performed by projecting a series of continuous photochemical radiation (e.g., UV) images (e.g., generated by a digital light processing imaging unit) onto an oxygen-permeable, photochemical radiation (e.g., UV) transparent window located below a bath of the curable composition (held in a liquid state). The liquid interface below the advancing (growing) article is maintained by the dead zone formed above the window. The cured article is continuously pulled out of the curable composition bath above the dead zone, which can be replenished by feeding an additional amount of curable composition into the bath to compensate for the amount of curable composition that is cured and incorporated into the grown article.

[0089] In another embodiment, the photocurable composition is supplied via jet from the printhead rather than from a cylinder. This type of process is commonly referred to as inkjet or multi-head 3D printing. One or more UV curing sources mounted immediately behind the inkjet printhead cure the photocurable composition immediately after it is applied to the build surface substrate or a previously applied layer. This process can use two or more printheads, allowing different compositions to be applied to different areas of each layer. For example, compositions of different colors or physical properties can be applied simultaneously to create 3D printed parts with different compositions. In common applications, a support material (removed later in post-processing) is deposited simultaneously with the composition used to create the desired 3D printed part. The printhead can operate at temperatures from about 25 °C to about 100 °C. At the printhead operating temperature, the viscosity of the curable composition is less than 30 mPa·s.

[0090] After 3D printed objects are created, one or more post-processing steps can be performed. These post-processing steps can be selected from one or more of the following: removing any printed support structures, cleaning with water and / or organic solvents to remove residual resin, and simultaneously or sequentially performing heat treatment and / or photochemical radiation for post-curing. Post-processing steps can be used to transform newly printed articles into finished or functional products for their intended applications.

[0091] The water contact angle of the 3D printed object can be greater than or equal to 60°, as described herein with respect to photocured compositions.

[0092] Methods for manufacturing thermoformed products

[0093] 3D printed objects formed from the photocurable compositions of this disclosure can be used in methods for manufacturing thermoformed products. For example, 3D printed objects formed from the photocurable compositions of this disclosure can be used as molds on which thermoplastics can be molded during the production of thermoformed products.

[0094] A method of manufacturing a thermoformed product may include: heating a thermoplastic material to provide a malleable thermoplastic material; pressing the malleable thermoplastic material against a mold comprising a 3D-printed object formed from a photocurable composition; cooling the malleable thermoplastic material to form a thermoformed product; and separating the thermoformed product from the mold. The 3D-printed object can be formed by any suitable 3D printing process. Embodiments of such 3D printing processes are described in detail above. The photocurable composition can be any photocurable composition described above. In one or more embodiments, the photocurable composition may comprise: a polymerizable resin containing one or more polymerizable components; about 2% to about 20% by weight of a non-polymerizable silicone-based additive based on the total weight of the polymerizable components; and a photoinitiator.

[0095] As described herein, "thermoplastic" refers to any plastic polymer material that becomes malleable or moldable at certain elevated temperatures and solidifies upon cooling. The thermoplastic material can be any suitable thermoplastic. Thermoplastics can include, for example, acrylics, nylon, polylactic acid, polybenzimidazole, polycarbonate, polyethersulfone, polyoxymethylene, polyetheretherketone, polyetherimide, polyethylene, polyphenylene ether, polyphenylene sulfide, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene fluoride, and polytetrafluoroethylene. Thermoplastic materials can be combinations of one or more thermoplastics. Thermoplastic materials can have any suitable shape. For example, thermoplastic materials can be in the form of sheets or discs.

[0096] Unbound by theory, thermoplastics can have relatively high molecular weights. The polymer chains of thermoplastics are bound together by intramolecular forces, which weaken as temperature increases, resulting in malleable thermoplastic materials. Thermoplastic materials can be heated to provide malleable forms. Malleable thermoplastic materials can be reshaped using various techniques, including thermoforming. "Thermoforming" refers to a manufacturing process in which thermoplastics are heated to a malleable temperature and molded into a specific shape, for example, to manufacture products.

[0097] In a thermoforming process, a malleable thermoplastic material can be pressed against a mold. In one or more embodiments, the mold may comprise a 3D-printed object formed from the photocurable composition described above. The mold may be a composite material comprising the 3D-printed object and other suitable materials. In embodiments, the mold may be shaped such that the 3D-printed object contacts the malleable thermoplastic material when it is pressed against the mold.

[0098] In one embodiment, the mold may have a generally convex shape, allowing a malleable thermoplastic material to be pressed onto the mold, thereby contacting the 3D-printed object. In other embodiments, the mold may have a generally concave shape, allowing a malleable thermoplastic material to be pressed into the mold, thereby contacting the 3D-printed object.

[0099] The plastic thermoplastic material can be pressed against the mold under vacuum. For example, a vacuum can be drawn between the plastic thermoplastic material and the mold to pull the plastic thermoplastic material toward the mold. Unbound by theory, applying a vacuum between the thermoplastic material and the mold can remove air that may be trapped between the plastic thermoplastic material and the mold, thereby improving the contact between the plastic thermoplastic material and the mold.

[0100] Pressing a plastic thermoplastic material against a mold allows the material to take the shape of the mold. The plastic thermoplastic material can be cooled to form a thermoformed product. The plastic thermoplastic material can be cooled while being pressed against the mold. The plastic thermoplastic material can be cooled by any suitable method known in the art. For example, the plastic thermoplastic material can be cooled by ambient cooling. “Ambient cooling” refers to heat exchange with air under ambient conditions. The plastic thermoplastic material can also be cooled by other methods. For example, without limitation, the plastic thermoplastic material can be cooled by contacting it with a cooling or freezing fluid.

[0101] Cooling a malleable thermoplastic material can reduce its plasticity. In one or more embodiments, cooling the thermoplastic material can reduce its plasticity, allowing the thermoformed product to retain the shape imparted to the thermoplastic material by the mold.

[0102] The thermoformed product can be separated from the mold. The thermoformed product can be separated from the mold by any suitable method known in the art. For example, the thermoformed product can be pulled off the mold. Mechanical devices, tools, hands, or even gravity can be used to pull the thermoformed product off the mold. In some embodiments where a vacuum is used to press the malleable thermoplastic material against the mold, a stream of pressurized air can be used to break the vacuum and eject the thermoformed product from the mold.

[0103] In some embodiments, the thermoformed product may contain an excess of thermoplastic material. In such embodiments, the excess thermoplastic material can be removed from the thermoformed product. The excess thermoplastic material can be removed by any suitable method known in the art. For example, the excess thermoplastic material can be removed by cutting, trimming, grinding, polishing, or any other suitable method.

[0104] Unbound by theory, using the photocurable compositions described herein to form molds for thermoforming processes yields molds with improved release properties. Improved release properties reduce the force required to remove the thermoformed product from the mold. This reduces the likelihood of damaging the thermoformed product or the mold during removal. For example, as the force required to remove the thermoformed product from the mold increases, the likelihood of deformation, warping, cracking, or other damage to the thermoformed product when pulled off the mold increases. This may be particularly evident in applications where the thermoformed product is removed from the mold by hand.

[0105] For example, thermoforming processes can be used, without limitation, to manufacture orthodontic appliances. In such processes, a mold with a tooth shape is formed, and the orthodontic appliance is formed by pressing a thermoplastic material against the mold using a thermoforming process. Importantly, for the patient's benefit, the orthodontic appliance should not deform or otherwise be damaged when removed from the mold. Traditionally, plaster molds have been used in such processes to form orthodontic appliances. However, removing the orthodontic appliance from such a plaster mold can be difficult. As described in more detail below, molds formed from the photocurable compositions of this disclosure can have improved demolding properties compared to conventional plaster molds, reducing the likelihood of damaging the orthodontic appliance when removing it from the mold. It should be understood that the thermoforming processes described herein are not limited to the production of orthodontic appliances. The discussion of this particular application of thermoforming processes is merely an example of thermoforming processes and is used to illustrate the benefits of improving the demolding properties of molds used in thermoforming processes.

[0106] aspect

[0107] Aspect 1. A photocurable composition comprising: (a) a polymerizable resin comprising one or more polymerizable components; (b) from about 2% to about 20% by weight of a nonpolymerizable silicone-based additive based on the total weight of the polymerizable components; (c) optionally, less than 10% by weight of a reactive additive based on the total weight of the nonpolymerizable silicone-based additive; and (d) a photoinitiator.

[0108] Aspect 2. The photocurable composition as described in aspect 1, wherein the nonpolymerizable silicone-based additive comprises at least one functionalized siloxane, wherein the functional group is selected from the group consisting of polyethers, polyesters, (poly)alkyl and (poly)araalkyl.

[0109] Aspect 3. The photocurable composition as described in aspect 2, wherein the functional group is a polyether.

[0110] Aspect 4. The photocurable composition as described in aspect 1 or 2, wherein the nonpolymerizable silicone-based additive comprises functionalized polydimethylsiloxane.

[0111] Aspect 5. The photocurable composition of any one of Aspects 1 to 4, wherein the nonpolymerizable silicone-based additive comprises polyether-functionalized polydimethylsiloxane.

[0112] Aspect 6. The photocurable composition according to any one of Aspects 1 to 5, wherein the reactive additive comprises at least one functional group selected from the group consisting of epoxy, oxetyl, vinyl ether, olefinic unsaturated group and alcohol.

[0113] Aspect 7. The photocurable composition as described in any one of Aspects 1 to 6, wherein the reactive additive is less than 5% by weight based on the total weight of the nonpolymerizable silicone-based additives.

[0114] Aspect 8. The photocurable composition as described in any one of Aspects 1 to 7, wherein the reactive additive is less than 1 wt% based on the total weight of the nonpolymerizable silicone-based additives.

[0115] Aspect 9. The photocurable composition of any one of Aspects 1 to 8, wherein the composition comprises 0% by weight of reactive additives based on the total weight of non-polymerizable silicone-based additives.

[0116] Aspect 10. The photocurable composition of any one of Aspects 1 to 9, wherein the polymerizable resin comprises at least one (meth)acrylate monomer.

[0117] Aspect 11. The photocurable composition of any one of Aspects 1 to 9, wherein the polymerizable resin comprises at least one (meth)acrylate oligomer.

[0118] Aspect 12. The photocurable composition of any one of Aspects 1 to 9, wherein the polymerizable resin comprises at least one (meth)acrylate monomer and at least one (meth)acrylate oligomer.

[0119] Aspect 13. The photocurable composition of any one of aspects 1 to 12 further comprises one or more additives selected from the group consisting of ultraviolet absorbers, pigments, stabilizers and defoamers.

[0120] Aspect 14. The photocurable composition as described in any one of Aspects 1 to 13, wherein the content of the polymerizable resin is from about 70% to about 95% by weight, based on the total weight of the photocurable composition.

[0121] Aspect 15. The photocurable composition according to any one of aspects 1 to 14, wherein the content of the photoinitiator is from about 0.1% by weight to about 10% by weight based on the total weight of the polymerizable components.

[0122] Aspect 16. The photocurable composition as described in any one of Aspects 1 to 15, wherein when the composition is photocured, a solid three-dimensional article is formed with a water contact angle greater than or equal to 60°.

[0123] Aspect 17. The photocurable composition of any one of Aspects 1 to 16, wherein the nonpolymerizable silicone-based additive does not have a urethane group.

[0124] Aspect 18. The photocurable composition of any one of Aspects 1 to 17, wherein the nonpolymerizable silicone-based additive is present in an amount of at least about 4.5% by weight, preferably at least 5% by weight, preferably at least 5.5% by weight, preferably at least 6% by weight, preferably at least 8.5% by weight, preferably at least 9% by weight, preferably at least 9.5% by weight, and most preferably at least 10% by weight, based on the total weight of the polymerizable components.

[0125] Aspect 19. The photocurable composition of any one of Aspects 1 to 17, wherein the nonpolymerizable silicone-based additive contains less than 0.1% by weight of a cyclic siloxane.

[0126] Aspect 20. The photocurable composition of any one of Aspects 1 to 19, wherein the nonpolymerizable silicone-based additive is not a block copolymer.

[0127] Aspect 21. The photocurable composition according to any one of Aspects 1 to 19, wherein the KOH value (measured according to DIN 53240-2) of the nonpolymerizable silicone additive is less than 20 mg KOH / g, less than 15 mg KOH / g, less than 10 mg KOH / g, less than 5 mg KOH / g, less than 1 mg KOH / g, less than 0.5 mg KOH / g, less than 0.1 mg KOH / g, preferably 0 mg KOH / g.

[0128] Aspect 22. The photocurable composition as described in any one of Aspects 1 to 21, wherein the composition is substantially solvent-free.

[0129] Aspect 23. A method of manufacturing a three-dimensional (3D) printed object, the method comprising curing a photocurable composition as described in any one of Aspects 1 to 22 in a 3D printing process to form a 3D printed object.

[0130] Aspect 24. The method of aspect 23, wherein the 3D printing process is selected from the group consisting of: VAT polymerization, digital light printing (DLP), stereolithography (SLA), inkjet printing, multi-nozzle printing, piezoelectric printing, photocurable extrusion, liquid crystal display (LCD) printing, volumetric printing, and gel deposition printing, and combinations thereof.

[0131] Aspect 25. The method as described in Aspect 23 or 24, wherein the water contact angle of the 3D printed object is greater than or equal to 60°.

[0132] Aspect 26. The method of any one of Aspects 23 to 25, wherein the non-polymerizable silicon-based additive component comprises at least one functionalized siloxane, wherein the functional group is selected from the group consisting of polyethers, polyesters, (poly)alkyl and (poly)araalkyl.

[0133] Aspect 27. The method as described in aspect 26, wherein the functional group is a polyether.

[0134] Aspect 28. The method of any one of Aspects 23 to 26, wherein the non-polymerizable silicon-based additive comprises a functionalized polydimethylsiloxane.

[0135] Aspect 29. The method of any one of Aspects 23 to 28, wherein the non-polymerizable silicon-based additive component comprises polyether-functionalized polydimethylsiloxane.

[0136] Aspect 30. The method of any one of Aspects 23 to 29, wherein the polymerizable resin comprises at least one (meth)acrylate monomer.

[0137] Aspect 31. The method of any one of Aspects 23 to 29, wherein the polymerizable resin comprises at least one (meth)acrylate oligomer.

[0138] Aspect 32. The method of any one of Aspects 23 to 29, wherein the polymerizable resin comprises at least one (meth)acrylate monomer and at least one (meth)acrylate oligomer.

[0139] Aspect 33. The method of any one of Aspects 23 to 32, wherein the photocurable composition further comprises one or more additives selected from the group consisting of ultraviolet absorbers, pigments, stabilizers, and defoamers.

[0140] Aspect 34. The method of any one of Aspects 23 to 33, wherein the photocurable composition comprises about 70% to about 95% by weight of a polymerizable resin based on the total weight of the photocurable composition.

[0141] Aspect 35. The method of any one of Aspects 23 to 34, wherein the photocurable composition comprises about 0.1% to about 10% by weight of a photoinitiator based on the total weight of the polymerizable components.

[0142] Aspect 36. The method of any one of Aspects 23 to 35, wherein the photocurable composition further comprises less than 10% by weight of reactive additives based on the total weight of the nonpolymerizable silicon-based additives.

[0143] Aspect 37. The photocurable composition as described in aspect 36, wherein the reactive additive comprises at least one functional group selected from the group consisting of epoxy, oxetyl, vinyl ether, olefinic unsaturated group and alcohol.

[0144] Aspect 38. The method as described in Aspect 36 or 37, wherein the photocurable composition comprises less than 5% by weight of reactive additives based on the total weight of the nonpolymerizable silicon-based additives.

[0145] Aspect 39. The method as described in Aspect 36 or 37, wherein the photocurable composition comprises less than 1% by weight of reactive additives based on the total weight of the nonpolymerizable silicon-based additives.

[0146] Aspect 40. The method of any one of Aspects 23 to 25, wherein the photocurable composition is free of reactive additives.

[0147] Aspect 41. A method of manufacturing a thermoformed product, the method comprising: heating a thermoplastic material to provide a malleable thermoplastic material; pressing the malleable thermoplastic material against a mold comprising a 3D printed object formed from any one of Aspects 1 to 22; cooling the malleable thermoplastic material to form a thermoformed product; and separating the thermoformed product from the mold.

[0148] Aspect 42. The method of aspect 41, wherein the plastic thermoplastic material is pressed against the mold by vacuum.

[0149] Aspect 43. The method of aspect 41 or 42, wherein the method further comprises trimming away excess thermoplastic material from the thermoformed product.

[0150] Aspect 44. The method of any one of Aspects 41 to 43, wherein the non-polymerizable silicon-based additive comprises at least one functionalized siloxane, wherein the functional group is selected from the group consisting of polyethers, polyesters, (poly)alkyl and (poly)araalkyl.

[0151] Aspect 45. The method as described in aspect 44, wherein the functional group is a polyether.

[0152] Aspect 46. The method of any one of Aspects 41 to 44, wherein the non-polymerizable silicon-based additive component comprises functionalized polydimethylsiloxane.

[0153] Aspect 47. The method of any one of Aspects 41 to 46, wherein the non-polymerizable silicone-based additive component comprises polyether-functionalized polydimethylsiloxane.

[0154] Aspect 48. The method of any one of Aspects 40 to 46, wherein the polymerizable resin comprises at least one (meth)acrylate monomer.

[0155] Aspect 48. The method of any one of aspects 41 to 47, wherein the polymerizable resin comprises at least one (meth)acrylate oligomer.

[0156] Aspect 50. The method of any one of Aspects 41 to 47, wherein the polymerizable resin comprises at least one (meth)acrylate monomer and at least one (meth)acrylate oligomer.

[0157] Aspect 51. The method of any one of Aspects 41 to 50, wherein the photocurable composition further comprises one or more additives selected from the group consisting of ultraviolet absorbers, pigments, stabilizers, and defoamers.

[0158] Aspect 52. The method of any one of aspects 41 to 51, wherein the photocurable composition comprises about 70% to about 95% by weight of a polymerizable resin based on the total weight of the photocurable composition.

[0159] Aspect 53. The method of any one of Aspects 41 to 52, wherein the photocurable composition comprises about 0.1% to about 10% by weight of a photoinitiator based on the total weight of the polymerizable components.

[0160] Aspect 54. The method of any one of Aspects 41 to 53, wherein the photocurable composition further comprises less than 10% by weight of reactive additives based on the total weight of the nonpolymerizable silicon-based additives.

[0161] Aspect 55. The photocurable composition as described in aspect 54, wherein the reactive additive comprises at least one functional group selected from the group consisting of epoxy, oxetyl, vinyl ether, olefinic unsaturated group and alcohol.

[0162] Aspect 56. The method as described in Aspect 54 or 55, wherein the photocurable composition comprises less than 5% by weight of reactive additives based on the total weight of the nonpolymerizable silicone-based additives.

[0163] Aspect 57. The method as described in Aspect 54 or 55, wherein the photocurable composition comprises less than 1% by weight of reactive additives based on the total weight of the nonpolymerizable silicone-based additives.

[0164] Aspect 58. The method of any one of Aspects 41 to 53, wherein the photocurable composition is free of reactive additives.

[0165] Example

[0166] A series of comparative examples and embodiments of photocurable compositions were prepared. For each comparative example and embodiment listed in Table 1, photocurable compositions were prepared using the resins and additives listed in the table.

[0167] The resins used in the comparative examples and embodiments were DMG303, SprintRay Tan, and SprintRay White. SprintRay Tan and SprintRay White were available from SprintRay. The additives used in the comparative examples and embodiments were BYK-333, BYK-3760, CN4004, and trifluoromethacrylate. BYK-333 is polyether-modified PDMS. BYK-3760 is solvent-free polyether-modified PDMS. BYK-333 and BYK-3760 were available from BYK-Chemie GmbH. CN4004 is the fluorinated monomer 1H,1H-perfluorooctyl acrylate. CN4004 was available from Sartomer Americas.

[0168] For each comparative example and embodiment, 200g of resin and additives were mixed and stirred at room temperature using a magnetic stirring plate until all solids dissolved and the photocurable composition was homogeneous. Once the photocurable composition was formed, a mold was created using the photocurable composition in a 3D printing process [i.e., a digital light processing (DLP) 3D printer]. This mold was a tooth model suitable for forming an orthodontic appliance. A 1mm thermoplastic sheet obtained from Great Lakes Dental Technologies under the trade name Clear Splint Biocryl was heated until the thermoplastic material became malleable. The malleable thermoplastic material was molded onto the mold and then cooled to prepare a thermoformed product. After cooling, the thermoformed product was removed from the mold.

[0169] The thermoformed products were removed from the molds by hand by a person skilled in thermoforming orthodontic appliances. The person removing the thermoformed products qualitatively evaluated the demolding performance of the thermoformed products from each mold. The demolding performance of the thermoformed products in each comparative and example mold was evaluated, and a demolding performance rating from 1 to 10 was given. A rating of 1 indicates that it is impossible to remove the thermoformed product from the mold without deforming or damaging it. A rating of 5 indicates that the demolding performance of the thermoformed product is comparable to that of thermoformed products made from conventional plaster molds. A rating of 10 indicates that the thermoformed product can be easily removed from the mold without the use of tools and with minimal physical exertion.

[0170] Table 1

[0171] As shown in Table 1, the inclusion of polyether-modified PDMS additives in the photocurable compositions improves the demolding performance between the mold and the thermoformed product formed from the photocurable composition. Unbound by theory, the inclusion of polyether-modified PDMS additives in the photocurable compositions can reduce the surface energy of the 3D printed mold and minimize surface texture on the 3D printed mold. This, in turn, improves the demolding performance of the mold and reduces the force required to remove the thermoformed product from the mold. Improved demolding performance due to the inclusion of polyether-modified PDMS additives was observed in several different resin compositions, including DMG303, SprintRay Tan, and SprintRay White. Furthermore, fluorinated additives, such as CN4004 and trifluoromethyl acrylate in Comparative Examples 4 and 5, did not show the same improvement in demolding performance as the polyether-modified PDMS additives.

[0172] It will be apparent to those skilled in the art that various modifications and variations can be made without departing from the scope of this disclosure. Since modifications, combinations, sub-combinations, and variations of the disclosed embodiments embodying the spirit and essence of this disclosure are readily apparent to those skilled in the art, the scope of this disclosure should be interpreted to include all contents within the scope of the appended claims and their equivalents.

[0173] For the purpose of limiting the present technology, the transitional phrase "consisting of..." may be introduced into the claims as a closing preposition to limit the scope of the claims to the listed components or steps and any naturally occurring impurities. For the purpose of limiting the present technology, the transitional phrase "consisting substantially of..." may be introduced into the claims to limit the scope of one or more claims to the listed elements, components, materials, or method steps and any unlisted elements, components, materials, or method steps, without materially affecting the novelty of the claimed subject matter.

[0174] Unless otherwise expressly indicated in the context, the singular forms “a,” “an,” and “the” used in this specification and the appended claims include multiple indicators. The verb “comprising” and its cognate forms shall be interpreted as referring to an element, component, or step in a non-exclusive manner. A mentioned element, component, or step may coexist, be used, or be combined with other elements, components, or steps not expressly mentioned.

[0175] It should be understood that any two quantitative values ​​assigned to a property can constitute a range for that property, and this disclosure covers all combinations of ranges formed by all said quantitative values ​​for a given property. The subject matter disclosed herein has been described in detail with reference to specific embodiments. It should be understood that any detailed description of a component or feature of a particular embodiment does not necessarily mean that the component or feature is essential for that particular embodiment or any other embodiment.

Claims

1. A photocurable composition comprising: a) A polymerizable resin comprising one or more polymerizable components; b) From about 2% to about 20% by weight of non-polymerizable silicone-based additives based on the total weight of polymerizable components; c) Optionally, less than 10% by weight of reactive additives based on the total weight of non-polymerizable silicon-based additives; and d) Photoinitiator.

2. The photocurable composition of claim 1, wherein the non-polymerizable silicone-based additive comprises at least one functionalized siloxane, wherein the functional group is selected from the group consisting of polyethers, polyesters, (poly)alkyl and (poly)araalkyl.

3. The photocurable composition of claim 2, wherein the functional group is a polyether.

4. The photocurable composition of claim 1 or 2, wherein the non-polymerizable silicon-based additive comprises functionalized polydimethylsiloxane.

5. The photocurable composition according to any one of claims 1 to 4, wherein the non-polymerizable silicone-based additive comprises polyether-functionalized polydimethylsiloxane.

6. The photocurable composition according to any one of claims 1 to 5, comprising a reactive additive, wherein the reactive additive comprises at least one functional group selected from the group consisting of epoxy, oxetyl, vinyl ether, olefinic unsaturated group and alcohol.

7. The photocurable composition according to any one of claims 1 to 7, wherein the composition comprises 0% by weight of reactive additives based on the total weight of non-polymerizable silicone-based additives.

8. The photocurable composition according to any one of claims 1 to 7, wherein the polymerizable resin comprises at least one (meth)acrylate monomer.

9. The photocurable composition according to any one of claims 1 to 8, wherein the polymerizable resin comprises at least one (meth)acrylate oligomer.

10. The photocurable composition according to any one of claims 1 to 9, further comprising one or more additives selected from the group consisting of ultraviolet absorbers, pigments, stabilizers, and defoamers.

11. The photocurable composition according to any one of claims 1 to 10, wherein when the composition is photocured, the composition forms a solid three-dimensional article with a water contact angle greater than or equal to 60°.

12. A method for manufacturing a three-dimensional (3D) printed object, the method comprising: A photocurable composition is cured in a 3D printing process to form a 3D printed object, wherein the photocurable composition comprises: A polymerizable resin comprising one or more polymerizable components; Based on the total weight of polymerizable components, approximately 2% to approximately 20% by weight of non-polymerizable silicone-based additives; and Photoinitiator.

13. The method of claim 12, wherein the 3D printing process is selected from the group consisting of: VAT polymerization, digital light printing (DLP), stereolithography (SLA), inkjet printing, multi-nozzle printing, piezoelectric printing, photocurable extrusion, liquid crystal display (LCD) printing, volumetric printing, and gel deposition printing, and combinations thereof.

14. A method for manufacturing a thermoformed product, the method comprising: Heating thermoplastic materials to provide plastic thermoplastic materials; The malleable thermoplastic material is pressed against a mold containing a 3D-printed object formed from a photocurable composition, wherein the photocurable composition comprises: A polymerizable resin comprising one or more polymerizable components; From about 2% to about 20% by weight of the total polymerizable components, nonpolymerizable silicone-based additives; and Photoinitiator; Cooling the plastic thermoplastic material to form a thermoformed product; and Separate the thermoformed product from the mold.

15. The method of claim 14, wherein the plastic thermoplastic material is pressed against the mold by vacuum.

16. A photocurable composition comprising: a) A polymerizable resin comprising one or more polymerizable components; b) at least about 4.5% to about 20% by weight of a nonpolymerizable silicone additive based on the total weight of the polymerizable components, wherein the nonpolymerizable silicone additive is free of any urethane groups; c) Optionally, less than 10% by weight of reactive additives based on the total weight of non-polymerizable silicon-based additives; and d) Photoinitiator, The composition described therein is substantially solvent-free.

17. A photocurable composition comprising: a) A polymerizable resin comprising one or more polymerizable components; b) at least about 8.5% to about 20% by weight of a nonpolymerizable silicone additive based on the total weight of the polymerizable components, wherein the nonpolymerizable silicone additive is free of any urethane groups; c) Optionally, less than 10% by weight of reactive additives based on the total weight of non-polymerizable silicon-based additives; and d) Photoinitiator.

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