Thermosetting composition and formation of three-dimensional object therefrom

Abstract

Disclosed herein are thermosetting compositions and methods for forming three-dimensional articles via additive manufacturing processes, as well as articles produced therefrom. In one embodiment, the composition comprises a first network-forming component comprising a first oligomer having a backbone and at least two polymerizable groups, one or more first network monomers, and a first network initiator. The backbone of the first oligomer comprises bisphenol A, F, or S polyepoxide, hydrogenated bisphenol A, F, or S polyepoxide, polycarbonate, or polyimide. The composition can further comprise a second network-forming component. [Selection diagram] None

Description

Detailed Description of the Invention

[0001] [Field] The present invention relates to a thermosetting composition, a method for manufacturing a three-dimensional object by a laminated manufacturing technique, and an article manufactured therefrom.

[0002] [Background] Laminated manufacturing, also known as three-dimensional printing, is a technique for constructing a three-dimensional object based on computer data, depositing the object in parts one at a time until the final three-dimensional object is manufactured. The additive technique can be contrasted with subtractive techniques such as cutting that manufacture a three-dimensional object by removing a portion of the material from a larger amount of material than the final three-dimensional object.

[0003] Various types of materials are used in the laminated manufacturing process. Generally, for example, thermoplastic materials are used in the fused filament fabrication (FFF) process and the selective laser sintering (SLS) process, while thermosetting materials are used in, for example, vat based processes and processes involving the injection of liquid materials.

[0004] Generally, electromagnetic radiation is utilized to accelerate the rapid curing of thermosetting materials. The electromagnetic radiation can be UV light, visible light, or infrared light, and can be applied, for example, by a laser, a lamp, or an LED. The electromagnetic radiation can be applied selectively, for example, by using a digital micromirror device (DMD) or a mask to draw a specific pattern with a laser, or non-selectively, for example, by passing a lamp over the entire surface. Post-treatment may be required by applying further temperature or light to the newly formed three-dimensional object in order to impart desired properties to the three-dimensional object formed from the thermosetting composition.

[0005] Thermosetting materials for additive manufacturing have undergone various evolutions to improve the mechanical properties of the final article. For example, U.S. Patent Application Publication No. 2010 / 0304088 describes a radiation-curable resin composition containing a cationically polymerizable component and an impact resistance improver (by which, after complete curing, a material having a high tensile elastic modulus and high toughness showing high impact strength and / or high crack propagation resistance is obtained).

[0006] U.S. Patent Application Publication No. 2011 / 0104500 describes a radiation-curable resin in which the cured product has a desirable combination of elastic modulus, impact strength, heat deflection temperature, and water absorption. This radiation-curable resin contains a combination of an epoxy-functional component, an oxetane component, a (meth)acrylate component, an impact resistance improver, a photo radical initiator, and a photo cationic initiator.

[0007] In recent years, thermosetting materials for additive manufacturing have undergone various evolutions, but in this industry, there has been a continuing demand for even better mechanical properties. Materials that have not yet been realized include, for example, photocurable materials having both a high glass transition temperature (Tg) and high toughness.

[0008] [Summary] The present invention utilizes an oligomer comprising i) a main chain containing bisphenol A, F, or S type polyepoxide, hydrogenated bisphenol A, F, or S type polyepoxide, polycarbonate, or polyimide, and ii) at least 2 polymerizable groups per molecule on average, wherein the polymerizable groups include acrylate, methacrylate, itaconate, vinyl ether, allyl ether, maleate, or fumarate (hereinafter, the "first oligomer"). The first oligomer has a number average molecular weight of 800 to 10,000 g / mol and a glass transition temperature (Tg) of 40°C or higher. The first oligomer can be used in a composition such as a composition for forming a three-dimensional object through an additive manufacturing process, or can be used as a kit of materials in which a composition is produced by combining the components of the kit of materials.

[0009] In one embodiment, the first oligomer is present as part of a first network-forming component comprising, in the composition, 19.95 to 80% by weight of the first oligomer, 19.95 to 80% by weight of one or more first network monomers having 0.95 to 1.1 polymerizable groups on average, 0.05 to 5% by weight of one or more first network-forming initiators, and optionally, one or more other first network monomers, oligomers, or polymers having two or more polymerizable groups on average and 15% by weight or less. The substituents of the first network-forming component are (co)polymerizable with the polymerizable groups of the first oligomer and / or one or more first network monomers. If the components of the polymerizable composition cannot (co)polymerize with any of the first network-forming components, this component cannot become a first network-forming component. A particulate filler containing a polymerizable group (co)polymerizable with the polymerizable group of the first oligomer is not part of the first network-forming component.

[0010] An optional second network-forming component can be present in the composition. The second network-forming component includes one or more second network compounds containing polymerizable groups that do not (co)polymerize with the polymerizable groups of the first oligomer, and a second network initiator for initiating the polymerization of the one or more second network compounds.

[0011] The components of the composition can also be provided separately as a kit of materials. Further embodiments of the present invention are described below.

[0012] [Detailed Description] A composition for forming a three-dimensional object via a stereolithography process includes at least a first network-forming component. In one embodiment, the composition for forming a three-dimensional object via a stereolithography process consists of the first network-forming component.

[0013] The first network-forming component includes at least a first oligomer, one or more first network monomers, and a first network initiator. In one embodiment, the first network-forming component consists of at least a first oligomer, one or more first network monomers, and a first network initiator. The first oligomer needs to be soluble in one or more first network monomers, so that when they are mixed together, a part of the first network-forming component needs to exist as a transparent liquid.

[0014] In one embodiment, the first network-forming component is present in an amount of 20% by weight or more, 25% by weight or more, 30% by weight or more, 35% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, 90% by weight or more, 95% by weight or more, or 100% by weight, based on the total weight of the composition. In one embodiment, the first network-forming component is present in an amount of 100% by weight or less, 90% by weight or less, 80% by weight or less, 70% by weight or less, or 60% by weight or less, based on the total weight of the composition.

[0015] In one embodiment, the first network-forming component is present in an amount of 20% by weight or more, 25% by weight or more, 30% by weight or more, 35% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, 90% by weight or more, 95% by weight or more, or 100% by weight, based on the total weight of the composition excluding the weight of the solvent (if present). The solvent is a non-reactive liquid in which the components of the composition are dissolved. Usually, the solvent is a low molecular weight alcohol or water depending on the reactive functional groups of the composition. In one embodiment, the first network-forming component is present in an amount of 100% by weight or less, 90% by weight or less, 80% by weight or less, 70% by weight or less, or 60% by weight or less, based on the total weight of the composition excluding the solvent (if present).

[0016] In one embodiment, the first network-forming component is present in an amount of 20% by weight or more, 25% by weight or more, 30% by weight or more, 35% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, 90% by weight or more, 95% by weight or more, or 100% by weight, based on the weight of the composition excluding the weight of the solvent (if present) and the weight of the component(s) not containing a polymerizable group (e.g., non-reactive particulate filler) (if present). In one embodiment, the first network-forming component is present in an amount of 100% by weight or less, 90% by weight or less, 80% by weight or less, 70% by weight or less, or 60% by weight or less, based on the total weight of the composition excluding the solvent (if present) and the component(s) not containing a polymerizable group (if present).

[0017] Optionally, the composition further comprises one or more additional first network monomers, oligomers, or polymers having, on average, two or more polymerizable groups that are (co)polymerizable with the polymerizable groups of the first oligomer or one or more first network monomers.

[0018] Optionally, the composition further comprises a second network-forming component comprising one or more second network compounds that do not (co)polymerize with the first network-forming component and a second network initiator for initiating the polymerization of the one or more second network compounds. For example, the first network-forming component can be polymerizable by radical polymerization, and the second network-forming component can be polymerizable by cationic polymerization.

[0019] The following is a non-limiting list of (co)polymerizable groups or non-(co)polymerizable groups for the purposes of this application. An acrylate group, a methacrylate group, an itaconate group, an allyl ether group, a maleate group, or a fumarate group (co)polymerizes with an acrylate group, a methacrylate group, an itaconate group, a vinyl ether group, an allyl ether group, a maleate group, or a fumarate group, and does not (co)polymerize with, for example, a hydroxyl group, an epoxy group, and an oxetane group. A hydroxyl group, an epoxy group, and an oxetane group (co)polymerize with a hydroxyl group, an epoxy group, an oxetane group, and a vinyl ether group, and do not (co)polymerize with an acrylate group, a methacrylate group, an itaconate group, an allyl ether group, a maleate group, or a fumarate group. A vinyl ether group (co)polymerizes with an acrylate group, a methacrylate group, an epoxy group, an oxetane group, a hydroxyl group, an itaconate group, a vinyl ether group, an allyl ether group, a maleate group, or a fumarate group.

[0020] Thus, when the first oligomer contains, on average per molecule, at least 2 acrylate groups, methacrylate groups, itaconate groups, allyl ether groups, maleate groups, or fumarate groups, one or more first network monomers contain acrylate groups, methacrylate groups, itaconate groups, vinyl ether groups, allyl ether groups, maleate groups, or fumarate groups, and any optional one or more additional first network monomers, oligomers, or polymers contain, on average, 2 or more acrylate groups, methacrylate groups, itaconate groups, vinyl ether groups, allyl ether groups, maleate groups, or fumarate groups. When the first oligomer contains, on average per molecule, at least 2 vinyl ether groups, one or more first network monomers contain acrylate groups, methacrylate groups, itaconate groups, hydroxyl groups, epoxy groups, oxetane groups, vinyl ether groups, allyl ether groups, maleate groups, or fumarate groups, and any optional one or more additional first network monomers, oligomers, or polymers contain, on average, 2 or more acrylate groups, methacrylate groups, itaconate groups, hydroxyl groups, epoxy groups, oxetane groups, vinyl ether groups, allyl ether groups, maleate groups, or fumarate groups.

[0021] In one embodiment, the first oligomer includes a plurality of different types of polymerizable groups. In one embodiment, the first oligomer includes a combination of methacrylate groups and acrylate groups. In one embodiment, the first oligomer includes radical polymerizable groups and cationic polymerizable groups. In one embodiment, the first oligomer includes i) at least one polymerizable group selected from acrylate, methacrylate, itaconate, allyl ether, maleate, or fumarate, and ii) at least one polymerizable group selected from hydroxyl, epoxy, or oxetane. In one embodiment, the first oligomer does not include cationic polymerizable groups. When the first oligomer includes i) at least one polymerizable group selected from acrylate, methacrylate, itaconate, allyl ether, maleate, or fumarate, and ii) at least one polymerizable group selected from hydroxyl, epoxy, or oxetane, one or more types of the first network monomers include acrylate groups, methacrylate groups, itaconate groups, hydroxyl groups, epoxy groups, oxetane groups, vinyl ether groups, allyl ether groups, maleate groups, or fumarate groups, and optional one or more additional first network monomers, oligomers, or polymers include, on average, two or more acrylate groups, methacrylate groups, itaconate groups, hydroxyl groups, epoxy groups, oxetane groups, vinyl ether groups, allyl ether groups, maleate groups, or fumarate groups. In one embodiment, the first oligomer includes i) at least one acrylate group or methacrylate group and ii) at least one epoxy group.

[0022] Throughout the present application, when a polymerizable group is referred to as "epoxy" or "epoxy group", this is intended to include, but is not limited to, epoxy groups, oxirane groups, oxiranyl groups, glycidyl groups, or alicyclic epoxy groups.

[0023] A further optional component is a particulate filler that may or may not be (co)polymerizable with the first network-forming component.

[0024] [First Oligomer Component] A composition for forming a three-dimensional object includes a first oligomer. The first oligomer includes a main chain and, on average, at least two polymerizable groups per molecule. The main chain includes bisphenol A, F, or S type polyepoxide, hydrogenated bisphenol A, F, or S type polyepoxide, polycarbonate, or polyimide. In one embodiment, the main chain includes bisphenol A type or hydrogenated bisphenol A type polyepoxide. In one embodiment, the main chain includes bisphenol A type polycarbonate. In one embodiment, the main chain includes a mixture of two or more of bisphenol A, F, or S type polyepoxide, hydrogenated bisphenol A, F, or S type polyepoxide, polycarbonate, or polyimide. In one embodiment, the main chain includes aromatic polycarbonate. In one embodiment, the main chain includes aromatic polyimide.

[0025] In one embodiment, the Tg of the first oligomer is at least 40°C, at least 45°C, at least 50°C, at least 55°C, at least 60°C, at least 65°C, or at least 70°C. In one embodiment, the Tg of the first oligomer is 150°C or lower, 125°C or lower, or 120°C or lower.

[0026] In one embodiment, the main chain further includes units formed from a polyol. A polyol is an alcohol having two or more hydroxyl groups. In one embodiment, the polyol includes a polyalkylene polyol or a polyalkylene oxide polyol. In one embodiment, the polyol is polyethylene glycol, polypropylene glycol, polytetramethylene oxide (PTMO) polyol, a random or block polypropylene oxide - polyethylene oxide copolymer polyol, a random or block polytetramethylene oxide - polyethylene oxide copolymer polyol, a polycarbonate polyol, a hydroxyl - terminated silicone, a hydroxyalkyl - terminated silicone, a random or block silicone - polyethylene oxide copolymer polyol, a polybutadiene polyol, a polyisobutylene polyol, a polybutylene oxide polyol, or a mixture thereof.

[0027] In one embodiment, the polyol includes 1,4 - butanediol, 1,2 - propylene glycol, 1,3 - propylene glycol, dipropylene glycol, tripropylene glycol, ethylene glycol, diethylene glycol, triethylene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, octametnylene glycol, decamethylene glycol, neopentyl glycol, 1,6 - hexanediol, hydrogenated bisphenol A, ethoxylated bisphenol A, propoxylated bisphenol A, glycerol, 1,2,6 - hexanetriol, 1,1,1 - tris(hydroxymethyl)propane, pentane - 1,2,3 - triol, propane - 1,1,1 - triol, 1,2 - cyclohexanediol, 1,4 - cyclohexanediol, 1,1 - cyclohexanedimethanol, cyclohexane - 1,2,4 - triol, cyclopropane - 1,2,3 - triol, benzenetriol, pentane - 1,1,5,5 - tetraol, hexane - 1,2,5,6 - tetraol, 1,2,4,5 - tetrahydroxybenzene, butane - 1,2,3,4 - tetraol, [1,1’ - biphenyl] - 3,3’,5,5’ - tetraol, trimethylolpropane, pentaerythritol, 1,4 - cyclohexanedimethanol, phenyldiethanolamine, or a mixture thereof.

[0028] In one embodiment, the first oligomer further comprises a reaction product of a polyvalent acid and a polyol. In one embodiment, the polyvalent acid is an aliphatic polyvalent acid or an aromatic polyvalent acid. In one embodiment, the polyvalent acid comprises a dicarboxylic acid represented by the general formula HOOC-Z-COOH (wherein Z is an aliphatic compound containing at least 2 carbon atoms). Examples of this type of dicarboxylic acid include adipic acid, sebacic acid, phthalic acid, terephthalic acid, isophthalic acid, octadecanedioic acid, pimelic acid, suberic acid, azelaic acid, brassilic acid, dodecanedioic acid, glutaric acid, maleic acid, fumaric acid, 6-naphthalenedicarboxylic acid, 4,4'-oxybisbenzoic acid, 3,6-dichlorophthalic acid, tetrachlorophthalic acid, tetrahydrophthalic acid, hexahydroterephthalic acid, hexachloroendomethylenetetrahydrophthalic acid, endomethylene tetrahydrophthalic acid, decanedicarboxylic acid, succinic acid, and trimellitic acid. In one embodiment, the additional polyvalent acid comprises phthalic acid, isophthalic acid, or terephthalic acid.

[0029] In one embodiment, at least 20 mol%, at least 30 mol%, at least 40 mol%, at least 50 mol%, at least 60 mol%, at least 70 mol%, at least 75 mol%, at least 80 mol%, at least 85 mol%, at least 90 mol%, at least 95 mol%, at least 98 mol%, or 100 mol% of the main chain of the first oligomer comprises bisphenol A, F, or S type polyepoxide, hydrogenated bisphenol A, F, or S type polyepoxide, polycarbonate, or polyimide. In one embodiment, up to 100 mol%, up to 98 mol%, up to 95 mol%, up to 90 mol%, up to 80 mol%, up to 70 mol%, or up to 60 mol% of the main chain of the first oligomer comprises bisphenol A, F, or S type polyepoxide, hydrogenated bisphenol A, F, or S type polyepoxide, polycarbonate, or polyimide.

[0030] The first oligomer contains a polymerizable group including acrylate, methacrylate, itaconate, vinyl ether, allyl ether, maleate, or fumarate. In one embodiment, the polymerizable group includes acrylate or methacrylate. In one embodiment, the polymerizable group includes methacrylate. The polymerizable group can be formed, for example, by reacting an OH group on the polymer with a diisocyanate or a higher isocyanate, and then reacting a hydroxyl-functional monomer containing the desired polymerizable group with the isocyanate group on the polymer. For example, the hydroxyl-functional monomer can be hydroxyethyl methacrylate.

[0031] In one embodiment, the polymerizable group contains a terminal group. The terminal group is a group present at the end of the polymer. In one embodiment, the polymerizable group is a terminal group, and there is no polymerizable group that is not a terminal group in the first oligomer.

[0032] In one embodiment, the first oligomer contains, on average per molecule, 2.0, at least 2.1, at least 2.2, at least 2.3, at least 2.4, at least 2.5, at least 2.6, or at least 2.7 polymerizable groups. In one embodiment, the first oligomer contains, on average per molecule, at most 10, at most 9, at most 8, at most 7, at most 6, at most 5, at most 4.5, at most 4, at most 3.5, or at most 3 polymerizable groups. In one embodiment, the first oligomer contains 2.3 to 3 polymerizable groups. Generally, as the functionality number of the first oligomer increases, the amount of the first oligomer in the composition may decrease.

[0033] In one embodiment, the number average molecular weight of the first oligomer is at least 800 g / mol, at least 900 g / mol, at least 1000 g / mol, at least 1100 g / mol, at least 1200 g / mol, at least 1300 g / mol, at least 1400 g / mol, or at least 1500 g / mol. In one embodiment, the number average molecular weight of the first oligomer is at most 10,000 g / mol, at most 9,000 g / mol, at most 8,000 g / mol, at most 7000 g / mol, at most 6,000 g / mol, at most 5,000 g / mol, at most 4,000 g / mol, or at most 3,000 g / mol.

[0034] In one embodiment, the first oligomer has 2 to 3 polymerizable groups on average, and the amount, number average molecular weight, and number average of polymerizable groups of the first oligomer in the composition are adjusted to the crosslink density of the network after curing by the following formula: [Number] (wherein R is the gas constant 8.314 cm 3 MPa K -1 mol -1 , T is 423.15 K, f is the number average of polymerizable groups of the first oligomer, ρ is the density of the first oligomer (g / cm 3 ), M oligomer is the number average molecular weight of the first oligomer (g / mol), and w oligomer is the weight fraction of the first oligomer in the first network-forming component) is satisfied. In one embodiment, X is 3, 5, 7, 10, 15, or 20. In one embodiment, Y is 50, 45, or 40. In one embodiment, the first oligomer has 2 to 3 end groups on average, and the amount, number average molecular weight, and number average of end groups of the first oligomer in the composition satisfy the above formula, and f is the number average of end groups of the first oligomer.

[0035] By blending first oligomers having different functional group numbers, it is also possible to impart 2 to 3 polymerizable groups per molecule on average to the first oligomers. For example, by using 70 mol% of a first oligomer having 2.3 polymerizable groups per molecule on average and 30 mol% of a first oligomer having 4.0 polymerizable groups per molecule on average, it is conceivable to obtain a first oligomer having 2.8 polymerizable groups per molecule on average. In this example, f in the above formula becomes 2.8, and M oligomer is determined based on the mol% of each first oligomer.

[0036] In one embodiment, the first oligomer is present in an amount of at least 5 wt%, at least 10 wt%, at least 15 wt%, at least 19.95 wt%, at least 20 wt%, at least 25 wt%, at least 30 wt%, at least 40 wt%, at least 50 wt%, at least 60 wt%, at least 70 wt%, or at least 80 wt% based on the total weight of the composition. In one embodiment, the first oligomer is present in an amount of up to 80 wt%, up to 78 wt%, up to 75 wt%, up to 70 wt%, up to 60 wt%, up to 50 wt%, up to 40 wt%, up to 30 wt%, or up to 20 wt% based on the total weight of the composition.

[0037] In one embodiment, the first oligomer is present in an amount of at least 5 wt%, at least 10 wt%, at least 15 wt%, at least 19.95 wt%, at least 20 wt%, at least 25 wt%, at least 30 wt%, at least 40 wt%, at least 50 wt%, at least 60 wt%, at least 70 wt%, or at least 80 wt% based on the total weight of the composition excluding the solvent (if present). In one embodiment, the first oligomer is present in an amount of up to 80 wt%, up to 78 wt%, up to 75 wt%, up to 70 wt%, up to 60 wt%, up to 50 wt%, up to 40 wt%, up to 30 wt%, or up to 20 wt% based on the total weight of the composition excluding the first oligomer and the solvent (if present).

[0038] In one embodiment, the first oligomer is present in an amount of 19.95 wt%, at least 20 wt%, at least 25 wt%, at least 30 wt%, at least 40 wt%, at least 50 wt%, at least 60 wt%, at least 70 wt%, or at least 80 wt% based on the total weight of the first network-forming component. In one embodiment, the first oligomer is present in an amount of up to 80 wt%, up to 78 wt%, up to 75 wt%, up to 70 wt%, up to 60 wt%, up to 50 wt%, up to 40 wt%, up to 30 wt%, or up to 20 wt% based on the total weight of the first network-forming component.

[0039] In one embodiment, the first oligomer is amorphous. In one embodiment, the first oligomer comprises a blend of an amorphous first oligomer and a semi-crystalline first oligomer. In one embodiment, the first oligomer comprises a blend of an amorphous first oligomer, a semi-crystalline first oligomer, and a crystalline first oligomer.

[0040] [First network monomer and first network initiator] A composition for forming a three-dimensional object via an additive manufacturing process comprises, in addition to the first oligomer, one or more first network monomers and a first network initiator. Depending on the polymerizable groups of the first oligomer, the first network monomer and any optional one or more further first network monomers, oligomers, or polymers may be radical-polymerizable compounds or cationically-polymerizable compounds, and the first network initiator may be a radical initiator or a cationic initiator. In one embodiment, the first oligomer comprises polymerizable groups including acrylate, methacrylate, itaconate, allyl ether, maleate, or fumarate, the first network monomer and any optional one or more further first network monomers, oligomers, or polymers are radical-polymerizable compounds, and the first network initiator is a radical initiator.

[0041] In one embodiment, the first oligomer contains at least two acrylate groups, methacrylate groups, itaconate groups, allyl ether groups, or fumarate groups on average per molecule, and one or more types of first network monomers contain acrylate groups, methacrylate groups, itaconate groups, vinyl ether groups, allyl ether groups, maleate groups, or fumarate groups. Optional one or more additional first network monomers, oligomers, or polymers contain two or more acrylate groups, methacrylate groups, itaconate groups, vinyl ether groups, allyl ether groups, maleate groups, or fumarate groups on average. In one embodiment, the first oligomer contains at least two vinyl ether groups on average per molecule, and one or more types of first network monomers contain acrylate groups, methacrylate groups, itaconate groups, hydroxyl groups, epoxy groups, oxetane groups, vinyl ether groups, allyl ether groups, maleate groups, or fumarate groups. Optional one or more additional first network monomers, oligomers, or polymers contain two or more acrylate groups, methacrylate groups, itaconate groups, hydroxyl groups, epoxy groups, oxetane groups, vinyl ether groups, allyl ether groups, maleate groups, or fumarate groups on average.

[0042] The polymerizable groups of the first network monomers can (co)polymerize with the polymerizable groups of the first oligomer. The first network monomers have 0.95 to 1.1 polymerizable groups on average. In one embodiment, the first network monomers have 0.95 or more polymerizable groups, 0.97 or more polymerizable groups, or 0.99 or more polymerizable groups on average. In one embodiment, the first network monomers have 1.1 or fewer polymerizable groups, 1.08 or fewer polymerizable groups, 1.06 or fewer polymerizable groups, 1.04 or fewer polymerizable groups, or 1.02 or fewer polymerizable groups on average. In one embodiment, the first network monomers have 1.0 polymerizable groups on average.

[0043] The Tg of the linear polymer formed from one or more first network monomers is 40 °C or higher. In one embodiment, the Tg of the linear polymer formed from one or more first network monomers is 50 °C or higher, 60 °C or higher, 65 °C or higher, 70 °C or higher, 75 °C or higher, 80 °C or higher, 85 °C or higher, 90 °C or higher, 95 °C or higher, or 100 °C or higher. In one embodiment, the Tg of the linear polymer formed from one or more first network monomers is 150 °C or lower, 130 °C or lower, 125 °C or lower, or 120 °C or lower. It is also possible to have multiple first network monomers with different molecular formulas present in one or more first network monomers, some of whose Tg values are higher than the claimed amount and some are lower than the claimed amount. The linear polymer is formed from all of the combined first network monomers, and the Tg of the linear polymer is measured to determine whether it is within the claimed range.

[0044] In one embodiment, the molecular weight of one or more first network monomers is 800 g / mol or lower, 700 g / mol or lower, 600 g / mol or lower, 500 g / mol or lower, 400 g / mol or lower, 350 g / mol or lower, 300 g / mol or lower, 250 g / mol or lower, or 200 g / mol or lower. In one embodiment, one or more first network monomers have a molecular weight of 100 g / mol or higher or 150 g / mol or higher.

[0045] In one embodiment, the first oligomer includes a polymerizable group including acrylate, methacrylate, itaconate, vinyl ether, allyl ether, maleate, or fumarate, and the first network monomer includes methyl (meth)acrylate, hydroxyethyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, isobornyl (meth)acrylate, isobutyl acrylate, acryloylmorpholine, dimethyl itaconate, N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole, or N-methyl-N-acetamide. In one embodiment, the first oligomer includes a polymerizable group including acrylate, methacrylate, itaconate, vinyl ether, allyl ether, maleate, or fumarate, and the first network monomer includes cyclohexyl vinyl ether, 1,4-cyclohexanedimethanol monovinyl ether, tert-butyl vinyl ether, phenyl vinyl ether, allyl phenyl ether, dimethyl maleate, diethyl maleate, dimethyl fumarate, or diethyl fumarate.

[0046] In one embodiment, the first oligomer includes a polymerizable group including hydroxyl, epoxy, oxetane, or vinyl ether, and the one or more first network monomers include cyclohexene oxide, tert-butyl glycidyl ether, 4-chlorophenyl glycidyl ether, cyclopentene oxide, exo-2,3-epoxynorbornane, 1,2-epoxy-3-phenoxypropane, (2,3-epoxypropyl)benzene, N-(2,3-epoxypropyl)phthalimide, exo-3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride, 3,4-epoxytetrahydrothiophene-1,1-dioxide, furfuryl glycidyl ether, 4-methoxyphenyl glycidyl ether, 2-methylphenyl glycidyl ether, isophorone oxide, α-pinene oxide, cis-stilbene oxide, styrene oxide, methyl, methyl 7-oxabicyclo[4.1.0]heptane-3-carboxylate, 2-ethylhexyl 7-oxabicyclo(4.1.0)heptane-3-carboxylate carboxylate, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(3-hydroxypropyl)oxymethyloxetane, 3-ethyl-3-(4-hydroxybutyl)oxymethyloxetane, cyclohexyl vinyl ether, 1,4,-cyclohexanedimethanol monovinyl ether, tert-butyl vinyl ether, or phenyl vinyl ether.

[0047] In one embodiment, the one or more first network monomers are present in an amount of at least 10 wt%, at least 15 wt%, at least 19.95 wt%, at least 20 wt%, at least 25 wt%, at least 30 wt%, at least 40 wt%, at least 50 wt%, at least 60 wt%, at least 70 wt%, or at least 80 wt% based on the total weight of the composition. In one embodiment, the one or more first network monomers are present in an amount of at most 80 wt%, at most 78 wt%, at most 75 wt%, at most 70 wt%, at most 60 wt%, at most 50 wt%, at most 40 wt%, at most 30 wt%, or at most 20 wt% based on the total weight of the composition.

[0048] In one embodiment, the one or more first network monomers are present in an amount of at least 10 wt%, at least 15 wt%, at least 19.95 wt%, at least 20 wt%, at least 25 wt%, at least 30 wt%, at least 40 wt%, at least 50 wt%, at least 60 wt%, at least 70 wt%, or at least 80 wt% based on the total weight of the composition excluding the solvent (if present). In one embodiment, the one or more first network monomers are present in an amount of up to 80 wt%, up to 78 wt%, up to 75 wt%, up to 70 wt%, up to 60 wt%, up to 50 wt%, up to 40 wt%, up to 30 wt%, or up to 20 wt% based on the total weight of the composition excluding the solvent (if present).

[0049] In one embodiment, the one or more first network monomers are present in an amount of at least 19.95 wt%, at least 20 wt%, at least 25 wt%, at least 30 wt%, at least 40 wt%, at least 50 wt%, at least 60 wt%, at least 70 wt%, or at least 80 wt% based on the total weight of the first network-forming component. In one embodiment, the one or more first network monomers are present in an amount of up to 80 wt%, up to 78 wt%, up to 75 wt%, up to 70 wt%, up to 60 wt%, up to 50 wt%, up to 40 wt%, up to 30 wt%, or up to 20 wt% based on the total weight of the first network-forming component.

[0050] The first network initiator serves to initiate the polymerization of a first oligomer, one or more first network monomers, optionally one or more additional first network monomers, oligomers, or polymers, and optionally particulate fillers containing polymerizable groups copolymerizable with the polymerizable groups of the first oligomer. In one embodiment, one or more first network initiators include a photoinitiator or a thermal initiator. In one embodiment, one or more first network initiators include a photoinitiator that reacts to UV light, visible light, or both UV light and visible light to initiate polymerization. In one embodiment, one or more first network initiators include a photoinitiator that initiates polymerization at a wavelength of 300 - 470 nm. In one embodiment, one or more first network initiators include a photoinitiator that initiates polymerization at a wavelength of 300 - 395 nm. In one embodiment, one or more first network initiators include a photoinitiator and a thermal initiator.

[0051] In one embodiment, one or more first network initiators include a thermal initiator. The thermal initiator can be used to further cure the composition when the article formed from the composition is thermally post-treated.

[0052] In one embodiment, one or more first network initiators are present in an amount of at least 0.01 wt%, at least 0.05 wt%, at least 0.1 wt%, at least 0.2 wt%, at least 0.3 wt%, at least 0.4 wt%, at least 0.5 wt%, at least 1.0 wt%, at least 1.5 wt%, at least 2 wt%, or at least 2.5 wt% based on the total weight of the composition. In one embodiment, one or more first network monomers are present in an amount of at most 10 wt%, at most 8 wt%, at most 7 wt%, at most 6 wt%, at most 5 wt%, or at most 4 wt% based on the total weight of the composition.

[0053] In one embodiment, the one or more first network initiators are present in an amount of at least 0.01 wt%, at least 0.05 wt%, at least 0.1 wt%, at least 0.2 wt%, at least 0.3 wt%, at least 0.4 wt%, at least 0.5 wt%, at least 1.0 wt%, at least 1.5 wt%, at least 2 wt%, or at least 2.5 wt% based on the total weight of the composition excluding the solvent (if present). In one embodiment, the one or more first network monomers are present in an amount of at most 10 wt%, at most 8 wt%, at most 7 wt%, at most 6 wt%, at most 5 wt%, or at most 4 wt% based on the total weight of the composition excluding the solvent (if present).

[0054] In one embodiment, the one or more first network initiators are present in an amount of at least 0.01 wt%, at least 0.05 wt%, at least 0.1 wt%, at least 0.2 wt%, at least 0.3 wt%, at least 0.4 wt%, at least 0.5 wt%, at least 1.0 wt%, at least 1.5 wt%, at least 2 wt%, or at least 2.5 wt% based on the total weight of the first network-forming components. In one embodiment, the one or more first network initiators are present in an amount of at most 10 wt%, at most 8 wt%, at most 7 wt%, at most 6 wt%, at most 5 wt%, or at most 4 wt% based on the total weight of the first network-forming components.

[0055] [Additional first network monomers, oligomers, or polymers] Optionally, the composition of the present invention comprises one or more additional first network monomers, oligomers, or polymers having, on average, two or more polymerizable groups copolymerizable with the polymerizable groups of the first oligomer or the one or more first network monomers.

[0056] In one embodiment, one or more additional first network monomers, oligomers, or polymers are present in an amount of up to 15 wt%, up to 12 wt%, up to 10 wt%, up to 8 wt%, up to 6 wt%, up to 5 wt%, up to 4 wt%, up to 3 wt%, or up to 2 wt% based on the total weight of the composition. In one embodiment, one or more additional first network monomers, oligomers, or polymers are present in an amount of at least 0.5 wt%, at least 1 wt%, at least 1.5 wt%, at least 2 wt%, at least 2.5 wt%, at least 4 wt%, or at least 5 wt% based on the total weight of the composition.

[0057] In one embodiment, one or more additional first network monomers, oligomers, or polymers are present in an amount of up to 15 wt%, up to 12 wt%, up to 10 wt%, up to 8 wt%, up to 6 wt%, up to 5 wt%, up to 4 wt%, up to 3 wt%, or up to 2 wt% based on the total weight of the composition excluding the solvent (if present). In one embodiment, one or more additional first network monomers, oligomers, or polymers are present in an amount of at least 0.5 wt%, at least 1 wt%, at least 1.5 wt%, at least 2 wt%, at least 2.5 wt%, at least 4 wt%, or at least 5 wt% based on the total weight of the composition excluding the solvent (if present).

[0058] In one embodiment, one or more additional first network monomers, oligomers, or polymers are present in an amount of up to 15 wt%, up to 12 wt%, up to 10 wt%, up to 8 wt%, up to 6 wt%, up to 5 wt%, up to 4 wt%, up to 3 wt%, or up to 2 wt% based on the total weight of the first network-forming components. In one embodiment, one or more additional first network monomers, oligomers, or polymers are present in an amount of at least 0.5 wt%, at least 1 wt%, at least 1.5 wt%, at least 2 wt%, at least 2.5 wt%, at least 4 wt%, or at least 5 wt% based on the total weight of the first network-forming components.

[0059] [Optional second network-forming component] Optionally, the composition of the present invention contains a second network-forming component. The second network-forming component includes one or more second network compounds containing polymerizable groups that do not (co)polymerize with the polymerizable groups of the first oligomer, and a second network initiator for initiating the polymerization of the one or more second network compounds. In one embodiment, the first oligomer contains polymerizable groups including acrylate, methacrylate, or itaconate, and the one or more second network compounds contain polymerizable groups including epoxy, oxetane, or hydroxyl.

[0060] In one embodiment, the second network-forming component is present in an amount of 5 wt% or more, 10 wt% or more, 15 wt% or more, 20 wt% or more, 25 wt% or more, 30 wt% or more, 35 wt% or more, 40 wt% or more, 50 wt% or more, 60 wt% or more, or 70 wt% or more based on the total weight of the composition. In one embodiment, the second network-forming component is present in an amount of 90 wt% or less, 80 wt% or less, 70 wt% or less, 60 wt% or less, 50 wt% or less, 40 wt% or less, 30 wt% or less, or 20 wt% or less based on the total weight of the composition. In one embodiment, the composition of the present invention does not contain a second network-forming component. In one embodiment, the composition of the present invention substantially does not contain a second network-forming component.

[0061] In one embodiment, the second network-forming component is present in an amount of 5 wt% or more, 10 wt% or more, 15 wt% or more, 20 wt% or more, 25 wt% or more, 30 wt% or more, 35 wt% or more, 40 wt% or more, 50 wt% or more, 60 wt% or more, or 70 wt% or more based on the total weight of the composition excluding the weight of the solvent (if present). In one embodiment, the second network-forming component is present in an amount of 90 wt% or less, 80 wt% or less, 70 wt% or less, 60 wt% or less, 50 wt% or less, 40 wt% or less, 30 wt% or less, or 20 wt% or less based on the total weight of the composition excluding the solvent (if present).

[0062] In one embodiment, the second network-forming component is present in an amount of 5 wt% or more, 10 wt% or more, 15 wt% or more, 20 wt% or more, 25 wt% or more, 30 wt% or more, 35 wt% or more, 40 wt% or more, 50 wt% or more, 60 wt% or more, or 70 wt% or more, based on the total weight of the composition excluding the solvent (if present) and the component(s) (if present) that do not contain a polymerizable group. In one embodiment, the second network-forming component is present in an amount of 90 wt% or less, 80 wt% or less, 70 wt% or less, 60 wt% or less, 50 wt% or less, 40 wt% or less, 30 wt% or less, or 20 wt% or less, based on the total weight of the composition excluding the solvent (if present) and the component(s) (if present) that do not contain a polymerizable group.

[0063] In one embodiment, the one or more second network compounds are present in an amount of at least 5 wt%, at least 10 wt%, at least 15 wt%, at least 19.95 wt%, at least 20 wt%, at least 25 wt%, at least 30 wt%, at least 40 wt%, at least 50 wt%, at least 60 wt%, at least 70 wt%, or at least 80 wt%, based on the total weight of the composition. In one embodiment, the one or more second network compounds are present in an amount of at most 80 wt%, at most 78 wt%, at most 75 wt%, at most 70 wt%, at most 60 wt%, at most 50 wt%, at most 40 wt%, at most 30 wt%, or at most 20 wt%, based on the total weight of the composition.

[0064] In one embodiment, one or more second network compounds are present in an amount of at least 5 wt%, at least 10 wt%, at least 15 wt%, at least 19.95 wt%, at least 20 wt%, at least 25 wt%, at least 30 wt%, at least 40 wt%, at least 50 wt%, at least 60 wt%, at least 70 wt%, or at least 80 wt% based on the total weight of the composition excluding the solvent (if present). In one embodiment, one or more second network compounds are present in an amount of at most 80 wt%, at most 78 wt%, at most 75 wt%, at most 70 wt%, at most 60 wt%, at most 50 wt%, at most 40 wt%, at most 30 wt%, or at most 20 wt% based on the total weight of the composition excluding the solvent (if present).

[0065] In one embodiment, one or more second network compounds are present in an amount of at least 50 wt%, at least 60 wt%, at least 70 wt%, at least 80 wt%, or at least 90 wt% based on the total weight of the second network-forming components. In one embodiment, one or more second network compounds are present in an amount of at most 99.9 wt%, at most 99.5 wt%, at most 99 wt%, at most 98 wt%, at most 97 wt%, at most 96 wt%, at most 95 wt%, at most 90 wt%, or at most 80 wt% based on the total weight of the second network-forming components.

[0066] In one embodiment, the second network initiator comprises a photoinitiator or a thermal initiator. In one embodiment, the second network initiator comprises a photoinitiator that reacts to initiate polymerization upon exposure to UV light, visible light, or both UV light and visible light. In one embodiment, the second network initiator comprises a photoinitiator and a thermal initiator.

[0067] In one embodiment, the second network initiator is present in an amount of at least 0.01 wt%, at least 0.05 wt%, at least 0.1 wt%, at least 0.2 wt%, at least 0.3 wt%, at least 0.4 wt%, at least 0.5 wt%, at least 1.0 wt%, at least 1.5 wt%, at least 2 wt%, or at least 2.5 wt% based on the total weight of the composition excluding the solvent (if present). In one embodiment, the second network initiator is present in an amount of at most 10 wt%, at most 8 wt%, at most 7 wt%, at most 6 wt%, at most 5 wt%, or at most 4 wt% based on the total weight of the composition excluding the solvent (if present).

[0068] In one embodiment, the second network initiator is present in an amount of at least 0.01 wt%, at least 0.05 wt%, at least 0.1 wt%, at least 0.2 wt%, at least 0.3 wt%, at least 0.4 wt%, at least 0.5 wt%, at least 1.0 wt%, at least 1.5 wt%, at least 2 wt%, or at least 2.5 wt% based on the total weight of the second network-forming component. In one embodiment, the second network initiator is present in an amount of at most 10 wt%, at most 8 wt%, at most 7 wt%, at most 6 wt%, at most 5 wt%, or at most 4 wt% based on the total weight of the second network-forming component.

[0069] Various components containing polymerizable groups can be present in the composition. Various radically polymerizable compounds and cationically polymerizable compounds are described below. Depending on the number average of the polymerizable groups of the first oligomer and the polymerizable groups of the compounds, these compounds can be the first network monomer, further first network monomers, oligomers, or polymers, or second network compounds containing polymerizable groups.

[0070] [Radically Polymerizable Compounds] In one embodiment, the first mesh-forming component or the second mesh-forming component comprises at least one radically polymerizable compound, i.e., a component that initiates polymerization by free radicals. The radically polymerizable compound is a monomer, oligomer, and / or polymer; these are monofunctional or polyfunctional materials, i.e., having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 100 or more functional groups capable of initiating polymerization by free radicals, each of which may contain one or more heteroatoms and may include aliphatic, aromatic, alicyclic, arylaliphatic, or any combination thereof.

[0071] According to one embodiment, the first mesh-forming component or the second mesh-forming component contains a component containing at least one polymerizable (meth)acrylate group. Examples of the component containing at least one polymerizable (meth)acrylate group include 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 (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 adduct of acrylic acid (caprolactoneAcrylate), isoamyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, tridecyl (meth)acrylate, undecyl (meth)acrylate, lauryl (meth)acrylate, tetradecyl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, butoxyethyl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, 2-(2-ethoxyethoxy)ethyl acrylate, acetoacetoxy (meth)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 acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, butylcarbamylethyl (meth)acrylate, n-isopropyl (meth)acrylamide, fluorinated (meth)acrylate ester, 7-amino-3,7-dimethyloctyl (meth)acrylate, 2-(phenylthio)ethyl acrylate, and acrylate esters and methacrylate esters such as nonylphenol acrylate, etc.

[0072] Examples of components containing more than one (meth)acrylate group include 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; dipentaerythritol monohydroxy penta(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated neopentyl glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene 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 of phosphoric acid, C7~C 20Alkyl di(meth)acrylate, 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, tricyclodecane diyl dimethyl di(meth)acrylate, and in addition to the alkoxylated forms (e.g., ethoxylated and / or propoxylated) of any of the above monomers, di(meth)acrylic acid esters of diols that are ethylene oxide or propylene oxide adducts of bisphenol A, di(meth)acrylic acid esters of diols that are ethylene oxide or propylene oxide adducts of hydrogenated bisphenol A, epoxy (meth)acrylates that are (meth)acrylate adducts of bisphenol A diglycidyl ether, diacrylic acid esters of polyoxyalkylated bisphenol A, and those having a (meth)acryloyl group such as adducts of triethylene glycol divinyl ether and hydroxyethyl acrylate are mentioned.

[0073] According to one embodiment, those included in the first mesh-forming component or the second mesh-forming component are all methacrylate groups, all acrylate groups, or any combination of methacrylate and acrylate groups.

[0074] In one embodiment, the radically polymerizable compound includes 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 hexa(meth)crylate, propoxylated trimethylolpropane tri(meth)acrylate, or propoxylated neopentyl glycol di(meth)acrylate, or any combination thereof.

[0075] In one embodiment, the radically polymerizable compound includes an ester formed from itaconic acid, citraconic acid, or mesaconic acid. In one embodiment, the radically polymerizable compound is dimethyl itaconate.

[0076] In one embodiment, the radically polymerizable compound includes a thiol-containing compound. In one embodiment, the radically polymerizable compound includes an aliphatic thiol, more preferably a primary aliphatic thiol. In one embodiment, the radically polymerizable compound includes an aromatic thiol. In one embodiment, the thiol-containing compound includes an aliphatic thiol and includes α-mercaptoacetic acid ester or β-mercaptopropionic acid ester or derivatives or mixtures thereof. In one embodiment, the thiol-containing compound includes dodecyl mercaptan or octyl mercaptan. In one embodiment, the radically polymerizable compound includes a dithioester, a thioether, a thione, a trithiocarbonate ester such as dibenzyl trithiocarbonate, a dithiocarbamate ester, a xanthate ester such as O-ethyl-S-(1-methoxycarbonyl)ethyl dithiocarbonate [RSC(=S)-OC2H5 (R is -CH(CH3)-C(=O)-OCH3)], or a mixture thereof.

[0077] [Cation-polymerizable compound] In one embodiment, the first network-forming component or the second network-forming component includes at least one cation-polymerizable compound, that is, a compound that undergoes cationic polymerization. The cation-polymerizable compound can be selected from the group consisting of cyclic ether compounds, cyclic acetal compounds, cyclic thioether compounds, spiro orthoester compounds, cyclic lactone compounds, and vinyl ether compounds, and any combination thereof. Among the cation-polymerizable groups that can be present in the composition, the ring-type epoxy group and the oxetane group generally react the fastest and are thus preferred for that reason.

[0078] Examples of cation-polymerizable compounds include cyclic ether compounds such as epoxy compounds, oxetane compounds, cyclic lactone compounds, cyclic acetal compounds, cyclic thioether compounds, spiro orthoester compounds, and vinyl ether compounds. Specific examples of cation-polymerizable compounds 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(epoxycyclohexcylmethyl)-3',4'-epoxycyclohexanecarboxylate, methylenebis(3,4-epoxycyclohexane), bicyclohexyl-3,3'-epoxide, -O-, -S-, -SO-, -SO2-, -C(CH3)2-, -CBr2-, -C(CBr3)2-, -C(CF3)2-, -C(CCl3)2-, or -CH(C6H5)-bonded bis(3,4-epoxycyclohexyl), dicyclopentadiene diepoxide, di(3,(4-Epoxycyclohexylmethyl) ether, ethylene bis(3,4-epoxycyclohexanecarboxylate), epoxyhexahydrodioctyl phthalate, epoxyhexahydro-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, polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol, and glycerol, diglycidyl esters of aliphatic long-chain dibasic acids, monoglycidyl ethers of aliphatic higher alcohols, monoglycidyl ethers of polyether alcohols obtained by adding alkylene oxides to phenol, cresol, butylphenol, or these compounds, glycidyl esters of higher fatty acids, epoxidized soybean oil, epoxybutyl stearate, epoxyoctyl stearate, 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 - ethyl - 3 - oxetanylmethoxy)methylbenzene, 4 - fluoro - [1 - (3 - ethyl - 3 - oxetanylmethoxy)methyl]benzene, 4 - methoxy - [1 - (3 - ethyl - 3 - oxetanylmethoxy)methyl] - benzene, [1 - (3 - ethyl - 3 - oxetanylmethoxy)ethyl]phenyl ether, isobutoxymethyl(3 - ethyl - 3 - oxetanylmethyl)ether, 2 - ethylhexyl(3 - ethyl - 3 - oxetanylmethyl)ether, ethyldiethylene glycol(3 - ethyl - 3 - oxetanylmethyl)ether, dicyclopentadiene(3 - ethyl - 3 - oxetanylmethyl)ether, dicyclopentenyl oxyethyl(3 - ethyl - 3 - oxetanylmethyl)ether, dicyclopentenyl(3 - ethyl - 3 - oxetanylmethyl)ether, tetrahydrofurfuryl(3 - ethyl - 3 - oxetanylmethyl)ether, 2 - hydroxyethyl(3 - ethyl - 3 - oxetanylmethyl)ether, 2 - hydroxypropyl(3 - ethyl - 3 - oxetanylmethyl)ether, and any combination thereof.,

[0079] Examples of cation-polymerizable polyfunctional materials include dendritic polymers such as dendrimers, linear dendritic polymers, dendrigraft polymers, hyperbranched polymers, star-branched polymers, and hypergraft polymers having epoxy, oxetane, or hydroxyl functional groups. The dendritic polymer can contain one type of polymerizable functional group or different types of polymerizable functional groups, for example, an epoxy functional group and an oxetane functional group.

[0080] In one embodiment, the cation-polymerizable compound includes a hydroxyl-functional component containing at least one primary OH group. In one embodiment, the cation-polymerizable compound includes a hydroxyl-functional component containing two primary OH groups.

[0081] In one embodiment, the cation-polymerizable compound includes a diol having a number average molecular weight of less than about 500 g / mol. In one embodiment, the cation-polymerizable compound includes a diol having a number average molecular weight of less than about 400 g / mol. In one embodiment, the cation-polymerizable compound includes ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, or tripropylene glycol. In one embodiment, the cation-polymerizable compound includes a polyol having three or more OH groups such as trimethylolpropane, glycerol, or pentaerythritol.

[0082] In one embodiment, the cationically polymerizable component includes an alkoxylated polyol such as an ethoxylated or propoxylated form of the polyol of the previous paragraph. However, the alkoxylated polyol may have the effect of lowering the Tg of an article produced by polymerizing the composition, and thus should be used with caution. In one embodiment, the cationically polymerizable component includes an alkoxylated aromatic diol. In one embodiment, the cationically polymerizable compound includes ethoxylated and / or propoxylated bisphenol A. This bisphenol A can include, for example, from about 1 to about 30 ethoxylated moieties and / or propoxylated moieties per hydroxyl group overall.

[0083] In one embodiment, the cationically polymerizable component includes poly(propylene glycol) or its copolymer, poly(ethylene glycol) or its copolymer, poly(teramethylene oxide) or its copolymer, poly(butylene oxide) or its copolymer, poly(butadiene) having a hydroxyl end, poly(caprolactone) diol, poly(caprolactam) diol, poly(acrylate) having a hydroxyl end, poly(ester) having a hydroxyl end, poly(carbonate) telechelic diol, poly(ether) telechelic diol, poly(urethane) telechelic diol, poly(dimethylsiloxane) having a hydroxyl end, and its copolymer.

[0084] Various types of initiators can be present in the composition. Various free radical initiators and cationic initiators are described below. Depending on the polymerizable group of the first oligomer, these initiators can be either the first network initiator or the second network initiator.

[0085] The polymerization can be initiated by any suitable method according to the initiation mechanism required for the initiator. In one embodiment, the polymerization is initiated by irradiating the composition with light or heat. Preferably, the polymerizable composition is polymerized by applying UV light or visible light. The radiation can be provided by a lamp, a laser, an LED, or other light source.

[0086] [Radical polymerization initiator] When the first network-forming component or the second network-forming component contains a radically polymerizable compound, the first network-forming component or the second network-forming component each also contains a radical polymerization initiator. Preferred examples of the radical polymerization initiator are thermal initiators and photoinitiators. Preferably, the radical polymerization initiator contains a photo-radical initiator.

[0087] According to one embodiment, the first network-forming component or the second network-forming component contains at least one photo-radical initiator. In one embodiment, the photo-radical initiator is selected from the group consisting of benzoylphosphine oxide, aryl ketone, benzophenone, hydroxylated ketone, I-hydroxyphenyl ketone, ketal, metallocene, and any combination thereof.

[0088] In one embodiment, the first mesh-forming component or the second mesh-forming component includes at least one photoinitiator selected from the group consisting of 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-methylbenzophenone, 2,4,6-trimethylbenzophenone, dimethoxybenzophenone, I-hydroxycyclohexyl phenyl ketone, phenyl(1-hydroxyisopropyl)ketone, 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-1-propanone, 4-isopropylphenyl(1-hydroxyisopropyl)ketone, oligo-[2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone], camphorquinone, 4,4'-bis(diethylamino)benzophenone, benzil dimethyl ketal, bis(η5-2-4-cyclopentadien-1-yl)bis[2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl]titanium, and any combination thereof.

[0089] Examples of further photoinitiators include: for example, 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 (Irgacure819 or BAPO from Ciba), 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone-1 (Irgacure907 from Ciba), 2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone (Irgacure369 from Ciba), 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one (Irgacure379 from Ciba), 4-benzoyl-4'-methyldiphenyl sulfide (Chivacure BMS from Chitec), 4,4'-bis(diethylamino)benzophenone (Chivacure EMK from Chitec), 4,4'-bis(N,N'-dimethylamino)benzophenone (Michler's ketone), camphorquinone, 4,4'-bis(diethylamino)benzophenone (Chivacure EMK from Chitec), 4,4'-bis(N,N'-dimethylamino)benzophenone (Michler's ketone), benzoylphosphine oxides such as bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (Irgacure819 or BAPO from Ciba), and metallocenes such as bis(η5-2-4-cyclopentadien-1-yl)bis[2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl]titanium (Irgacure784 from Ciba), or mixtures thereof.

[0090] Examples of thermal radical polymerization initiators include, but are not limited to, for example, azo compounds such as azoisobutyronitrile (AIBN), 1,1'-azobis(cyclohexanenitrile), 1,1'-azobis(2,4,4-trimethylpentane), compounds with unstable C-C bonds such as benzopinacol and peroxides, and mixtures thereof.

[0091] In one embodiment, the radical polymerization includes a peroxide. Suitable potential peroxides include organic and inorganic peroxides. In one embodiment, the thermal initiator is soluble in the composition.

[0092] Examples of peroxides include, for example, percarbonates (represented by the formula -OC(O)O-), peroxy esters (represented by the formula -C(O)OO-), diacyl peroxides also known as peranhydrides (represented by the formula -C(O)OOC(O)-), dialkyl peroxides or perethers (represented by the formula -OO-), hydroperoxides (represented by the formula -OOH), etc. The peroxide can also have the properties of a low polymer or a polymer.

[0093] The thermal radical polymerization initiator can include, for example, a percarbonate, a peroxy ester, or a peranhydride. Peranhydrides are, for example, benzoyl peroxide (BPO) and lauroyl peroxide (commercially available as Laurox™). Peroxy esters are, for example, t-butyl perbenzoate and 2-ethylhexyl perlaurate. Percarbonates are, for example, di-t-butyl percarbonate and di-2-ethylhexyl percarbonate or mono percarbonate esters.

[0094] In one embodiment, the thermal radical polymerization initiator is an organic peroxide. Examples of organic peroxides are: tertiary alkyl hydroperoxides (e.g., t-butyl hydroperoxide, etc.), other hydroperoxides (e.g., cumene hydroperoxide, etc.), peroxy ketones (peroxy ketones which are addition products of hydrogen peroxide and ketones, e.g., methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, and acetylacetone peroxide, etc.), peroxy esters or peracids (e.g., t-butyl peroxide, benzoyl peroxide, peracetic acid esters and perbenzoic acid esters, lauroyl peroxide ((di)peroxy esters included), peroxy ethers (e.g., diethyl ether peroxide, etc.)).

[0095] In one embodiment, the thermal radical polymerization initiator includes peroxy anhydrides, such as benzoyl peroxide or lauroyl peroxide, percarbonates, such as di(4-t-butylcyclohexyl) peroxydicarbonate, dicetyl peroxydicarbonate, or dimyristyl peroxydicarbonate.

[0096] [Cationic polymerization initiator] When the first network-forming component or the second network-forming component contains a radically polymerizable compound, the first network-forming component or the second network-forming component can each also contain a cationic polymerization initiator. Preferred examples of the cationic polymerization initiator are thermal initiators and photoinitiators. Preferably, the cationic polymerization initiator is a photo-cationic initiator. The photo-cationic initiator initiates cationic ring-opening polymerization when irradiated with light.

[0097] In one embodiment, the photo-cationic initiator contains cations of onium salts, halonium salts, iodosyl salts, selenium salts, sulfonium salts, sulfoxonium salts, diazonium salts, metallocene salts, isoquinolinium salts, phosphonium salts, arsonium salts, tropylium salts, dialkylphenacylsulfonium salts, thiopyrylium salts, diaryliodonium salts, triarylsulfonium salts, ferrocene, di(cyclopentadienyliron)arene salt compounds, and pyridinium salts, or any combination thereof.

[0098] In other embodiments, the cation of the photo cationic initiator is selected from the group consisting of aromatic diazonium salts, aromatic sulfonium salts, aromatic iodonium salts, metallocene compounds, aromatic phosphonium salts, polymeric sulfonium salts, naphthylsulfonium salts, and any combination thereof. In one embodiment, the photo cationic initiator is selected from the group consisting of triaryl sulfonium salts, diaryl iodonium salts, and metallocene compounds, and any combination thereof.

[0099] In one embodiment, the photo cationic initiator is BF4 - , 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] - , tetra (3,5-difluoro-4-alkyloxyphenyl) borate ion, tetra (2,3,5,6-tetrafluoro-4-alkyloxyphenyl) borate ion, perfluoroalkyl sulfonate ion, tris [(perfluoroalkyl) sulfonyl] methide ion, bis [(perfluoroalkyl) sulfonyl] imide ion, perfluoroalkyl phosphate ion, tris (perfluoroalkyl) trifluorophosphate ion, bis (perfluoroalkyl) tetrafluorophosphate ion, tris (pentafluoroethyl) trifluorophosphate ion, and (CH6B 11 Br6) - , CH6B 11 Cl6) - , and has an anion selected from the group consisting of other halogenated carbonate anions.

[0100] In one embodiment, the photo cationic initiator is SbF6 - , PF6 - , B(C6F5)4 - , [B(CF3)4] - , tetra (3,5-difluoro-4-methoxyphenyl) borate ion, perfluoroalkyl sulfonate ion, perfluoroalkyl phosphate ion, tris [(perfluoroalkyl) sulfonyl] methide ion, and [(C2F5)3PF3] - and has a cation selected from the group consisting of an aromatic sulfonium salt, an aromatic iodonium salt, and a metallocene compound, having at least an anion selected from the group consisting of

[0101] Examples of photo cationic initiators useful for curing at 300 to 475 nm without using a sensitizer 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® PAG290 from BASF), tris(4-(4-acetylphenyl)thiophenyl)sulfonium tris[(trifluoromethyl)sulfonyl]methide (Irgacure® GSID26-1 from BASF), tris(4-(4-acetylphenyl)thiophenyl)sulfonium hexafluorophosphate (Irgacure® 270 from BASF), and HS-1 available from San-Apro Ltd.

[0102] Preferred photo cationic initiators include, either alone or as a mixture: bis[4-diphenylsulfoniumphenyl]sulfide bis(hexafluoroantimonate); thiophenoxyphenylsulfonium hexafluoroantimonate (available from Chitec as Chivacure 1176), tris(4-(4-acetylphenyl)thiophenyl)sulfonium tetrakis(pentafluorophenyl)borate (Irgacure® PAG290 from BASF), tris(4-(4-acetylphenyl)thiophenyl)sulfonium tris[(trifluoromethyl)sulfonyl]methide (Irgacure® GSID26-1 from BASF), and tris(4-(4-acetylphenyl)thiophenyl)sulfonium hexafluorophosphate (Irgacure® 270 from BASF), [4-(1-methylethyl)phenyl](4-methylphenyl)iodonium tetrakis(pentafluorophenyl)borate (available from Rhodia as Rhodorsil 2074), 4-[4-(2-chlorobenzoyl)phenylthio]phenylbis(4-fluorophenyl)sulfonium hexafluoroantimonate (from Adeka as SP-172), SP-300 from Adeka Corporation (Adeka), and an aromatic sulfonium salt having an anion (PF 6-m (C n F 2n+1 ) m ) - where m is an integer from 1 to 5 and n is an integer from 1 to 4) (a monovalent sulfonium salt available from San-Apro Ltd. as CPI-200K or CPI-200S, TK-1 available from San-Apro Ltd., or HS-1 available from San-Apro Ltd.).

[0103] [Optional particulate filler] In certain embodiments, the composition comprises particulate fillers. Examples of particulate fillers include both organic and inorganic particulate fillers. The particulate filler may or may not have surface functional groups, and the surface functional groups include polymerizable groups copolymerizable with the first network-forming component or the second network-forming component. The particulate filler can be micro-particles or nano-particles including organic particles such as core-shell type particles, inorganic particles, pigments, or plasticizers. In one embodiment, the particulate filler includes inorganic fillers such as SiO2, AlO2, TiO2, ZnO2, SnO2, Am-SnO2, ZrO2, Sb-SnO2, Al2O3, or carbon black. In one embodiment, the particulate filler includes organic fillers such as polyurethane particles, polystyrene particles, poly(methyl methacrylate) particles, polycarbonate particles, or core-shell type particles.

[0104] In one embodiment, the particulate filler includes polymerizable groups copolymerizable with the polymerizable groups of the first oligomer. In one embodiment, the particulate filler includes polymerizable groups copolymerizable with the polymerizable groups of one or more second network compounds. In one embodiment, the particulate filler includes polymerizable groups including acrylate, methacrylate, epoxy, oxetane, hydroxyl, itaconate, vinyl ether, allyl ether, maleate, or fumarate. In one embodiment, the particulate filler includes polymerizable groups including acrylate, methacrylate, epoxy, oxetane, hydroxyl, or itaconate. In one embodiment, the particulate filler includes polymerizable groups including acrylate or methacrylate. In one embodiment, the particulate filler includes polymerizable groups including epoxy, oxetane, or hydroxyl.

[0105] In one embodiment, the particulate filler includes an impact resistance improver. An example of the impact resistance improver is elastomer particles. In one embodiment, the impact resistance improving component that can be dispersed in the composition is an elastomer based on a copolymer of ethylene or propylene and one or more C2-C 12 α-olefin monomers.

[0106] Materials of this kind are, for example, ethylene / propylene copolymers, or ethylene / propylene copolymers (EPDM) optionally containing a third copolymerizable diene monomer such as 1,4 - hexadiene, dicyclopentadiene, dicyclooctadiene, methylene norbornene, ethylidene norbornene, and tetrahydroindene; ethylene / α - olefin copolymers such as ethylene - octene copolymers and ethylene / α - olefin / polyene copolymers.

[0107] In one embodiment, the particulate filler includes polybutadiene, polyisoprene, styrene / butadiene random copolymer, styrene / isoprene random copolymer, acrylic rubber (e.g., polybutyl acrylate), poly(hexamethylene carbonate).

[0108] The elastomer particles can be prepared by various means such as isolation from a latex produced by emulsion polymerization. The average size of these elastomer particles is preferably between about 10 nm and about 10 μm. In one embodiment, the average size of the elastomer particles is from 10 nm to 1 μm.

[0109] Optionally, the elastomer can be modified to contain reactive groups copolymerizable with the first or second network - forming component. This modification can be introduced by reactive grafting or copolymerization. Commercially available products of the latter are, for example, Arkema's Lotader ethylene / acrylic ester random copolymers AX8840 (glycidyl methacrylate / GMA modified), AX8900, and AX8930 (GMA and maleic anhydride modified / MA).

[0110] Optionally, a shell that can be introduced, for example, by grafting or during the second stage of emulsion polymerization, can also be present on the particles. Examples of this type of particle are core-shell type impact modifiers particles containing a rubber core and a glassy shell. Examples of core materials are polybutadiene, polyisoprene, acrylic rubber (e.g., polybutyl acrylate rubber), styrene / butadiene random copolymer, styrene / isoprene random copolymer, or polysiloxane. Examples of shell materials or graft copolymers are (co)polymers of vinyl aromatic compounds (e.g., styrene) and vinyl cyanide (e.g., acrylonitrile) or (meth)acrylate esters (e.g., MMA).

[0111] Optionally, polymerizable groups can be incorporated into the shell by copolymerization such as copolymerization with glycidyl methacrylate or by treating the shell to form reactive functional groups.

[0112] Commercially available products of these core-shell type elastomer particles are Resinous Bond RKB (a dispersion in which core-shell type particles are dispersed in epoxy, manufactured by Resinous Chemical Industries Co., Ltd.), Durastrength D400, Durastrength 400R (manufactured by Arkema Group), Paraloid EXL-2300 (non-functional shell), Paraloid EXL-2314 (epoxy-functional shell), Paraloid EXL-2600, Paraloid EXL-3387, and Paraloid KM-365 (manufactured by Dow), Genioperl P53, Genioperl P23, Genioperl P22 (manufactured by Wacker Chemical), Kane Ace MX products (manufactured by Kaneka Corporation), etc.

[0113] Other examples of this type of elastomeric particles are crosslinked polyorganosiloxane rubbers that can include dialkylsiloxane repeating units, where "alkyl" is C1-C6 alkyl. The particles can be modified to include reactive groups, preferably on the particle surface.

[0114] Examples of commercially available polyorganosiloxane elastomeric particles are Albidur EP 2240(A), Albidur EP 2640, Albidur VE 3320, Albidur EP 5340, Albidur EP 5640, and Albiflex 296 (a dispersion with the particles dispersed in an epoxy or vinyl ether resin, Hanse Chemie, Germany), Genioperl M41 C (a dispersion in epoxy, Wacker Chemical), Chemisnow MX series and MP series (Soken Chemical and Engineering Co.).

[0115] In one embodiment, impact modifiers having two different diameters are used in a specific ratio. In one embodiment, the composition of the impact modifier has a diameter ratio of about 7-1 (e.g., 140 nm particles to 20 nm particles) and a weight % ratio of about 4-1. In other embodiments, the composition of the impact modifier has a diameter ratio of about 5-1 and a weight % ratio of about 4-1. In other embodiments, the composition of the impact modifier has a diameter ratio of about 5-1 and a weight % ratio of about 6-1.

[0116] In one embodiment, the particulate filler is present in the composition in an amount of 1 wt% or more, 5 wt% or more, 10 wt% or more, 15 wt% or more, 20 wt% or more, 30 wt% or more, 40 wt% or more, or 50 wt% or more, based on the total weight of the composition. In one embodiment, the particulate filler is present in the composition in an amount of 90 wt% or less, 80 wt% or less, 70 wt% or less, 60 wt% or less, 50 wt% or less, 40 wt% or less, 30 wt% or less, or 20 wt% or less, based on the total weight of the composition.

[0117] [Additional Optional Components] Additional components that can be present in the composition include stabilizers such as viscosity stabilizers or light stabilizers, UV absorbers, dyes, pigments, plasticizers, surfactants, antioxidants, wetting agents, photosensitizers, defoamers, flame retardants, silane coupling agents, acid scavengers, accelerators for thermal initiators, and / or bubble breakers.

[0118] In one embodiment, the polymerizable composition includes a non-particulate impact modifier. In one embodiment, the non-particulate impact modifier includes a block copolymer that is soluble in the composition or dispersed as micelles. In one embodiment, this block copolymer includes ethylene / acrylic acid ester random copolymers and acrylic block copolymers, styrene / butadiene / (meth)acrylate (SBM) block copolymers, styrene / butadiene block copolymers (styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), and their hydrogenated forms, SEBS, SEPS), and (SIS), and ionomers.

[0119] Examples of commercially available block copolymers are Kraton (SBS, SEBS, SIS, SEBS, and SEPS) block copolymers from Shell, Nanostrength block copolymers E20, E40 (SBM type) and M22 (full-acrylic) from Arkema, Lotryl ethyl / acrylic acid ester random copolymer (Arkema), ethylene oxide-butylene oxide block copolymer from Olin Chemicals, and Surlyn ionomers (DuPont).

[0120] The non-particulate impact modifier can include polymerizable groups. When the non-particulate impact modifier includes polymerizable groups, the non-particulate impact modifier can be a further first network monomer, oligomer, or polymer according to the polymerizable groups of the first oligomer, or can also be a second network compound.

[0121] The composition of the present invention can optionally contain a solvent. The solvent does not contain a polymerizable group. The solvent can be a mixture of more than one solvent. Examples of the solvent include alcohol, ketone, ester, or ether; preferably, alcohols such as methanol, ethanol, or isopropanol. In one embodiment, the composition contains 50% by weight or less of the solvent, for example, 40% by weight or less, 30% by weight or less, 20% by weight or less, 10% by weight or less, 5% by weight or less, or 0% by weight based on the total weight of the composition.

[0122] [Use] According to an embodiment of the present invention, an article can be formed by polymerizing the composition. In one embodiment, the tensile modulus measured at 150 °C of the film formed by polymerizing 90% or more of the total polymerizable groups in the composition is from 3 MPa, from 5 MPa, from 7 MPa, from 10 MPa, from 15 MPa, or from 20 MPa to 50 MPa, to 45 MPa, or to 40 MPa. In one embodiment, the yield stress at 23 °C of the film formed by polymerizing 90% or more of the polymerizable groups in the composition is 50 to 90 MPa, the elongation at break at 23 °C exceeds 3%, and optionally has the above-mentioned tensile modulus measured at 150 °C. In one embodiment, the tensile modulus at 23 °C of the film formed by polymerizing 90% or more of the total polymerizable groups in the composition is 2000 to 3500 MPa. The tensile modulus at 150 °C is measured by DMTA in accordance with ASTM D5026. The tensile modulus at 23 °C, the yield strength at 23 °C, and the elongation at break at 23 °C are measured in accordance with ISO 37:2011 Rubber, vulcanized or thermoplastic - Determination of tensile stress - strain properties.

[0123] The amount of the overlapping composition is measured using IR by the method shown below. The sample is subjected to measurement with a Perkin Elmer Spectrum One equipped with a Universal ATR Sampling accessory. Normalize the peak height to the carbonyl peak at 1727 cm -1 or other peaks that do not change. The reaction rate is determined using the following formula: Reaction rate (%) = ((A0 - A t ) / A0) × 100% (where A0 is the absorbance before curing after normalization, and A t is the absorbance after curing after normalization). For example, the reaction rate of the acrylate bond can be measured by tracking the decrease in the peak of the IR absorbance at 810 cm -1 .

[0124] A preferred use of the composition is in a stereolithography process. The stereolithography process, also known as 3D printing, constructs three-dimensional objects using computer-aided design (CAD) data of the object. These three-dimensional objects can be formed from liquid resins, powders, or other materials. A computer that has loaded the CAD data controls an apparatus that forms and bonds layers of the material to form the desired shape. This desired shape corresponds to a part of the three-dimensional object, such as an individual cross-section of the three-dimensional object. This desired shape can be formed by selectively ejecting the composition in the desired shape with an inkjet printing mechanism or the like and then curing or melting the composition if necessary. Other methods of forming the desired shape involve selectively curing or melting the desired shape from a large material bed or material bath in stereolithography or powder sintering stereolithography, etc.

[0125] In one embodiment, an article is formed by forming a layer from a first composition comprising a first oligomer and selectively ejecting a second composition comprising one or more first network monomers onto the first composition according to the shape of a portion of the three-dimensional object. One or more first network initiators can be present either within the layer of the first oligomer, within a composition comprising one or more first network monomers, or both. The composition comprising one or more first network monomers can be selectively ejected by spraying, for example, by inkjet.

[0126] In one embodiment, a method of forming a three-dimensional object includes forming a layer of a composition, curing the layer by radiation to form a desired shape, and repeating the forming step and the curing step a plurality of times to obtain the three-dimensional object. In one embodiment, a method of forming a three-dimensional object includes selectively ejecting a composition, curing the composition by radiation to form a desired shape, and repeating the selective ejection step and the curing step a plurality of times to obtain the three-dimensional object. In one embodiment, a method of forming a three-dimensional object includes forming a layer of a composition, selectively curing the layer by radiation to form a desired shape, and repeating the step of forming a layer of the composition and the step of selectively curing a plurality of times to obtain the three-dimensional object.

[0127] In one embodiment, the viscosity of the composition at 30°C is 4000 cps or less, 3000 cps or less, 2000 cps or less, 1500 cps or less, or 1200 cps or less. The viscosity of the composition at 30°C is typically 300 cps or more.

[0128] In one embodiment, the composition exists as a liquid at the point when the polymerization reaction is initiated by the application of light or heat. In one embodiment, the temperature of the liquid composition at the point when polymerization is initiated is 25°C, 30°C or higher, 35°C or higher, 40°C or higher, or 45°C or higher. This temperature is usually 200°C or lower, such as 180°C or lower. In one embodiment, this temperature is 150°C or lower, 100°C or lower, 80°C or lower, or 50°C or lower.

[0129] In one embodiment, the article can be formed by first introducing the polymerizable composition into a mold or coating the surface with the polymerizable composition.

[0130] In one embodiment, the composition exists as separate parts in a kit of materials. This kit includes a particulate composition component (sub - composition) containing a first oligomer and a liquid composition component containing one or more first network monomers. The first network initiator can be present together with either the first oligomer or one or more of the first network monomers, or can be present as another part of the kit.

[0131] In one embodiment, the particulate composition component or the liquid composition component further includes an absorbent. The absorbent absorbs electromagnetic radiation. In one embodiment, the absorbent absorbs one or more of infrared light, near - infrared light, and visible light. The wavelength absorbed by the absorbent needs to overlap with the wavelength of the electromagnetic radiation. In one embodiment, the absorbent is a pigment, a dye, metal particles, or carbon black.

[0132] The particulate composition component can further contain additives such as dyes, coloring pigments, or absorbents. In one embodiment, the particulate composition component further contains a particulate filler. In one embodiment, the particulate filler contains a polymerizable group copolymerizable with the polymerizable group of the first oligomer. In one embodiment, the average particle diameter of the particulate composition component measured by laser diffraction in accordance with ISO 13320 (2009) is 10 to 100 μm. In one embodiment, the average particle diameter of the particulate composition component measured by laser diffraction in accordance with ISO 13320 (2009) is 30 to 80 μm.

[0133] The liquid composition component can further contain additives such as absorbents, reflectants, dyes, or coloring pigments.

[0134] In one embodiment, the composition or the liquid composition component further contains a dispersion medium so that a specific component of the composition is dispersed in the dispersion medium. In one embodiment, at least one or more first network monomers are dispersed in the dispersion medium. In one embodiment, at least one or more first network monomers and one or more first network initiators are dispersed in the dispersion medium. When the dispersion medium is present, this is usually present in an amount of 20 to 70% by weight based on the total weight of the composition, or in an amount of 20 to 80% by weight based on the liquid composition component. The dispersion medium is a non-solvent, preferably water. When the dispersion medium is water, it is preferable that no cationically curable component is present in the composition. In one embodiment, the composition contains 50% by weight or more of water based on the total weight of the composition. The article or coating can be formed by forming a layer of the composition, evaporating the dispersion medium if necessary, and polymerizing the composition.

[0135] Some potential uses of the articles disclosed herein include molded articles, shoe soles, glasses, three-dimensional objects formed by additive manufacturing processes, coatings for optical fibers, medical devices and coatings for medical devices, and paints. [Examples]

[0136] The following examples are included for the purpose of further illustrating the present invention and should not be regarded as limiting its scope in any way.

[0137] [Synthesis of the First Oligomer Containing a Main Chain Comprising Bisphenol A-Type Polyepoxide] Bisphenol A-type epoxy resin and toluene were charged into a 1-liter jacketed reaction vessel equipped with a stirrer, a cooler, a dosing point, and an aeration needle. After heating the vessel until the mixture reached 100 °C, methylhydroquinone was added together with the first methacrylic acid (5 ml) for acidifying the mixture. Then triphenylphosphine was added, the temperature was raised to 130 °C, and toluene was refluxed. While refluxing toluene, the remaining methacrylic acid was added within 15 minutes. The reaction mixture was stirred at 130 °C overnight. After reacting for 10 hours, a sample was taken and the acid value and epoxy value were confirmed. Additional methacrylic acid (3 ml) was added and the reaction was continued at the reflux temperature for another 2 hours, after which the temperature was lowered to 110 °C. The cooler was replaced with a distillation cooler equipped with a recovery flask. Hydroxyethyl methacrylate (HEMA) was added and toluene was removed at 110 °C over 2 hours using the air flow from the aeration needle. The internal temperature of the cooler reached 60 - 70 °C. After 2 hours, the temperature was raised to 135 °C in a short time (20 minutes) and then the reaction was stopped. Finally, trimethylhydroquinone (0.2 g) was added and the product was transferred to an aluminum can.

[0138] The amounts of each component used in the above procedure are shown in Table 0.1 below.

[0139] [Table 1]

[0140] The reaction rate and solid content measured by NMR are shown in Table 0.2 below.

[0141] [Table 2]

[0142] [Measurement of Acid Value (AV) and Epoxy Value] The acid value (AV) and epoxy value of the vinyl ester resin (VR) were measured by H-NMR and titration in accordance with ISO 2114-2000 and ISO 4629-1978. The reaction rates were all derived from NMR. The AV of the final product could not be detected (<1), and the reaction rate of epoxy was >95%.

[0143] [DMTA] Test pieces with a width of approximately 2 mm are punched out from the cured film. The thickness is measured with a calibrated Heidenhain thickness measuring device. Dynamic mechanical analysis is carried out in accordance with ASTM D5026, using an RSA-G2 test device, with a frequency of 1 Hz and a heating rate of 5 °C / min at temperatures in the range of -100 °C to 200 °C. In this measurement, the storage modulus (E’), loss modulus (E’’), and loss tangent (tanδ) are obtained as functions of temperature.

[0144] [Tensile Test] Tensile properties are measured in accordance with the international standard ISO 37 (3rd edition 1994-05-15) "Rubber, vulcanized or thermoplastic - Determination of tensile stress-strain properties" using a Zwick Z010 type digital tensile testing machine. The parameters of the tensile test are shown in Table 0.3.

[0145]

Table 3

[0146] [Examples 1 to 7] The first oligomer in HEMA generated above is charged into a UV-protected vial having a screw cap lined with PTFE. Then a chain transfer agent (CTA) and a photoinitiator are added. To homogenize the mixture, it is left overnight on a roller bench.

[0147] The first oligomer is assumed to be the one generated as described above, and the CTA is trimethylolpropane mercaptopropionate (TMPMP: trifunctional thiol) or N-butyl mercaptopropionate (N-BuMP: monofunctional thiol). The photoinitiator is Darocur® 1173. The generated composition is shown in Table 1.1 below.

[0148]

Table 4

[0149] A mold was fabricated using two 10×15 cm glass plates with a gap formed by sandwiching a 2 mm U-shaped EPDM gasket in between. The glass plates were treated twice with Frekote NC-55 and baked at 80 °C for 4 minutes. The formulation was heated to reduce viscosity and cast using tape to pour in the viscous resin.

[0150] All samples except Example 5 RT are heated to 90 °C before UV exposure. Example 5 RT was cured at room temperature.

[0151] At a distance of 7 cm, the intensity is 3 - 4 mW / cm 2 (measured with a Silverline Intensometer), and the samples are cured under a VL-215.L lamp manufactured by Vilber Lourmat. Curing shrinkage was observed within 5 minutes in all cases. After curing for 1 hour, the UV lamp was switched off, and all samples were post-cured in an oven set at 80 °C for 1 hour. The samples were demolded, machined into tensile test specimens of standard 1 BA, and subjected to a tensile test. The remaining material was used for DMTA. The results of DMTA are shown in Table 1.2 below.

[0152]

Table 5

[0153] [Examples 7 - 12] To confirm the effects when using different reactive diluent portions in the final reaction mixture, six additional samples were prepared. For this purpose, toluene was removed from each. The solvent was exchanged using an appropriate amount of reactive diluent, and the residual toluene was removed using a rotary evaporator (40 mbar, 80 °C). The compositions of Examples 7 - 12 are shown in Table 1.3 below.

[0154]

Table 6

[0155] Next, the room temperature curing conditions of Examples 7 - 12 were evaluated by preparing films of each material. The films were prepared using a doctor blade (500 μm) on pretreated glass, and then cured using a UV irradiation device (UV - rig) made by Fusion equipped with a nitrogen stream and a D - valve type UV light source (doped mercury lamp). The total UV irradiation dose was about 16 J / cm 2 at 6.4 W / cm 2 (total of UVA and UVB).

[0156] Furthermore, the samples after UV exposure were thermally post - cured at 80 °C for 1 hour. There were still samples that did not cure sufficiently (Examples 7 and 8). To ensure complete conversion of the materials, the remaining samples were post - cured at 100 °C for 2 hours before measuring the mechanical properties, and they were completely converted. The DMTA results of the obtained materials are shown in Table 1.4 below.

[0157]

Table 7

[0158] [Synthesis of the Second Oligomer] Next, a second resin was prepared by performing the same synthesis as the first resin (composition for NBK-015217-018 reaction), with the only difference being that a larger excess amount of methacrylic acid used in the synthesis was used. This resin is based on a shorter-chain bisphenol A type epoxy resin.

[0159] The amounts of each component used in the above procedure are shown in Table 0.4 below.

[0160] [Table 8]

[0161] The reaction rate and solid content measured by NMR are shown in Table 0.5 below.

[0162] [Table 9]

[0163] [Examples 13 to 20] [Formulation] In the examples shown below, the second oligomer was used in combination with the HEMA monomer and loaded into a UV-protected vial having a screw cap lined with PTFE. Next, a chain transfer agent (CTA) and a photoinitiator (Darocure 173) were added. The mixture was left on a roller mixer overnight to homogenize it. The contents of the composition are shown in Table 1.5 below.

[0164] [Table 10]

[0165] Examples 13 to 16 were prepared as castings (described later), and Examples 17 to 20 were prepared by a film-forming method (described later).

[0166] [Casting method] A casting was made using two 10×15 cm glass plates with a gap by sandwiching a 2 mm U-shaped EPDM gasket in between. The glass plates were treated twice with Frekote NC-55 and "baked" at 80 °C for 4 minutes. The formulation was heated to reduce viscosity and poured into the mold using tape to pour the viscous resin.

[0167] At a distance of 7 cm, the intensity is 3 - 4 mW / cm 2 The UV light was cured under a Vilber Lourmat VL-215.L lamp (measured with a Silverline Intensometer). Curing shrinkage was observed within 5 minutes in all cases. After curing for 1 hour, the UV lamp was switched off and all samples were post-cured in an oven at 100 °C for 2 hours. The samples were demolded and used for DMTA measurement.

[0168] [Film formation method] Room temperature curing conditions: A film was made on the pretreated glass with a doctor blade (500 μm), and then cured with a Fusion UV irradiation device equipped with a nitrogen gas flow and a D-valve type UV light source (doped mercury lamp). The total UV irradiation dose was 6.4 W / cm 2 which was about 16 J / cm 2 (total of UVA and UVB).

[0169] An overview of the DMTA results of the obtained materials is shown in Table 1.6 below.

[0170]

Table 11

[0171] The effect of using shorter-chain oligomers is illustrated in Table 1.7 below. This is a direct comparison of the DMTA data of Example 18 and Example 5 RT.

[0172]

Table 12

[0173] [Supplementary description of specific exemplary embodiments] 1) A composition for forming a three-dimensional object via additive manufacturing, comprising: a. A first network-forming component, comprising: i. A first oligomer having a main chain containing bisphenol A, F, or S type polyepoxide, hydrogenated bisphenol A, F, or S type polyepoxide, polycarbonate, or polyimide, and having at least 2 polymerizable groups on a number average basis, wherein the polymerizable groups include acrylate, methacrylate, itaconate, vinyl ether, allyl ether, maleate, or fumarate, and the first oligomer has a number average molecular weight of 800 to 10,000 g / mol and a Tg of 40 °C or higher, the first oligomer being 19.95 to 80 wt% based on the total weight of the first network-forming component; ii. One or more first network monomers having 0.95 to 1.1 polymerizable groups copolymerizable with the polymerizable groups of the first oligomer on a number average basis, wherein the linear polymer formed from the one or more first network monomers has a Tg of 40 °C or higher, the first network monomers being 19.95 to 80 wt% based on the total weight of the network-forming component; iii. One or more first network initiators capable of initiating the polymerization of the first oligomer and the first network monomers, the first network initiators being 0.05 to 5 wt% based on the total weight of the first network-forming component; iv. Optionally, one or more additional first network monomers, oligomers, or polymers having 2 or more polymerizable groups copolymerizable with the polymerizable groups of the first oligomer or the one or more first network monomers on a number average basis, up to 15 wt%; The first network-forming component consisting of is 30 to 100 wt% based on the total weight of the composition; b. Optionally, a second network-forming component comprising one or more second network compounds containing polymerizable groups that do not copolymerize with the polymerizable groups of the first oligomer, and a second network initiator for initiating the polymerization of the one or more second network compounds; c. Optionally, a particulate filler containing polymerizable groups copolymerizable with the polymerizable groups of the first oligomer; A composition comprising...

[0174] 2) A kit of materials for generating a composition for forming an object by a laminated fabrication process, the composition comprising particulate composition components and liquid composition components which, when combined, comprise a first network-forming component containing polymerizable groups and an optional second network-forming component which does not (co)polymerize with the polymerizable groups of the first network-forming component, the kit comprising: a. Particulate composition components comprising: i. A first oligomer having a main chain comprising bisphenol A, F, or S type polyepoxide, hydrogenated bisphenol A, F, or S type polyepoxide, polycarbonate, or polyimide and having at least 2 polymerizable groups on average, the polymerizable groups including acrylate, methacrylate, itaconate, vinyl ether, allyl ether, maleate, or fumarate, the first oligomer having a number average molecular weight of 800 to 10,000 g / mol and a Tg of 40 °C or higher, in an amount of 19.95 to 80% by weight based on the total weight of the first network-forming component; ii. Optionally, a particulate filler containing polymerizable groups capable of (co)polymerizing with the polymerizable groups of the first oligomer; and a particulate composition component; b. Liquid composition components comprising: i. One or more first network monomers having on average 0.95 to 1.1 polymerizable groups capable of (co)polymerizing with the polymerizable groups of the first oligomer, the linear polymer formed from the one or more first network monomers having a Tg of 40 °C or higher, in an amount of 19.95 to 80% by weight based on the total weight of the network-forming component; ii. Optionally, one or more further first network monomers, oligomers, or polymers having on average 2 or more polymerizable groups capable of (co)polymerizing with the polymerizable groups of the first oligomer or the one or more first network monomers, up to 15% by weight; and a liquid composition component; c. One or more first network initiators capable of initiating the polymerization of the first oligomer and the first network monomer, which can be present in the particulate composition component, the liquid composition component, or both, and the one or more first network initiators are 0.05 to 5% by weight based on the total weight of the first network-forming component; d. Optionally, a second network-forming component comprising one or more second network compounds containing polymerizable groups that do not (co)polymerize with the polymerizable groups of the first oligomer, and a second network initiator for initiating the polymerization of the one or more second network compounds, wherein the substituents of the second network-forming component may be present in the particulate composition component, in the liquid composition component, or partly in the particulate composition component and partly in the liquid composition component; A kit comprising.

[0175] 3) The first network-forming component consists of a first oligomer, one or more first network monomers, one or more first network initiators, and optionally up to 15% by weight of additional first network monomers, oligomers, or polymers, according to any one of the previous exemplary embodiments.

[0176] 4) The first network-forming component consists of a first oligomer, one or more first network monomers, and one or more first network initiators, according to any one of the above exemplary embodiments.

[0177] 5) The first oligomer is soluble in one or more first network monomers, according to any one of the above exemplary embodiments.

[0178] 6) The first network-forming component is present in an amount of 20% by weight or more, 25% by weight or more, 30% by weight or more, 35% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, 90% by weight or more, 95% by weight or more, or 100% by weight based on the total weight of the composition, according to any one of the above exemplary embodiments.

[0179] 7) The first network-forming component is present in an amount of 100% by weight or less, 90% by weight or less, 80% by weight or less, 70% by weight or less, or 60% by weight or less, based on the total weight of the composition, and is a composition or kit according to any one of the above exemplary embodiments.

[0180] 8) The first network-forming component is present in an amount of 20% by weight or more, 25% by weight or more, 30% by weight or more, 35% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, 90% by weight or more, 95% by weight or more, or 100% by weight, based on the total weight of the composition excluding the weight of the solvent (if present), and is a composition or kit according to any one of the above exemplary embodiments.

[0181] 9) The first network-forming component is present in an amount of 100% by weight or less, 90% by weight or less, 80% by weight or less, 70% by weight or less, or 60% by weight or less, based on the total weight of the composition excluding the weight of the solvent (if present), and is a composition or kit according to any one of the above exemplary embodiments.

[0182] 10) The first network-forming component is present in an amount of 20% by weight or more, 25% by weight or more, 30% by weight or more, 35% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, 90% by weight or more, 95% by weight or more, or 100% by weight, based on the total weight of the composition excluding the weight of the solvent (if present) and the weight of the component that does not contain a polymerizable group (for example, a non-reactive particulate filler) (if present), and is a composition or kit according to any one of the above exemplary embodiments.

[0183] 11) The first network-forming component is present in an amount of 100% by weight or less, 90% by weight or less, 80% by weight or less, 70% by weight or less, or 60% by weight or less, based on the total weight of the composition excluding the weight of the solvent (if present) and the weight of the component that does not contain a polymerizable group (for example, a non-reactive particulate filler) (if present), and is a composition or kit according to any one of the above exemplary embodiments.

[0184] 12) A composition or kit according to any one of the above exemplary embodiments, wherein there is a further first mesh monomer, oligomer, or polymer.

[0185] 13) A composition or kit according to any one of the above exemplary embodiments, wherein the first oligomer is linear.

[0186] 14) A composition or kit according to any one of the above exemplary embodiments, wherein the first oligomer is branched.

[0187] 15) A composition or kit according to any one of the above exemplary embodiments, wherein the main chain comprises bisphenol A or a hydrogenated bisphenol A type polyepoxide.

[0188] 16) A composition or kit according to any one of the above exemplary embodiments, wherein the main chain comprises bisphenol A polycarbonate.

[0189] 17) A composition or kit according to any one of the above exemplary embodiments, wherein the main chain comprises a mixture of two or more of bisphenol A, F, or S type polyepoxides, hydrogenated bisphenol A, F, or S type polyepoxides, polycarbonate, or polyimide.

[0190] 18) A composition or kit according to any one of the above exemplary embodiments, wherein the main chain comprises an aromatic polycarbonate.

[0191] 19) A composition or kit according to any one of the above exemplary embodiments, wherein the main chain comprises an aromatic polyimide.

[0192] 20) A composition or kit according to any one of the above exemplary embodiments, wherein the main chain comprises units formed from a polyol, and the polyol is an aliphatic polyol or an aromatic polyol.

[0193] 21) The main chain includes units formed from a polyol, and the polyol has at least 2, at least 3, at least 4, at least 5, or at least 6 hydroxyl groups, and the composition or kit according to any one of the above exemplary embodiments.

[0194] 22) The main chain includes units formed from a polyol, and the polyol has a maximum of 2, a maximum of 3, a maximum of 4, a maximum of 5, a maximum of 6, a maximum of 8, or a maximum of 10 hydroxyl groups, and the composition or kit according to any one of the above exemplary embodiments.

[0195] 23) The Tg of the first oligomer is at least 45°C, at least 50°C, at least 55°C, at least 60°C, at least 65°C, or at least 70°C, and the composition or kit according to any one of the above exemplary embodiments.

[0196] 24) The Tg of the first oligomer is 150°C or lower, 125°C or lower, or 120°C or lower, and the composition or kit according to any one of the above exemplary embodiments.

[0197] 25) The main chain includes units formed from a polyol, and the polyol includes a polyalkylene polyol, and the composition or kit according to any one of the above exemplary embodiments.

[0198] 26) The first oligomer includes a reaction product of a polyvalent acid and a polyol, and the composition or kit according to any one of the above exemplary embodiments.

[0199] 27) The first oligomer includes a reaction product of a polyvalent acid and a polyol, and the polyvalent acid includes terephthalic acid, phthalic acid, or isophthalic acid, and the composition or kit according to any one of the above exemplary embodiments.

[0200] 28) The first oligomer contains a reaction product of a polyvalent acid and a polyol, and the polyvalent acid includes adipic acid, sebacic acid, octadecanedioic acid, pimelic acid, suberic acid, azelaic acid, brassilic acid, dodecanedioic acid, glutaric acid, maleic acid, fumaric acid, 6-naphthalenedicarboxylic acid, 4,4'-oxybisbenzoic acid, 3,6-dichlorophthalic acid, tetrachlorophthalic acid, tetrahydrophthalic acid, hexahydroterephthalic acid, hexachlorendomethylenetetrahydrophthalic acid, endomethylenetetrahydrophthalic acid, decanedicarboxylic acid, succinic acid, or trimellitic acid, and is a composition or kit according to any one of the above exemplary embodiments.

[0201] 29) At least 20 mol%, at least 30 mol%, at least 40 mol%, at least 50 mol%, at least 60 mol%, at least 70 mol%, at least 75 mol%, at least 80 mol%, at least 85 mol%, at least 90 mol%, at least 95 mol%, at least 98 mol%, or 100 mol% of the main chain of the first oligomer contains bisphenol A, F, or S type polyepoxide, hydrogenated bisphenol A, F, or S type polyepoxide, polycarbonate, or polyimide, and is a composition or kit according to any one of the above exemplary embodiments.

[0202] 30) At most 100 mol%, at most 98 mol%, at most 95 mol%, at most 90 mol%, at most 80 mol%, at most 70 mol%, or at most 60 mol% of the main chain of the first oligomer contains bisphenol A, F, or S type polyepoxide, hydrogenated bisphenol A, F, or S type polyepoxide, polycarbonate, or polyimide, and is a composition or kit according to any one of the above exemplary embodiments.

[0203] 31) At least 20 mol%, at least 30 mol%, at least 40 mol%, at least 50 mol%, at least 60 mol%, at least 70 mol%, at least 75 mol%, at least 80 mol%, at least 85 mol%, at least 90 mol%, at least 95 mol%, at least 98 mol%, or 100 mol% of the main chain of the first oligomer is a composition or kit according to any one of the above exemplary embodiments, including bisphenol A, F, or S type polyepoxide, hydrogenated bisphenol A, F, or S type polyepoxide, polycarbonate, or polyimide.

[0204] 32) At most 100 mol%, at most 98 mol%, at most 95 mol%, at most 90 mol%, at most 80 mol%, at most 70 mol%, or at most 60 mol% of the main chain of the first oligomer is a composition or kit according to any one of the above exemplary embodiments, including bisphenol A, F, or S type polyepoxide, hydrogenated bisphenol A, F, or S type polyepoxide, polycarbonate, or polyimide.

[0205] 33) The first oligomer has at least 2 polymerizable groups on average, and the polymerizable groups include acrylate, methacrylate, or itaconate, and it is a composition or kit according to any one of the above exemplary embodiments.

[0206] 34) The first oligomer has at least 2 polymerizable groups on average, and the polymerizable groups consist of acrylate, methacrylate, or itaconate, and it is a composition or kit according to any one of the above exemplary embodiments.

[0207] 35) The first oligomer has at least 2 polymerizable groups on average, and the polymerizable groups include acrylate or methacrylate, and it is a composition or kit according to any one of the above exemplary embodiments.

[0208] 36) The first oligomer has at least two polymerizable groups on average number, and the polymerizable groups consist of acrylate or methacrylate, and the composition or kit according to any one of the above exemplary embodiments.

[0209] 37) The first oligomer has at least two polymerizable groups on average number, and the polymerizable groups include methacrylate, and the composition or kit according to any one of the above exemplary embodiments.

[0210] 38) The first oligomer has at least two polymerizable groups on average number, and the polymerizable groups consist of methacrylate, and the composition or kit according to any one of the above exemplary embodiments.

[0211] 39) The first oligomer has at least two polymerizable groups on average number, and the polymerizable groups include end groups, and the composition or kit according to any one of the above exemplary embodiments.

[0212] 40) The first oligomer has at least two polymerizable groups on average number, and the polymerizable groups consist of end groups, and the composition or kit according to any one of the above exemplary embodiments.

[0213] 41) The first oligomer has at least two polymerizable groups on average number, and the polymerizable groups consist of end groups, and there are no polymerizable groups other than end groups in the first oligomer, and the composition or kit according to any one of the above exemplary embodiments.

[0214] 42) The first oligomer has at least 2.0, at least 2.1, at least 2.2, at least 2.3, at least 2.4, at least 2.5, at least 2.6, or at least 2.7 polymerizable groups per molecule on average number, and the composition or kit according to any one of the above exemplary embodiments.

[0215] 43) The first oligomer is a composition or kit according to any one of the above exemplary embodiments, having a maximum of 10, 9, 8, 7, 6, 5, 4.5, 4, 3.5, or 3 polymerizable groups per molecule on a number-average basis.

[0216] 44) The first oligomer is a composition or kit according to any one of the above exemplary embodiments, having a number-average molecular weight of at least 800 g / mol, at least 900 g / mol, at least 1000 g / mol, at least 1100 g / mol, at least 1200 g / mol, at least 1300 g / mol, at least 1400 g / mol, or at least 1500 g / mol.

[0217] 45) The first oligomer is a composition or kit according to any one of the above exemplary embodiments, having a number-average molecular weight of at most 10,000 g / mol, at most 9,000 g / mol, at most 8,000 g / mol, at most 7000 g / mol, at most 6,000 g / mol, at most 5,000 g / mol, at most 4,000 g / mol, or at most 3,000 g / mol.

[0218] 46) The first oligomer has 2 to 3 polymerizable groups on a number-average basis, and the amount, number-average molecular weight, and number-average of polymerizable groups of the first oligomer in the composition satisfy the following formula:

Number

[0219] 47) The first oligomer has 2 to 3 polymerizable groups on average, and the amount, number average molecular weight, and number average of polymerizable groups of the first oligomer in the composition satisfy the following formula: [Number] (In the formula, R is the gas constant 8.314 cm 3 MPa K -1 mol -1 , T is 423.15 K, f is the number average of polymerizable groups of the first oligomer, ρ is the density of the first oligomer (g / cm 3 ), M oligomer is the number average molecular weight (g / mol) of the first oligomer, w oligomer is the weight fraction of the first oligomer in the first network-forming component, X is 3, 5, 7, 10, 15, or 20, and Y is 50, 45, or 40). A composition or kit according to any one of the above exemplary embodiments.

[0220] 48) The first oligomer is present in an amount of at least 5 wt%, at least 10 wt%, at least 15 wt%, at least 19.95 wt%, at least 20 wt%, at least 25 wt%, at least 30 wt%, at least 40 wt%, at least 50 wt%, at least 60 wt%, at least 70 wt%, or at least 80 wt% based on the total weight of the composition. A composition or kit according to any one of the above exemplary embodiments.

[0221] 49) The first oligomer is present in an amount of at most 80 wt%, at most 78 wt%, at most 75 wt%, at most 70 wt%, at most 60 wt%, at most 50 wt%, at most 40 wt%, at most 30 wt%, or at most 20 wt% based on the total weight of the composition. A composition or kit according to any one of the above exemplary embodiments.

[0222] 50) The first oligomer is present in an amount of at least 5 wt%, at least 10 wt%, at least 15 wt%, at least 19.95 wt%, at least 20 wt%, at least 25 wt%, at least 30 wt%, at least 40 wt%, at least 50 wt%, at least 60 wt%, at least 70 wt%, or at least 80 wt% based on the total weight of the composition excluding the solvent (if present), of the composition or kit according to any one of the above exemplary embodiments.

[0223] 51) The first oligomer is present in an amount of at most 80 wt%, at most 78 wt%, at most 75 wt%, at most 70 wt%, at most 60 wt%, at most 50 wt%, at most 40 wt%, at most 30 wt%, or at most 20 wt% based on the total weight of the composition excluding the solvent (if present), of the composition or kit according to any one of the above exemplary embodiments.

[0224] 52) The first oligomer is present in an amount of at least 19.95 wt%, at least 20 wt%, at least 25 wt%, at least 30 wt%, at least 40 wt%, at least 50 wt%, at least 60 wt%, at least 70 wt%, or at least 80 wt% based on the total weight of the first mesh-forming component, of the composition or kit according to any one of the above exemplary embodiments.

[0225] 53) The first oligomer is present in an amount of at most 80 wt%, at most 78 wt%, at most 75 wt%, at most 70 wt%, at most 60 wt%, at most 50 wt%, at most 40 wt%, at most 30 wt%, or at most 20 wt% based on the total weight of the first mesh-forming component, of the composition or kit according to any one of the above exemplary embodiments.

[0226] 54) The first oligomer contains a polymerizable group including acrylate, methacrylate, itaconate, allyl ether, maleate, or fumarate, the first network monomer and any optional additional first network monomer, oligomer, or polymer are radical polymerizable compounds, and the first network initiator is a radical initiator, a composition or kit according to any one of the above exemplary embodiments.

[0227] 55) The first oligomer contains at least two acrylate groups, methacrylate groups, itaconate groups, allyl ether groups, maleate groups, or fumarate groups on average per molecule, one or more first network monomers contain acrylate groups, methacrylate groups, itaconate groups, vinyl ether groups, allyl ether groups, maleate groups, or fumarate groups, and any optional additional first network monomer, oligomer, or polymer contains two or more acrylate groups, methacrylate groups, itaconate groups, vinyl ether groups, allyl ether groups, or fumarate groups on average, a composition or kit according to any one of the above exemplary embodiments.

[0228] 56) The first oligomer contains at least two vinyl ether groups on average per molecule, one or more first network monomers contain acrylate groups, methacrylate groups, itaconate groups, hydroxyl groups, epoxy groups, oxetane groups, vinyl ether groups, allyl ether groups, or fumarate groups, and any optional additional first network monomer, oligomer, or polymer contains two or more acrylate groups, methacrylate groups, itaconate groups, hydroxyl groups, epoxy groups, oxetane groups, vinyl ether groups, allyl ether groups, maleate groups, or fumarate groups on average, a composition or kit according to any one of the above exemplary embodiments.

[0229] 57) The first network initiator is a photo radical initiator, a composition or kit according to any one of the above exemplary embodiments.

[0230] 58) The first network initiator is a photo cationic initiator, a composition or kit according to any one of the above exemplary embodiments.

[0231] 59) The first oligomer is amorphous, a composition or kit according to any one of the above exemplary embodiments.

[0232] 60) The first oligomer includes a blend of an amorphous first oligomer and a semi-crystalline first oligomer, a composition or kit according to any one of the above exemplary embodiments.

[0233] 61) The first oligomer includes a blend of an amorphous first oligomer, a semi-crystalline first oligomer, and a crystalline first oligomer, a composition or kit according to any one of the above exemplary embodiments.

[0234] 62) The first oligomer includes a blend of at least two different first oligomers. The first first oligomer has more than 3 polymerizable groups per molecule on average, and the second first oligomer has less than 3 polymerizable groups per molecule on average. The number average of polymerizable groups per molecule of the first oligomer is 2 to 3 polymerizable groups per molecule, a composition or kit according to any one of the above exemplary embodiments.

[0235] 63) The first oligomer includes at least one acrylate group and at least one methacrylate group, a composition or kit according to any one of the above exemplary embodiments.

[0236] 64) The first oligomer contains: i) at least one acrylate group or methacrylate group; and ii) at least one epoxy group. One or more first crosslinking monomers contain an acrylate group, a methacrylate group, an itaconate group, a hydroxyl group, an epoxy group, an oxetane group, a vinyl ether group, an allyl ether group, a maleate group, or a fumarate group. An optional further first crosslinking monomer, oligomer, or polymer contains, on average, two or more acrylate groups, methacrylate groups, itaconate groups, hydroxyl groups, epoxy groups, oxetane groups, vinyl ether groups, allyl ether groups, maleate groups, or fumarate groups. A composition or kit according to any one of the above exemplary embodiments.

[0237] 65) The first oligomer contains: i) at least one polymerizable group selected from acrylate, methacrylate, itaconate, allyl ether, maleate, or fumarate; and ii) at least one polymerizable group selected from hydroxyl, epoxy, or oxetane. One or more first crosslinking monomers contain an acrylate group, a methacrylate group, an itaconate group, a hydroxyl group, an epoxy group, an oxetane group, a vinyl ether group, an allyl ether group, a maleate group, or a fumarate group. An optional further first crosslinking monomer, oligomer, or polymer contains, on average, two or more acrylate groups, methacrylate groups, itaconate groups, hydroxyl groups, epoxy groups, oxetane groups, vinyl ether groups, allyl ether groups, maleate groups, or fumarate groups. A composition or kit according to any one of the above exemplary embodiments.

[0238] 66) A composition or kit according to any one of the above exemplary embodiments, wherein the first oligomer does not contain a hydroxyl group, an epoxy group, or an oxetane group.

[0239] 67) A composition or kit according to any one of the above exemplary embodiments, wherein the first crosslinking monomer has, on average, 0.95 or more polymerizable groups, 0.97 or more polymerizable groups, or 0.99 or more polymerizable groups.

[0240] 68) The first network monomer is a composition or kit according to any one of the above exemplary embodiments, having 1.1 or fewer polymerizable groups, 1.08 or fewer polymerizable groups, 1.06 or fewer polymerizable groups, 1.04 or fewer polymerizable groups, or 1.02 or fewer polymerizable groups on a number average basis. In one embodiment, the first network monomer has 1.0 polymerizable groups on a number average basis.

[0241] 69) A linear polymer formed from one or more first network monomers has a Tg of 50°C or higher, 60°C or higher, 65°C or higher, 70°C or higher, 75°C or higher, 80°C or higher, 85°C or higher, 90°C or higher, 95°C or higher, or 100°C or higher, and is a composition or kit according to any one of the above exemplary embodiments.

[0242] 70) A linear polymer formed from one or more first network monomers has a Tg of 150°C or lower, 130°C or lower, 125°C or lower, or 120°C or lower, and is a composition or kit according to any one of the above exemplary embodiments.

[0243] 71) One or more first network monomers have a molecular weight of 800 g / mol or lower, 700 g / mol or lower, 600 g / mol or lower, 500 g / mol or lower, 400 g / mol or lower, 350 g / mol or lower, 300 g / mol or lower, 250 g / mol or lower, or 200 g / mol or lower, and are a composition or kit according to any one of the above exemplary embodiments.

[0244] 72) One or more first network monomers have a molecular weight of 100 g / mol or higher or 150 g / mol or higher, and are a composition or kit according to any one of the above exemplary embodiments.

[0245] 73) The first oligomer contains a polymerizable group including acrylate, methacrylate, itaconate, vinyl ether, allyl ether, or fumarate, and the first network monomer is a composition or kit according to any one of the above exemplary embodiments, including methyl (meth)acrylate, hydroxyethyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, isobornyl (meth)acrylate, isobutyl acrylate, acryloylmorpholine, dimethyl itaconate, N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole, or N-methyl-N-acetamide.

[0246] 74) The first oligomer contains a polymerizable group including acrylate, methacrylate, itaconate, vinyl ether, allyl ether, or fumarate, and the first network monomer is a composition or kit according to any one of the above exemplary embodiments, including cyclohexyl vinyl ether, 1,4-cyclohexanedimethanol monovinyl ether, tert-butyl vinyl ether, phenyl vinyl ether, allyl phenyl ether, dimethyl maleate, diethyl maleate, dimethyl fumarate, or diethyl fumarate.

[0247] 75) One or more of the first network monomers are present in an amount of at least 10 wt%, at least 15 wt%, at least 19.95 wt%, at least 20 wt%, at least 25 wt%, at least 30 wt%, at least 40 wt%, at least 50 wt%, at least 60 wt%, at least 70 wt%, or at least 80 wt% based on the total weight of the composition, according to any one of the above exemplary embodiments, in a composition or kit.

[0248] 76) One or more first network monomers are present in an amount of up to 80 wt%, up to 78 wt%, up to 75 wt%, up to 70 wt%, up to 60 wt%, up to 50 wt%, up to 40 wt%, up to 30 wt%, or up to 20 wt% based on the total weight of the composition, a composition or kit according to any one of the above exemplary embodiments.

[0249] 77) One or more first network monomers are present in an amount of at least 10 wt%, at least 15 wt%, at least 19.95 wt%, at least 20 wt%, at least 25 wt%, at least 30 wt%, at least 40 wt%, at least 50 wt%, at least 60 wt%, at least 70 wt%, or at least 80 wt% based on the total weight of the composition excluding the solvent (if present), a composition or kit according to any one of the above exemplary embodiments.

[0250] 78) One or more first network monomers are present in an amount of up to 80 wt%, up to 78 wt%, up to 75 wt%, up to 70 wt%, up to 60 wt%, up to 50 wt%, up to 40 wt%, up to 30 wt%, or up to 20 wt% based on the total weight of the composition excluding the solvent (if present), a composition or kit according to any one of the above exemplary embodiments.

[0251] 79) One or more first network monomers are present in an amount of at least 19.95 wt%, at least 20 wt%, at least 25 wt%, at least 30 wt%, at least 40 wt%, at least 50 wt%, at least 60 wt%, at least 70 wt%, or at least 80 wt% based on the total weight of the first network-forming components, a composition or kit according to any one of the above exemplary embodiments.

[0252] 80) One or more first network monomers are present in an amount of up to 80 wt%, up to 78 wt%, up to 75 wt%, up to 70 wt%, up to 60 wt%, up to 50 wt%, up to 40 wt%, up to 30 wt%, or up to 20 wt% based on the total weight of the first network-forming component, in accordance with any one of the above exemplary embodiments, in a composition or kit.

[0253] 81) One or more first network initiators include a photoinitiator or a thermal initiator, in accordance with any one of the above exemplary embodiments, in a composition or kit.

[0254] 82) One or more first network initiators include a photoinitiator that reacts to UV light, visible light, or both UV light and visible light to initiate polymerization, in accordance with any one of the above exemplary embodiments, in a composition or kit.

[0255] 83) One or more first network initiators include a photoinitiator that initiates polymerization at a wavelength of 300 - 470 nm, in accordance with any one of the above exemplary embodiments, in a composition or kit.

[0256] 84) One or more first network initiators include a photoinitiator that initiates polymerization at a wavelength of 300 - 395 nm, in accordance with any one of the above exemplary embodiments, in a composition or kit.

[0257] 85) One or more first network initiators include a photoinitiator and a thermal initiator, in accordance with any one of the above exemplary embodiments, in a composition or kit.

[0258] 86) One or more first network initiators include a thermal initiator, in accordance with any one of the above exemplary embodiments, in a composition or kit.

[0259] 87) One or more first reticulation initiators are present in an amount of at least 0.01 wt%, at least 0.05 wt%, at least 0.1 wt%, at least 0.2 wt%, at least 0.3 wt%, at least 0.4 wt%, at least 0.5 wt%, at least 1.0 wt%, at least 1.5 wt%, at least 2 wt%, or at least 2.5 wt% based on the total weight of the composition, according to any one of the exemplary embodiments described above, for a composition or kit.

[0260] 88) One or more first reticulation monomers are present in an amount of at most 10 wt%, at most 8 wt%, at most 7 wt%, at most 6 wt%, at most 5 wt%, or at most 4 wt% based on the total weight of the composition, according to any one of the exemplary embodiments described above, for a composition or kit.

[0261] 89) One or more first reticulation initiators are present in an amount of at least 0.01 wt%, at least 0.05 wt%, at least 0.1 wt%, at least 0.2 wt%, at least 0.3 wt%, at least 0.4 wt%, at least 0.5 wt%, at least 1.0 wt%, at least 1.5 wt%, at least 2 wt%, or at least 2.5 wt% based on the total weight of the composition excluding the solvent (if present), according to any one of the exemplary embodiments described above, for a composition or kit.

[0262] 90) One or more first reticulation monomers are present in an amount of at most 10 wt%, at most 8 wt%, at most 7 wt%, at most 6 wt%, at most 5 wt%, or at most 4 wt% based on the total weight of the composition excluding the solvent (if present), according to any one of the exemplary embodiments described above, for a composition or kit.

[0263] 91) One or more first network initiators are present in an amount of at least 0.01 wt%, at least 0.05 wt%, at least 0.1 wt%, at least 0.2 wt%, at least 0.3 wt%, at least 0.4 wt%, at least 0.5 wt%, at least 1.0 wt%, at least 1.5 wt%, at least 2 wt%, or at least 2.5 wt% based on the total weight of the first network forming components, in accordance with any one of the above exemplary embodiments, for a composition or kit.

[0264] 92) One or more first network initiators are present in an amount of up to 10 wt%, up to 8 wt%, up to 7 wt%, up to 6 wt%, up to 5 wt%, or up to 4 wt% based on the total weight of the first network forming components, in accordance with any one of the above exemplary embodiments, for a composition or kit.

[0265] 93) Further first network monomers, oligomers, or polymers are present in an amount of up to 15 wt%, up to 12 wt%, up to 10 wt%, up to 8 wt%, up to 6 wt%, up to 5 wt%, up to 4 wt%, up to 3 wt%, or up to 2 wt% based on the total weight of the composition, in accordance with any one of the above exemplary embodiments, for a composition or kit.

[0266] 94) Further first network monomers, oligomers, or polymers are present in an amount of at least 0.5 wt%, at least 1 wt%, at least 1.5 wt%, at least 2 wt%, at least 2.5 wt%, at least 4 wt%, or at least 5 wt% based on the total weight of the composition, in accordance with any one of the above exemplary embodiments, for a composition or kit.

[0267] 95) Further first network monomers, oligomers, or polymers are present in an amount of up to 15 wt%, up to 12 wt%, up to 10 wt%, up to 8 wt%, up to 6 wt%, up to 5 wt%, up to 4 wt%, up to 3 wt%, or up to 2 wt% based on the total weight of the composition excluding the solvent (if present), in accordance with any one of the above exemplary embodiments, for a composition or kit.

[0268] 96) The additional first network monomer, oligomer, or polymer is present in an amount of at least 0.5 wt%, at least 1 wt%, at least 1.5 wt%, at least 2 wt%, at least 2.5 wt%, at least 4 wt%, or at least 5 wt% based on the total weight of the composition excluding the solvent (if present), in a composition or kit according to any one of the above exemplary embodiments.

[0269] 97) The additional first network monomer, oligomer, or polymer is present in an amount of up to 15 wt%, up to 12 wt%, up to 10 wt%, up to 8 wt%, up to 6 wt%, up to 5 wt%, up to 4 wt%, up to 3 wt%, or up to 2 wt% based on the total weight of the first network-forming component, in a composition or kit according to any one of the above exemplary embodiments.

[0270] 98) The additional first network monomer, oligomer, or polymer is present in an amount of at least 0.5 wt%, at least 1 wt%, at least 1.5 wt%, at least 2 wt%, at least 2.5 wt%, at least 4 wt%, or at least 5 wt% based on the total weight of the first network-forming component, in a composition or kit according to any one of the above exemplary embodiments.

[0271] 99) The first oligomer contains a polymerizable group including acrylate, methacrylate, or itaconate, and the one or more second network compounds contain a polymerizable group including epoxy, oxetane, or hydroxyl, in a composition or kit according to any one of the above exemplary embodiments.

[0272] 100) The second network-forming component is present in an amount of 5 wt% or more, 10 wt% or more, 15 wt% or more, 20 wt% or more, 25 wt% or more, 30 wt% or more, 35 wt% or more, 40 wt% or more, 50 wt% or more, 60 wt% or more, or 70 wt% or more based on the total weight of the composition, in a composition or kit according to any one of the above exemplary embodiments.

[0273] 101) The second network-forming component is present in an amount of 90% by weight or less, 80% by weight or less, 70% by weight or less, 60% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, or 20% by weight or less, based on the total weight of the composition, of a composition or kit according to any one of the above exemplary embodiments.

[0274] 102) The composition is a composition or kit according to any one of the above exemplary embodiments that does not contain a second network-forming component.

[0275] 103) The composition is a composition or kit according to any one of the above exemplary embodiments that substantially does not contain a second network-forming component.

[0276] 104) The second network-forming component is present in an amount of 5% by weight or more, 10% by weight or more, 15% by weight or more, 20% by weight or more, 25% by weight or more, 30% by weight or more, 35% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, or 70% by weight or more, based on the total weight of the composition excluding the solvent (if present), of a composition or kit according to any one of the above exemplary embodiments.

[0277] 105) The second network-forming component is present in an amount of 90% by weight or less, 80% by weight or less, 70% by weight or less, 60% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, or 20% by weight or less, based on the total weight of the composition excluding the solvent (if present), of a composition or kit according to any one of the above exemplary embodiments.

[0278] 106) The second network-forming component is present in an amount of 5% by weight or more, 10% by weight or more, 15% by weight or more, 20% by weight or more, 25% by weight or more, 30% by weight or more, 35% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, or 70% by weight or more, based on the total weight of the composition excluding the solvent (if present) and the component(s) (if present) that do not contain a polymerizable group, of a composition or kit according to any one of the above exemplary embodiments.

[0279] 107) The second network-forming component is present in an amount of 90% by weight or less, 80% by weight or less, 70% by weight or less, 60% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, or 20% by weight or less, based on the total weight of the composition excluding the solvent (if present) and the component(s) (if present) that do not contain a polymerizable group, in a composition or kit according to any one of the above exemplary embodiments.

[0280] 108) One or more second network compounds are present in an amount of at least 5% by weight, at least 10% by weight, at least 15% by weight, at least 19.95% by weight, at least 20% by weight, at least 25% by weight, at least 30% by weight, at least 40% by weight, at least 50% by weight, at least 60% by weight, at least 70% by weight, or at least 80% by weight, based on the total weight of the composition, in a composition or kit according to any one of the above exemplary embodiments.

[0281] 109) One or more second network compounds are present in an amount of at most 80% by weight, at most 78% by weight, at most 75% by weight, at most 70% by weight, at most 60% by weight, at most 50% by weight, at most 40% by weight, at most 30% by weight, or at most 20% by weight, based on the total weight of the composition, in a composition or kit according to any one of the above exemplary embodiments.

[0282] 110) One or more second network compounds are present in an amount of at least 5% by weight, at least 10% by weight, at least 15% by weight, at least 19.95% by weight, at least 20% by weight, at least 25% by weight, at least 30% by weight, at least 40% by weight, at least 50% by weight, at least 60% by weight, at least 70% by weight, or at least 80% by weight, based on the total weight of the composition excluding the solvent (if present), in a composition or kit according to any one of the above exemplary embodiments.

[0283] 111) One or more second network compounds are present in an amount of up to 80 wt%, up to 78 wt%, up to 75 wt%, up to 70 wt%, up to 60 wt%, up to 50 wt%, up to 40 wt%, up to 30 wt%, or up to 20 wt% based on the total weight of the composition excluding the solvent (if present), in a composition or kit according to any one of the above exemplary embodiments.

[0284] 112) One or more second network compounds are present in an amount of at least 50 wt%, at least 60 wt%, at least 70 wt%, at least 80 wt%, or at least 90 wt% based on the total weight of the second network-forming component, in a composition or kit according to any one of the above exemplary embodiments.

[0285] 113) One or more second network compounds are present in an amount of up to 99.9 wt%, up to 99.5 wt%, up to 99 wt%, up to 98 wt%, up to 97 wt%, up to 96 wt%, up to 95 wt%, up to 90 wt%, or up to 80 wt% based on the total weight of the second network-forming component, in a composition or kit according to any one of the above exemplary embodiments.

[0286] 114) The second network initiator comprises a photoinitiator or a thermal initiator, in a composition or kit according to any one of the above exemplary embodiments.

[0287] 115) The second network initiator comprises a photoinitiator that reacts to initiate polymerization upon exposure to UV light, visible light, or both UV light and visible light, in a composition or kit according to any one of the above exemplary embodiments.

[0288] 116) The second network initiator comprises a photoinitiator and a thermal initiator, in a composition or kit according to any one of the above exemplary embodiments.

[0289] 117) The second network initiator is present in an amount of at least 0.01 wt%, at least 0.05 wt%, at least 0.1 wt%, at least 0.2 wt%, at least 0.3 wt%, at least 0.4 wt%, at least 0.5 wt%, at least 1.0 wt%, at least 1.5 wt%, at least 2 wt%, or at least 2.5 wt% based on the total weight of the composition excluding the solvent (if present), for a composition or kit according to any one of the above exemplary embodiments.

[0290] 118) The second network initiator is present in an amount of at most 10 wt%, at most 8 wt%, at most 7 wt%, at most 6 wt%, at most 5 wt%, or at most 4 wt% based on the total weight of the composition excluding the solvent (if present), for a composition or kit according to any one of the above exemplary embodiments.

[0291] 119) The second network initiator is present in an amount of at least 0.01 wt%, at least 0.05 wt%, at least 0.1 wt%, at least 0.2 wt%, at least 0.3 wt%, at least 0.4 wt%, at least 0.5 wt%, at least 1.0 wt%, at least 1.5 wt%, at least 2 wt%, or at least 2.5 wt% based on the total weight of the second network-forming component, for a composition or kit according to any one of the above exemplary embodiments.

[0292] 120) The second network initiator is present in an amount of at most 10 wt%, at most 8 wt%, at most 7 wt%, at most 6 wt%, at most 5 wt%, or at most 4 wt% based on the total weight of the second network-forming component, for a composition or kit according to any one of the above exemplary embodiments.

[0293] 121) The composition further comprises an organic or inorganic particulate filler such as SiO2, AlO2, TiO2, ZnO2, SnO2, Am-SnO2, ZrO2, Sb-SnO2, Al2O3, or carbon black, for a composition or kit according to any one of the above exemplary embodiments.

[0294] 122) The composition further includes a particulate filler containing polymerizable groups copolymerizable with the polymerizable groups of the first oligomer, the composition or kit according to any one of the above exemplary embodiments.

[0295] 123) The particulate filler contains polymerizable groups copolymerizable with the polymerizable groups of one or more second network compounds, the composition or kit according to any one of the above exemplary embodiments.

[0296] 124) The particulate filler contains polymerizable groups including acrylate, methacrylate, itaconate, vinyl ether, allyl ether, maleate, or fumarate, the composition or kit according to any one of the above exemplary embodiments.

[0297] 125) The particulate filler contains polymerizable groups including acrylate, methacrylate, epoxy, oxetane, hydroxyl, or itaconate, the composition or kit according to any one of the above exemplary embodiments.

[0298] 126) The particulate filler contains polymerizable groups including acrylate or methacrylate, the composition or kit according to any one of the above exemplary embodiments.

[0299] 127) The particulate filler contains polymerizable groups including epoxy, oxetane, or hydroxyl, the composition or kit according to any one of the above exemplary embodiments.

[0300] 128) The particulate filler includes an impact resistance improver, the composition or kit according to any one of the above exemplary embodiments.

[0301] 129) The particulate filler is present in the composition in an amount of 1% by weight or more, 5% by weight or more, 10% by weight or more, 15% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, or 50% by weight or more based on the total weight of the composition, the composition or kit according to any one of the above exemplary embodiments.

[0302] 130) The particulate filler is present in the composition in an amount of 90% by weight or less, 80% by weight or less, 70% by weight or less, 60% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, or 20% by weight or less, based on the total weight of the composition, of the composition or kit according to any one of the above exemplary embodiments.

[0303] 131) The composition further comprises a stabilizer such as a viscosity stabilizer or a light stabilizer, a UV absorber, a dye, a pigment, a plasticizer, a surfactant, an antioxidant, a wetting agent, a photosensitizer, an antifoaming agent, a flame retardant, a silane coupling agent, an acid scavenger, an accelerator for a thermal initiator, and / or a defoaming agent, of the composition or kit according to any one of the above exemplary embodiments.

[0304] 132) The composition further comprises a non-particulate impact modifier, of the composition or kit according to any one of the above exemplary embodiments.

[0305] 133) The composition further comprises a non-particulate impact modifier that does not contain a polymerizable group, of the composition or kit according to any one of the above exemplary embodiments.

[0306] 134) The composition further comprises a non-particulate impact modifier that contains a polymerizable group, of the composition or kit according to any one of the above exemplary embodiments.

[0307] 135) The non-particulate impact modifier comprises a block copolymer, of the composition or kit according to any one of the above exemplary embodiments.

[0308] 136) The further first network monomer, oligomer, or polymer comprises a non-particulate impact modifier containing a polymerizable group, of the composition or kit according to any one of the above exemplary embodiments.

[0309] 137) The second network compound comprises a non-particulate impact modifier containing a polymerizable group, of the composition or kit according to any one of the above exemplary embodiments.

[0310] 138) The composition contains a solvent in an amount of 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, 10% by weight or less, 5% by weight or less, or 0% by weight based on the total weight of the composition, and is a composition or kit according to any one of the above exemplary embodiments.

[0311] 139) The viscosity of the composition at 30 °C is 4000 cps or less, 3000 cps or less, 2000 cps or less, 1500 cps or less, or 1200 cps or less, and is a composition or kit according to any one of the above exemplary embodiments.

[0312] 140) The viscosity of the composition at 30 °C is 300 cps or more, and is a composition or kit according to any one of the above exemplary embodiments.

[0313] 141) The composition or the liquid composition component further contains a dispersion medium, and is a composition or kit according to any one of the above exemplary embodiments.

[0314] 142) The composition further contains 20 to 70% by weight of a dispersion medium, and is a composition according to any one of the above exemplary embodiments.

[0315] 143) The liquid composition component further contains 20 to 80% by weight of a dispersion medium, and is a kit according to any one of the above exemplary embodiments.

[0316] 144) The composition or the liquid composition component further contains a dispersion medium, and the dispersion medium contains water, and is a composition or kit according to any one of the above exemplary embodiments.

[0317] 145) The composition or the liquid composition component further contains a dispersion medium, and the dispersion medium consists of water, and is a composition or kit according to any one of the above exemplary embodiments.

[0318] 146) An article formed by polymerizing the composition, wherein the composition is optionally produced by combining the components of a kit according to any one of the above exemplary embodiments.

[0319] 147) The composition is optionally produced by combining the components of a kit according to any one of the above exemplary embodiments, and the tensile modulus measured at 150 °C by DMTA, in accordance with ASTM D5026, of a film formed by polymerizing 90% or more of the total polymerizable groups of the composition is from 3 MPa, from 5 MPa, from 7 MPa, from 10 MPa, from 15 MPa, or from 20 MPa to 50 MPa, to 45 MPa, or to 40 MPa. An article formed by polymerizing the composition.

[0320] 148) The composition is optionally produced by combining the components of a kit according to any one of the above exemplary embodiments, and the yield stress at 23 °C, determined in accordance with ISO 37:2011, of a film formed by polymerizing 90% or more of the total polymerizable groups of the composition is 50 to 90 MPa, and the elongation at break at 23 °C exceeds 3%. An article formed by polymerizing the composition.

[0321] 149) The composition is optionally produced by combining the components of a kit according to any one of the above exemplary embodiments, and the tensile modulus at 23 °C, determined in accordance with ISO 37:2011, of a film formed by polymerizing 90% or more of the total polymerizable groups of the composition is 2000 to 3500 MPa. An article formed by polymerizing the composition.

[0322] 150) The composition is optionally produced by combining the components of a kit according to any one of the above exemplary embodiments, and the elongation at break at 23 °C of a film formed by polymerizing 90% or more of the total polymerizable groups exceeds 3% and is less than 20%, less than 15%, or less than 10%. An article formed by polymerizing the composition.

[0323] A method of forming a three-dimensional object, comprising: preparing a composition according to any one of the above exemplary embodiments, or a composition generated by combining components of a kit according to any one of the above exemplary embodiments; and polymerizing the composition.

[0324] 152) A method of forming a three-dimensional object, comprising: forming a layer of a composition according to any one of the above exemplary embodiments, or a composition generated by combining components of a kit according to any one of the above exemplary embodiments; forming a desired shape by curing the composition with radiation; and repeating the forming step and the curing step a plurality of times to obtain a three-dimensional object.

[0325] 153) A method of forming a three-dimensional object, comprising: selectively discharging a composition according to any one of the above exemplary embodiments, or a composition generated by combining components of a kit according to any one of the above exemplary embodiments; forming a desired shape by curing the composition with radiation; and repeating the selective discharging step and the curing step a plurality of times to obtain a three-dimensional object.

[0326] 154) A method of forming a three-dimensional object, comprising: forming a layer of a composition according to any one of the above exemplary embodiments, or a composition generated by combining components of a kit according to any one of the above exemplary embodiments; forming a desired shape by selectively curing the layer with radiation; and repeating the forming step of the composition layer and the selective curing step a plurality of times to obtain a three-dimensional object.

[0327] 155) A method for forming a three-dimensional article by polymerizing a composition according to any one of the above exemplary embodiments or by polymerizing a composition generated by combining the components of a kit according to any one of the above exemplary embodiments, the method comprising: forming a layer from a first composition comprising a first oligomer; and selectively ejecting a second composition comprising one or more first network monomers onto the first composition according to the shape of a portion of the three-dimensional object, wherein one or more first network initiators are present in either the layer of the first oligomer, the composition comprising one or more first network monomers, or both.

[0328] 156) A method for forming a three-dimensional article from a kit according to any one of the above exemplary embodiments, the method comprising: forming a layer of particulate composition components; selectively ejecting or non-selectively ejecting liquid composition components by spraying or the like; optionally, selectively applying or non-selectively applying radiation to thereby induce curing of the particulate composition components and the liquid composition components; and repeating the forming step, the ejecting step, and the selective curing step a plurality of times to form a three-dimensional object.

[0329] 157) The method according to any one of the above exemplary embodiments, further comprising the step of evaporating the dispersion medium.

[0330] 158) The method according to any one of the above exemplary embodiments, wherein the composition is present as a liquid at the time of curing the composition, such as by initiating a polymerization reaction by applying radiation such as light or heat.

[0331] 159) The method according to any one of the above exemplary embodiments, wherein the composition is present as a liquid at the time of curing the composition, such as by initiating a polymerization reaction by applying radiation such as light or heat, and the temperature at the time when the liquid composition starts to polymerize is 25° or higher, 30°C or higher, 35°C or higher, 40°C or higher, or 45°C or higher.

[0332] The composition exists as a liquid when the composition is cured, for example, by initiating a polymerization reaction by applying radiation such as light or heat. The temperature at which the liquid composition starts to polymerize is 200°C or lower, 180°C or lower, 150°C or lower, 100°C or lower, 80°C or lower, or 50°C or lower, according to any one of the exemplary embodiments described above.

[0333] In the context of the present invention (particularly in the context of the claims set forth below), the use of the words "a," "an," and "the," and similar indicatives, should be construed to include both the singular and the plural, unless otherwise specified herein or clearly contradicted by the 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 specified. When a range of values is recited herein, unless otherwise specified herein, this is merely intended to serve as a convenient method for referring individually to each separate value within the range, and each separate value is incorporated herein as if it were individually recited herein. The use of any example or exemplary language (e.g., "such as") presented herein is merely intended to more appropriately illustrate the invention and is not limiting of the invention unless otherwise claimed. No language in the specification should be construed as suggesting that any non-claimed element is essential to the practice of the invention.

[0334] Preferred embodiments of the present invention, including the best mode contemplated by the inventors for carrying out the invention, are described herein. Variations of these preferred embodiments will be apparent to those skilled in the art upon reading the above description. The inventors expect those skilled in the art to appropriately utilize such variations, and the inventors intend for the invention to be practiced in a manner different from that specifically described herein. Accordingly, the present invention includes all modifications and equivalents of the subject matter taught in the claims appended hereto that are permitted in the applicable law. Specific optional features are described for embodiments of the present invention, and this description is meant to cover any combination of these embodiments, as long as there is no specific indication to the contrary or it is physically impossible, and is specifically disclosed.

Brief Description of the Drawings

[0335]

Figure 1

Claims

1. A composition for forming a three-dimensional object via a stereolithography process, comprising: a. A first network-forming component, comprising: i. A first oligomer having a main chain containing bisphenol A, F, or S type polyepoxide, or hydrogenated bisphenol A, F, or S type polyepoxide, and having at least 2 polymerizable groups on average number, wherein the polymerizable groups include acrylate, methacrylate, itaconate, vinyl ether, allyl ether, maleate, or fumarate, the number average molecular weight of the first oligomer is 1200 - 10000 g / mol, and Tg is 25 °C or higher, the first oligomer being 19.95 - 80 wt% based on the total weight of the first network-forming component; ii. One or more first network monomers having 0.95 - 1.1 polymerizable groups on average number that are (co)polymerizable with the polymerizable groups of the first oligomer, wherein the linear polymer formed from the one or more first network monomers has a Tg of 25 °C or higher, the one or more first network monomers being 19.95 - 80 wt% based on the total weight of the network-forming component; iii. One or more first network initiators capable of initiating the polymerization of the first oligomer and the first network monomers, the one or more first network initiators being 0.05 - 5 wt% based on the total weight of the first network-forming component; iv. Optionally, one or more additional first network monomers, oligomers, or polymers having 2 or more polymerizable groups on average number that are (co)polymerizable with the polymerizable groups of the first oligomer or the one or more first network monomers, up to 15 wt%; The first network-forming component, consisting of the above, being 30 - 100 wt% based on the total weight of the composition; b. Optionally, one or more second network compounds containing polymerizable groups that do not (co)polymerize with the polymerizable groups of the first oligomer, and a second network initiator for initiating the polymerization of the one or more second network compounds, a second network-forming component; c. Optionally, a particulate filler containing polymerizable groups that are (co)polymerizable with the polymerizable groups of the first oligomer; Including, The polymerizable groups include end groups, The linear polymer formed from the one or more first network monomers has a Tg of 60 °C or higher, the composition.

2. The composition according to claim 1, wherein the first network initiator includes a photoinitiator.

3. The film formed by polymerizing 90% or more of the total polymerizable groups in the composition has a tensile modulus of elasticity measured at 150 °C of 3 to 50 MPa and a Tg of 40 °C or higher. The composition according to claim 1 or 2.

4. The polymerizable group consists of a terminal group. The composition according to any one of claims 1 to 3.

5. The first oligomer has 2 to 3 terminal groups on average, and the amount, number average molecular weight, and number average of terminal groups of the first oligomer in the composition are represented by the following formula: 【Number 1】 (wherein, R is the gas constant 8.314 cm ３ MPa K －１ mol －１ , T is 423.15 K, f is the number average of the end groups of the first oligomer, ρ is the density of the first oligomer (g / cm ３ ), Moligomer is the number average molecular weight (g / mol) of the first oligomer, woligomer is the weight fraction of the first oligomer in the first network-forming component, X is 3, and Y is 50), the composition according to any one of claims 1 to 4.

6. At least 50 mol% of the main chain of the first oligomer contains bisphenol A, F, or S type polyepoxide, or hydrogenated bisphenol A, F, or S type polyepoxide. The composition according to any one of claims 1 to 5.

7. The first oligomer has 2 to 3 terminal groups on average. The composition according to any one of claims 1 to 6.

8. The first oligomer has a number average molecular weight of 1200 to 8000 g / mol. The composition according to any one of claims 1 to 7.

9. The one or more first network monomers have a molecular weight of 300 g / mol or less. The composition according to any one of claims 1 to 8.

10. The one or more first network monomers include methyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, or isobutyl (meth)acrylate. The composition according to any one of claims 1 to 9.

11. An article formed by polymerizing the composition according to any one of claims 1 to 10, wherein the tensile modulus of elasticity measured at 150 °C of the film formed by polymerizing 90% or more of the total polymerizable groups in the composition, determined by DMTA in accordance with ASTM D5026, is 3 MPa to 50 MPa. Article.

12. A method for forming a three-dimensional object: a. Forming a layer of the composition according to any one of claims 1 to 10; b. Curing the layer by electromagnetic radiation to form a desired shape; c. Repeating the forming step and the curing step a plurality of times to obtain a three-dimensional object; Including the method.

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