Method and composition for forming a 3D printable material that enables low dielectric loss

Abstract

Photocurable compositions and methods are disclosed for producing 3D high frequency dielectric materials for use as insulators in circuits, e.g., high performance RF components, such as antennas for electromagnetic wave transmission, filters, transmission lines, or high frequency interconnects. The high frequency circuit structures have very low dielectric losses at operating frequencies (1-60 GHz).

Description

[Technical Field]

[0001] This disclosure provides a photocurable composition and its use as a 3D printing ink for printing 3D high-frequency dielectric materials used, for example, as circuit structures such as insulators for antennas. [Background technology]

[0002] With the advancement of electronic information technology, the miniaturization and increased density of electronic devices, and the increase in data capacity and frequency, there has been a growing demand for high overall performance of circuit boards in recent years, including heat resistance, water absorption, chemical resistance, mechanical properties, and dielectric properties.

[0003] Regarding dielectric properties, the signal transmission speed in high-frequency circuits and the dielectric constant Dk of the insulating material have the following relationship: the lower the dielectric constant Dk of the insulating material, the faster the signal transmission speed. Therefore, in order to achieve high-speed signal transmission, it is necessary to develop substrates with low dielectric constants. As the signal frequency increases, the signal loss (Df) from the substrate cannot be ignored. For this reason, developing high-frequency circuit boards with low dielectric loss DF and low but tuned dielectric constant Dk has become a common research objective for copper-clad laminate (CCL) manufacturers.

[0004] 3D printing enables the design of new substrates, and more specifically, RF structures such as antennas. Traditionally, antennas are fabricated on planar 2D substrates where the substrate material has low loss at the frequencies used. In most cases, this material is based on PTFE, LCP, or other non-polar resins (including epoxy, SMA, polybutadiene, and PPE / PPO) and filled with inorganic materials that help lower the coefficient of thermal expansion, reduce losses, and increase fracture strength. In this case, the antenna conductors must be deposited on a 2D substrate and cannot always be positioned in the optimal direction. With the advent of 3D printing, antenna designs can now be optimized for signal propagation / reception, but the dielectric materials surrounding the antenna have suboptimal electronic properties. While fused deposition modeling (FDM) based extrusion 3D printing has low-loss thermoplastic resins such as PC, PEI, PPS, PP, and ABS, FDM printing cannot provide the high resolution and low surface roughness required to enclose high-frequency signals such as UV or other energy-curing systems. This is because the signal is located in the outermost region of the conductor (typically conductive ink or rod, foil, or wire), and signal propagation depends on the surface roughness and current capacity of this conductor, as well as the surface roughness of the surrounding dielectric material.

[0005] Recent studies have shown that 3D-printed RF structures can provide a 43 dB increase in maximum S-parameter rejection over a wider frequency range compared to their planar counterparts (Hester et al). Current 3D-printed UV-based materials do not have sufficiently low dielectric loss compared to conventional FDM thermoplastic materials, but they possess the resolution / surface roughness required for high-frequency applications. Traditional UV-curable 3D printing resins are acrylic-based, and because many of the skeletal and end groups of these materials are highly polar, they typically exhibit very high dielectric loss over a wide range of usable frequencies.

[0006] Therefore, in this art, there is a demand for low-loss dielectric materials that are UV or energy-curable and highly nonpolar. A long, nonpolar skeleton that is low to non-water-absorbing is desired to counteract the polarity required by terminal groups (or other functional groups) of polar acrylate and methacrylate bases, while keeping the Mw of the nonpolar skeleton as high as possible (while being processable at printing temperatures). [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] International Publication No. 2014 / 126830 [Patent Document 2] International Publication No. 2014 / 126834 [Patent Document 3] International Publication No. 2014 / 126837 [Non-patent literature]

[0008] [Non-Patent Document 1] Tumbleston et al., “Continuous Liquid Interface Production of 3D Objects,” Science Vol. 347, Issue 6228, pp. 1349-1352 (March 20, 2015) [Overview of the Initiative] [Means for solving the problem]

[0009] In one embodiment, a photocurable composition suitable for printing a three-dimensional (3D) high-frequency circuit structure is described herein, a. At least one (meth)acrylated polydiene derivative; b. At least one ethylenically unsaturated isocyanurate or cyanurate; c. Optionally, at least one aromatic vinyl monomer; d. Optionally, at least one functionalized poly(phenylene ether) having the following structure: [ka] In the equation, 1≦x≦100, 1≦y≦100, 2≦x+y≦100; for example, 15 <x+y<30、25<x+y<40、30<x+y<55、60<x+y<85、80<x+y<98であり; M [ka] Or, [ka] Selected from the group consisting of: In the formula, Q is one selected from the group consisting of -O-, -CO-, SO, -SO2-, and -CH2-, -C(CH3)2-; R2, R4, R6, R8, R 11 , R 13 , R 15 and R 17 Each of these is independently selected from the group consisting of a hydrogen atom, a substituted or unsubstituted C1-C8 linear alkyl group, a substituted or unsubstituted C1-C8 branched alkyl group, and a substituted or unsubstituted phenyl compound; R1, R3, R5, R7, R 10 , R 12 , R 14 and R 16 All of these are independently selected from the group consisting of hydrogen atoms, substituted or unsubstituted C1-C8 linear alkyl groups, substituted or unsubstituted C1-C8 branched alkyl groups, and substituted or unsubstituted phenyl; and, R9 [ka] and [ka] Selected from the group consisting of: Wherein, A is selected from the group consisting of arylene, carbonyl or alkylene having 1 to 10 carbon atoms; Z is an integer from 0 to 10; R 21 R 22 and R 23 are each independently selected from a hydrogen atom or alkyl having 1 to 10 carbon atoms; e. at least one photoinitiator; f. at least one diluent selected from the group consisting of aryl difunctional (meth)acrylate monomer, alkyl (meth)acrylate monomer and polyfunctional (meth)acrylate monomer; and g. optionally at least one light blocker, A photocurable composition comprising, consisting essentially of or consisting of is disclosed.

[0010] In another aspect, a method for forming a three-dimensional (3D) high-frequency dielectric material for use as an insulating component of a circuit herein, the following steps: I) irradiating a region of the photocurable composition at an irradiation site to form a cured region; and, II) causing relative movement between the irradiation site and the cured region to grow the cured region in the direction of the moving layer comprising, wherein the photocurable composition is a. at least one (meth)acrylated polydiene derivative; b. at least one ethylenically unsaturated isocyanurate or cyanurate; c. optionally, at least one aromatic vinyl monomer; d. optionally, at least one functionalized poly(phenylene ether) having the following structure:

Chemical formula

[0011] In another aspect, the present invention considers an electrical circuit comprising a conductor and an insulating component made by a method for forming a three-dimensional (3D) high-frequency dielectric material as described herein. [Brief explanation of the drawing]

[0012] [Figure 1] Figure 1 clearly shows the statistical difference between a sample composed of SR351H, characterized by lower fracture strength and shape factor (426–452 V / μm), and a sample composed of SR533, characterized by higher fracture strength and shape factor (501–507 V / μm). [Figure 2] Figure 2 clearly shows the statistical difference between a sample composed of SR351H, characterized by lower fracture strength and shape factor (426–452 V / μm), and a sample composed of SR533, characterized by higher fracture strength and shape factor (501–507 V / μm). [Modes for carrying out the invention]

[0013] The embodiments described herein may be more readily understood by referring to the following detailed description, examples, and drawings. However, the elements, apparatus, and methods described herein are not limited to the specific embodiments presented in the detailed description, examples, and drawings. It should be recognized that these embodiments are merely illustrative of the principles of the disclosure. Numerous modifications and applications will be readily apparent to those skilled in the art without departing from the spirit and scope of the disclosure.

[0014] Furthermore, it should be understood that all scopes disclosed herein encompass all sub-scopes contained therein. For example, the defined scope "1.0 to 10.0" should be considered to include all sub-scopes beginning with a minimum value of 1.0 or greater and ending with a maximum value of 10.0 or less, such as 1.0 to 5.3, 4.7 to 10.0, or 3.6 to 7.9.

[0015] All scopes disclosed herein are considered to include the endpoints of the scope unless otherwise expressly stated. For example, the scopes "between 5 and 10," "from 5 to 10," or "5 to 10" are generally considered to include the endpoints 5 and 10.

[0016] When the phrase "(up to)" is used in relation to an amount or quantity, it should be understood that the amount is at least a detectable amount or quantity. For example, a material that exists "up to" a specified amount may exist in quantities ranging from a detectable amount to an amount containing the specified amount.

[0017] In this specification, a range may be expressed as "approximately" from a particular value and / or "approximately" from another particular value. When this range is expressed, in another aspect it includes a certain value and / or other particular values. Similarly, by using the antecedent "approximately," it will be understood that when a value is expressed as an approximation, a particular value forms another aspect. It will also be understood that each endpoint of a range is significant both in relation to and independently of the other endpoints.

[0018] As used herein and in the claims, the phrase “at least one” means, with respect to a list of one or more elements, at least one element selected from any one or more elements in the list of elements, but not necessarily including at least one of all elements specifically described in the list of elements, nor excluding any combination of elements in the list of elements. Furthermore, this definition means that elements other than those specifically identified in the list of elements referred to by the phrase “at least one” may exist at will, whether related to or unrelated to those specifically identified elements. Therefore, as a non-restrictive example, “at least one of A and B” (in other words, “at least one of A or B” or in other words, “at least one of A and / or B”) could mean, in one embodiment, at least one A that optionally includes one or more elements other than B, in the absence of B (and optionally including elements other than B); in another embodiment, at least one B that optionally includes one or more elements other than A, in the absence of A (and optionally including elements other than A); and in yet another embodiment, at least one A that optionally includes one or more elements and at least one B that optionally includes one or more elements other than A.

[0019] The terms "3D printing system," "3D printing," and "printing" generally refer to various solid freeform fabrication techniques for creating three-dimensional parts or objects, including stereolithography, selective additive manufacturing, jetting, fused deposition modeling, multi-jet modeling, digital photoprocessing, gel additive manufacturing, continuous light interface printing, and other additive manufacturing techniques currently known or potentially known in the art for manufacturing three-dimensional objects using building materials or inks.

[0020] As used herein, "(meth)acrylate" includes both acrylate and methacrylate functional groups.

[0021] As intended herein, “resin” means a composition that can be polymerized or cured, and can be further polymerized, cured or crosslinked. Resins may comprise monomers, oligomers, prepolymers, or mixtures thereof.

[0022] As used herein, a dash ("―") between two letters or symbols is used to indicate a substituent bond. For example, (C1-C4 alkyl)S― is bonded through a sulfur atom.

[0023] As used herein, "alkyl" includes both branched and linear saturated aliphatic hydrocarbon groups having a specific number of carbon atoms. Examples of alkyls include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, 3-methylbutyl, t-butyl, n-pentyl, and sec-pentyl.

[0024] As used herein, the term “monomer” means an organic compound having a relatively low molecular weight (for example, generally less than 200 Da) that can undergo chemical self-reaction (e.g., polymerization) or chemical reaction with other monomers (e.g., copolymerization) to form longer-chain oligomers, polymers, and copolymers.

[0025] As used herein, the term “oligomer” is understood to mean an organic substance containing multiple repeating units (e.g., oxyalkylene repeating units) and a polydispersity greater than 1 (Mw / Mn). A monomer is a distinct single molecule that may or may not contain multiple repeating units. For example, 2(2-ethoxyethoxy)ethyl acrylate contains two oxyethylene repeating units, but is considered a monomer rather than an oligomer because it is a compound with a defined structure, not a mixture of structurally related compounds with a molecular weight distribution (and therefore polydispersity > 1).

[0026] As used throughout this specification, the term "molecular weight" means, unless otherwise specified, a separate molecular weight for monomers, and, for oligomers or polymers, the number-average molecular weight determined by gel permeation chromatography using polystyrene standard material and THF as the mobile phase, unless otherwise specified, measured within 5 minutes after completion of oligomer synthesis.

[0027] composition This disclosure provides a resin composition that has a low dielectric constant Dk, a low dielectric loss coefficient Df, remarkable heat resistance and interlayer adhesion, and is suitable for preparing high-frequency circuit boards, in order to meet the requirements of high-frequency circuit boards regarding dielectric properties, heat resistance and mixed layer adhesion.

[0028] In one embodiment, a photocurable composition suitable for 3D printing materials for realizing high-performance RF components such as antennas, filters, transmission lines, and interconnects is provided herein. The compositions disclosed herein produce high-performance isolated RF components that exhibit lower dielectric loss, lower surface roughness, and better print resolution than prior art compositions. The compositions disclosed herein are as follows: a. At least one (meth)acrylated polydiene derivative; b. At least one ethylenically unsaturated isocyanurate or cyanurate; c. Optionally, at least one aromatic vinyl monomer; d. Optionally, at least one functionalized poly(phenylene ether) having the following structure: [ka] In the equation, 1≦x≦100, 1≦y≦100, 2≦x+y≦100; for example, 15 <x+y<30、25<x+y<40、30<x+y<55、60<x+y<85、80<x+y<98であり; M [ka] Or, [ka] Selected from the group consisting of: In the formula, Q is one selected from the group consisting of -O-, -CO-, SO, -SO2-, and -CH2-, -C(CH3)2-; R2, R4, R6, R8, R 11 , R 13 , R 15 and R 17 Each of these is independently selected from the group consisting of a hydrogen atom, a substituted or unsubstituted C1-C8 linear alkyl group, a substituted or unsubstituted C1-C8 branched alkyl group, and a substituted or unsubstituted phenyl compound; R1, R3, R5, R7, R 10 , R 12 , R 14 and R 16 All of these are independently selected from the group consisting of hydrogen atoms, substituted or unsubstituted C1-C8 linear alkyl groups, substituted or unsubstituted C1-C8 branched alkyl groups, and substituted or unsubstituted phenyl; and, R9 [ka] and [ka] Selected from the group consisting of: In the formula, A is selected from the group consisting of arylene, carbonyl, or alkylene having 1 to 10 carbon atoms; Z is an integer between 0 and 10; R 21 , R 22 and R 23 All of these are independently selected from alkyl groups having hydrogen atoms or 1 to 10 carbon atoms; e. At least one photoinitiator; f. At least one diluent selected from the group consisting of aryl difunctional (meth)acrylate monomers, alkyl (meth)acrylate monomers, and polyfunctional (meth)acrylate monomers; and g. At least one optical blocker, optionally Includes.

[0029] Each component will be described in more detail in this specification.

[0030] at least one (meth)acrylated polydiene derivative The compositions disclosed herein comprise at least one (meth)acrylic polydiene derivative. This component functions as an elastomer and helps to block moisture.

[0031] Suitable (meth)acrylic polydiene derivatives include oligomers that may be described as substances comprising an oligomeric polydiene skeleton functionalized with one or more (meth)acrylate groups (which may be terminal and / or suspended from the polydiene skeleton). The polydiene skeleton may be at least partially hydrogenated. The polydiene skeleton may be alkoxylated. The polydiene skeleton may be a homopolymer, a random copolymer, or a block copolymer comprising repeating units resulting from the polymerization of at least one diene monomer. Suitable diene monomers may be any monomer-conjugated dienes such as 1,3-butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, 2,4-hexadiene, and mixtures thereof, preferably 1,3-butadiene. The polydiene skeleton may further include repeating units resulting from the polymerization of at least one non-diene monomer, such as monoethylenically unsaturated monomers (e.g., styrene, acrylonitrile), polycarboxylic acids, cyclic anhydrides, polyols, cyclic ethers, polyisocyanates, polyepoxides, and mixtures thereof. Preferably, the (meth)acrylic polydiene derivative includes a (meth)acrylic homopolymer or copolymer of 1,3-butadiene that can be optionally hydrogenated.

[0032] At least one (meth)acrylic polydiene derivative may be selected from at least one of (meth)acrylic hydroxy-polydiene, polydiene-based epoxy (meth)acrylate, polydiene-based polyester (meth)acrylate, polydiene-based urethane (meth)acrylate, and combinations thereof.

[0033] (Meth)acrylic hydroxy-polydienes may be reaction products of hydroxy-polydienes and (meth)acrylic acid or derivatives thereof. The term "hydroxy-polydiene" as used herein means a polydiene having one or more hydroxyl groups. Hydroxy-polydienes may be hydroxylated polybutadienes, particularly hydroxylated polybutadienes having two hydroxyl groups. Derivatives of (meth)acrylic acid include (meth)acryloyl halide, (meth)acrylic anhydride, and C1-C (meth)acrylic acid derivatives. 10 This includes any compound having a (meth)acryloyl group that can form an ester bond with hydroxy-functionalized compounds such as alkyl esters.

[0034] Polydiene-based epoxy (meth)acrylates may be epoxy (meth)acrylates containing one or more groups derived from epoxy-polydienes. As used herein, the term “epoxy (meth)acrylate” means the reaction product of at least one epoxy-functionalized compound and (meth)acrylic acid. As used herein, the term “epoxy-polydiene” means a polydiene having one or more epoxy groups. Epoxy-polydienes can be obtained by epoxidizing at least some of the double bonds contained in a polydiene. In particular, epoxy-polydienes may be epoxidized polybutadienes.

[0035] Polydiene-based polyester (meth)acrylates may be polyester (meth)acrylates containing one or more groups derived from hydroxy-polydiene or carboxy-polydiene. As used herein, the term "carboxy-polydiene" means a polydiene having one or more carboxylic acid groups. As used herein, the term "polyester (meth)acrylate" means a reaction product of at least one hydroxyl-terminated polyester with (meth)acrylic acid or a derivative thereof, or a reaction product of at least one carboxylic acid-terminated polyester with glycidyl (meth)acrylate. Hydroxyl-terminated polyesters or carboxylic acid-terminated polyesters may be obtained by polycondensation of at least one polyol (particularly a diol) and at least one polycarboxylic acid or a derivative thereof (particularly a dicarboxylic acid or cyclic anhydride). In particular, the polyol may include polybutadiene polyols, more particularly polybutadiene diols. In particular, the polycarboxylic acid may include polybutadiene polycarboxylic acids, more particularly polybutadiene dicarboxylic acids.

[0036] Polydiene-based urethane (meth)acrylates may be urethane (meth)acrylates containing one or more groups derived from hydroxy-polydienes. As used herein, the term “urethane (meth)acrylate” means the reaction product of at least one polyol, at least one polyisocyanate, and at least one hydroxy-functionalized (meth)acrylate.

[0037] Examples of (meth)acrylic polydiene derivative oligomers include, for example, hydrophobic aliphatic urethane diacrylates (CN310, available from Sartomer Chemical Co., Exton, PA); hydrophobic diacrylate esters (e.g., CN307, CN308); polydiene methacrylates (CN303, available from Sartomer Chemical Co., Exton, PA); and mixtures of polydiene methacrylates and alkyl diacrylates (CN301, available from Sartomer Americas of Exton, PA).

[0038] The structures defined above are characterized by low water absorption, a highly symmetrical skeleton, high molecular weight, low shrinkage, and good flexibility. They provide flexibility to otherwise rigid and / or brittle matrices, but have high viscosity, which must be considered as a processing challenge.

[0039] At least one (meth)acrylic polydiene derivative may be present in the composition in an amount of about 2% to about 30% by mass, preferably about 10% to about 25% by mass, more preferably about 11% to about 20% by mass, and most preferably about 12% to about 18% by mass, based on the total mass of the composition.

[0040] at least one ethylenically unsaturated isocyanurate The compositions disclosed herein comprise at least one ethylenically unsaturated isocyanurate. The at least one ethylenically unsaturated isocyanurate primarily functions to reduce dielectric loss at high frequencies while maintaining good crosslinking properties.

[0041] In some embodiments, at least one ethylenically unsaturated isocyanurate or cyanurate is at least one compound of formula I: [ka] In the formula, R 2These are identical or different and are selected from the group consisting of hydrogen, lower alkyl, aryl, aralkyl, polynuclear aryl, heteroaryl, monofunctional lower alkenyl and their substituted derivatives. Alkyl and substituted alkyl are intended to contain 1 to about 20 carbon atoms, linear or branched chains, and include, for example, (meth)acrylate, methyl, ethyl, chloroethyl, cyanopropyl, propyl, isopropyl, butyl, dibromobutyl, isobutyl, pentyl, hexyl, dodecyl, etc. Aryl, aralkyl, polynuclear aryl, heteroaryl and their substituted derivatives are intended to include phenyl, chlorophenyl, dibromophenyl, naphthyl, benzyl, pyridyl, cyanophenyl, tolyl, xylyl, phenanthryl, etc.

[0042] In a preferred embodiment, at least one ethylenically unsaturated isocyanurate is triallyl isocyanurate (TAIC) (product name SR533, manufactured by Sartomer Americas, Exton, PA). [ka]

[0043] In another embodiment, at least one ethylenically unsaturated isocyanurate is tris(2-hydroxyethyl)isocyanurate triacrylate (THEICTA) (product name SR368 Sartomer Americas, Exton, PA). [ka]

[0044] Another example is tris(2-hydroxyethyl)isocyanurate trimhaacrylate (THEICTMA) (product name SR290 Sartomer Americas, Exton, PA), which contains at least one ethylenically unsaturated isocyanurate. [ka]

[0045] An example of an ethylenically unsaturated cyanurate is triallyl cyanurate (TAC) (product name SR 507A, Sartomer Americas, Exton, PA). [ka]

[0046] The structure defined above is characterized by very low dielectric loss due to high symmetry, moderate viscosity, and low water uptake, but can become brittle in the matrix at high loading levels.

[0047] At least one ethylenically unsaturated isocyanurate or cyanurate may be present in the composition at an amount of about 1% to about 70% by mass, preferably about 10% to about 55% by mass, and more preferably about 35% to about 50% by mass, based on the total mass of the composition.

[0048] It is preferable that at least one ethylenically unsaturated isocyanurate or cyanurate be present in the composition at the highest possible concentration without making the final product extremely brittle.

[0049] Selective aromatic vinyl monomers The compositions disclosed herein optionally comprise at least one aromatic vinyl monomer. The at least one aromatic vinyl monomer primarily functions to enhance Tg and crosslink density while maintaining low dielectric properties.

[0050] Examples of aromatic vinyl monomers include styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, α-methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 4-tert-butylstyrene, divinylbenzene, dibromostyrene, p-tertiary-butylstyrene, tert-butoxystyrene, vinylbenzyldimethylamine, (4-vinylbenzyl)dimethylaminoethyl ether, N,N-dimethylaminoethylstyrene, vinylpyridine, and the like. In some embodiments, at least one aromatic vinyl monomer is selected from the group consisting of p-methylstyrene, divinylbenzene, dibromostyrene, and 4-tert-butylstyrene.

[0051] If used, at least one aromatic vinyl monomer may be present in the composition at a concentration of about 1% to about 25% by mass, preferably about 3% to about 20% by mass, and more preferably about 5% to about 10% by mass, based on the total mass of the composition.

[0052] Optionally functionalized polyphenylene ethers The compositions disclosed herein optionally comprise at least one functionalized polyphenylene ether. The at least one functionalized polyphenylene ether may be used to provide the composition with hydrophobicity, very low dielectric loss components, and improved mechanical properties.

[0053] Preferably, the functionalized polyphenylene ether resin has the following structure: [ka] In the equation, 1≦x≦100, 1≦y≦100, 2≦x+y≦100; for example, 15 <x+y<30、25<x+y<40、30<x+y<55、60<x+y<85、80<x+y<98であり; M [ka] Or, [ka] Selected from the group consisting of: In the formula, N is one selected from the group consisting of -O-, -CO-, SO-, -SC-, -SO2-, and -C(CH3)2-; R2, R4, R6, R8, R 11 , R 13 , R 15 and R 17 All of these are independently selected from the group consisting of substituted or unsubstituted C1-C8 linear alkyl groups, substituted or unsubstituted C1-C8 branched alkyl groups, and substituted or unsubstituted phenyl groups; R1, R3, R5, R7, R 10 , R 12 , R 14 and R 16 All of these are independently selected from the group consisting of hydrogen atoms, substituted or unsubstituted C1-C8 linear alkyl groups, substituted or unsubstituted C1-C8 branched alkyl groups, and substituted or unsubstituted phenyl; and, R9 [ka] and [ka] Selected from the group consisting of: In the formula, A is selected from the group consisting of arylene, carbonyl, or alkylene having 1 to 10 carbon atoms; Z is an integer between 0 and 10; R 21 , R 22 and R 23 All of these are independently selected from alkyl groups having hydrogen atoms or 1 to 10 carbon atoms.

[0054] Preferably, the functionalized polyphenylene ether resin has a number-average molecular weight of 500 to 10,000 g / mol, preferably 800 to 8,000 g / mol, more preferably 1,000 to 7,000 g / mol, as determined by a method provided by the supplier. This material is solid at room temperature and tends to increase the viscosity of the composition, thereby limiting the maximum usable amount in the matrix. However, it is characterized by low dielectric loss, low water uptake and a high glass transition temperature (Tg) due to its symmetrical framework, while adding a more rigid component to the matrix.

[0055] One example of a methacrylate-functionalized polyphenylene ether resin is SA9000 (SABIC, Saudi Basic Industries Corporation), which is bifunctional and has the following structure: [ka] It has, In the equation, x and y are defined above.

[0056] At least one functionalized polyphenylene ether may be present in the composition in an amount of about 0% to about 30% by mass or about 1% to about 30% by mass, preferably about 3% to about 25% by mass, and more preferably about 5% to about 20% by mass, based on the total mass of the composition.

[0057] Preferably, the compositions disclosed herein have as much as possible of at least one functionalized polyphenylene ether without losing control of the viscosity of the composition or without completely dissolving it in solution.

[0058] Photoinitiator The compositions disclosed herein include, for example, photoinitiators that function to initiate the curing of the composition upon exposure to chemical radiation such as UV or visible radiation.

[0059] A single type of photoinitiator may be used, or a combination of different types of photoinitiators may be used. For example, any photoinitiator that absorbs radiation, such as UV or visible radiation, to induce a free radical polymerization reaction between selected oligomers and / or selected monomers may be used. Suitable, exemplary photoinitiators such as benzophenones, benzoin ethers, benzyl ketals, α-hydroxyalkylphenones, α-alkoxyalkylphenones, aminoalkylphenones, and acylphosphine photoinitiators may be used. The photoinitiator 2,4,6-trimethylbenzoyldiphenylphosphine oxide (TPO) may be used.

[0060] The photoinitiator may be included in the composition in various appropriate amounts. In some embodiments, the composition contains about 0.2% to about 15% by mass of the photoinitiator, based on the total mass of the composition. This includes embodiments in which the composition contains about 0.2% to about 10% by mass or about 1.0% to about 5% by mass of the photoinitiator, based on the total mass of the composition. In embodiments in which more than one type of photoinitiator is present in the composition, these amounts may refer to the total amount of photoinitiators in the composition.

[0061] at least one diluent The compositions disclosed herein include a diluent selected from the group consisting of aryl difunctional (meth)acrylate monomers, alkyl (meth)acrylate monomers, and polyfunctional (meth)acrylate monomers. Preferably, the sole diluent is either an alkyl difunctional (meth)acrylate monomer or stearyl methacrylate, and preferably an alkyl difunctional (meth)acrylate monomer. The first diluent is a compound with low loss, high hardness, and low viscosity. Preferably, the first diluent contributes to the hardness of the cured product produced by curing the photocurable composition of the present invention. Preferably, the first diluent functions to maintain crosslinking to enable printing, while simultaneously maintaining the viscosity within a printable range.

[0062] In embodiments of the present invention, the diluent comprises an alkyl (meth)acrylate monomer, which is at least one of an alkyl monofunctional acrylate and an alkyl monofunctional methacrylate. In another embodiment of the present invention, the diluent comprises a polyfunctional (meth)acrylate monomer, which is at least one of an alkyl bifunctional acrylate and an alkyl bifunctional methacrylate. In embodiments, the diluent comprises one or more of these or a combination thereof.

[0063] The first monomer may be an alkyl difunctional (meth)acrylate monomer, where the alkyl group has 1 to 20 carbon atoms. Specific examples of these include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, and other suitable di(meth)acrylates. These can be used individually or in combination of two or more. In embodiments of the present invention, the first diluent is a cycloalkyl bifunctional methacrylate.

[0064] Most preferably, the first diluent is tricyclodecanedimethanol dimethacrylate, which is commercially available from Sartomer Americas as SR834. The first diluent preferably has a high Tg (e.g., at least about 160°C, preferably at least about 180°C and most preferably at least about 200°C), and preferably a Tg of at most 240°C, more preferably at most 220°C.

[0065] The first diluent preferably has a viscosity of at most 2500 mPas, more preferably at most 1000 mPas, even more preferably at most 500 mPas, and most preferably at most 200 mPas (at 25°C) when used with 21 spindles at 50 RPM at 25°C.

[0066] The first diluent may be included in the curable composition of the present invention in various appropriate amounts. In embodiments, the first diluent may be present in the curable composition in an amount ranging from about 1% to about 40% by mass, based on the total mass of the curable composition. Preferably, the first diluent is present in an amount ranging from about 1% to about 30% by mass, about 5% to about 20% by mass, or about 8% to about 18% by mass, based on the total mass of the curable composition.

[0067] In embodiments of the present invention, the photocurable composition further comprises a second diluent selected from the group consisting of alkyl (meth)acrylate monomers and polyfunctional (meth)acrylate monomers, preferably bifunctional (meth)acrylate monomers. The second diluent functions to further reduce viscosity, maintain low dielectric loss, and prevent brittleness. A second diluent is not necessary if the viscosity, dielectric loss, and brittleness are sufficient for a particular application in the absence of any second diluent.

[0068] Alkyl (meth)acrylate compounds can be alkyl (meth)acrylates having 1 to 20 carbon atoms in the alkyl group. Specific examples include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, etc. These can be used individually or in combination of two or more.

[0069] Preferred (meth)acrylate monomers include lauryl acrylate; SR 587 (acrylic acid ester, behenyl acrylate); CD 421A / SR421 (3,3,5-trimethylcyclohexyl methacrylate); SR 484 (octyldecyl acrylate); SR 489D (tridecyl acrylate); SR 242 (isodecyl methacrylate); SR 313 (lauryl methacrylate); SR 257 (stearyl acrylate); and SR 324 (stearyl methacrylate), all of which are commercially available from Sartomer Americas, Exton, PA. In preferred embodiments that achieve particularly low dielectric loss, the alkyl (meth)acrylate monomer is stearyl or lauryl (meth)acrylate, preferably stearyl methacrylate.

[0070] Polyfunctional (meth)acrylate monomers include difunctional and trifunctional (meth)acrylates. Suitable, exemplary difunctional (meth)acrylates include 1,12-dodecanediol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate (e.g., SR238B of Sartomer Chemical Co.), alkoxylated hexanediol diacrylate, alkoxylated neopentyl glycol diacrylate, cyclohexanedimethanol diacrylate, diethylene glycol diacrylate (e.g., SR230 of Sartomer Chemical Co.), ethoxylated (4) bisphenol A diacrylate (e.g., SR601 of Sartomer Chemical Co.), neopentyl glycol diacrylate, polyethylene glycol (400) diacrylate (e.g., SR344 of Sartomer Chemical Co.), propoxylated (2) neopentyl glycol diacrylate (e.g., SR9003B of Sartomer Chemical Co.), tetraethylene glycol diacrylate (e.g., Sartomer Chemical Co. This includes tricyclodecane dimethanol diacrylate (e.g., SR833S from Sartomer Chemical Co.), triethylene glycol diacrylate (e.g., SR272 from Sartomer Chemical Co.), and tripropylene glycol diacrylate.

[0071] Suitable, exemplary trifunctional (meth)acrylates include ethoxylated (9) trimethylolpropane triacrylate, pentaerythritol triacrylate, propoxylated (3) glyceryl triacrylate (e.g., SR9020 from Sartomer Chemical Co.), and propoxylated (3) trimethylolpropane triacrylate (e.g., SR492 from Sartomer Chemical Co.).

[0072] Preferred examples of suitable polyfunctional (meth)acrylate monomers include SR 834 (tricyclodecanedimethanol dimethacrylate), SR 348 (ethoxylated (n)bisphenol A dimethacrylate), SR 238 (1,6-hexanediol diacrylate), SR 262 (1,12-dodecanediol dimethacrylate), CD 595 (acrylate ester), SR 239 (1,6-hexanediol dimethacrylate), SR 214 (1,4-butanediol dimethacrylate), and SARBIO 5201 (acrylate ester), all of which are commercially available from Sartomer Chemical Co. Exton, PA.

[0073] At least one unsaturated compound selected from the group consisting of alkyl (meth)acrylate monomers and polyfunctional (meth)acrylate monomers may be included in the curable composition of the present invention in various appropriate amounts. In embodiments, at least one unsaturated compound selected from the group consisting of alkyl (meth)acrylate monomers and polyfunctional (meth)acrylate monomers is present in the curable composition in an amount ranging from about 1% to about 40% by mass, based on the total mass of the curable composition. This includes embodiments in which at least one unsaturated compound selected from the group consisting of alkyl (meth)acrylate monomers and polyfunctional (meth)acrylate monomers is present in an amount ranging from about 1% to about 30% by mass, about 5% to about 20% by mass, and about 10% to about 18% by mass, based on the total mass of the curable composition.

[0074] At least one unsaturated compound selected from the group consisting of alkyl (meth)acrylate monomers and polyfunctional (meth)acrylate monomers disclosed above can be partially or completely hydrogenated.

[0075] In the embodiments, the total amount of at least one unsaturated compound selected from the group consisting of alkyl (meth)acrylate monomers and polyfunctional (meth)acrylate monomers present in the curable composition is 70% by mass or less, based on the total mass of the curable composition. This includes embodiments in which the total amount is 65% by mass or less, 60% by mass or less, 55% by mass or less, 50% by mass or less, 45% by mass or less, or 40% by mass or less, based on the total mass of the curable composition. This includes embodiments in which the total amount is in the range of about 35% by mass to less than 60% by mass, about 35% by mass to less than 55% by mass, about 35% by mass to about 50% by mass, or about 35% by mass to about 45% by mass, based on the total mass of the curable composition.

[0076] Selective optical blockers The compositions disclosed herein may include photoblockers that function to prevent light from being transmitted or to absorb light, thereby functioning to reduce the curing rate of the composition upon exposure to chemical radiation, such as UV or visible radiation. Specific photoblockers may be selected based on the specific wavelength of radiation to be blocked, the extinction coefficient of the photoabsorbent material at a given wavelength, and the absence of harmful involvement in harmful photoreactions or polymerization reactions. One example of a photoblocker used for an ultraviolet source having a peak emission wavelength of 350 nm is 2,2'-dihydroxy-4,4'-dimethoxybenzophenone. Another example is Reactint Yellow X36HS, a colorant-containing polyol, commercially available from Milliken.

[0077] When used, the photoblocker may be included in the composition in various appropriate amounts. In embodiments, the composition contains about 0.2% to about 15% by mass of photoblockers based on the total mass of the composition. This includes embodiments in which the composition contains about 0.2% to about 10% by mass or about 1.0% to about 5% by mass of photoblockers based on the total mass of the composition. In embodiments in which more than one type of photoblocker is present in the composition, these amounts may refer to the total amount of photoinitiators in the composition.

[0078] Various optional components In addition to these compounds, the curable compositions disclosed herein may include conventional polymerization inhibitors, conventional fillers, further pigments, and conventional additives used in the 2D RF industry, the coatings industry, or the printing inks industry. Suitable pigments include phyllosilicates, titanium dioxide, colored pigments, calcium carbonate, and kaolin, and suitable fillers include, for example, silicon dioxide or aluminum silicate. As additives, conventional additives from the coatings industry or the printing inks industry can be used, particularly dispersants, redispersants, polymerization inhibitors, antifoaming agents, catalysts, adhesion promoters, flowing agents, thickeners, or matting agents.

[0079] In some embodiments, fillers are added to enhance thermal conductivity and mechanical strength and / or reduce thermal expansion. Suitable fillers may be fused silica, quartz, talc-aluminum silicate, and soft silica. Suitable fillers may have particle sizes ranging from 0.5 μm to 15 μm.

[0080] When used, the filler may be present in the composition disclosed herein in an amount of about 1 to about 60% by mass, preferably about 5 to about 45% by mass, and most preferably about 20 to about 35% by mass.

[0081] In other embodiments, at least one polymerization inhibitor is added in an amount that prevents the photocurable composition from gelling.

[0082] The compositions disclosed herein optionally contain flame retardants to reduce the flammability of low dielectric materials. Halogen-containing and halogen-free flame retardants may be used. Halogen-containing flame retardants may include decabromodiphenylethane. Halogen-free flame retardants may include phosphorus-containing flame retardants and phosphates. Phosphorus-containing flame retardants and phosphates are manufactured by ALBEMARLE CO., LTD.

[0083] When used, the flame retardant may be present in the composition disclosed herein in an amount of about 1 to about 35% by mass, preferably about 5 to about 28% by mass.

[0084] The components of the compositions disclosed herein can be mixed by any means known to those skilled in the art. A method for preparing the resin compositions of the present invention involves the preparation, stirring, and mixing of a methacrylate-modified polyphenylene ether resin, an MQ organosilicon resin containing unsaturated double bonds, having a three-dimensional network structure, and hydrolytically condensed from monofunctional siloxane units (M units) and tetrafunctional silica units (Q units), a radical initiator, a flame retardant, a powder filler, various thermosetting resins, and additives by a general method.

[0085] The photocurable compositions disclosed herein may have a wide range of viscosities. Preferably, the compositions have a viscosity within a range suitable for processing by 3D printing at printing temperatures. In most cases, the printing temperature is room temperature (e.g., about 25°C), but some 3D printers are configured to print products at higher temperatures. Preferably, the compositions of the present invention exhibit a viscosity at printing temperatures of about 200 cPs to about 100 kcPs, preferably 500 cPs to about 20 kcPs and most preferably 1000 cPs to about 10 kcPs, as measured by a Brookfield viscometer at 25°C with a spindle 31sp at 50 to 100 rpm.

[0086] In embodiments of the present invention, the following components are used: (1) a hydrophobic aliphatic urethane diacrylate in about 12% to about 18% by mass of a (meth)acrylic polydiene derivative; (2) a triallyl isocyanurate in about 35% to about 50% by mass; (3) SA9000 in about 10% to about 20% by mass; (4) a first diluent in about 10% to about 15% by mass of tricyclodecanedimethanol dimethacrylate; (5) a second diluent in about 10% to about 18% by mass of stearyl methacrylate; and (6) a photoinitiator in about 2% to about 5% by mass of BPO Speedcure.

[0087] method For example, photocurable compositions and methods are disclosed for producing 3D high-frequency inductive materials used as insulators in circuits such as high-performance RF components, including antennas, filters, transmission lines, or interconnects for electromagnetic wave transmission. The high-frequency circuit structure has very low dielectric loss at operating frequencies (1 to 60 GHz).

[0088] A method for forming a three-dimensional (3D) high-frequency circuit structure is disclosed herein, comprising the steps: I) irradiating a region of a photocurable composition with an irradiation site to form a cured region; and II) causing relative movement between the irradiation site and the cured region to grow the cured region in the direction of movement, wherein the photocurable ink composition is: a. at least one (meth)acrylic polydiene derivative; b. at least one ethylenically unsaturated isocyanurate or cyanurate; c. optionally at least one aromatic vinyl monomer; d. optionally at least one functionalized poly(phenylene ether) having the following structure: [ka] In the equation, 1≦x≦100, 1≦y≦100, 2≦x+y≦100; for example, 15 <x+y<30、25<x+y<40、30<x+y<55、60<x+y<85、80<x+y<98であり; M [ka] Or, [ka] Selected from the group consisting of: In the formula, Q is one selected from the group consisting of -O-, -CO-, SO, -SO2-, and -CH2-, -C(CH3)2-; R2, R4, R6, R8, R 11 , R 13 , R 15 and R 17Each of these is independently selected from the group consisting of a hydrogen atom, a substituted or unsubstituted C1-C8 linear alkyl group, a substituted or unsubstituted C1-C8 branched alkyl group, and a substituted or unsubstituted phenyl compound; R1, R3, R5, R7, R 10 , R 12 , R 14 and R 16 All of these are independently selected from the group consisting of hydrogen atoms, substituted or unsubstituted C1-C8 linear alkyl groups, substituted or unsubstituted C1-C8 branched alkyl groups, and substituted or unsubstituted phenyl; and, R9 [ka] and [ka] Selected from the group consisting of: In the formula, A is selected from the group consisting of arylene, carbonyl, or alkylene having 1 to 10 carbon atoms; Z is an integer between 0 and 10; R 21 , R 22 and R 23 All of these are independently selected from alkyl groups having hydrogen atoms or 1 to 10 carbon atoms; at least one photoinitiator; at least one first diluent comprising an unsaturated alkyl bifunctional (meth)acrylate monomer; and optionally at least one photoblocker.

[0089] This method may be continuous or discontinuous (e.g., stepwise or layered). Suitable continuous methods are often referred to in the art as “Continuous Liquid Interface (or Interlayer) Fabrication (or Printing)” (“CLIP”) methods. These methods are described, for example, in International Publication Nos. 2014 / 126830; 2014 / 126834; 2014 / 126837 and in Tumbleston et al., “Continuous Liquid Interface Production of 3D Objects,” Science Vol. 347, Issue 6228, pp. 1349-1352 (March 20, 2015), the entire disclosure thereof is incorporated herein by reference for all purposes.

[0090] When stereolithography is performed on an oxygen-permeable build window, the manufacture of articles using the curable composition of the present invention can be made possible by the CLIP procedure by creating an oxygen-containing "dead zone," which is a thin uncured layer of the curable composition, between the window and the surface of the cured article being manufactured. In these methods, a curable composition is used in which curing (polymerization) is inhibited by the presence of oxygen molecules, and these inhibitions are typically observed in curable compositions that are curable by, for example, a free radical mechanism. The desired dead zone thickness can be maintained by the selection of various control parameters such as the photon flux and the optical and curing properties of the curable composition. The CLIP method proceeds by projecting a continuous chemical beam (e.g., UV) image (e.g., which can be generated by, for example, a digital photoprocessing imaging unit) through an oxygen-permeable chemical beam (e.g., UV) transparent window below a tank of curable composition maintained in liquid form. The liquid interface below the advancing (growing) article (e.g., cured region) is maintained by the dead zone created above the window. The cured product can be continuously drawn from the tank of curable composition above the dead zone and replenished by supplying additional amounts of curable composition to the tank to compensate for the amount of curable composition that is cured and incorporated into the growing article. In another example, the continuous method typically involves transporting the target substrate on which printing is carried out, for example, by means of a conveyor belt.

[0091] In a discontinuous or layered method, the cured region is a first cured layer, and the method further includes: III) irradiating the first cured layer with a photocurable composition adjacent to it to form a subsequent cured layer; and IV) optionally repeating steps II) and III) to form any additional layers to form a 3D high-frequency circuit structure.

[0092] The optionally existing layers (or first, prior, or previous layers), subsequent layers (or second or later layers), and any additional layers described below are collectively referred to as “layers” in this specification. In this specification, “layers” as used in the plural may refer to layers at any stage of the method, for example, layers in the uncured state, the partially cured state, and the final cured state.

[0093] Similar to the layer, subsequent layers (or any subsequent layers) formed by printing a photocurable composition may have any shape and dimensions. For example, subsequent layers do not need to be continuous or have a constant thickness. Furthermore, subsequent layers may differ from the layer in terms of shape, dimensions, size, etc.

[0094] In certain embodiments, printing of subsequent layers occurs before at least partially cured layers reach a final cured state, i.e., while at least partially cured layers are still “green.” As used herein, “green” includes partial curing but does not include a final cured state. The difference between partial curing and a final cured state is whether the partially cured layer can undergo further curing or crosslinking. Functional groups may still be present in the final cured state, but may remain unreacted due to steric hindrance or other reasons. In these embodiments, the printing of layers can be considered “wet-on-wet,” meaning that adjacent layers can bond to each other at least physically and chemically.

[0095] Each layer can have various dimensions, including thickness and width. Thickness and / or width tolerances of layers may depend on the 3D printing method used, with some methods having high resolution and others low resolution. Layer thickness may be uniform or varied, and the average thickness of layers may be the same or varied. Average thickness is generally related to the thickness of the layer immediately after printing. In various embodiments, layers independently have average thicknesses of about 1–10000, about 2–1000, about 5–750, about 10–500, about 25–250, or about 50–100 μm. Thinner and thicker thicknesses are also conceivable. This disclosure does not limit any particular dimensions of any given layer.

[0096] In embodiments of the present invention, step III) irradiating a photocurable composition adjacent to the first cured layer to form a subsequent cured layer includes irradiating the subsequent layer using an energy source to form a subsequent layer that is at least partially cured. This step may be identical or different from step I) irradiating a region of the photocurable composition at the irradiation site to form a cured region, in terms of curing conditions and applicable relevant parameters.

[0097] The photocurable compositions disclosed herein can also be printed on substrates, such as electronic substrates, so that layers of the intended components are formed on the substrate. The substrate may be rigid or flexible and may be discontinuous or continuous in at least one of its thickness and composition.

[0098] As is understood in this art, the rate and mechanism of curing of a photocurable ink composition depend on various factors, including its components, the functional groups of those components, and the parameters of the curing conditions. When irradiated, the layer generally begins to cure. Heat generation and / or application of heat can accelerate the curing of the layer.

[0099] In certain embodiments, the cured layer substantially retains its shape when exposed to ambient conditions. Ambient conditions refer to at least temperature, pressure, relative humidity, and any other conditions that may affect the shape or dimensions of at least the partially cured layer. For example, the ambient temperature is room temperature.

[0100] More specifically, prior to irradiation, the photocurable ink composition is generally viscous but fluid and may be in the form of a liquid, slurry, or gel, or alternatively, a liquid or slurry, or alternatively, a liquid. The viscosity of the photocurable ink composition may be adjusted depending on the type of 3D printer and its dispensing technology and other considerations. Viscosity adjustment may be achieved, for example, by heating or cooling the photocurable ink composition, by adding or removing solvents, carriers and / or diluents, or by adding fillers or thixotropic agents, etc.

[0101] For the curing process, the independently used energy source may emit various wavelengths across the entire electromagnetic spectrum. In various embodiments, the energy source emits at least one of ultraviolet (UV), infrared (IR), visible light, X-rays, gamma rays, or electron beams (e-beams). One or more energy sources may be used.

[0102] In certain embodiments, the energy source emits at least UV rays. In physics, UV rays are traditionally divided into four regions: near-ultraviolet (400–300 nm), mid-ultraviolet (300–200 nm), far-ultraviolet (200–100 nm), and extreme ultraviolet (less than 100 nm). Three traditional divisions of ultraviolet rays have been observed: near-ultraviolet (400–315 nm); chemical ultraviolet (315–200 nm); and vacuum ultraviolet (less than 200 nm). In certain embodiments, the energy source emits UV rays, or alternatively, chemical rays. The terms UVA, UVB, and UVC are also common in industry to describe different wavelength ranges of UV rays.

[0103] In certain embodiments, the radiation used to cure the layer may have wavelengths outside the UV range. For example, visible light with wavelengths between 400 nm and 800 nm may be used. Another example is the use of IR rays with wavelengths greater than 800 nm.

[0104] In other embodiments, electron beams may be used to cure the layers. In these embodiments, the accelerating voltage may be about 0.1 to about 100 keV, and the vacuum degree may be about 10 to about 10 -3 The pressure can be Pa, the electron current can be approximately 0.0001 to approximately 1 ampere, and the power can vary from approximately 0.1 watts to approximately 1 kilowatt. The radiation dose is typically about 100 microcoulombs / cm³. 2 ~Approximately 100 coulombs / cm² 2 Alternatively, approximately 1 to 10 coulombs / cm² 2 Depending on the voltage, the exposure time is typically about 10 seconds to 1 hour, however, shorter or longer exposure times may also be used.

[0105] Steps II) and III) can be optionally repeated for any additional layers to form the 3D article. The total number of layers required depends, for example, on the desired RF components or other articles.

[0106] Furthermore, a composite including all or some of the layers may be subjected to a final curing step, if desired. For example, a composite formed by printing and at least partially curing layers may be subjected to a further irradiation step to ensure that the 3D article is in a desired cured state. The final curing step may be identical or different from the previous curing step in terms of curing conditions, relevant parameters and the radiation source used, if desired.

[0107] This disclosure generally incorporates the entirety of ASTM Designation F2792-12a, “Standard Terminology for Additive Manufacturing Technologies,” by reference. Under this ASTM standard, “3D printing machine” is defined as “a machine used for 3D printing,” and “3D printing” is defined as “the manufacture of an object through a volume of material using a print head, nozzle or other printing machine technology.” “Additive manufacturing (AM)” is defined as “a method of joining materials to create an object from 3D model data,” which is usually in multiple layers and is in contrast to subtractive manufacturing methods. Synonyms related to and encompassed by 3D printing include additive fabrication, additive methods, additive technology, additive layer manufacturing, layer manufacturing, and freeform fabrication. AM may also be referred to as rapid prototyping (RP). As used herein, “3D printing” is generally interchangeable with “additive manufacturing,” and vice versa.

[0108] The disclosed method makes it possible to manufacture insulating elements for 3D high-frequency circuit structures, such as high-performance RF components, including antennas, filters, transmission lines, or interconnects for electromagnetic wave transmission. The high-frequency circuit structures have very low dielectric loss at operating frequencies (1 GHz to 60 GHz).

[0109] The photocurable compositions disclosed herein, when printed and photocured, exhibit very good fracture strength at 10 MHz to 20 GHz and dielectric loss (D) of 0.007 or less, 0.006 or less, 0.005 or less, 0.004 or less, and 0.003 or less. f The photocurable compositions disclosed herein, when printed and photocured, exhibit a dielectric constant (D) of 2.4 to 2.9 at 10 MHz to 20 GHz. k The cured composition may be tested at a wide range of frequencies, including values ​​such as 1, 5, 7, 8, 10, 12, 15, and 20 GHz.

[0110] In one embodiment, the printed and photocured 3D structure has a dielectric loss (D) of less than 0.0035, preferably less than 0.0030, and most preferably less than 0.0028, measured at 25°C using a network analyzer. f ) and at a frequency of 10.04 GHz, it exhibits at least one, preferably both, of the dielectric constants (Dk) of less than 2.75, preferably less than about 2.70, and most preferably less than about 2.68.

[0111] In another embodiment of the present invention, the articles produced by the 3D printing method described herein are smooth, preferably less than 10 microns, more preferably less than 5 microns, and most preferably less than 3 microns, as measured by a surface shape measuring device, R z It has a rough surface.

[0112] Embodiments of the present invention The present invention relates to the following embodiments: [Aspect 1] A photocurable composition suitable for three-dimensional (3D) printing, a. At least one (meth)acrylated polydiene derivative; b. At least one ethylenically unsaturated isocyanurate or cyanurate; c. Optionally, at least one aromatic vinyl monomer; d. Optionally, at least one functionalized poly(phenylene ether) having the following structure: [ka] In the equation, 1≦x≦100, 1≦y≦100, 2≦x+y≦100; for example, 15 <x+y<30、25<x+y<40、30<x+y<55、60<x+y<85、80<x+y<98であり; M [ka] Or, [ka] Selected from the group consisting of: In the formula, Q is one selected from the group consisting of -O-, -CO-, SO, -SO2-, and -CH2-, -C(CH3)2-; R2, R4, R6, R8, R 11 , R 13 , R 15 and R 17 Each of these is independently selected from the group consisting of a hydrogen atom, a substituted or unsubstituted C1-C8 linear alkyl group, a substituted or unsubstituted C1-C8 branched alkyl group, and a substituted or unsubstituted phenyl compound; R1, R3, R5, R7, R 10 , R 12 , R 14 and R 16 All of these are independently selected from the group consisting of hydrogen atoms, substituted or unsubstituted C1-C8 linear alkyl groups, substituted or unsubstituted C1-C8 branched alkyl groups, and substituted or unsubstituted phenyl; and, R9 [ka] and [ka] Selected from the group consisting of: In the formula, A is selected from the group consisting of arylene, carbonyl, or alkylene having 1 to 10 carbon atoms; Z is an integer between 0 and 10; R 21 , R 22 and R 23 All of these are independently selected from alkyl groups having hydrogen atoms or 1 to 10 carbon atoms; e. At least one photoinitiator; f. At least one diluent selected from the group consisting of aryl difunctional (meth)acrylate monomers, alkyl (meth)acrylate monomers, and polyfunctional (meth)acrylate monomers; and g. At least one optical blocker, optionally A photocurable composition containing the following:

[0113] [Aspect 2] The composition according to embodiment 1, wherein at least one diluent comprises an unsaturated alkyl bifunctional (meth)acrylate monomer, and the composition further comprises at least one second diluent selected from the group consisting of alkyl (meth)acrylate monomers and polyfunctional (meth)acrylate monomers.

[0114] [Aspect 3] The composition according to embodiment 1 or 2, wherein at least one (meth)acrylic polydiene derivative is selected from at least one of (meth)acrylic hydroxy-polydiene, polydiene-based epoxy (meth)acrylate, polydiene-based polyester (meth)acrylate, polydiene-based urethane (meth)acrylate, and combinations thereof, and in particular is selected from the group consisting of hydrophobic aliphatic urethane acrylate, hydrophobic acrylate ester, and polybutadiene diacrylate.

[0115] [Aspect 4] The composition according to any one of embodiments 1 to 3, wherein at least one ethylenically unsaturated isocyanurate or cyanurate is selected from the group consisting of triallyl cyanurate, triallyl isocyanurate, and tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate.

[0116] [Aspect 5] The composition according to any one embodiment of embodiments 1 to 4, wherein at least one aromatic vinyl monomer is present, and at least one selected from the group consisting of p-methylstyrene, divinylbenzene, dibromostyrene, and p-tert-butylstyrene.

[0117] [Aspect 6] At least one methacrylate-functionalized poly(phenylene ether) is present; preferably, the methacrylate-functionalized poly(phenylene ether) is bifunctional and has the following structure: [ka] A composition according to any one of embodiments 1 to 5, having the following characteristics.

[0118] [Aspect 7] The composition according to any one of embodiments 1 to 6, wherein the photoinitiator is selected from the group consisting of bensophenone and its derivatives, benzoin and its derivatives, acetophenone and its derivatives, anthraquinone, thioxanthone and its derivatives, and organophosphorus compounds.

[0119] [Aspect 8] A composition according to any one embodiment of embodiments 1 to 7, which does not contain bismaleimide resin.

[0120] [Aspect 9] The composition according to any one embodiment of Embodiments 1 and 3 to 8, wherein the diluent is a cycloalkyl bifunctional methacrylate.

[0121] [Aspect 10] The composition according to any one embodiment of embodiments 2 to 9, wherein the second diluent is selected from the group consisting of stearyl methacrylate, lauryl methacrylate, stearyl acrylate, lauryl acrylate, behenyl acrylate, 3,3,5-trimethylcyclohexyl methacrylate, octyldecyl acrylate, tridecyl acrylate, and isodecyl methacrylate.

[0122] [Aspect 11] The composition according to any one embodiment of embodiments 2 to 9, wherein the second diluent is stearyl or lauryl (meth)acrylate, preferably stearyl methacrylate.

[0123] [Aspect 12] The composition according to any one embodiment of embodiments 2 to 9, wherein the second diluent is a polyfunctional (meth)acrylate monomer.

[0124] [Aspect 13] The composition according to embodiment 12, wherein the polyfunctional (meth)acrylate monomer is selected from the group consisting of ethoxylated (n)bisphenol A dimethacrylate, tricyclodecanedimethanol dimethacrylate, 1,6-hexanediol diacrylate, 1,12-dodecanediol dimethacrylate, 1,10-decanediol diacrylate, 1,6-hexanediol dimethacrylate, and 1,4-butanediol dimethacrylate.

[0125] [Aspect 14] A composition according to any one embodiment of embodiments 1 to 13, which does not contain a thermal initiator.

[0126] [Aspect 15] A composition according to any one embodiment of embodiments 1 to 14, further comprising a flame-retardant compound.

[0127] [Aspect 16] A composition according to any one embodiment of embodiments 1 to 15, further comprising an inorganic filler.

[0128] [Aspect 17] The composition according to embodiment 16, wherein the inorganic filler is selected from the group consisting of high-purity quartz, alumina, peryllium, aluminum nitride, and glass.

[0129] [Aspect 18] A composition according to any one embodiment of embodiments 1 to 17, wherein a light blocker is present.

[0130] [Aspect 19] A method for forming a three-dimensional (3D) high-frequency circuit structure, comprising the following steps: I) A step of irradiating a region of the photocurable composition with an irradiation site to form a cured region; and, II) A process of causing relative movement between the irradiated area and the hardened area, thereby growing the hardened area in the direction of movement. The photocurable composition includes, a. At least one (meth)acrylated polydiene derivative; b. At least one ethylenically unsaturated isocyanurate or cyanurate; c. Optionally, at least one aromatic vinyl monomer; d. Optionally, at least one functionalized poly(phenylene ether) having the following structure: [ka] In the equation, 1≦x≦100, 1≦y≦100, 2≦x+y≦100; for example, 15 <x+y<30、25<x+y<40、30<x+y<55、60<x+y<85、80<x+y<98であり; M [ka] Or, [ka] Selected from the group consisting of: In the formula, Q is one selected from the group consisting of -O-, -CO-, SO, -SO2-, and -CH2-, -C(CH3)2-; R2, R4, R6, R8, R 11 , R 13 , R 15 and R 17 Each of these is independently selected from the group consisting of a hydrogen atom, a substituted or unsubstituted C1-C8 linear alkyl group, a substituted or unsubstituted C1-C8 branched alkyl group, and a substituted or unsubstituted phenyl compound; R1, R3, R5, R7, R 10 , R 12 , R 14 and R 16 All of these are independently selected from the group consisting of hydrogen atoms, substituted or unsubstituted C1-C8 linear alkyl groups, substituted or unsubstituted C1-C8 branched alkyl groups, and substituted or unsubstituted phenyl; and, R9 [ka] and [ka] Selected from the group consisting of: In the formula, A is selected from the group consisting of arylene, carbonyl, or alkylene having 1 to 10 carbon atoms; Z is an integer between 0 and 10; R 21 , R 22 and R 23 All of these are independently selected from alkyl groups having hydrogen atoms or 1 to 10 carbon atoms; e. At least one photoinitiator; f. At least one diluent selected from the group consisting of aryl difunctional (meth)acrylate monomers, alkyl (meth)acrylate monomers, and polyfunctional (meth)acrylate monomers; and g. At least one optical blocker, optionally A method that includes this.

[0131] [Aspect 20] The method according to embodiment 19, wherein the 3D structure is a curing resin for housing an antenna for electromagnetic wave transmission.

[0132] [Aspect 21] The method according to embodiment 19 or 20, wherein at least part of the method is performed on a conveyor device in a continuous manner.

[0133] [Aspect 22] The hardened region is the first hardened layer, and the following steps are taken: III) A step of irradiating the first cured layer with a photocurable composition adjacent to it to form a subsequent cured layer; and, IV) A step of forming a 3D high-frequency circuit structure by optionally repeating steps II) and III) to form any additional layer. The method according to any one embodiment of embodiments 19 to 21, further including the method described herein.

[0134] [Aspect 23] The 3D structure has a dielectric loss (D) of less than approximately 0.0028, measured using a network analyzer at 25°C. f The method according to any one embodiment of embodiments 19 to 22, which shows ).

[0135] [Aspect 24] The method according to any one of Aspects 19 to 23, wherein at least one diluent contains an unsaturated alkyl difunctional (meth)acrylate monomer, and the photocurable composition further contains at least one second diluent selected from the group consisting of alkyl (meth)acrylate monomers and polyfunctional (meth)acrylate monomers.

[0136] [Aspect 25] The method according to any one of Aspects 19 to 24, wherein at least one (meth)acrylated polydiene derivative is selected from the group consisting of hydrophobic aliphatic urethane acrylates, hydrophobic acrylate esters, and polybutadiene diacrylate.

[0137] [Aspect 26] The method according to any one of Aspects 19 to 25, wherein at least one ethylenically unsaturated isocyanurate or cyanurate is selected from the group consisting of triallyl cyanurate, triallyl isocyanurate, and tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate.

[0138] [Aspect 27] The method according to any one of Aspects 19 to 26, wherein at least one aromatic vinyl monomer is present and is at least one selected from the group consisting of p-methylstyrene, divinylbenzene, dibromostyrene, and p-tert-butylstyrene.

[0139] [Aspect 28] At least one methacrylate-functionalized poly(phenylene ether) is present; preferably, the methacrylate-functionalized poly(phenylene ether) is difunctional and has the following structure: [Chemical formula] The method according to any one of Aspects 19 to 27.

[0140] [Aspect 29] The method according to any one embodiment of embodiments 19 to 28, wherein the photoinitiator is selected from the group consisting of bensophenone and its derivatives, benzoin and its derivatives, acetophenone and its derivatives, anthraquinone, thioxanthone and its derivatives, and organophosphorus compounds.

[0141] [Aspect 30] The method according to any one embodiment of embodiments 19 to 29, which does not contain bismaleimide resin.

[0142] [Aspect 31] The method according to any one embodiment of embodiments 19-23 and 25-30, wherein the first diluent is a cycloalkyl bifunctional methacrylate.

[0143] [Aspect 32] The method according to any one embodiment of embodiments 24 to 30, wherein the second diluent is selected from the group consisting of stearyl methacrylate, lauryl methacrylate, stearyl acrylate, lauryl acrylate, behenyl acrylate, 3,3,5-trimethylcyclohexyl methacrylate, octyldecyl acrylate, tridecyl acrylate, and isodecyl methacrylate.

[0144] [Aspect 33] The method according to any one embodiment of embodiments 24 to 30, wherein the second diluent is stearyl or lauryl (meth)acrylate, preferably stearyl methacrylate.

[0145] [Aspect 34] The method according to any one embodiment of embodiments 24 to 30, wherein the second diluent is a polyfunctional (meth)acrylate monomer.

[0146] [Aspect 35] The method according to embodiment 34, wherein the polyfunctional (meth)acrylate monomer is selected from the group consisting of ethoxylated (n)bisphenol A dimethacrylate, tricyclodecanedimethanol dimethacrylate, 1,6-hexanediol diacrylate, 1,12-dodecanediol dimethacrylate, 1,10-decanediol diacrylate, 1,6-hexanediol dimethacrylate, and 1,4-butanediol dimethacrylate.

[0147] [Aspect 36] The method according to any one embodiment of embodiments 19 to 35, which does not contain a thermal initiator.

[0148] [Aspect 37] The method according to any one embodiment of embodiments 19 to 36, further comprising a flame-retardant compound.

[0149] [Aspect 38] The method according to any one embodiment of embodiments 19 to 37, further comprising an inorganic filler.

[0150] [Aspect 39] The method according to embodiment 38, wherein the inorganic filler is selected from the group consisting of high-purity quartz, alumina, beryllia, aluminum nitride, and glass.

[0151] [Aspect 40] The method according to any one embodiment of embodiments 19 to 39, wherein a light blocker is present in the composition.

[0152] [Aspect 41] A composition according to any one embodiment of embodiments 1, 3-9 and 14-18, wherein at least one diluent comprises stearyl methacrylate.

[0153] [Aspect 42] The method according to any one embodiment of embodiments 19-23, 24-30, and 36-40, wherein at least one diluent comprises stearyl methacrylate.

[0154] The compositions and methods disclosed herein are illustrated in greater detail by the following examples, which are not to be construed as limiting.

Examples

[0155] Materials The following materials were used in the examples.

Table 1

[0156] Methods The following methods were used herein. Curing The liquid curing composition was UV cured in a Dymax flood lamp for 15 seconds per side, between glass sheets, to a target thickness of 500 μm, with a thickness uniformity of less than ±4%. Then, to ensure the removal of moisture, the cured product was dried in a thermal chamber at 60 °C for 1 hour before testing.

[0157] Thickness The thickness was measured with a Heidenhain Metro gauge with an accuracy of ±0.2 μm. The five thicknesses of the test area and their average were used in the calculation.

[0158] Dielectric Constant and Dissipation Factor The dielectric constant (Dk) and dissipation factor (Df) were measured at 25 °C using a Keysight N5222A PNA with an 85072A 10 GHz split cylinder test fixture.

[0159] Breaking Strength and Shape Factor The breaking strength (BDS) was measured at 25°C according to the ASTM D-149 standard (500 V / s ramping). This test uses a 1 / 4-inch stainless steel ball on a brass plate immersed in silicone oil to minimize the possibility of electric field inhomogeneity and film defects present at the test location. ASTM D-149 returns a value close to the sample's entitlement BDS. The breaking strength thickness was measured on each 20–30 μm thick form using a 2 mm diameter circle drawn with a marker, and each thickness was recorded before fracture. This was done to allow for precise placement of the ball-in-plane measurement at the exact location where the thickness measurement was performed. Twenty measurements were performed for each test film, and the dataset was fitted using a two-parameter Weibull distribution.

[0160] Example 1 A curable composition was obtained by mixing the following materials at 60°C until they were completely mixed and homogeneous (amounts are in mass %) based on the mass of the composition.

[0161] [Table 2]

[0162] The compositions were cured according to the method described herein, and the dielectric constant (Dk) and dielectric loss (Df) were measured according to the method described herein. The table below shows the dielectric properties obtained for samples 1 to 18. The effects of various monomers and oligomers can be confirmed by the Dk and Df properties at 10 GHz.

[0163] [Table 3]

[0164] Example 2 A curable composition was obtained by mixing the following materials (the amounts are in mass %) based on the mass of the composition. The composition was cured by the method described herein, and the dielectric constant (Dk) and dielectric loss (Df) were measured by the method described herein.

[0165] [Table 4]

[0166] This example demonstrates that trifunctional acrylate monomers having an isocyanurate structure (such as SR533) have the advantageous effect of reducing Df and increasing Dk at 10 GHz compared to conventional trifunctional acrylate monomers (such as SR351H or SR523).

[0167] The fracture strength and shape factor were measured by the method described herein. Figures 1 and 2 clearly show the statistical difference between a sample consisting of SR351H, characterized by lower fracture strength and shape factor (426–452 V / μm), and a sample consisting of SR533, characterized by higher fracture strength and shape factor (501–507 V / μm). The fracture strength of this resin is a very important characteristic for the end-use application, where these materials must conduct very high currents and maintain their insulating properties throughout their service life.

[0168] Virtual Execution

[0169] Formulations according to the following embodiments of the present invention can be prepared. The following amounts of the following components may be used: (1) a hydrophobic aliphatic urethane diacrylate, about 12% to about 18% by mass of a (meth)acrylic polydiene derivative; (2) a triallyl isocyanurate, about 35% to about 50% by mass; (3) SA9000, about 10% to about 20% by mass; (4) a first diluent, tricyclodecanedimethanol dimethacrylate, about 10% to about 15% by mass; (5) a second diluent, stearyl methacrylate, about 10% to about 18% by mass; and (6) a photoinitiator, Speedcure BPO, about 3% to about 5% by mass. The viscosity of these formulations may be in the range of 2000 to 10000 cPs. These compositions can be cured using any known 3D printer. Subsequently, the cured product may be tested for dielectric loss and dielectric constant at 10.04 GHz according to IPC Test Method TM-650 2.5.5.13. A particular optimal formulation of the present invention exhibits a dielectric loss (D) of less than approximately 0.0035, as measured using a network analyzer at 25°C. f It is submitted that it may have a dielectric constant (Dk) of approximately 2.68.

[0170] The following components may be used in the following amounts: (1) a hydrophobic aliphatic urethane diacrylate, about 15% to about 22% by mass of a (meth)acrylic polydiene derivative; (2) a triallyl isocyanurate, about 35% to about 50% by mass; (3) SA9000, about 4% to about 10% by mass; (4) a first diluent, tricyclodecanedimethanol dimethacrylate, about 10% to about 20% by mass; (5) a second diluent, stearyl methacrylate, about 10% to about 18% by mass; and (6) a photoinitiator, Speedcure BPO, about 1% to about 5% by mass. The viscosity of these formulations may range from 2000 to 20000 cPs. These compositions can be cured using any known 3D printer. Subsequently, the cured product may be tested for dielectric loss and dielectric constant at 10.04 GHz according to IPC test method TM-650 2.5.5.13. A particular optimal formulation of this embodiment of the present invention exhibits a dielectric loss (D) of less than approximately 0.004, as measured using a network analyzer at 25°C.f ) and a proposed dielectric constant (Dk) of about 2.70 may be obtained.

[0171] The following amounts of the following components may be used: (1) about 20% to about 27% by mass of a (meth)acrylated polydiene derivative, which is a hydrophobic aliphatic urethane diacrylate; (2) about 35% to about 50% by mass of triallyl isocyanurate; (3) about 10% to about 20% by mass of SA9000; (4) about 10% to about 18% by mass of a second diluent, which is stearyl methacrylate; and (5) about 1% to about 5% by mass of a photoinitiator, which is Speedcure BPO. The viscosities of these formulations can be in the range of 2000 to 20000 cPs. These compositions can be cured using any known 3D printer. Thereafter, the cured product can be tested for dielectric loss and dielectric constant at 10.04 GHz by the IPC test method TM-650 2.5.5.13. The specific optimal formulation of this embodiment of the present invention has a dielectric loss (D f ) and a proposed dielectric constant (Dk) of about 2.67 may be obtained.

[0172] The following amounts of the following components may be used: (1) about 10% to about 15% by mass of a (meth)acrylated polydiene derivative, which is a hydrophobic aliphatic urethane diacrylate; (2) about 35% to about 50% by mass of triallyl isocyanurate; (3) about 15% to about 20% by mass of SA9000; (4) about 18% to about 28% by mass of a diluent, which is lauryl methacrylate; and (5) about 1% to about 5% by mass of a photoinitiator, which is Speedcure BPO. The viscosities of these formulations can be in the range of 2000 to 20000 cPs. These compositions can be cured using any known 3D printer. Thereafter, the cured product can be tested for dielectric loss and dielectric constant at 10.04 GHz by the IPC test method TM-650 2.5.5.13. The specific optimal formulation of this embodiment of the present invention has a dielectric loss (D f ) and a proposed dielectric constant (Dk) of about 2.67 may be obtained.

[0173] The following components may be used in the following amounts: (1) a hydrophobic aliphatic urethane diacrylate, about 10% to about 15% by mass of a (meth)acrylic polydiene derivative; (2) a triallyl isocyanurate, about 35% to about 50% by mass; (3) SA9000, about 15% to about 20% by mass; (4) a diluent, stearyl acrylate, about 18% to about 28% by mass; and (5) a photoinitiator, Speedcure BPO, about 1% to about 5% by mass. The viscosity of these formulations may range from 2000 to 20000 cPs. These compositions can be cured using any known 3D printer. The cured products can then be tested for dielectric loss and dielectric constant at 10.04 GHz according to IPC test method TM-650 2.5.5.13. A particular optimal formulation of this embodiment of the present invention has a dielectric loss (D) of less than approximately 0.0040, as measured using a network analyzer at 25°C. f It is submitted that it may have a dielectric constant (Dk) of approximately 2.69.

[0174] The following components may be used in the following amounts: (1) a hydrophobic aliphatic urethane diacrylate, about 10% to about 15% by mass of a (meth)acrylic polydiene derivative; (2) a triallyl isocyanurate, about 35% to about 50% by mass; (3) SA9000, about 15% to about 20% by mass; (4) a diluent, stearyl methacrylate, about 18% to about 28% by mass; and (5) a photoinitiator, Speedcure BPO, about 1% to about 5% by mass. The viscosity of these formulations may range from 2000 to 15000 cPs. These compositions can be cured using any known 3D printer. The cured products can then be tested for dielectric loss and dielectric constant at 10.04 GHz according to IPC test method TM-650 2.5.5.13. A particular optimal formulation of this embodiment of the present invention has a dielectric loss of less than approximately 0.0035 (D) as measured using a network analyzer at 25°C. f It is submitted that it may have a dielectric constant (Dk) of approximately 2.74.

[0175] The following components may be used in the following amounts: (1) a hydrophobic aliphatic urethane diacrylate, about 10% to about 15% by mass of a (meth)acrylic polydiene derivative; (2) a triallyl isocyanurate, about 35% to about 50% by mass; (3) SA9000, about 15% to about 20% by mass; (4) a diluent, stearyl methacrylate, about 18% to about 28% by mass; and (5) a photoinitiator, Speedcure TPOL, about 1% to about 5% by mass. The viscosity of these formulations may range from 2000 to 15000 cPs. These compositions can be cured using any known 3D printer. The cured products can then be tested for dielectric loss and dielectric constant at 10.04 GHz according to IPC test method TM-650 2.5.5.13. A particular optimal formulation of this embodiment of the present invention has a dielectric loss of less than approximately 0.0036 (D) as measured using a network analyzer at 25°C. f It is submitted that it may have a dielectric constant (Dk) of approximately 2.75.

[0176] The following components may be used in the following amounts: (1) a hydrophobic acrylate ester, about 10% to about 15% by mass of a (meth)acrylic polydiene derivative; (2) about 35% to about 50% by mass of triallyl isocyanurate; (3) about 15% to about 25% by mass of SA9000; (4) a stearyl methacrylate, about 10% to about 23% by mass of a diluent; and (5) Speedcure BPO, about 1% to about 5% by mass of a photoinitiator. The viscosity of these formulations may range from 2000 to 15000 cPs. These compositions may be cured using any known 3D printer. The cured product may then be tested for dielectric loss and dielectric constant at 10.04 GHz according to IPC test method TM-650 2.5.5.13. A particular optimal formulation of this embodiment of the present invention has a dielectric loss (D) of less than about 0.0035, as measured using a network analyzer at 25°C. f It is submitted that it may have a dielectric constant (Dk) of approximately 2.77.

[0177] The following amounts of the following components can be used: (1) about 20% to about 28% by weight of a (meth)acrylated polydiene derivative, which is a hydrophobic aliphatic urethane diacrylate; (2) about 10% to about 20% by weight of triallyl isocyanurate; (3) about 17% to about 25% by weight of SA9000; (4) about 10% to about 20% by weight of a first diluent, which is tricyclodecane dimethanol dimethacrylate; (5) about 10% to about 18% by weight of a second diluent, which is stearyl methacrylate; (6) about 10% to about 18% by weight of a third diluent, which is 1,12 - dodecanediol dimethacrylate; and (7) about 1% to about 5% by weight of a photoinitiator, which is Speedcure BPO. The viscosity of these formulations can be in the range of 2000 - 20000 cPs. These compositions can be cured using any known 3D printer. Thereafter, the cured product can be tested for dielectric loss and dielectric constant at 10.04 GHz by the IPC test method TM - 650 2.5.5.13. It is proposed that a specific optimal formulation of this embodiment of the present invention can have a dielectric loss (D f ) less than about 0.0037 and a dielectric constant (Dk) of about 2.45, measured using a network analyzer at 25°C.

[0178] Although specific specific embodiments and virtual examples have been illustrated and described above, the embodiments disclosed herein are not intended to be limited to the details shown. Rather, various changes can be made in the details without departing from the spirit of the invention within the scope of the claims and the equivalent scope of the claims. For example, it is explicitly intended that all ranges broadly referred to herein include all narrower ranges included within that broader range.

Claims

1. A photocurable composition suitable for 3D printing, a. At least one (meth)acrylated polydiene derivative; b. At least one ethylenically unsaturated isocyanurate or cyanurate; c. Optionally, at least one aromatic vinyl monomer; d. At least one functionalized poly(phenylene ether) having the following structure: 【Chemistry 1】 In the equation, 1 ≤ x ≤ 100, 1 ≤ y ≤ 100, and 2 ≤ x + y ≤ 100; M 【Chemistry 2】 Or, 【Transformation 3】 Selected from the group consisting of: In the formula, Q is -O-, -CO-, SO, -SO 2 ─and─CH 2 ─,─C(CH 3 ) 2 One of the following selected from the group consisting of: R 2 、R 4 、R 6 、R 8 、R 11 、R 13 、R 15 and R 17 are each independently selected from the group consisting of a hydrogen atom, a substituted or unsubstituted C 1 -C 8 linear alkyl group, a substituted or unsubstituted C 1 -C 8 branched alkyl group and a substituted or unsubstituted phenyl; R 1 , R 3 , R 5 , R 7 , R 10 , R 12 , R 14 and R 16 All of them are hydrogen atoms, substituted or unsubstituted C 1 ~C 8 Linear alkyl groups, substituted or unsubstituted C 1 ~C 8 Independently selected from the group consisting of branched alkyl groups and substituted or unsubstituted phenyls; and, R 9 but, 【Chemistry 4】 and 【Transformation 5】 Selected from the group consisting of: In the formula, A is selected from the group consisting of arylene, carbonyl, or alkylene having 1 to 10 carbon atoms; Z is an integer between 0 and 10; R 21 , R 22 and R 23 All of these are independently selected from alkyl groups having hydrogen atoms or 1 to 10 carbon atoms; e. At least one photoinitiator; f. At least one diluent selected from the group consisting of aryl difunctional (meth)acrylate monomers, alkyl (meth)acrylate monomers, and polyfunctional (meth)acrylate monomers; and At least one optical blocker, optionally A photocurable composition containing the following.

2. The composition according to claim 1, wherein the at least one diluent comprises an unsaturated alkyl bifunctional (meth)acrylate monomer, and the composition further comprises at least one second diluent selected from the group consisting of alkyl (meth)acrylate monomers and polyfunctional (meth)acrylate monomers.

3. The composition according to claim 1 or 2, wherein the at least one (meth)acrylic polydiene derivative is selected from at least one of (meth)acrylic hydroxypolydiene, polydiene-based epoxy (meth)acrylate, polydiene-based polyester (meth)acrylate, polydiene-based urethane (meth)acrylate, and combinations thereof.

4. The composition according to any one of claims 1 to 3, wherein the at least one ethylenically unsaturated isocyanurate or cyanurate is selected from the group consisting of triallyl cyanurate, triallyl isocyanurate, and tris(2-hydroxyethyl) isocyanurate tri(meth)acrylate.

5. The composition according to any one of claims 1 to 4, wherein at least one aromatic vinyl monomer is present, and is selected from the group consisting of p-methylstyrene, divinylbenzene, dibromostyrene, and p-tert-butylstyrene.

6. The methacrylate-functionalized poly(phenylene ether) is bifunctional and has the following structure: 【Transformation 6】 A composition according to any one of claims 1 to 5, having the following characteristics.

7. The composition according to any one of claims 1 to 6, wherein the photoinitiator is selected from the group consisting of bensophenone and its derivatives, benzoin and its derivatives, acetophenone and its derivatives, anthraquinone, thioxanthone and its derivatives, and organophosphorus compounds.

8. A composition according to any one of claims 1 to 7, which does not contain bismaleimide resin.

9. The composition according to any one of claims 1 and 3 to 8, wherein the diluent is a cycloalkyl bifunctional methacrylate.

10. The second diluent is selected from the group consisting of stearyl methacrylate, lauryl methacrylate, stearyl acrylate, lauryl acrylate, behenyl acrylate, 3,3,5-trimethylcyclohexyl methacrylate, octyldecyl acrylate, tridecyl acrylate, and isodecyl methacrylate, and the composition according to any one of claims 2 to 9.

11. The composition according to any one of claims 2 to 9, wherein the second diluent is a polyfunctional (meth)acrylate monomer.

12. A composition according to any one of claims 1 to 11, which does not contain a thermal initiator.

13. The composition according to any one of claims 1 to 12, further comprising a flame-retardant compound.

14. The composition according to any one of claims 1 to 13, further comprising an inorganic filler.

15. The composition according to any one of claims 1 to 14, wherein the light blocker is present.

16. The composition according to any one of claims 1, 3 to 8 and 12 to 15, wherein the at least one diluent comprises stearyl methacrylate.

17. A method for forming a three-dimensional (3D) high-frequency circuit structure, comprising the following steps: I) A step of irradiating a region of the photocurable composition described in any one of claims 1 to 16 with an irradiation site to form a cured region; and, II) A step of causing relative movement between the irradiated area and the hardened area, thereby growing the hardened area in the direction of movement. Methods that include...

18. The method according to claim 17, wherein the 3D structure is a cured resin for housing an antenna for transmitting electromagnetic waves.

19. The method according to claim 17 or 18, wherein at least a portion of the method is performed on a conveyor device.

20. The aforementioned hardened region is the first hardened layer, and the following steps are taken: III) A step of irradiating the first cured layer with a photocurable composition adjacent to it to form a subsequent cured layer; and, IV) A step of forming the 3D high-frequency circuit structure by optionally repeating steps II) and III) to form any additional layer, The method according to any one of claims 17 to 19, further comprising:

21. The aforementioned 3D structure has a dielectric loss (D) of less than approximately 0.0028, as measured using a network analyzer at 25°C. f The method according to any one of claims 17 to 20, which shows )

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