CURABLE COMPOSITION FOR 3D PRINTING PROCESSES, AND 3D PRINTED OBJECTS FORMED FROM THE COMPOSITIONS AND 3D PRINTING PROCESSES USING THE COMPOSITIONS

Abstract

The present invention provides a curable composition comprising (A) at least one component containing an ethylenically unsaturated group, which is component (A) comprising component (A1) containing a structure (K) selected from an isocyanurate structure and / or a tricyclodecane ring structure, and (B) at least one photoinitiator, the curable composition having an average glass transition temperature (Tg,av) calculated from the curable composition using the following Fox formula of at least 373.15 K, preferably at least 393.15 K, more preferably at least 423.15 K, where Tg,i is the glass transition temperature in Kelvin of the homopolymer of component (i) constituting component (A), and w i The present invention relates to a curable composition, a method of forming a 3D printed object from the composition, and a 3D printed object formed from the composition, the mass fraction of component (i) in component (A). The 3D printed object obtained from the curable composition of the present invention has a high HDT and excellent mechanical performance. [0010] TIFF2025511887000032.tif1940

Description

[Technical field]

[0001] The present invention relates to compositions for three-dimensional (hereinafter "3D") printing. In particular, the present invention relates to curable compositions for 3D printing. The present invention further relates to methods of forming 3D printed objects using the compositions, and 3D printed objects formed from the compositions.

[0002] 3D printing or additive manufacturing (AM) is a manufacturing method that seeks to circumvent traditional manufacturing techniques that are either subtractive (e.g. machining and ablation) or formative (e.g. molding and casting). Moreover, 3D printing exploits considerable advantages in terms of design freedom. UV-curable photopolymers are one type of 3D printable material and are widely used in various applications such as prototyping plastic parts, metal investment casting, and dental applications. To date, commercially available UV-curable photopolymers are suitable for creating prototypes and demonstrations, but are generally not suitable for real applications where thermal and mechanical properties are required. To bridge the gap from prototyping to real manufacturing, it is important to have advanced materials with specific properties according to the targeted industrial application.

[0003] The automotive industry is one of the most important consumer sectors of polymers. Increasing demands for fuel efficiency and lightweighting make 3D printing a promising technology for manufacturing plastic components inside vehicles, such as interior parts, connectors and functional prototypes. These applications usually require materials to have suitable heat distortion temperature (HDT) and mechanical performance, which is currently a challenging task.

[0004] Therefore, there is a strong need to provide curable compositions that have a high heat distortion temperature (HDT) and at the same time provide 3D printed objects with excellent mechanical performance. Summary of the Invention [Problem to be solved by the invention]

[0005] The object of the present invention is to provide a curable composition comprising at least one component (A) containing an ethylenically unsaturated group, the component (A) comprising a component (A1) containing a structure (K) selected from an isocyanurate structure and / or a tricyclodecane ring structure. A cured product from the curable composition has a high HDT and excellent mechanical properties, in particular it can reach an HDT of at least 100°C under a load of 1.82 MPa measured according to the test standard ASTM D648-07, and has excellent mechanical properties, such as properties that are particularly suitable for applications where high stiffness is required.

[0006] Another object of the present invention is to provide a 3D printed object formed from the curable composition of the present invention.

[0007] It is a further object of the present invention to provide a method of forming a 3D printed object by using the curable composition of the present invention. [Means for solving the problem]

[0008] Surprisingly, it has been found that the above object can be achieved by the following embodiments: 1. The following ingredients: (A) at least one component containing an ethylenically unsaturated group, which is a component (A) including a component (A1) containing a structure (K) selected from an isocyanurate structure and / or a tricyclodecane ring structure; and (B) at least one photoinitiator A curable composition comprising: The curable composition has an average glass transition temperature (Tg,av) of at least 373.15K, preferably at least 393.15K, and more preferably at least 423.15K, as calculated using the Fox equation:

number

[0009] 2. A curable composition according to embodiment 1, wherein component (A1) contains at least one ethylenically unsaturated group, preferably contains 1 to 5 ethylenically unsaturated groups, and more preferably contains 2 to 4 ethylenically unsaturated groups.

[0010] 3. The curable composition according to embodiment 1 or 2, wherein the ethylenically unsaturated groups are selected from the group consisting of allyl, vinyl, acrylate, methacrylate, acryloxy, methacryloxy, acrylamide, methacrylamide, acetylenyl, and maleimide.

[0011] 4. Ingredient (A1) is tris(hydroxy-C 1~30 4. The curable composition according to any one of the preceding embodiments, wherein component (A1) comprises or is a tri(meth)acrylate of tris-(2-hydroxyethyl)isocyanurate, a tri(meth)acrylate of tris(hydroxymethyl)isocyanurate, a tri(meth)acrylate of tris(3-hydroxy-n-propyl)isocyanurate, or any combination thereof.

[0012] 5. Component (A1) is tricyclodecane-di-C 1~20 The curable composition according to any one of the preceding embodiments, comprising or being an -alkanol di(meth)acrylate, preferably tricyclodecane di-methanol di(meth)acrylate, tricyclodecane di-ethanol di(meth)acrylate, tricyclodecane di-propanol di(meth)acrylate, tricyclodecane di-butanol di(meth)acrylate, or tricyclodecane di-pentanol di(meth)acrylate.

[0013] 6. The curable composition according to any one of the preceding embodiments, wherein the photoinitiator is a free radical photoinitiator and / or an ionic photoinitiator, preferably a free radical photoinitiator.

[0014] 7. The curable composition according to any one of embodiments 1 to 6, wherein the amount of component (A) is in the range of 80% by mass to 99.9% by mass, preferably 90% by mass to 99.9% by mass, and more preferably 97% by mass to 99.5% by mass, based on the total amount of the curable composition.

[0015] 8. The curable composition according to any one of embodiments 1 to 7, wherein the amount of component (A1) is in the range of 10% by mass to 90% by mass, preferably 15% by mass to 85% by mass, and more preferably 20% by mass to 80% by mass, based on the total amount of component (A).

[0016] 9. The curable composition according to any one of embodiments 1 to 8, wherein the amount of photoinitiator is in the range of 0.1% by weight to 8% by weight, preferably 0.1% by weight to 5% by weight, more preferably 0.5% by weight to 3% by weight, based on the total amount of the curable composition.

[0017] 10. The curable composition according to any one of embodiments 1 to 9, further comprising auxiliaries as component (C), such as surfactants, flame retardants, pigments, fillers, dyes, catalysts, UV absorbers and stabilizers, and reinforcing materials, preferably in an amount ranging from 0 to 18% by weight, preferably from 0 to 15% by weight, more preferably from 0 to 10% by weight, based on the total amount of the curable composition.

[0018] 11. The curable composition according to any one of the preceding embodiments, wherein a cured product formed from the curable composition has an HDT value of at least 100°C, preferably at least 140°C, more preferably at least 190°C, at a load of 1.82 MPa, measured according to test standard ASTM D648-07.

[0019] 12. The curable composition according to any one of embodiments 1 to 11, wherein component (A) further comprises component (A2) that does not contain structure (K).

[0020] 13. A method of forming a 3D printed object comprising using a curable composition according to any one of embodiments 1 to 12.

[0021] 14. The following steps: (i) applying a curable composition and curing the applied curable composition layer-by-layer with radiation to form an intermediate 3D printed object; and (ii) curing the entire intermediate 3D printed object with radiation to form a cured 3D printed object. Item 13. The method according to item 13,

[0022] 15. The method according to embodiment 14, wherein stereolithography, photopolymer jetting, digital light processing, or LCD techniques are used in step (i) to form the intermediate 3D printed object.

[0023] 16. The method according to embodiment 14 or 15, wherein the radiation is UV radiation.

[0024] 17. A 3D printed object formed from a curable composition according to any one of embodiments 1 to 12, or obtained by a method according to any one of embodiments 13 to 16.

[0025] 18. 3D printed objects according to embodiment 17, including plastic parts within a vehicle, such as interior parts, connectors and functional prototypes.

[0026] The 3D printed objects obtained from the curable compositions of the present invention have high HDT and excellent mechanical performance, in particular they can reach an HDT of at least 100°C at a load of 1.82 MPa, for example an HDT of at least 110°C, or at least 120°C, preferably at least 140°C, more preferably at least 190°C at a load of 1.82 MPa measured according to the test standard ASTM D648-07, and have excellent mechanical performance, such as performance that is particularly suitable for applications where high stiffness is required. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0027] Unless otherwise defined, all technical and scientific terms used herein have the meaning commonly understood by one of ordinary skill in the art to which this invention belongs. As used herein, the following terms have the meanings ascribed to them unless specified otherwise.

[0028] The singular articles "a," "an," and "the" refer to one or more of the species designated by the term following the article.

[0029] The relationship between Celsius (°C) and Kelvin (K) used in this disclosure is T(K)=T(°C)+273.15.

[0030] In the context of this disclosure, any specific values ​​recited for a characteristic (including the specific values ​​recited in a range as endpoints) may be recombined to form new ranges.

[0031] Further embodiments of the invention are discernible from the claims, the description, the examples and the drawings. It will be understood that the above-mentioned features of the subject matter of the invention and the features still elucidated herein can be used not only in the specific combinations shown but also in other combinations without departing from the domain of the invention.

[0032] One aspect of the invention is a method for producing a composition comprising the following components: (A) at least one component containing an ethylenically unsaturated group, which is a component (A) including a component (A1) containing a structure (K) selected from an isocyanurate structure and / or a tricyclodecane ring structure; and (B) at least one photoinitiator A curable composition comprising: The curable composition has an average glass transition temperature (Tg,av) of at least 373.15K, preferably at least 393.15K, and more preferably at least 423.15K, as calculated using the Fox equation:

number

[0033] Component (A) The curable compositions of the present invention include at least one component containing an ethylenically unsaturated group as component (A). In an embodiment of the present invention, the ethylenically unsaturated group contains a carbon-carbon unsaturated bond such as those found in the following functional groups: allyl, vinyl, acrylate, methacrylate, acryloxy, methacryloxy, acrylamide, methacrylamide, acetylenyl, maleimide, and the like.

[0034] The amount of component (A) can be in the range of 80 to 99.9 mass%, for example, 80 mass%, 82 mass%, 84 mass%, 86 mass%, 88 mass%, 90 mass%, 92 mass%, 94 mass%, 96 mass%, 98 mass%, 99 mass%, or 99.9 mass%, for example, 85 to 99.9 mass%, preferably 90 to 99.9 mass%, more preferably 95 to 99.9 mass%, or 97 to 99.5 mass%, relative to the total mass of the curable composition of the present invention.

[0035] Ingredient (A1) The component (A) of the present invention includes a component (A1) containing an ethylenically unsaturated group and a structure (K) selected from an isocyanurate structure and / or a tricyclodecane ring structure. Preferably, the component (A1) contains at least one ethylenically unsaturated group, preferably 1 to 5 ethylenically unsaturated groups, more preferably 2 to 4 ethylenically unsaturated groups. In a preferred embodiment of the present invention, the ethylenically unsaturated group is selected from the group consisting of allyl, vinyl, acrylate, methacrylate, acryloxy, methacryloxy, acrylamide, methacrylamide, acetylenyl, and maleimide.

[0036] In one embodiment of the present invention, component (A1) is a tri(meth)acrylate of a tris(hydroxy-alkyl)isocyanurate, preferably a tris(hydroxy-C 1~30 -alkyl)isocyanurate tri(meth)acrylate. Preferably, the hydroxy-C of the tri(meth)acrylate of tris(hydroxy-alkyl)isocyanurate 1~30 -Alkyl is hydroxy-methyl, hydroxy-ethyl, hydroxy-propyl, hydroxy-butyl, hydroxy-pentyl, hydroxy-hexyl, hydroxy-octyl, hydroxy-nonyl, hydroxy-decyl, hydroxy-C 11 -Alkyl, Hydroxy-C 12 -Alkyl, Hydroxy-C 13 -Alkyl, Hydroxy-C 14 -Alkyl, Hydroxy-C 15 -Alkyl, Hydroxy-C 16 -Alkyl, Hydroxy-C 17 -Alkyl, Hydroxy-C 18 -Alkyl, Hydroxy-C 19 -Alkyl, Hydroxy-C 20 -Alkyl, Hydroxy-C 21 -Alkyl, Hydroxy-C 22 -Alkyl, Hydroxy-C 23 -Alkyl, Hydroxy-C 24 -Alkyl, Hydroxy-C 25 -Alkyl, Hydroxy-C 26 -Alkyl, Hydroxy-C 27 -Alkyl, Hydroxy-C 28 -Alkyl, Hydroxy-C 29 -Alkyl, Hydroxy-C 30 -alkyl, more preferably selected from hydroxy-methyl, hydroxy-ethyl, hydroxy-propyl, hydroxy-butyl, hydroxy-pentyl, hydroxy-hexyl, hydroxy-octyl, hydroxy-nonyl, and hydroxy-decyl.

[0037] Preferably, component (A1) comprises or is the tri(meth)acrylate of tris-(2-hydroxyethyl)isocyanurate, the tri(meth)acrylate of tris(hydroxymethyl)isocyanurate, the tri(meth)acrylate of tris(3-hydroxy-n-propyl)isocyanurate, or any combination thereof.

[0038] In one embodiment of the present invention, component (A1) comprises or is a tricyclodecane-di-alkanol di(meth)acrylate.

[0039] In a preferred embodiment of the present invention, component (A1) is tricyclodecane di-C 1~20 -alkanol di(meth)acrylates, for example tricyclodecane di-methanol di(meth)acrylate, tricyclodecane di-ethanol di(meth)acrylate, tricyclodecane di-propanol di(meth)acrylate, tricyclodecane di-butanol di(meth)acrylate, tricyclodecane di-pentanol di(meth)acrylate, tricyclodecane di-C6-alkanol di(meth)acrylate, tricyclodecane di-C7-alkanol di(meth)acrylate, tricyclodecane di-C8-alkanol di(meth)acrylate, tricyclodecane di-C9-alkanol di(meth)acrylate, tricyclodecane di-C 10 -Alkanol di(meth)acrylate, tricyclodecane di-C 12 -Alkanol di(meth)acrylate, tricyclodecane di-C 14 -Alkanol di(meth)acrylate, tricyclodecane di-C 16 -Alkanol di(meth)acrylate, tricyclodecane di-C 18 -Alkanol di(meth)acrylate, tricyclodecane di-C 20 -alkanol di(meth)acrylates, and any combination thereof. Preferably, tricyclodecane di-C 1~20-Alkanol di(meth)acrylates include tricyclodecane dimethanol di(meth)acrylate, tricyclodecane diethanol di(meth)acrylate, tricyclodecane dipropanol di(meth)acrylate, tricyclodecane dibutanol di(meth)acrylate, tricyclodecane dipentanol di(meth)acrylate, tricyclodecane di-C6-alkanol di(meth)acrylate, tricyclodecane di-C7-alkanol di(meth)acrylate, tricyclodecane di-C8-alkanol di(meth)acrylate, tricyclodecane di-C9-alkanol di(meth)acrylate, tricyclodecane di-C10-alkanol di(meth)acrylate, tricyclodecane di-C11-alkanol di(meth)acrylate, tricyclodecane di-C12-alkanol di(meth)acrylate, tricyclodecane di-C13-alkanol di(meth)acrylate, tricyclodecane di-C14-alkanol di(meth)acrylate, tricyclodecane di-C15-alkanol di(meth)acrylate, tricyclodecane di-C16-alkanol di(meth)acrylate, tricyclodecane di-C17-alkanol di(meth)acrylate, tricyclodecane di-C18-alkanol di(meth)acrylate, tricyclodecane di-C19-alkanol di(meth)acrylate, tricyclodecane di-C20-alkanol di(meth)acrylate, tricyclodecane di-C21-alkanol di(meth)acrylate, tricyclodecane di-C22-alkanol di(meth)acrylate, tricyclodecane di-C23-alkanol di(meth)acrylate, tricyclodecane di-C24-alkanol di(meth)acrylate, tricyclodecane di-C25-alkanol di(meth)acrylate, tricyclodecane di-C26-alkanol di(meth)acrylate, tricyclodecane di-C27-alkanol di(meth)acrylate, tricyclodecane di-C28-alkanol di(meth)acrylate, 10 -alkanol di(meth)acrylate.

[0040] In one embodiment of the present invention, component (A1) is an isocyanurate having two or three allyl-alkyl groups as ethylenically unsaturated groups, or a tricyclodecane having one or two allyl-alkyl groups as ethylenically unsaturated groups, e.g., a tricyclodecane having two or three allyl-C 1~20 Isocyanurates with alkyl or one or two allyl-C 1~20 It may include or be a tricyclodecane having an alkyl group. For example, the allyl-alkyl group may be allyl-methyl, allyl-ethyl, allyl-propyl, allyl-butyl, allyl-pentyl, allyl-hexyl, allyl-octyl, allyl-nonyl, allyl-decyl, allyl-C 11 -Alkyl, aryl-C 12 -Alkyl, aryl-C 13 -Alkyl, aryl-C 14 -Alkyl, aryl-C 15 -Alkyl, aryl-C 16 -Alkyl, aryl-C 17 -Alkyl, aryl-C 18 -Alkyl, aryl-C 19 -Alkyl and aryl-C 20-alkyl, more preferably the allyl-alkyl is selected from allyl-methyl, allyl-ethyl, allyl-propyl, allyl-butyl, allyl-pentyl, allyl-hexyl, allyl-octyl, allyl-nonyl, and allyl-decyl. Preferably, the alkyl in the allyl-alkyl is interrupted at the end or in the middle of the alkyl by one or more heteroatoms, preferably one or two or three heteroatoms, such as O, N or S, preferably O or N, or the alkyl in the allyl-alkyl is interrupted at the end or in the middle of the alkyl by groups such as carbonyl, amino, and acyloxy groups.

[0041] In a preferred embodiment of the present invention, Sartomer SR368, available from Sartomer Co., Exton, PA, and Sartomer SR833S, available from Sartomer Co., Exton, PA, are useful as component (A1) of the present invention.

[0042] The amount of component (A1) can be in the range of 10 to 90 mass%, for example, 15 mass%, 20 mass%, 25 mass%, 30 mass%, 35 mass%, 40 mass%, 45 mass%, 50 mass%, 55 mass%, 60 mass%, 70 mass%, 80 mass%, 85 mass%, 90 mass%, preferably 10 to 85 mass%, or 15 to 85 mass%, or 20 to 85 mass%, or 25 to 85 mass%, or 30 to 85 mass%, or 10 to 80 mass%, or 15 to 80 mass%, or 20 to 80 mass%, or 25 to 80 mass%, or 30 to 80 mass%, based on the total amount of component (A) of the present invention.

[0043] Ingredients (A2) Preferably, component (A) of the present invention further comprises component (A2). Component (A2) of the present invention contains an ethylenically unsaturated group but does not contain structure (K). In a preferred embodiment of the present invention, the ethylenically unsaturated group is selected from the group consisting of allyl, vinyl, acrylate, methacrylate, acryloxy, methacryloxy, acrylamide, methacrylamide, acetylenyl, maleimide, and the like.

[0044] In an embodiment of the present invention, component (A2) of the present invention contains, in addition to ethylenically unsaturated groups, urethane groups, ether groups, ester groups, carbonate groups, and any combination thereof.

[0045] In one embodiment of the present invention, component (A2) of the present invention comprises monomers and / or oligomers containing ethylenically unsaturated groups.

[0046] Component (A2) of the present invention may include oligomers containing ethylenically unsaturated groups and a core structure optionally linked via a linking group, where the core structure is not structure (K) and does not contain structure (K). The linking group can be an ether, ester, amide, urethane, or carbonate group that does not contain structure (K). In some cases, the linking group is part of the ethylenically unsaturated group, such as an acryloxy group or an acrylamide group. The core group can be an alkyl (straight and branched alkyl group), aryl (e.g., phenyl), polyether, polyester, siloxane, urethane, or other core structure and oligomers thereof.

[0047] In one embodiment, as component (A2) of the present invention, the oligomer having an ethylenically unsaturated group can be selected from the following types: urethane (i.e., urethane-based oligomer having an ethylenically unsaturated group), polyether (i.e., polyether-based oligomer having an ethylenically unsaturated group), polyester (i.e., polyester-based oligomer having an ethylenically unsaturated group), polycarbonate (i.e., polycarbonate-based oligomer having an ethylenically unsaturated group), polyestercarbonate (i.e., polyestercarbonate-based oligomer having an ethylenically unsaturated group), epoxy (i.e., epoxy-based oligomer having an ethylenically unsaturated group), silicone (i.e., silicone-based oligomer having an ethylenically unsaturated group), or any combination thereof. Preferably, the oligomer having an ethylenically unsaturated group can be selected from the following types: urethane-based oligomer, epoxy-based oligomer, polyester-based oligomer, polyether-based oligomer, polyetherurethane-based oligomer, polyesterurethane-based oligomer, or silicone-based oligomer, and any combination thereof.

[0048] In a preferred embodiment of the present invention, the oligomer having ethylenically unsaturated groups as component (A2) of the present invention includes urethane-based oligomers having urethane repeat units and one, two or more ethylenically unsaturated groups, such as those containing carbon-carbon unsaturated double bonds, such as (meth)acrylate groups, (meth)acrylamide groups, allyl groups and vinyl groups. Preferably, the oligomer contains at least one urethane bond (e.g., one, two or more urethane bonds) in the backbone of the oligomer molecule and at least one acrylate and / or methacrylate functional group (e.g., one, two or more acrylate and / or methacrylate functional groups) pendantly attached to the oligomer molecule. In some embodiments, aliphatic, cycloaliphatic, or mixed aliphatic and cycloaliphatic urethane repeat units are suitable. Urethanes are typically prepared by condensation of diisocyanates and diols. Aliphatic urethanes having at least two urethane moieties per repeat unit are useful. Additionally, the diisocyanates and diols used to prepare the urethanes contain divalent aliphatic groups which may be the same or different.

[0049] In one embodiment, as component (A2) of the present invention, the oligomer having an ethylenically unsaturated group includes a polyester urethane-based oligomer or a polyether urethane-based oligomer having at least one ethylenically unsaturated group. The ethylenically unsaturated group can be one containing a carbon-carbon unsaturated double bond, such as an acrylate group, a methacrylate group, a vinyl group, an allyl group, an acrylamide group, a methacrylamide group, etc., preferably an acrylate group and a methacrylate group.

[0050] Suitable urethane-based oligomers are known in the art and can be readily synthesized by many different procedures. For example, a polyfunctional alcohol can be reacted with a polyisocyanate (preferably a stoichiometric excess of the polyisocyanate) to form an NCO-terminated pre-oligomer, which can then be reacted with a hydroxy-functional ethylenically unsaturated monomer, such as a hydroxy-functional (meth)acrylate. The polyfunctional alcohol can be any compound containing two or more OH groups per molecule, and can be a monomeric polyol (e.g., glycol), polyester polyol, polyether polyol, etc. In one embodiment of the present invention, the urethane-based oligomer is an aliphatic urethane-based oligomer with (meth)acrylate functionality.

[0051] Suitable polyether or polyester urethane-based oligomers include the reaction products of aliphatic or aromatic polyether or polyester polyols and aliphatic or aromatic polyisocyanates functionalized with monomers containing ethylenically unsaturated groups, such as (meth)acrylate groups. In a preferred embodiment, the polyethers and polyesters are aliphatic polyethers and polyesters, respectively. In a preferred embodiment, the polyether and polyester urethane-based oligomers are aliphatic polyether and polyester urethane-based oligomers and contain (meth)acrylate groups.

[0052] In one embodiment, the viscosity at 60 ° C. of the oligomer having an ethylenically unsaturated group as component (A2) of the present invention is in the range of 2000 to 100000 cP, for example, 3000 cP, 4000 cP, 5000 cP, 6000 cP, 7000 cP, 8000 cP, 10000 cP, 20000 cP, 30000 cP, 40000 cP, 50000 cP, 60000 cP, 70000 cP, 80000 cP, 90000 cP, 95000 cP, preferably 4000 to 60000 cP, for example, 4000 to 15000 cP, or 20000 cP to 60000 cP, which are measured according to DIN EN ISO3219.

[0053] The monomer can reduce the viscosity of the curable composition of the present invention. As component (A2) of the present invention, the monomer can be monofunctional or polyfunctional (e.g., difunctional, trifunctional). In one embodiment, the monomer can be selected from the group consisting of (meth)acrylate monomers, (meth)acrylamide monomers, vinyl aromatics having 20 or less carbon atoms, vinyl esters of carboxylic acids having 20 or less carbon atoms, α,β-unsaturated carboxylic acids having 3 to 8 carbon atoms, and anhydrides thereof.

[0054] In the context of this disclosure, the term "(meth)acrylate monomer" refers to a monomer that includes a (meth)acrylate moiety. The structure of the (meth)acrylate moiety is as follows: [ka] where R is H or methyl.

[0055] As component (A2) of the present invention, the (meth)acrylate monomer can be a monofunctional or polyfunctional (e.g., difunctional, trifunctional) (meth)acrylate monomer. Examples of the (meth)acrylate monomer include C1-C 20 Alkyl (meth)acrylate, C1-C 10 Included are hydroxyalkyl (meth)acrylate, caprolactone (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, and phenethyl (meth)acrylate.

[0056] C1~C 20Specific examples of alkyl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, sec-butyl (meth)acrylate, pentyl (meth)acrylate, n-hexyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, n-lauryl (meth)acrylate, n-tridecyl (meth)acrylate, n-cetyl (meth)acrylate, n-stearyl (meth)acrylate, isomyristyl (meth)acrylate, stearyl (meth)acrylate, and isostearyl (meth)acrylate (ISTA). C6~C 18 Alkyl (meth)acrylates, especially C6-C 16 Alkyl (meth)acrylate or C8-C 12 Alkyl (meth)acrylates are preferred.

[0057] C1~C 10 Specific examples of hydroxyalkyl (meth)acrylates, for example, C2 to C8 hydroxyalkyl (meth)acrylates, include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and 3-hydroxy-2-ethylhexyl (meth)acrylate.

[0058] In the context of this disclosure, the term "(meth)acrylamide monomer" means that the monomer comprises a (meth)acrylamide moiety. The structure of the (meth)acrylamide moiety is CH2=CR 1 -CO-N, where R 1is hydrogen or methyl. Specific examples of (meth)acrylamide monomers include N-(hydroxymethyl)acrylamide, N-hydroxyethylacrylamide, N-isopropylacrylamide, N-isopropylmethacrylamide, N-tert-butylacrylamide, N,N'-methylenebisacrylamide, N-(isobutoxymethyl)acrylamide, N-(butoxymethyl)acrylamide, N-[3-(dimethylamino)propyl]methacrylamide, N,N-dimethylacrylamide, N,N-diethyl ... amides, N-(hydroxymethyl)methacrylamide, N-hydroxyethylmethacrylamide, N-isopropylmethacrylamide, N-isopropylmethacrylamide, N-tert-butylmethacrylamide, N,N'-methylenebismethacrylamide, N-(isobutoxymethyl)methacrylamide, N-(butoxymethyl)methacrylamide, N-[3-(dimethylamino)propyl]methacrylamide, N,N-dimethylmethacrylamide and N,N-diethylmethacrylamide. The (meth)acrylamide monomers may be used alone or in combination.

[0059] Examples of vinyl aromatics having up to 20 carbon atoms include, for example, styrene and C1-C4-alkyl substituted styrenes such as vinyltoluene, p-tert-butylstyrene and α-methylstyrene.

[0060] Examples of vinyl esters of carboxylic acids having 20 or fewer carbon atoms (eg, 2 to 20 or 8 to 18 carbon atoms) include vinyl laurate, vinyl stearate, vinyl propionate, and vinyl acetate.

[0061] Examples of the α,β-unsaturated carboxylic acid having 3 to 8 carbon atoms include acrylic acid and methacrylic acid.

[0062] Preferred monomers are (meth)acrylate monomers, (meth)acrylamide monomers, and vinyl aromatics having up to 20 carbon atoms.

[0063] In a preferred embodiment, component (A2) of the present invention comprises both oligomers and monomers containing ethylenically unsaturated groups. The weight ratio of oligomer to monomer can range from 10:1 to 1:10, preferably 8:1 to 1:8, or 5:1 to 1:5, or 3:1 to 1:5, or 1:1 to 1:4.

[0064] In a preferred embodiment of the present invention, component (A2) of the present invention is selected from the group consisting of Rahn Genomer 4247 available from Rahn, Dymax BR952 available from Dymax, acryloylmorpholine (ACMO) available from Rahn, and isobornyl methacrylate (IBOMA) available from Miwon.

[0065] Photoinitiator (B) The curable composition of the present invention comprises at least one photoinitiator as component (B). For example, the photoinitiator component (B) may comprise at least one free radical photoinitiator and / or at least one ionic photoinitiator, and preferably at least one (e.g., one or two) free radical photoinitiator. Any photoinitiator known in the art for use in 3D printing compositions can be used, for example, photoinitiators known in the art suitable for stereolithography (SLA), digital light processing (DLP) and photopolymer jetting (PPJ) processes can be used.

[0066] As examples of photoinitiators for the present invention, it is possible to use those mentioned in "Advances in Polymer Science", Volume 14, Springer Berlin 1974 or KK Dietliker, Chemistry and Technology of UV and EB Formulation for Coatings, Inks and Paints, Volume 3; Photo-initiators for Free Radical and Cationic Polymerization, PKT Oldring (Ed.), SITA Technology Ltd, London.

[0067] Suitable examples include phosphine oxides, benzophenones, α-hydroxyalkylaryl ketones, thioxanthones, anthraquinones, acetophenones, benzoins and benzoin ethers, ketals, imidazoles or phenylglyoxylic acids, and mixtures thereof.

[0068] Phosphine oxides which may be mentioned, for example, are monoacyl- or bisacylphosphine oxides, such as Irgacure® 819 (bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide), as described, for example, in EP-A 7 508, EP-A 57 474, DE-A 196 18 720, EP-A 495 751 or EP-A 615 980, such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Lucirin® TPO), ethyl 2,4,6-trimethylbenzoylphenylphosphineate or bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide;

[0069] Benzophenones include, for example, benzophenone, 4-aminobenzophenone, 4,4'-bis(dimethylamino)benzophenone, 4-phenylbenzophenone, 4-chlorobenzophenone, Michler's ketone, o-methoxybenzophenone, 2,4,6-trimethylbenzophenone, 4-methylbenzophenone, 2,4-dimethylbenzophenone, 4-isopropylbenzophenone, 2-chlorobenzophenone, 2,2'-dichlorobenzophenone, 4-methoxybenzophenone, 4-propoxybenzophenone or 4-butoxybenzophenone;

[0070] α-Hydroxyalkylaryl ketones include, for example, 1-benzoylcyclohexan-1-ol (1-hydroxycyclohexyl phenyl ketone), 2-hydroxy-2,2-dimethylacetophenone (2-hydroxy-2-methyl-1-phenylpropan-1-one), 1-hydroxyacetophenone, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one or a polymer containing 2-hydroxy-2-methyl-1-(4-isopropen-2-ylphenyl)propan-1-one in copolymerized form (Esacure® KIP150);

[0071] Xanthones and thioxanthones include, for example, 10-thioxanthenone, thioxanthenone-9-one, xanthen-9-one, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-dichlorothioxanthone or chloroxanthenone;

[0072] Examples of anthraquinones include β-methylanthraquinone, tert-butylanthraquinone, anthraquinone carboxylic acid esters, benz[de]anthracene-7-one, benz[a]anthracene-7,12-dione, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, and 2-amylanthraquinone;

[0073] Examples of acetophenones include acetophenone, acetonaphthoquinone, valerophenone, hexanophenone, α-phenylbutyrophenone, p-morpholinopropiophenone, dibenzosuberone, 4-morpholinobenzophenone, p-diacetylbenzene, 4'-methoxyacetophenone, α-tetralone, 9-acetylphenanthrene, 2-acetylphenanthrene, 3-acetylphenanthrene, 3-acetylindole, 9-fluorenone, 1-indanone, 1,3,4-triacetylbenzene, 1- acetonaphthone, 2-acetonaphthone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxyacetophenone, 2,2-diethoxyacetophenone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2,2-dimethoxy-1,2-diphenylethan-2-one or 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one;

[0074] Benzoins and benzoin ethers include, for example, 4-morpholinodeoxybenzoin, benzoin, benzoin isobutyl ether, benzoin tetrahydropyranyl ether, benzoin methyl ether, benzoin ethyl ether, benzoin butyl ether, benzoin isopropyl ether or 7H-benzoin methyl ether; and

[0075] Ketals include, for example, acetophenone dimethyl ketal, 2,2-diethoxyacetophenone, or benzil ketals, such as benzyl dimethyl ketal.

[0076] Phenylglyoxylic acid is described, for example, in DE-A 198 26 712, DE-A 199 13 353 or WO 98 / 33761.

[0077] Photoinitiators which can likewise be used are, for example, benzaldehyde, methyl ethyl ketone, 1-naphthaldehyde, triphenylphosphine, tri-o-tolylphosphine or 2,3-butanedione.

[0078] Suitable mixtures of photoinitiators can also be used. Typical mixtures include, for example: A mixture of 2-hydroxy-2-methyl-1-phenylpropan-2-one and 1-hydroxycyclohexyl phenyl ketone; A mixture of bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide and 2-hydroxy-2-methyl-1-phenylpropan-1-one; A mixture of benzophenone and 1-hydroxycyclohexyl phenyl ketone; Mixture of bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide and 1-hydroxycyclohexyl phenyl ketone; A mixture of 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 2-hydroxy-2-methyl-1-phenylpropan-1-one; A mixture of 2,4,6-trimethylbenzophenone and 4-methylbenzophenone; or A mixture of 2,4,6-trimethylbenzophenone, 4-methylbenzophenone and 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

[0079] The amount of the photoinitiator (B) can be in the range of 0.1 to 8 mass%, for example, 0.2 mass%, 0.3 mass%, 0.4 mass%, 0.5 mass%, 0.6 mass%, 0.7 mass%, 0.8 mass%, 0.9 mass%, 1 mass%, 2 mass%, 3 mass%, 4 mass%, 5 mass%, 6 mass%, 7 mass%, or 8 mass%, preferably 0.1 to 7 mass%, or 0.1 to 6 mass%, or 0.1 to 5 mass%, more preferably 0.4 to 6 mass%, or 0.4 to 5 mass%, or 0.5 to 5 mass%, or 0.5 to 3 mass%, based on the total mass of the curable composition of the present invention.

[0080] curable composition The curable composition of the present invention comprises the following components: (A) at least one component containing an ethylenically unsaturated group, which is a component (A) including a component (A1) containing a structure (K) selected from an isocyanurate structure and / or a tricyclodecane ring structure; and (B) at least one photoinitiator Including, The curable composition has an average glass transition temperature (Tg,av) of at least 373.15K, preferably at least 393.15K, and more preferably at least 423.15K, as calculated using the Fox equation:

number

[0081] Preferably, component (A) further comprises component (A2) which does not contain structure (K).

[0082] Surprisingly, it has been found that the cured products obtained from the curable compositions of the present invention have high HDT and excellent mechanical properties. In particular, the cured products obtained from the curable compositions of the present invention can reach HDT of at least 100°C, preferably at least 140°C, more preferably at least 190°C, at a load of 1.82 MPa, measured according to the test standard ASTM D648-07, and have excellent mechanical properties, such as properties that are particularly suitable for applications requiring high stiffness.

[0083] In one embodiment, the curable composition of the present invention comprises the following components: (A) at least one component containing 80% by mass to 99.9% by mass of an ethylenically unsaturated group, which is a component (A) containing a component (A1) containing a structure (K) selected from an isocyanurate structure and / or a tricyclodecane ring structure; and (B) 0.1% to 8% by weight of at least one photoinitiator Including, the amount of component (A1) is in the range of 10% by mass to 90% by mass, preferably 15% by mass to 85% by mass, and more preferably 20% by mass to 80% by mass, based on the total amount of component (A); The curable composition has an average glass transition temperature (Tg,av) of at least 373.15K, preferably at least 393.15K, and more preferably at least 423.15K, as calculated using the Fox equation:

number

[0084] In one embodiment, the curable composition of the present invention comprises the following components: (A) at least one component containing 90% by mass to 99.9% by mass of an ethylenically unsaturated group, which is a component (A) containing a component (A1) containing a structure (K) selected from an isocyanurate structure and / or a tricyclodecane ring structure; and (B) 0.1% to 5% by weight of at least one photoinitiator Including, the amount of component (A1) is in the range of 10% by mass to 90% by mass, preferably 15% by mass to 85% by mass, and more preferably 20% by mass to 80% by mass, based on the total amount of component (A); The curable composition has an average glass transition temperature (Tg,av) of at least 373.15K, preferably at least 393.15K, and more preferably at least 423.15K, as calculated using the Fox equation:

number

[0085] In one embodiment, the curable composition of the present invention comprises the following components: (A) at least one component containing 97% by mass to 99.5% by mass of an ethylenically unsaturated group, which is a component (A) containing a component (A1) containing a structure (K) selected from an isocyanurate structure and / or a tricyclodecane ring structure; and (B) 0.1% to 3% by weight of at least one photoinitiator Including, the amount of component (A1) is in the range of 10% by mass to 90% by mass, preferably 15% by mass to 85% by mass, and more preferably 20% by mass to 80% by mass, based on the total amount of component (A); The curable composition has an average glass transition temperature (Tg,av) of at least 373.15K, preferably at least 393.15K, and more preferably at least 423.15K, as calculated using the Fox equation:

number

[0086] In one embodiment, the curable composition of the present invention comprises the following components: (A) at least one component containing 80% by mass to 99.9% by mass of an ethylenically unsaturated group, which is a component (A) containing a component (A1) containing a structure (K) selected from an isocyanurate structure and / or a tricyclodecane ring structure; and (B) 0.1% to 8% by weight of at least one photoinitiator Including, the amount of component (A1) is in the range of 10% by mass to 90% by mass, preferably 15% by mass to 85% by mass, and more preferably 20% by mass to 80% by mass, based on the total amount of component (A); The curable composition has an average glass transition temperature (Tg,av) of at least 373.15K, preferably at least 393.15K, and more preferably at least 423.15K, as calculated using the Fox equation:

number

[0087] In one embodiment, the curable composition of the present invention comprises the following components: (A) at least one component containing 90% by mass to 99.9% by mass of an ethylenically unsaturated group, which is a component (A) containing a component (A1) containing a structure (K) selected from an isocyanurate structure and / or a tricyclodecane ring structure; and (B) 0.1% to 5% by weight of at least one photoinitiator Including, the amount of component (A1) is in the range of 10% by mass to 90% by mass, preferably 15% by mass to 85% by mass, and more preferably 20% by mass to 80% by mass, based on the total amount of component (A); The curable composition has an average glass transition temperature (Tg,av) of at least 373.15K, preferably at least 393.15K, and more preferably at least 423.15K, as calculated using the Fox equation:

number

[0088] In one embodiment, the curable composition of the present invention comprises the following components: (A) at least one component containing 97% by mass to 99.5% by mass of an ethylenically unsaturated group, which is a component (A) containing a component (A1) containing a structure (K) selected from an isocyanurate structure and / or a tricyclodecane ring structure; and (B) 0.1% to 3% by weight of at least one photoinitiator Including, the amount of component (A1) is in the range of 10% by mass to 90% by mass, preferably 15% by mass to 85% by mass, and more preferably 20% by mass to 80% by mass, based on the total amount of component (A); The curable composition has an average glass transition temperature (Tg,av) of at least 373.15K, preferably at least 393.15K, and more preferably at least 423.15K, as calculated using the Fox equation:

number

[0089] In one embodiment, the curable composition of the present invention comprises the following components: (A) at least one component containing 80% by mass to 99.9% by mass of an ethylenically unsaturated group, which is a component (A) containing a component (A1) containing a structure (K) selected from an isocyanurate structure and / or a tricyclodecane ring structure; and (B) 0.1% to 8% by weight of at least one photoinitiator Including, the amount of component (A1) is in the range of 10% by mass to 90% by mass, preferably 15% by mass to 85% by mass, and more preferably 20% by mass to 80% by mass, based on the total amount of component (A); The curable composition has an average glass transition temperature (Tg,av) of at least 373.15K, preferably at least 393.15K, and more preferably at least 423.15K, as calculated using the Fox equation:

number

[0090] In one embodiment, the curable composition of the present invention comprises the following components: (A) at least one component containing 90% by mass to 99.9% by mass of an ethylenically unsaturated group, which is a component (A) containing a component (A1) containing a structure (K) selected from an isocyanurate structure and / or a tricyclodecane ring structure; and (B) 0.1% to 5% by weight of at least one photoinitiator Including, the amount of component (A1) is in the range of 10% by mass to 90% by mass, preferably 15% by mass to 85% by mass, and more preferably 20% by mass to 80% by mass, based on the total amount of component (A); The curable composition has an average glass transition temperature (Tg,av) of at least 373.15K, preferably at least 393.15K, and more preferably at least 423.15K, as calculated using the Fox equation:

number

[0091] In one embodiment, the curable composition of the present invention comprises the following components: (A) at least one component containing 97% by mass to 99.5% by mass of an ethylenically unsaturated group, which is a component (A) containing a component (A1) containing a structure (K) selected from an isocyanurate structure and / or a tricyclodecane ring structure; and (B) 0.1% to 3% by weight of at least one photoinitiator Including, the amount of component (A1) is in the range of 10% by mass to 90% by mass, preferably 15% by mass to 85% by mass, and more preferably 20% by mass to 80% by mass, based on the total amount of component (A); The curable composition has an average glass transition temperature (Tg,av) of at least 373.15K, preferably at least 393.15K, and more preferably at least 423.15K, as calculated using the Fox equation:

number

[0092] In one embodiment, the curable composition of the present invention comprises the following components: (A) at least one component containing 80% by mass to 99.9% by mass of an ethylenically unsaturated group, which is a component (A) containing a component (A1) containing a structure (K) selected from an isocyanurate structure and / or a tricyclodecane ring structure; and (B) 0.1% to 8% by weight of at least one photoinitiator Including, the amount of component (A1) is in the range of 10% by mass to 90% by mass, preferably 15% by mass to 85% by mass, and more preferably 20% by mass to 80% by mass, based on the total amount of component (A); The curable composition has an average glass transition temperature (Tg,av) of at least 373.15K, preferably at least 393.15K, and more preferably at least 423.15K, as calculated using the Fox equation:

number

[0093] In one embodiment, the curable composition of the present invention comprises the following components: (A) at least one component containing 90% by mass to 99.9% by mass of an ethylenically unsaturated group, which is a component (A) containing a component (A1) containing a structure (K) selected from an isocyanurate structure and / or a tricyclodecane ring structure; and (B) 0.1% to 5% by weight of at least one photoinitiator Including, the amount of component (A1) is in the range of 10% by mass to 90% by mass, preferably 15% by mass to 85% by mass, and more preferably 20% by mass to 80% by mass, based on the total amount of component (A); The curable composition has an average glass transition temperature (Tg,av) of at least 373.15K, preferably at least 393.15K, and more preferably at least 423.15K, as calculated using the Fox equation:

number

[0094] In one embodiment, the curable composition of the present invention comprises the following components: (A) at least one component containing 97% by mass to 99.5% by mass of an ethylenically unsaturated group, which is a component (A) containing a component (A1) containing a structure (K) selected from an isocyanurate structure and / or a tricyclodecane ring structure; and (B) 0.1% to 3% by weight of at least one photoinitiator Including, the amount of component (A1) is in the range of 10% by mass to 90% by mass, preferably 15% by mass to 85% by mass, and more preferably 20% by mass to 80% by mass, based on the total amount of component (A); The curable composition has an average glass transition temperature (Tg,av) of at least 373.15K, preferably at least 393.15K, and more preferably at least 423.15K, as calculated using the Fox equation:

number

[0095] Ingredients (C) In practical applications, optionally, the curable composition of the present invention may further comprise an adjuvant as component (C).

[0096] Preferred examples of auxiliaries include surfactants, flame retardants, dyes, pigments, catalysts, UV absorbers and stabilizers, such as stabilizers against oxidation, hydrolysis, light, heat or discoloration, inorganic and / or organic fillers, and reinforcing materials. Preferred hydrolysis inhibitors are oligomeric and / or polymeric aliphatic or aromatic carbodiimides. In order to stabilize the cured material of the present invention against aging and destructive environmental influences, in a preferred embodiment stabilizers are added to the system.

[0097] Surfactants include surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, and mixtures thereof. Such surfactants can be used, for example, as dispersants, solubilizers, etc. Examples of surfactants are described in McCutcheon's, Vol. 1: Emulsifiers & Detergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.). Suitable anionic surfactants may be alkali metal, alkaline earth metal or ammonium sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof. Suitable nonionic surfactants may be alkoxylates, N-substituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof. Suitable cationic surfactants may be quaternary surfactants, such as quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines. Suitable amphoteric surfactants may be alkyl betaines and imidazolines.

[0098] Further details regarding the abovementioned adjuvants can be found in the specialist literature, for example in Plastics Additive Handbook, 5th Edition, edited by H. Zweifel, Hanser Publishers, Munich, 2001.

[0099] When present, the amount of component (C) in the curable composition of the present invention may be in the range of 0 to 18% by weight, for example 1%, 3%, 5%, 7%, 9%, 11%, 13%, 15%, 17%, 18% by weight, preferably 0 to 16%, or 0 to 15%, or 0 to 13%, or 0 to 10% by weight, based on the total weight of the curable composition of the present invention.

[0100] Preparation of the Composition One aspect of the invention relates to a method for preparing a curable composition of the invention for 3D printing, comprising mixing the components of the composition.

[0101] According to an embodiment of the present invention, mixing can be carried out with stirring at a temperature ranging from room temperature to about 80° C., for example, from 30° C. to about 80° C., preferably from 40° C. to about 60° C., for example, at room temperature of about 50° C. There are no particular limitations on the mixing time and stirring speed, so long as the compositions are mixed together uniformly. In a specific embodiment, mixing can be carried out at 1000-3000 RPM, preferably 1500-2500 RPM, for 5-60 minutes, more preferably 6-30 minutes.

[0102] 3D Printed Objects and Their Preparation One aspect of the invention relates to a method of forming a 3D printed object comprising using a curable composition of the invention.

[0103] In one embodiment of the present invention, a method of forming a 3D printed object comprises the steps of: (i) applying a curable composition and curing the applied curable composition layer-by-layer with radiation to form an intermediate 3D printed object; and (ii) curing the entire intermediate 3D printed object with radiation to form a cured 3D printed object. Includes.

[0104] According to the present invention, the curing time in steps (i) and (ii) can be determined by those skilled in the art according to the actual application. For example, in step (i) of the method, the curing time of each layer may be 0.5-15 seconds, for example 1-10 seconds. In step (ii) of the method, the curing time of the entire intermediate 3D printed object may be in the range of 3 minutes to 500 minutes, for example 3 minutes, 5 minutes, 10 minutes, 20 minutes, 30 minutes, 40 minutes, 60 minutes, 80 minutes, 100 minutes, 120 minutes, 180 minutes, 250 minutes, 300 minutes, 400 minutes, preferably 10 minutes to 250 minutes.

[0105] There is no particular limitation on the temperature during step (i) or step (ii). Specifically, the temperature may be selected depending on the material and 3D printer used.

[0106] The radiation used in steps (i) and (ii) of the method for forming the 3D printed object of the present invention may be adopted by those skilled in the art according to the actual 3D printing application. For example, the radiation may be actinic radiation having sufficient energy to initiate a polymerization reaction or a crosslinking reaction. Actinic radiation may include, but is not limited to, alpha radiation, gamma radiation, ultraviolet light (UV radiation), visible light, and electron beam, with UV radiation and electron beam, especially UV radiation, being preferred.

[0107] In a specific embodiment, the wavelength of the irradiating light can be in the range of 350 to 480 nm, for example, 355 nm, 365 nm, 385 nm, 395 nm, 405 nm, 420 nm, 440 nm, 460 nm, or 480 nm.

[0108] Stereolithography (SLA), digital light processing (DLP), photopolymer jetting (PPJ), LCD technology or other techniques known to those skilled in the art can be used in step (i) of the method of forming a 3D printed object of the present invention. Preferably, the manufacture of a hardened 3D object of complex shape is carried out, for example, by stereolithography, which has been known for many years. In this technique, a molded article of the desired shape is assembled from a radiation curable composition, alternating between two steps (1) and (2). In step (1), a layer of the radiation curable composition, one of whose boundaries is the surface of the composition, is hardened in a surface area corresponding to the desired cross-sectional area of ​​the molded article to be formed by suitable imaging radiation, preferably imaging radiation from a computer-controlled scanning laser beam, and in step (2), the hardened layer is covered with a new layer of radiation curable composition, and the succession of steps (1) and (2) is often repeated until the desired shape is completed.

[0109] The present invention further relates to 3D printed objects formed from the curable compositions of the present invention or obtained by the methods of the present invention.

[0110] Non-limiting examples of 3D printed objects of the present invention include plastic parts within a vehicle, such as interior parts, connectors, and functional prototypes. EXAMPLES

[0111] The invention will be better understood in light of the following non-limiting examples.

[0112] Materials and Abbreviations

[0113] [Table 1]

[0114] method (1) Heat distortion temperature (HDT) Heat distortion temperature was measured according to ASTM D648-07.

[0115] (2) Average Tg(Tg,av) The average glass transition temperature (Tg,av) in the examples was calculated using the following Fox formula:

number

[0116] Example 1 Curable compositions 1-5 were prepared by adding all of the components shown in Table 1 in the amounts shown in Table 2 to a plastic vial and mixing at 2000 RPM for 10 minutes at 50°C using a speed mixer to obtain a liquid curable composition.

[0117] Curable compositions 1 to 5 were printed using a MiiCraft150 3D printer, a tabletop digital light processing (DLP) 3D printer with a light wavelength of 405 nm. In a typical printing process, the curable compositions were placed in a vat in the printer. The detailed printing parameters are summarized as follows: UV energy 4.75 mW / cm 2 , base cure time 6.0 sec, base layer 1, cure time 2.0 sec, buffer layer 5.

[0118] After the 3D printing process, the resulting object was immersed in ethanol and shaken for 10 seconds to remove any uncured material on the surface, then dried with compressed air. After 40 minutes of UV post-curing using NextDent's post-curing unit (LC-3DPrint box), the final object with a smooth, dry surface was obtained.

[0119] The HDT of the final objects prepared from each composition is shown in Table 2.

[0120] The mechanical properties of the final objects prepared from each composition are shown in Table 3.

[0121] [Table 2]

[0122] [Table 3]

[0123] [Table 4]

[0124] Example 2: Curable compositions 6-7 and comparative composition 1 were prepared by adding all of the components shown in Table 4 to a plastic vial in the amounts shown in Table 5 and mixing at 2000 RPM for 10 minutes at 50°C using a speed mixer to obtain a liquid curable composition.

[0125] Curable compositions 6-7 and comparative composition 1 were each printed using a MiiCraft150 3D printer, a tabletop digital light processing (DLP) 3D printer with a light wavelength of 405 nm. In a typical printing process, the curable compositions were placed in a vat in the printer. The detailed printing parameters are summarized as follows: UV energy 4.75 mW / cm 2 , base cure time 6.0 sec, base layer 1, cure time 2.0 sec, buffer layer 5.

[0126] After the 3D printing process, the resulting object was immersed in ethanol and shaken for 10 seconds to remove any uncured material on the surface, then dried with compressed air. After 40 minutes of UV post-curing using NextDent's post-curing unit (LC-3DPrint box), the final object with a smooth, dry surface was obtained.

[0127] The HDT of the final objects prepared from each composition is shown in Table 5.

[0128] The mechanical properties of the final objects prepared from each composition are shown in Table 6.

[0129] [Table 5]

[0130] [Table 6]

[0131] [Table 7]

[0132] Example 3: Curable compositions 8-11 were prepared by adding all of the components shown in Table 7 in the amounts shown in Table 8 to a plastic vial and mixing in a speed mixer at 2000 RPM for 10 minutes at 50°C to obtain a liquid curable composition.

[0133] Curable compositions 8 to 11 were printed using a MiiCraft150 3D printer, a tabletop digital light processing (DLP) 3D printer with a light wavelength of 405 nm. In a typical printing process, the curable compositions were placed in a vat in the printer. The detailed printing parameters are summarized as follows: UV energy 4.75 mW / cm 2 , base cure time 6.0 sec, base layer 1, cure time 2.0 sec, buffer layer 5.

[0134] After the 3D printing process, the resulting object was immersed in ethanol and shaken for 10 seconds to remove any uncured material on the surface, then dried with compressed air. After 40 minutes of UV post-curing using NextDent's post-curing unit (LC-3DPrint box), the final object with a smooth, dry surface was obtained.

[0135] The HDT of the final objects prepared from each composition is shown in Table 8.

[0136] [Table 8]

[0137] [Table 9]

[0138] Example 4: Curable composition 12 was prepared by adding all of the components shown in Table 9 in the amounts shown in Table 10 to a plastic vial and mixing in a Speedmixer at 2000 RPM for 10 minutes at 50° C. to obtain a liquid curable composition.

[0139] The curable composition 12 was printed using a MiiCraft150 3D printer, which is a tabletop digital light processing (DLP) 3D printer with a light wavelength of 405 nm. In a typical printing process, the curable composition 12 was placed in a vat in the printer. The detailed printing parameters are summarized as follows: UV energy 4.75 mW / cm 2 , base cure time 6.0 sec, base layer 1, cure time 2.0 sec, buffer layer 5.

[0140] After the 3D printing process, the resulting object was immersed in ethanol and shaken for 10 seconds to remove the uncured resin on the surface, then dried with compressed air. After 40 minutes of UV post-curing using NextDent's post-curing unit (LC-3DPrint box), the final object with a smooth and dry surface was obtained.

[0141] The HDT of the final object prepared from composition 12 is shown in Table 10.

[0142] The mechanical properties of the final objects prepared from composition 12 are shown in Table 11.

[0143] [Table 10]

[0144] [Table 11]

[0145] [Table 12]

Claims

1. Ingredients below: (A) at least one component containing an ethylenically unsaturated group, which is a component (A) including a component (A1) containing a structure (K) selected from an isocyanurate structure and / or a tricyclodecane ring structure; and (B) at least one photoinitiator A curable composition comprising: The curable composition has an average glass transition temperature (Tg,av) of at least 373.15K, preferably at least 393.15K, and more preferably at least 423.15K, as calculated using the Fox equation: [0010] where Tg,i is the glass transition temperature in Kelvin of the homopolymer of component (i) constituting component (A), and w ｉ is the mass fraction of component (i) in component (A).

2. 2. The curable composition of claim 1, wherein component (A1) contains at least one ethylenically unsaturated group, preferably contains 1 to 5 ethylenically unsaturated groups, and more preferably contains 2 to 4 ethylenically unsaturated groups.

3. 3. The curable composition of claim 1 or 2, wherein the ethylenically unsaturated group is selected from the group consisting of allyl, vinyl, acrylate, methacrylate, acryloxy, methacryloxy, acrylamide, methacrylamide, acetylenyl, and maleimide.

4. Component (A1) is tris(hydroxy-C １～３０ 3. The curable composition of claim 1 or 2, wherein component (A1) comprises or is a tri(meth)acrylate of tris-(2-hydroxyethyl)isocyanurate, a tri(meth)acrylate of tris(hydroxymethyl)isocyanurate, a tri(meth)acrylate of tris(3-hydroxy-n-propyl)isocyanurate, or any combination thereof.

5. Component (A1) is tricyclodecane-di-C １～２０ 3. The curable composition according to claim 1 or 2, which comprises or is a tricyclodecane di-alkanol di(meth)acrylate, preferably tricyclodecane di-methanol di(meth)acrylate, tricyclodecane di-ethanol di(meth)acrylate, tricyclodecane di-propanol di(meth)acrylate, tricyclodecane di-butanol di(meth)acrylate or tricyclodecane di-pentanol di(meth)acrylate.

6. 3. The curable composition according to claim 1 or 2, wherein the photoinitiator is a free radical photoinitiator and / or an ionic photoinitiator, preferably a free radical photoinitiator.

7. 3. The curable composition according to claim 1 or 2, wherein the amount of component (A) is in the range of 80% to 99.9% by weight, preferably 90% to 99.9% by weight, more preferably 97% to 99.5% by weight, based on the total amount of the curable composition.

8. 3. The curable composition according to claim 1 or 2, wherein the amount of component (A1) is in the range of 10% to 90% by weight, preferably 15% to 85% by weight, more preferably 20% to 80% by weight, based on the total amount of component (A).

9. 3. The curable composition according to claim 1 or 2, wherein the amount of the photoinitiator is in the range of 0.1% to 8% by weight, preferably 0.1% to 5% by weight, more preferably 0.5% to 3% by weight, based on the total amount of the curable composition.

10. 3. The curable composition according to claim 1 or 2, further comprising auxiliaries as component (C), such as surfactants, flame retardants, pigments, fillers, dyes, catalysts, UV absorbers and stabilizers, and reinforcing materials, preferably in an amount ranging from 0 to 18% by weight, preferably from 0 to 15% by weight, more preferably from 0 to 10% by weight, based on the total amount of the curable composition.

11. 3. The curable composition of claim 1 or 2, wherein a cured product formed from the curable composition has a HDT value of at least 100°C, preferably at least 140°C, more preferably at least 190°C, at a load of 1.82 MPa, measured according to test standard ASTM D648-07.

12. The curable composition according to claim 1 or 2, wherein component (A) further comprises component (A2) that does not contain structure (K).

13. 13. A method of forming a 3D printed object comprising using the curable composition of claim 1.

14. The following steps: (i) applying the curable composition and curing the applied curable composition layer-by-layer with radiation to form an intermediate 3D printed object; and (ii) curing the entire intermediate 3D printed object with radiation to form a cured 3D printed object. The method of claim 13, comprising:

15. 15. The method of claim 14, wherein stereolithography, photopolymer jetting, digital light processing, or LCD techniques are used in step (i) to form the intermediate 3D printed object.

16. The method of claim 14, wherein the radiation is UV radiation.

17. 14. A 3D printed object formed from the curable composition of claim 1 or obtained by the method of claim 13.

18. 20. The 3D printed object of claim 17, comprising plastic parts within a vehicle, such as interior parts, connectors and functional prototypes.

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