Curable composition

Abstract

The present invention relates to a curable composition, preferably a photocurable composition, comprising at least a first monomer compound, a second monomer compound and a polymerization initiator.

Description

Technical Field

[0001] This invention relates to a curable composition (preferably a photocurable composition), a method for preparing the curable composition, a method for preparing a cured layer, a cured layer, and a stacked layer. Background Technology

[0002] In the semiconductor industry, miniaturization is a continuous trend in order to improve the performance of microchips. However, achieving 7-nanometer node technology and higher technologies significantly increases complexity and requires some new process and material solutions.

[0003] Multilayer patterning plays a significant role in transferring fine photolithographic patterns onto substrates, and its importance will only increase as the industry advances to the next stage of advanced nodes.

[0004] Spin-on carbon (SOC) materials, with their high corrosion resistance and good gap-filling properties, are key materials in these multilayer processes. When the critical size reaches tens of nanometers, existing topography becomes a major performance challenge. A reliable method for planarizing such layers using conventional chemical mechanical polishing (CMP) processes has not yet been established. Therefore, industry has shown great interest in novel strategies to achieve high levels of planarization.

[0005] Inkjet Adaptive Planarization (IAP) is a process used to planarize the surface of a substrate. For this purpose, droplets of a photocurable composition are printed onto the substrate surface. The droplet pattern can be customized to the existing morphology. A flat top layer is brought into direct contact with the liquid, forming a flat liquid layer. This flat liquid layer is typically cured under UV light, and after removing the top layer, a planar surface is obtained, which can then be used for subsequent processing steps.

[0006] These cured layers combine high etch resistance, high mechanical strength, and good thermal stability to meet the requirements of multilayer processes for hard mask materials in order to develop next-generation microchips.

[0007] The most advanced photocurable compositions typically contain high levels of acrylate monomers.

[0008] For example, US2020 / 0339828A1 (Canon) claims the use of a photocurable composition comprising a polymerizable material and a photoinitiator, wherein at least 90% by weight of the polymerizable material comprises an acrylate monomer including an aromatic group; and the photocurable composition has a total carbon content of at least 70% after curing.

[0009] US2021 / 0070906A1 (Canon) covers the use of a curable composition comprising a polymerizable material and an initiator, wherein the polymerizable material comprises a first monomer and a second monomer, the second monomer comprising a cyclic structure selected from maleimide-ring, pyrone-ring, or 2-furanone-ring, and the second monomer is soluble in the first monomer, and the viscosity of the curable composition is less than 10 cP. Furthermore, the formulation may further comprise a monomer comprising substituted or unsubstituted divinylbenzene.

[0010] US2021 / 0198400A1 (Canon) relates to a light-curable composition comprising 1,3-benzoxazine and an acrylate monomer.

[0011] US2022 / 0185914A1 (Canon) describes a photocurable composition comprising, based on the total weight of the photocurable composition, about 15% to 85% by weight of a polymerizable material (divinylbenzene; in the examples) and 15% to 85% by weight of at least one polyfunctional acrylate monomer (examples, claims).

[0012] In another prior art document (US2023 / 0203210A1), polymerizable compositions based on a dual aromatic system containing vinylbenzene or alkynes are reported. These compositions may contain acrylates, as permitted by the dependent claims of that reference. Summary of the Invention

[0013] However, the inventors have recently discovered one or more significant problems that still need improvement, as listed below: improved thermal stability after curing, preferably at a temperature of about 350°C or higher; lower shrinkage after curing; improved etch resistance of the cured layer; improved planarization properties of the cured layer, i.e., on different pattern morphologies of the substrate; lower viscosity and / or lower vapor pressure of the composition, preferably suitable for inkjet printing.

[0014] The inventors aim to solve one or more of the above-mentioned problems.

[0015] Then, the inventors were surprised to find that one or more of the above-mentioned technical problems could be solved by the features defined in the claims.

[0016] That is, a novel curable composition, preferably a photocurable composition, has been discovered, comprising at least a first monomer compound, a second monomer compound, and a polymerization initiator;

[0017] The first monomer compound is represented by chemical formula (I);

[0018] -(I)

[0019] in

[0020] 1≤x≤5, 0≤y≤4, 0≤z≤5;

[0021] When n and m are both 0, 3≤x≤5; when m is 1 and n is 0, 3≤x+z≤10; when m is 0 and n is 1, 3≤x+y≤9; when m and n are both 1, 3≤x+z+y≤14.

[0022] n is 1 or 0, m is 1 or 0, 0≤n+m≤2;

[0023] L, in each occurrence, is selected from the group consisting of direct bonds, alkylene groups having 1 to 15 carbon atoms, and alkenyl groups having 2 to 15 carbon atoms.

[0024] One or more non-adjacent CH2 groups in the alkylene or alkenylene group may be replaced by an oxygen atom, C=O, C=S, C=Se, C=NH, SiH2, SO, SO2, OS, or CONH, and one or more H atoms may be replaced by D, F, Cl, Br, I, CN, or NO2.

[0025] The second monomer compound is represented by the chemical formula (I'); and the first monomer compound is different from the second monomer compound.

[0026] (I')

[0027] in

[0028] 1≤x≤5, 0≤y≤4, 0≤z≤5;

[0029] n is 1 or 0, m is 1 or 0, and 1 ≤ n + m ≤ 2;

[0030] L, in each occurrence, is selected from the group consisting of direct bonds, alkylene groups having 1 to 15 carbon atoms, and alkenyl groups having 2 to 15 carbon atoms.

[0031] One or more non-adjacent CH2 groups in the alkylene or alkenylene group may be replaced by an oxygen atom, C=O, C=S, C=Se, C=NH, SiH2, SO, SO2, OS, or CONH, and one or more H atoms may be replaced by D, F, Cl, Br, I, CN, or NO2.

[0032] In another embodiment, the present invention relates to a method for preparing the composition of the present invention, which includes at least the step (A);

[0033] (A) A mixture of at least a first monomer compound of formula (I), a second monomer compound of formula (I'), and a polymerization initiator.

[0034] In another embodiment, the invention further relates to a method for preparing a cured layer, which includes at least the following steps (i a ) and (i b ):

[0035] (i a The composition of the present invention is provided onto a substrate, preferably by printing, more preferably by spin coating or inkjet printing;

[0036] (i d Optionally, the composition may be brought into contact with the upper substrate;

[0037] (i b The composition is cured by heating and / or by irradiating it with light to form a cured layer;

[0038] (i e Optionally, the upper substrate can be removed from the cured layer.

[0039] In another embodiment, the present invention relates to a curing layer, preferably a light-curing layer obtained by the method of the present invention or a light-curing layer that can be obtained by the method.

[0040] In another embodiment, the present invention relates to a curing layer, preferably a photocurable layer formed from the composition of the present invention.

[0041] In another embodiment, the present invention relates to a stack layer comprising a substrate and a cured layer of the present invention that at least partially covers the substrate.

[0042] The present invention provides one or more of the following technical effects: improved thermal stability after curing, preferably at a temperature of about 350°C or higher; lower shrinkage after curing; improved etch resistance of the cured layer; improved planarization properties of the cured layer, i.e., on different pattern morphologies of the substrate; lower viscosity and / or lower vapor pressure as a composition, preferably suitable for inkjet printing. Attached Figure Description

[0043] Figure 1 Comparison of isothermal baking performance of Example 2 with mixtures of Example 2 (75% by weight) and Example 7 (25% by weight).

[0044] Figure 2 Comparison of isothermal baking performance of Example 2 with mixtures of Example 2 (80 wt%) and Example 5 (20 wt%).

[0045] Figure 3Comparison of isothermal baking performance of Example 1 and mixtures of Example 1 (50 wt%) and Example 2 (50 wt%).

[0046] Figure 4 Comparison of isothermal baking performance between Example 2 and a mixture of Example 2 (80 wt%) and material CAS: 2934745-89-6 (20 wt%).

[0047] Figure 5 Comparison of isothermal baking performance of Example 6 with mixtures of Example 6 (80 wt%) and Example 12 (20 wt%). Detailed Implementation

[0048] The terms used in this article have the following meanings:

[0049] The articles “a,” “one,” and “the” include multiple references unless otherwise explicitly and unambiguously limited to one reference.

[0050] Since all figures, values ​​and / or expressions relating to the amount of ingredients, reaction conditions, etc., as used herein and in the appended claims are subject to various measurement uncertainties encountered in obtaining such values, they shall in all cases be understood to be modified by the term “about”, unless otherwise stated.

[0051] The numerical ranges disclosed herein are continuous and include the minimum and maximum values ​​of the range, as well as every value between the minimum and maximum values. Furthermore, when the range refers to integers, it includes every integer between the minimum and maximum values ​​of the range. Additionally, when multiple ranges are provided to describe a feature or property, these ranges may be combined. In other words, unless otherwise stated, all ranges disclosed herein should be understood to include any and all subranges contained therein.

[0052] For example, it is stated that the range "1 to 10" should be considered as including any and all subranges between the minimum value of 1 and the maximum value of 10. Indicative subranges of the range 1 to 10 include, but are not limited to, 1 to 6.1, 3.5 to 7.8, and 5.5 to 10, etc.

[0053] As used in this article, the term "adhesion promoter" refers to an additive that can increase the adhesion of a given formulation.

[0054] As used herein, the term "surfactant" refers to an additive that can reduce the adhesiveness of the composition.

[0055] According to the present invention, the curable composition, preferably a photocurable composition, comprises at least a first monomer compound, a second monomer compound, and a polymerization initiator;

[0056] The first monomer compound is represented by chemical formula (I):

[0057] -(I)

[0058] in

[0059] 1≤x≤5, 0≤y≤4, 0≤z≤5;

[0060] When n and m are both 0, 3≤x≤5; when m is 1 and n is 0, 3≤x+z≤10; when m is 0 and n is 1, 3≤x+y≤9; when m and n are both 1, 3≤x+z+y≤14.

[0061] n is 1 or 0, m is 1 or 0, 0≤n+m≤2;

[0062] L, in each occurrence, is selected from the group consisting of direct bonds, alkylene groups having 1 to 15 carbon atoms, and alkenyl groups having 2 to 15 carbon atoms.

[0063] One or more non-adjacent CH2 groups in the alkylene or alkenylene group may be replaced by an oxygen atom, C=O, C=S, C=Se, C=NH, SiH2, SO, SO2, OS, or CONH, and one or more H atoms may be replaced by D, F, Cl, Br, I, CN, or NO2.

[0064] The second monomer compound is represented by the chemical formula (I'), and the first monomer compound is different from the second monomer compound;

[0065] (I')

[0066] in

[0067] 1≤x≤5, 0≤y≤4, 0≤z≤5;

[0068] n is 1 or 0, m is 1 or 0, and 1 ≤ n + m ≤ 2;

[0069] L, in each occurrence, is selected from the group consisting of direct bonds, alkylene groups having 1 to 15 carbon atoms, and alkenyl groups having 2 to 15 carbon atoms.

[0070] One or more non-adjacent CH2 groups in the alkylene or alkenylene group may be replaced by an oxygen atom, C=O, C=S, C=Se, C=NH, SiH2, SO, SO2, OS, or CONH, and one or more H atoms may be replaced by D, F, Cl, Br, I, CN, or NO2.

[0071] First monomer compound

[0072] According to the present invention, the first monomeric compound is represented by chemical formula (I).

[0073] -(I)

[0074] in

[0075] 1≤x≤5, 0≤y≤4, 0≤z≤5;

[0076] When n and m are both 0, 3≤x≤5; when m is 1 and n is 0, 3≤x+z≤10; when m is 0 and n is 1, 3≤x+y≤9; when m and n are both 1, 3≤x+z+y≤14.

[0077] n is 1 or 0, m is 1 or 0, 0≤n+m≤2;

[0078] L, in each occurrence, is selected from the group consisting of direct bonds, alkylene groups having 1 to 15 carbon atoms, and alkenyl groups having 2 to 15 carbon atoms.

[0079] One or more non-adjacent CH2 groups in the alkylene or alkenylene group may be replaced by an oxygen atom, C=O, C=S, C=Se, C=NH, SiH2, SO, SO2, OS, or CONH, and one or more H atoms may be replaced by D, F, Cl, Br, I, CN, or NO2.

[0080] In a preferred embodiment of the invention, the composition is used for inkjet adaptation planarization (IAP).

[0081] According to the present invention, the first monomer compound has at least one or more carbon rings and at least three vinyl groups.

[0082] It is believed that when the monomer compound has one or more carbon rings and at least three vinyl groups, the crosslinking density can be increased. This may also result in improved thermal stability and chemical resistance of the cured film.

[0083] It is believed that compounds containing high carbon content (preferably 80% or more) can be used to achieve carbon-rich, flat underlayers, and their low viscosity with relatively low vapor pressure is ideal for inkjet printing processes, specifically the Inkjet Adaptation Planarization (IAP) process according to the invention. Furthermore, it is believed that the first monomer compound of the invention can form a highly crosslinked thermoset after UV-initiated free radical polymerization. High crosslinking density contributes to improved chemical and thermal stability and is key to its function as a hard mask. A first monomer having four or more vinyl groups can achieve improved crosslinking properties.

[0084] Preferably, L in chemical formula (I) is a direct bond, a straight-chain alkylene group having up to 5 carbon atoms, or a straight-chain alkenyl group having 2 to 5 carbon atoms, wherein one or more non-adjacent CH2 groups in the alkylene group or alkenyl group may be replaced by an oxygen atom, C=O, C=S, C=Se, C=NH, SiH2, SO, SO2, OS, or CONH, and one or more H atoms may be replaced by D, F, Cl, Br, I, CN, or NO2.

[0085] Table A below shows preferred examples of the first monomer compound.

[0086] Table A:

[0087]

[0088] In a preferred embodiment of the invention, the total amount of the first monomer compound is in the range of 10% to 99.9% by weight, preferably 50% to 99.9% by weight, and more preferably 80% to 99% by weight, based on the total amount of the composition.

[0089] Second monomer compound

[0090] According to the present invention, the composition contains a second monomeric compound represented by chemical formula (I'), wherein the first monomeric compound is different from the second monomeric compound.

[0091] (I')

[0092] in

[0093] 1≤x≤5, 0≤y≤4, 0≤z≤5;

[0094] n is 1 or 0, m is 1 or 0, and 1 ≤ n + m ≤ 2;

[0095] L, in each occurrence, is selected from the group consisting of direct bonds, alkylene groups having 1 to 15 carbon atoms, and alkenyl groups having 2 to 15 carbon atoms.

[0096] One or more non-adjacent CH2 groups in the alkylene or alkenylene group may be replaced by an oxygen atom, C=O, C=S, C=Se, C=NH, SiH2, SO, SO2, OS, or CONH, and one or more H atoms may be replaced by D, F, Cl, Br, I, CN, or NO2.

[0097] As discussed above regarding the first monomer compound, it is believed that compounds containing a high carbon content (preferably 80% or more) can be used to achieve a carbon-rich, flat underlayer, and their low viscosity with relatively low vapor pressure is ideal for inkjet printing processes, i.e., the Inkjet Adapted Planarization (IAP) process according to the invention. Furthermore, the second monomer compound is considered to be a vinylbenzene derivative, which can form a highly crosslinked thermoset after UV-initiated free radical polymerization. The high crosslink density contributes to improved chemical and thermal stability and is key to its function as a hard mask.

[0098] By adding a second monomer compound in addition to the first monomer compound and controlling their mixing ratio, the viscosity, crosslinking properties, vapor pressure and / or thermal stability of the composition, and shrinkage after curing can be controlled; the etch resistance of the cured layer is improved; and the planarization properties of the cured layer are improved.

[0099] In a preferred embodiment of the invention, the total amount of the first monomer compound and the second monomer compound is in the range of 10% to 99.9% by weight, preferably 50% to 99.9% by weight, and more preferably 80% to 99% by weight, based on the total amount of the composition.

[0100] Table B below shows preferred examples of this second monomer compound.

[0101] Table B:

[0102]

[0103]

[0104] Third / fourth monomeric compounds

[0105] In some embodiments of the invention, the composition may optionally comprise a third and / or a fourth monomeric compound. The third and / or fourth monomeric compounds are different from each other and also different from the first and second monomeric compounds. The third and / or fourth monomeric compounds are represented by chemical formula (I'). The third and / or fourth monomeric compounds may be selected from Table B.

[0106] Polymerization initiator

[0107] The polymerization initiators in this invention include polymerization initiators that generate acids, bases or free radicals by radiation, and polymerization initiators that generate acids, bases or free radicals by heating.

[0108] Preferably, the polymerization initiator is selected from photoradical initiators, photoacid generators, or combinations of photoradical initiators and photoacid generators. Examples include Irgacure OXE02 (Boc Sciences, CAS: 478556-66-0), Omnirad1316 (IGM Resins), Irgacure 651 (Merck, CAS: 24650-42-8), and Irgacure 819 (Merck, CAS: 162881-26-7).

[0109] According to the present invention, publicly available substances as described in EP3717966A1 or WO2021 / 099236A1 may preferably be used.

[0110] Composition

[0111] In a preferred embodiment of the invention, the composition comprises 10% by weight or less of acrylate monomers based on the total amount of the composition, preferably in the range of 0 to 10% by weight, more preferably in the range of 0 to 5% by weight, and even more preferably an acrylate-free composition comprising 0% by weight of acrylate monomers.

[0112] It is believed that containing 10% by weight or less of acrylate monomers results in a significantly higher carbon content in the cured film obtained from the composition compared to compositions containing more than 10% by weight of acrylate. This higher carbon content improves etch resistance, which is crucial for the function of carbon-rich hard masks and pattern etching transfer. Furthermore, it is believed that acrylates reduce the temperature stability of the cured film and lead to greater UV-induced shrinkage in photocuring systems. These disadvantages of using acrylates can be reduced or eliminated by reducing the total amount of acrylate monomers in the composition to 10% by weight or less, more preferably in the range of 0 to 5% by weight.

[0113] On the other hand, it is believed that adding a small amount of acrylate can provide flexibility in adjusting the viscosity, inkjetability, and / or vapor pressure of the composition. It can also improve the photocuring speed of the composition.

[0114] Preferably, the composition of the present invention contains 10% by weight or less of solvent based on the total amount of the composition, preferably in the range of 0 to 10% by weight, more preferably in the range of 0 to 5% by weight, and even more preferably a solvent-free composition containing 0% by weight of solvent.

[0115] It is believed that setting the total solvent content in the composition to 10% by weight or less based on the total amount of the composition is beneficial for reducing process steps, minimizing process time, facilitating handling (i.e. for inkjet printing), and / or minimizing / avoiding contamination by impurities.

[0116] additive

[0117] According to the invention, in some embodiments, the composition may optionally include an additive selected from the group consisting of surfactants, wetting agents, release agents, oxygen quenchers, and stabilizers. In some embodiments, the amount of the additive may be zero.

[0118] As the additive, a known material preferably used in the semiconductor industry can be used in this invention.

[0119] Surfactants and release agents are believed to be used to reduce the adhesion of the composition (preferably to the upper material) to improve processability.

[0120] viscosity

[0121] In a preferred embodiment of the invention, the viscosity of the composition at 23°C is in the range of 5 to 50 cP, and preferably 5 to 20 cP from the perspective of achieving smooth inkjet printing.

[0122] The viscosity of the composition can be controlled, for example, by changing the type of the first monomer and / or the second monomer, and the amount of the first monomer and / or the second monomer.

[0123] The viscosity of the compositions of this invention can be measured using an Anton Paar MCR92 rheometer (Anton Paar, Granz, Austria) using a conical plate geometry. Viscosity values ​​were measured at 23°C using a rotating conical plate geometry (d=25mm) for 500 s. -1 The shear rate was measured.

[0124] Method for preparing the composition

[0125] In another embodiment, the present invention relates to a method for preparing the composition of the present invention, which includes at least the following step (A):

[0126] (A) A mixture of at least a first monomer compound of formula (I), a second monomer compound of formula (I'), and a polymerization initiator.

[0127] -(I)

[0128] in

[0129] 1≤x≤5, 0≤y≤4, 0≤z≤5;

[0130] When n and m are both 0, 3≤x≤5; when m is 1 and n is 0, 3≤x+z≤10; when m is 0 and n is 1, 3≤x+y≤9; when m and n are both 1, 3≤x+z+y≤14.

[0131] n is 1 or 0, m is 1 or 0, 0≤n+m≤2;

[0132] L, in each occurrence, is selected from the group consisting of direct bonds, alkylene groups having 1 to 15 carbon atoms, and alkenyl groups having 2 to 15 carbon atoms.

[0133] One or more non-adjacent CH2 groups in the alkylene or alkenylene group may be replaced by an oxygen atom, C=O, C=S, C=Se, C=NH, SiH2, SO, SO2, OS, or CONH, and one or more H atoms may be replaced by D, F, Cl, Br, I, CN, or NO2.

[0134] The second monomer compound is represented by the chemical formula (I'); and the first monomer compound is different from the second monomer compound.

[0135] (I')

[0136] in

[0137] 1≤x≤5, 0≤y≤4, 0≤z≤5; n is 1 or 0, m is 1 or 0, 1≤n+m≤2; L, in each occurrence, is selected from the group consisting of a direct bond, an alkylene group having 1 to 15 carbon atoms, and an alkenyl group having 2 to 15 carbon atoms, wherein one or more non-adjacent CH2 groups in the alkylene or alkenyl group may be replaced by an oxygen atom, C=O, C=S, C=Se, C=NH, SiH2, SO, SO2, OS, or CONH, and one or more H atoms may be replaced by D, F, Cl, Br, I, CN, or NO2.

[0138] In another embodiment, the invention further relates to a method for preparing the cured layer, which includes at least the following steps (i a ) and (i b ):

[0139] (i a The composition of the present invention is provided onto a substrate, preferably by printing, more preferably by spin coating or inkjet printing;

[0140] (i d Optionally, the composition may be brought into contact with the upper substrate;

[0141] (i b The composition is cured by heating and / or by irradiating it with light to form a cured layer;

[0142] (i e Optionally, the upper substrate can be removed from the cured layer.

[0143] As for the top layer material, known materials can be used. For example, the top layer material and method described by Niyaz Khusnatdinov et al. in “Development of an inkjet-enabled Adaptive Planarization Process”, Proceedings Volume 10451, Photomask Technology 2017; 104511A (2017) are preferred.

[0144] In some implementations, the curing can be photocuring, thermocuring, or a combination of photocuring and thermocuring.

[0145] In a preferred embodiment, the photocuring is performed at a curing energy of 0.1 to 30 J / cm². 2 The UV light irradiation composition is more preferably 0.3 to 25 J / cm. 2 Further preferably, it is 0.5 to 2 J / cm. 2 The preferred UV light wavelength is 250 nm to 400 nm, more preferably about 350 nm.

[0146] In a preferred embodiment, the method further comprises step (i) b The following steps are included after (i) c );

[0147] (i c Bake the cured layer at a temperature ranging from 180°C to 450°C for a time ranging from 0.5 minutes to 10 minutes.

[0148] In a preferred embodiment, the method for preparing the cured layer is inkjet adaptive planarization (IAP).

[0149] In another embodiment, the present invention further relates to a curing layer, preferably a photocurable layer obtained by the method of the present invention or a photocurable layer obtainable by the method.

[0150] In another embodiment, the present invention relates to a curing layer, preferably a photocurable layer formed from the composition of the present invention. In a preferred embodiment, the photocurable layer serves as an interlayer insulating film for a semiconductor device, or as a spin-on carbon substrate (SOC) for manufacturing semiconductors, such as LSI, system LSI, DRAM, SDRAM, RDRAM, or D-RDRAM.

[0151] In another embodiment, the invention further relates to a stack layer comprising a substrate and a cured layer of the invention at least partially covering the substrate.

[0152] The present invention is further illustrated by the following embodiments, which should not be construed as limiting. Those skilled in the art will recognize that various modifications, additions, and alterations can be made to the invention without departing from the spirit and scope of the invention as defined in the appended claims.

[0153] Example

[0154] Part A: Synthesis of Chemical Compounds

[0155] Synthetic Example 1: Preparation of bis(3-vinylphenyl)methane

[0156]

[0157] Step 1: Synthesis of bis(3-bromophenyl)methanol

[0158]

[0159] 1,3-Dibromobenzene (Merck, CAS: 108-36-1, 33.7 g, 143 mmol) was dissolved in anhydrous diethyl ether (Merck, 585 mL). The solution was cooled to -78 °C, and a solution of n-butyllithium (1.6 M in hexane, 98 mL, 156 mmol) was added dropwise. Then, 3-bromobenzaldehyde (Merck, CAS: 3132-99-8, 24 g, 130 mmol) was added, and the reaction mixture was stirred while allowing it to reach room temperature. The reaction was carefully stopped with 100 mL of brine, and the aqueous phase was separated and extracted three times with DCM. The combined organic phases were dried over Na2SO4, filtered, and the solvent was removed under vacuum to give 51.6 g (116%) of a brown oil, which was ready for use without further purification.

[0160] Step 2: Synthesis of bis(3-bromophenyl)methane

[0161]

[0162] Bis(3-bromophenyl)methanol (51.6 g, 140 mmol) was dissolved in 400 mL of DCM, treated with triethylsilane (Merck, CAS: 617-86-7, 88 mL, 550 mmol), and cooled to 0 °C. Trifluoromethanesulfonic acid (Merck, CAS: 1493-13-6, 48 mL, 550 mmol) was added dropwise, and the mixture was stirred at room temperature for 3 hours. Ice was carefully added, and the aqueous phase was separated three times with DCM. The combined organic phases were dried over Na2SO4, filtered, and the solvent was removed under vacuum to give 110 g of a yellow oil. Crystallization in ethanol gave the product (35 g, 78%).

[0163] 1HNMR (500 MHz, chloroform-d): δ = 7.38 (dt, J = 7.9, 1.4 Hz, 2H), 7.35 (d,J = 1.9 Hz, 2H), 7.19 (t, J = 7.7 Hz, 2H), 7.12 (d, J = 7.7 Hz, 2H), 3.93 (s,2H) ppm.

[0164] Step 3: Synthesis of bis(3-vinylphenyl)methane

[0165]

[0166] Bis(3-bromophenyl)methanol (29 g, 90 mmol) was dissolved in anhydrous THF (1.4 L), treated with potassium vinyltrifluoroborate (Merck, CAS: 13682-77-4, 196 mmol, 26 g), and stirred at room temperature under nitrogen for 1 hour. NaOH solution (250 mL, 10 wt%) and Pd(amphos)Cl2 (Merck, CAS: 887919-35-9, 2.5 g, 3.6 mmol) were added, and the reaction mixture was stirred at 50 °C for 12 hours. The mixture was cooled to room temperature, treated with water, and extracted three times with ethyl acetate. The combined organic phases were dried over Na2SO4, filtered, and the solvent was removed under vacuum. The crude product was purified by silica column chromatography using heptane as solvent, finally yielding 12.3 g (62.5%) of a colorless liquid.

[0167] 1 HNMR (500 MHz, chloroform-d): δ = 7.35 - 7.26 (m, 6H), 7.13 (dt, J = 6.7, 2.0 Hz, 2H), 6.74 (dd, J = 17.6, 10.9 Hz, 2H), 5.77 (d, J = 17.5 Hz, 2H), 5.27 (d, J = 10.9 Hz, 2H), 4.02 (s, 2H) ppm.

[0168] Synthetic Example 2: Preparation of 1,3-divinyl-5-(3-vinylphenyl)benzene

[0169]

[0170] In summary, the same synthesis conditions as in Example 1 were used. In step 1, 1,3,5-tribromobenzene (Merck, CAS: 626-39-1) was used instead of 1,3-dibromobenzene.

[0171] 18.5 g (78%) of colorless liquid was obtained in the Suzuki step.

[0172] 1 ¹H NMR (500 MHz, chloroform-d) δ = 7.35 (d, J = 1.8 Hz, 1H), 7.34 - 7.26 (m, 3H), 7.18 (d, J = 1.5 Hz, 2H), 7.13 (dt, J = 6.9, 1.9 Hz, 1H), 6.73 (ddd, J = 17.6, 10.8, 3.7 Hz, 3H), 5.78 (ddd, J = 17.6, 4.4, 0.9 Hz, 3H), 5.28 (ddd, J = 10.9, 5.6, 1.0 Hz, 3H), 4.01 (s, 2H) ppm.

[0173] Synthetic Example 3: Preparation of 1,3-divinyl-5-(2-vinylbenzyl)benzene

[0174]

[0175] In summary, the same synthesis conditions as in Example 1 were used. In step 1, 1,3,5-tribromobenzene (Merck, CAS: 626-39-1) was used instead of 1,3-dibromobenzene, and 2-bromobenzaldehyde (Merck, CAS: 6630-33-7) was used instead of 3-bromobenzaldehyde.

[0176] 4.4 g (90%) of colorless liquid was obtained in the Suzuki step.

[0177] 1HNMR (500 MHz, chloroform-d) δ = 7.57 (dd, J = 7.1, 2.1 Hz, 1H), 7.35 -7.19 (m, 3H), 7.16 (dd, J = 7.0, 2.0 Hz, 1H), 7.10 (d, J = 1.5 Hz, 2H), 6.99(dd, J = 17.3, 11.0 Hz, 1H), 6.70 (dd, J = 17.6, 10.8 Hz, 2H), 5.76 (d, J =1.0 Hz, 1H), 5.72 (d, J = 1.0Hz, 1H), 5.68 (dd, J = 17.3, 1.4 Hz, 1H), 5.30(dd, J = 11.0, 1.4Hz, 1H), 5.26 (dd, J = 10.8, 0.9 Hz, 2H), 4.09 (s, 2H) ppm.

[0178] Synthetic Example 4: Preparation of 1,3-divinyl-5-(4-vinylbenzyl)benzene

[0179]

[0180] In summary, the same synthesis conditions as in Example 1 were used. In step 1, 1,3,5-tribromobenzene (Merck, CAS: 626-39-1) was used instead of 1,3-dibromobenzene, and 4-bromobenzaldehyde (Merck, CAS: 1122-91-4) was used instead of 3-bromobenzaldehyde.

[0181] 17.5 g (97%) of colorless liquid was obtained in the Suzuki step.

[0182] 1 ¹H NMR (500 MHz, chloroform-d) δ = 7.42 - 7.38 (m, 2H), 7.36 (s, 1H), 7.24 - 7.17 (m, 4H), 6.75 (d, J = 17.6, 10.9, 8.1 Hz, 3H), 5.81 (s, 1H), 5.82 - 5.73 (m, 2H), 5.31 (s, 1H), 5.30 - 5.24 (m, 2H), 4.01 (s, 2H) ppm.

[0183] Synthetic Example 5: Preparation of bis(3,5-divinylphenyl)methane

[0184]

[0185] In summary, the same synthesis conditions as in Example 1 were used. In step 1, 1,3,5-tribromobenzene (Merck, CAS: 626-39-1) was used instead of 1,3-dibromobenzene, and 3,5-dibromobenzaldehyde (Merck, CAS: 56990-02-4) was used instead of 3-bromobenzaldehyde.

[0186] 4.5 g (63%) of colorless solid was obtained in the Suzuki step.

[0187] 1 HNMR (500 MHz, chloroform-d) δ = 7.34 (d, J = 1.7 Hz, 2H), 7.17(d, J = 1.6Hz, 4H), 6.71 (dd, J = 17.6, 10.8 Hz, 4H), 5.77 (dd, J = 17.7, 0.9 Hz, 4H), 5.27 (dd, J = 10.8, 0.9 Hz, 4H), 3.99 (s, 2H) ppm.

[0188] Synthetic Example 6: Preparation of 3,3'-divinyl-1,1'-biphenyl

[0189]

[0190] Example 6 was synthesized using 3,3'-dibromo-1,1'-biphenyl (abcr, CAS: 16400-51-4) under the same conditions as step 3 of Example 1.

[0191] 1 HNMR (500 MHz, chloroform-d) δ = 7.68 (q, J = 1.5 Hz, 2H), 7.55(dt, J =6.2, 2.2 Hz, 2H), 7.51 - 7.44 (m, 4H), 6.85 (dd, J = 17.6, 10.9 Hz, 2H), 5.89 (dd, J = 17.6, 0.9 Hz, 2H), 5.36 (dd, J = 10.9, 0.9 Hz, 2H) ppm.

[0192] Synthetic Example 7: Preparation of 3,3',5,5'-Tetravinyl-1,1'-Biphenyl

[0193]

[0194] Example 7 was synthesized using 3,3'-5,5'-tetrabromobiphenyl (abcr, CAS: 16400-50-3) under the same conditions as step 3 of Example 1.

[0195] 1 HNMR (500 MHz, THF-d8) δ = 7.65 (d, J = 1.5 Hz, 4H), 7.55 (t, J = 1.7Hz, 2H), 6.85 (dd, J = 17.6, 10.9 Hz, 4H), 5.93 (dd, J = 17.6, 0.9 Hz, 4H),5.31 (dd, J = 10.8, 0.9 Hz, 4H) ppm.

[0196] Synthetic Example 8: Preparation of 1,2,4,5-Tetravinylbenzene

[0197]

[0198] Example 8 was synthesized using 1,2,4,5-tetrabromobenzene (Merck, CAS: 636-28-2) under the same conditions as step 3 of Example 1.

[0199] 1 HNMR (500 MHz, Methylene Chloride-d2) δ = 7.54 (s, 2H), 6.98 (dd, J =17.4, 11.0 Hz, 4H), 5.66 (dd, J = 17.4, 1.3 Hz, 4H), 5.32 (dd, J = 11.0, 1.3Hz, 4H).

[0200] Synthetic Example 9: Preparation of 3,3',5-trivinyl-1,1'-biphenyl

[0201]

[0202] Step 1: Preparation of 3,3',5-tribromo-1,1'-biphenyl

[0203]

[0204] 3-Bromo-1-iodobenzene (Merck, CAS: 591-18-4, 20 g, 70.7 mmol) and 3,5-dibromophenyl (Merck, CAS: 117695-55-3, 19.8 g, 70.7 mmol) were dissolved together in toluene (325 mL) and water (300 mL). K₂CO₃ (48.9 g, 353 mmol) and tetrakis(triphenylphosphine)palladium (Merck, 0.41 g, 0.35 mmol) were added, and the mixture was refluxed under nitrogen with stirring overnight. The mixture was cooled to room temperature, and the phases were separated. The aqueous phase was extracted three times with ethyl acetate, and the organic phases were combined, dried over Na₂SO₄, filtered, and evaporated to dryness. The crude product was purified by silica chromatography using heptane as the eluent to give 18.5 g (67%) of colorless solid.

[0205] Step 2: Preparation of 3,3',5-trivinyl-1,1'-biphenyl

[0206] Example 9 was synthesized using 3,3',5-tribromo-1,1'-biphenyl (step 1) under the same conditions as step 3 of Example 1.

[0207] 1 ¹H NMR (500 MHz, chloroform-d) δ = 7.68 (d, J = 1.9 Hz, 1H), 7.60 - 7.50 (m, 3H), 7.52 - 7.43 (m, 3H), 6.85 (ddd, J = 17.6, 10.9, 4.3 Hz, 3H), 5.94 - 5.85 (m, 3H), 5.37 (dd, J = 11.0, 4.6 Hz, 3H) ppm.

[0208] Synthetic Example 10: Preparation of 1,3-divinyl-5-(3-vinylphenoxy)benzene

[0209]

[0210] Step 1: Synthesis of 1,3-dibromo-5-(3-bromophenoxy)benzene

[0211]

[0212] 3-Bromophenol (Merck, CAS: 591-20-8, 6.8 g, 39.4 mmol) was dissolved together with 1,3-dibromo-5-fluorobenzene (Merck, CAS: 1435-51-4, 10 g, 39.4 mmol) and K₂CO₃ (5.4 g, 39.4 mmol) in DMF (91.5 mL) and treated overnight at 160 °C under nitrogen. The reaction mixture was cooled to room temperature and treated with water to form an oil. The aqueous phase was extracted twice with MTBE, and the combined organic phases were dried over Na₂SO₄, filtered, and evaporated to dryness. Finally, the crude product was purified by silica chromatography (heptane / ethyl acetate, 9:1) to give 13 g (81%) of colorless solid.

[0213] 1 HNMR (500 MHz, chloroform-d) δ = 7.45 (t, J = 1.6 Hz, 1H), 7.35 (ddd, J =7.9, 1.8, 1.0 Hz, 1H), 7.27 (t, J = 8.1 Hz, 1H), 7.21(t, J = 2.1 Hz, 1H), 7.10 (d, J = 1.6 Hz, 2H), 6.98 (ddd, J = 8.2, 2.4, 1.0 Hz, 1H) ppm.

[0214] Step 2: Synthesis of 1,3-divinyl-5-(3-vinylphenoxy)benzene

[0215] Example 10 was synthesized using 1,3-dibromo-5-(3-bromophenoxy)-benzene (step 1) under the same conditions as step 3 of Example 1.

[0216] 1 ¹H NMR (500 MHz, chloroform-d) δ = 7.33 (t, J = 7.9 Hz, 1H), 7.25 - 7.17 (m, 2H), 7.13 (t, J = 2.1 Hz, 1H), 7.02 (d, J = 1.4 Hz, 2H), 6.95 (dd, J = 8.1, 2.4 Hz, 1H), 6.71 (ddd, J = 17.6, 10.8, 6.7Hz, 3H), 5.77 (d, J = 17.6 Hz, 3H), 5.31 (dd, J = 10.8, 3.1Hz, 3H) ppm.

[0217] Synthetic Example 11: Preparation of 1,3-divinyl-5-(4-vinylphenoxy)benzene

[0218]

[0219] Step 1: Synthesis of 1,3-dibromo-5-(4-bromophenoxy)benzene

[0220] The synthesis was performed according to step 1 of Example 10, wherein 3-bromophenol was replaced with bromophenol (Merck, CAS: 106-41-2). 11 g (69%) of colorless solid was obtained.

[0221] 1 HNMR (500 MHz, THF-d8) δ = 7.55 - 7.50 (m, 2H), 7.48 (t, J = 1.7 Hz,1H), 7.16 (d, J = 1.7 Hz, 2H), 7.03 - 6.95 (m, 2H) ppm.

[0222] Step 2: Synthesis of 1,3-divinyl-5-(4-vinylphenoxy)benzene

[0223] Example 11 was synthesized using 1,3-dibromo-5-(4-bromophenoxy)-benzene (step 1) under the same conditions as step 3 of Example 1.

[0224] 1 HNMR (500 MHz, THF- d8 ) δ = 7.42 - 7.36 (m, 2H), 7.25 (t, J = 1.6 Hz,1H), 7.02 (d, J = 1.6 Hz, 2H), 6.99 - 6.93 (m, 2H), 6.68 (ddd, J = 17.6,10.9, 3.0 Hz, 3H), 5.76 (dd, J =17.6, 1.0 Hz, 2H), 5.67 (dd, J = 17.6, 1.0Hz, 1H), 5.22 (dd, J = 11.0, 1.0 Hz, 2H), 5.14 (dd, J = 11.0, 1.0 Hz, 1H)ppm.

[0225] Synthetic Example 12: Preparation of 5,5'-oxybis(1,3-divinylbenzene)

[0226]

[0227] Step 1: Synthesis of 5,5'-oxybis(1,3-dibromobenzene)

[0228] The synthesis was performed according to step 1 of Example 10, with 3,5-dibromophenol (Merck, CAS: 626-41-5) replacing 3-bromophenol. 6.8 g (69%) of colorless solid was obtained.

[0229] 1 HNMR (500 MHz, CDCl3) δ = 7.50 (t, J = 1.7 Hz, 2H), 7.12 (d, J= 1.6Hz, 4H) ppm.

[0230] Step 2: Synthesis of 5,5'-oxybis(1,3-divinylbenzene)

[0231] Example 12 was synthesized using 5,5'-oxybis(1,3-dibromobenzene) (step 1) under the same conditions as step 3 of Example 1. 3.3 g (89%) of a pale yellow liquid was obtained.

[0232] 1 HNMR (500 MHz, CDCl3) δ = 7.23 (d, J = 1.6 Hz, 2H), 7.01 (d, J = 1.5Hz, 4H), 6.70 (dd, J = 17.6, 10.9 Hz, 4H), 5.77 (dd, J = 17.5, 0.8 Hz, 4H),5.35 - 5.23 (m 4H) ppm.

[0233] Part B: Preparation of Photocurable Compositions

[0234] Working Examples 13 to 25: Preparation of Photocurable Compositions

[0235] The photocurable compositions (WE13 to WE25) contain at least one polystyrene compound and are formulated based on the proportions shown in Table 2. Additionally, WE14 and WE25 contain a polyfunctional acrylate monomer (SR295, CAS: 4986-89-4), while WE23 is characterized by a mixed vinyl-acrylate compound (CAS: 2934745-89-6), as described in the prior art. All compositions also contain a certain amount of photoinitiator, details of which are described in Table 2 below.

[0236] viscosity

[0237] The viscosity of this light-curable composition was measured using an Anton Paar MCR 92 rheometer (Anton Paar, Graz, Austria) with a conical plate geometry. Viscosity was measured at 23°C for 500 s using a rotating conical plate geometry (d=25 mm).-1 The shear rate was measured.

[0238] Thermal stability of the photocured layer

[0239] The photocurable film was prepared by coating a 60µm thick photocurable composition layer in a sandwich device consisting of two glass plates, and then curing it at room temperature with UV light of wavelength 365nm at different curing energies (5.5J / cm²). 2 or 10J / cm 2 The film was prepared by curing. After UV curing on a hot plate at 250°C for 2 minutes, the film was baked and then measured using TGA (TA Discovery or TA TGA Q50). The thermal stability of the composition can be measured using the 2% decomposition temperature (T). d2% It can be assessed using either the percentage of weight loss per minute or both. d2% The polymer was heated and cured at a controlled rate of 10 K / min. The percentage weight loss per minute was measured by isothermal baking, which involved heating the sample to a predetermined temperature (400 °C) over 20 minutes and holding that temperature constant for 60 minutes.

[0240] Figure 1 The isothermal baking performance of Example 2 and the mixture of Example 2 (75% by weight) and Example 7 (25% by weight) is shown.

[0241] Curing: +3 wt% Irgacure OXE02 and 3 wt% Irgacure 651, 5.5 J / cm 2 (At 365 nm) +250 °C / 2 min. TGA method: Heat the sample from room temperature to 400 °C over 20 min, then hold at 400 °C for 60 min.

[0242] Figure 2 The isothermal baking performance of Example 2 and the mixture of Example 2 (80 wt%) and Example 5 (20 wt%) is shown.

[0243] Curing: +3 wt% Irgacure OXE02 and 3 wt% Irgacure 651, 5.5 J / cm 2 (At 365 nm) +250 °C / 2 min. TGA method: Heat the sample from room temperature to 400 °C over 20 min, then hold at 400 °C for 60 min.

[0244] Figure 3 The isothermal baking performance of Example 1 and the mixture of Example 1 (50 wt%) and Example 2 (50 wt%) is shown.

[0245] Curing: +3 wt% Irgacure OXE02 and 3 wt% Irgacure 651, 10 J / cm 2 (At 365 nm) +250 °C / 2 min. TGA method: Heat the sample from room temperature to 400 °C over 20 min, then hold at 400 °C for 60 min.

[0246] Figure 4 The isothermal baking performance of Example 2 and the mixture of Example 2 (80 wt%) and CAS: 2934745-89-6 (20 wt%) is shown.

[0247] Curing: +2 wt% Omnirad 1316 and 4 wt% Irgacure 651, 10 J / cm 2 (365nm) +250℃ / 2 minutes. TGA method: Heat the sample from room temperature to 400℃ over 20 minutes, and then hold at 400℃ for 60 minutes.

[0248] Figure 5 The isothermal baking performance of Example 6 and the mixture of Example 6 (80 wt%) and Example 12 (20 wt%) is shown.

[0249] Curing: +3 wt% Irgacure OXE02 and 3 wt% Irgacure 819, 10 J / cm 2 (365nm) +250℃ / 2 minutes. TGA method: Heat the sample from room temperature to 400℃ over 20 minutes, and then hold at 400℃ for 60 minutes.

[0250] Table 1 shows an overview of different compositions based on only one vinylbenzene component and non-limiting amounts of a) 3 wt% Irgacure OXE02 (BocSciences, CAS: 478556-66-0) and 3 wt% Irgacure 651 (Merck, CAS: 24650-42-8) or b) 3 wt% Irgacure OXE02 and 3 wt% Irgacure 819 (Merck, CAS: 162881-26-7) or c) 6 wt% Irgacure OXE02. The curing energy at 365 nm is 5.5 J / cm². 2 or 10J / cm 2 After exposure, the sample was baked on a hot plate at 250°C for 2 minutes.

[0251] For example, Example 1 in Table 1 aThis indicates that the compound in Synthesis Example 1 was used with a) 3 wt% Irgacure OXE02 and 3 wt% Irgacure 651.

[0252] Example 6 in Table 1 b This indicates that the compound in Synthesis Example 6 was used with b) 3 wt% Irgacure OXE02 and 3 wt% Irgacure 819.

[0253] And in Example 10 of Table 1 c This indicates that the compound in Synthesis Example 10 was used with 6% by weight of Irgacure OXE02.

[0254] Table 2 summarizes examples using different proportions of various polyethylene compounds, including a) 3 wt% Irgacure OXE02 and 3 wt% Irgacure 651, b) 3 wt% Irgacure OXE02 and 3 wt% Irgacure 819, c) 6 wt% Irgacure OXE02, and d) 2 wt% Omnirad 1316 (IGM Resins, CAS: 2417522-91-7). The curing energy at 365 nm was 5.5 J / cm². 2 or 10J / cm 2 After exposure, the sample was baked on a hot plate at 250°C for 2 minutes.

[0255] Table 1:

[0256]

[0257] a 3% by weight Irgacure OXE02 and 3% by weight Irgacure 651

[0258] b 3% by weight Irgacure OXE02 and 3% by weight Irgacure 819

[0259] c 6% by weight Irgacure OXE02

[0260] Table 2:

[0261]

[0262] 3% by weight Irgacure OXE02 and 3% by weight Irgacure 651 (5.5 J / cm³) 2 +250°C / 2min)

[0263] b 3% by weight Irgacure OXE02 and 3% by weight Irgacure 651 (10 J / cm) 2 +250°C / 2min)

[0264] c 3% by weight Irgacure OXE02 and 3% by weight Irgacure 819 (10 J / cm) 2 +250°C / 2min)

[0265] d 6% by weight Irgacure OXE02 (10 J / cm³) 2 +250°C / 2min)

[0266] e 2% wt% Omnirad 1316 and 4% wt% Irgacure 651 (10 J / cm) 2 - 250°C / 2min)

[0267] Part C: Etching resistance relative to a benchmark acrylate-based photocurable composition.

[0268] The printing composition of the present invention was etched using a reactive ion etching apparatus with O2, CF4, and Cl2 plasmas. Etching resistance was compared to a benchmark acrylate-based photocurable composition (CE1) (see Table 3). CE1 consisted of 50 parts benzyl acrylate, 30 parts 1-naphthyl acrylate, and 20 parts bisphenol A dimethacrylate, with 3 parts Irgacure 819 as a photoinitiator.

[0269] Photocurable films were formed on silicon wafers using J-FILImprint Tool I450 in Examples 6 (Ex6), 25 (WE25), and CE1. For Ex6 and WE25, the films were cured at 20 J / cm². 2 It is completely cured under UV light irradiation; for CE1, the film is cured at 2.4 J / cm. 2 The film was completely cured under UV light irradiation. The cured film thickness was approximately 80 to 100 nm. To measure etch resistance, a Trion Oracle 3-Chamber Cluster System was used as the etching tool for dry etching. Three different dry etching chemistry reactions were tested: 1) etching with an oxygen / argon combination (O2 / Ar); 2) etching with a CF4 / Ar gas combination; and 3) etching with a chlorine and oxygen combination (Cl2 / O2), under the following conditions:

[0270]

[0271] Table 3:

[0272]

[0273] a +3% by weight Irgacure OXE02 and 3% by weight Irgacure 651

[0274] b WE 25: Ex6 (60 wt%), Ex8 (40 wt%), 3 wt% Irgacure OXE02, 3 wt% Irgacure 651

[0275] Part D: Nanoindentation Testing

[0276] The mechanical properties of the printed compositions of this invention were evaluated using nanoindentation. Nanoindentation was performed on photocurable films of Ex6, WE25, WE26, and CE1 to measure reduced modulus and hardness. Testing was conducted using a Hysitron TI 950 Triboindenter with the Oliver-Pharr method integrated into the TriboScan control software. Briefly, three 2μl drops of each sample were dropped onto a silicon wafer coated with an adhesive layer and then covered with a quartz glass slide. A 20 J / cm² pressure was used. 2 (For WE25 and WE26) or 2.4 J / cm 2 (For CE1) UV light exposure cured the material. Then, within 72 hours of curing, the resulting silicon wafer with the cured film was placed on the platform of a Triboindenter. Indentation was performed using a diamond indenter (90-degree cubic tip), the shape of which was corrected using standard fused silica. The reduced modulus Er (GPa) was determined by measuring the load P and displacement h (contact depth, in nanometers). The hardness H (GPa) was obtained by dividing the load by the contact area. Both Er and H values ​​were generated using integrated software. The Er value was averaged using an indentation depth of 200 nm with a 5x5 dot array. The thickness of the cured film was greater than 3 μm to eliminate the influence of the substrate. The results are listed in Table 4.

[0277] Table 4

[0278]

[0279] a WE25: Ex6 (60 wt%), Ex8 (40 wt%), 3 wt% Irgacure OXE02, 3 wt% Irgacure 651

[0280] b WE26: Ex6 (50 wt%), Ex7 (50 wt%, 3 wt%) Irgacure OXE02, 3 wt% Irgacure 651

[0281] c +3% wt% Irgacure OXE02 and 3% wt% Irgacure 651.

Claims

1. A curable composition, preferably a photocurable composition, comprising at least a first monomer compound, a second monomer compound, and a polymerization initiator; The first monomer compound is represented by chemical formula (I). -(I) in 1≤x≤5, 0≤y≤4, 0≤z≤5; When n and m are both 0, 3≤x≤5; when m is 1 and n is 0, 3≤x+z≤10; when m is 0 and n is 1, 3≤x+y≤9; when m and n are both 1, 3≤x+z+y≤14. n is 1 or 0, m is 1 or 0, 0≤n+m≤2; L, in each occurrence, is selected from the group consisting of direct bonds, alkylene groups having 1 to 15 carbon atoms, and alkenyl groups having 2 to 15 carbon atoms. One or more non-adjacent CH2 groups in the alkylene or alkenylene group may be replaced by an oxygen atom, C=O, C=S, C=Se, C=NH, SiH2, SO, SO2, OS, or CONH, and one or more H atoms may be replaced by D, F, Cl, Br, I, CN, or NO2. The second monomer compound is represented by the chemical formula (I'); and the first monomer compound is different from the second monomer compound. (I’) in 1≤x≤5, 0≤y≤4, 0≤z≤5; n is 1 or 0, m is 1 or 0, 1≤n+m≤2; L, in each occurrence, is selected from the group consisting of direct bonds, alkylene groups having 1 to 15 carbon atoms, and alkenyl groups having 2 to 15 carbon atoms. One or more non-adjacent CH2 groups in the alkylene or alkenylene group may be replaced by an oxygen atom, C=O, C=S, C=Se, C=NH, SiH2, SO, SO2, OS, or CONH, and one or more H atoms may be replaced by D, F, Cl, Br, I, CN, or NO2.

2. The composition according to claim 1, wherein L is a direct bond, a straight-chain alkylene group having 1 to 5 carbon atoms, or a straight-chain alkenyl group having 2 to 5 carbon atoms. One or more non-adjacent CH2 groups in the alkylene or alkenylene group may be replaced by an oxygen atom, C=O, C=S, C=Se, C=NH, SiH2, SO, SO2, OS, or CONH, and one or more H atoms may be replaced by D, F, Cl, Br, I, CN, or NO2.

3. The composition according to any one of the preceding claims, wherein the total amount of the first monomer compound is in the range of 10% to 99.9% by weight, preferably 50% to 99.9% by weight, more preferably 80% to 99% by weight, based on the total amount of the composition.

4. The composition according to any one of the preceding claims, wherein the total amount of the first monomer compound and the second monomer compound is in the range of 10% by weight to 99.9% by weight, preferably 50% to 99.9% by weight, more preferably 80% to 99% by weight, based on the total amount of the composition.

5. The composition according to any one of the preceding claims, comprising 0 to 10% by weight of acrylate monomer based on the total amount of the composition, preferably in the range of 0 to 5% by weight, more preferably an acrylate-free composition comprising 0% by weight of acrylate monomer.

6. The composition according to any one of the preceding claims, comprising 10% by weight or less of solvent based on the total amount of the composition, preferably in the range of 0 to 10% by weight, more preferably in the range of 0 to 5% by weight, and even more preferably a solvent-free composition comprising 0% by weight of solvent.

7. The composition according to any one of the preceding claims, comprising an additive selected from one or more of the group consisting of surfactants, wetting agents, release agents, oxygen quenchers and stabilizers.

8. The composition according to any one of the preceding claims, wherein the viscosity at 23°C is in the range of 5 to 50 cP.

9. A method for preparing the composition according to any one of claims 1 to 8, comprising at least the step (A); (A) A mixture of at least a first monomer compound of formula (I), a second monomer compound of formula (I'), and a polymerization initiator; -(I) in 1≤x≤5, 0≤y≤4, 0≤z≤5; When n and m are both 0, 3≤x≤5; when m is 1 and n is 0, 3≤x+z≤10; when m is 0 and n is 1, 3≤x+y≤9; when m and n are both 1, 3≤x+z+y≤14. n is 1 or 0, m is 1 or 0, 0≤n+m≤2; L, in each occurrence, is selected from the group consisting of direct bonds, alkylene groups having 1 to 15 carbon atoms, and alkenyl groups having 2 to 15 carbon atoms. One or more non-adjacent CH2 groups in the alkylene or alkenylene group may be replaced by an oxygen atom, C=O, C=S, C=Se, C=NH, SiH2, SO, SO2, OS, or CONH, and one or more H atoms may be replaced by D, F, Cl, Br, I, CN, or NO2. The second monomer compound is represented by the chemical formula (I'); and the first monomer compound is different from the second monomer compound. (I’) in 1≤x≤5, 0≤y≤4, 0≤z≤5; n is 1 or 0, m is 1 or 0, 1≤n+m≤2; L, in each occurrence, is selected from the group consisting of direct bonds, alkylene groups having 1 to 15 carbon atoms, and alkenyl groups having 2 to 15 carbon atoms. One or more non-adjacent CH2 groups in the alkylene or alkenylene group may be replaced by an oxygen atom, C=O, C=S, C=Se, C=NH, SiH2, SO, SO2, OS, or CONH, and one or more H atoms may be replaced by D, F, Cl, Br, I, CN, or NO2.

10. A method for preparing a cured layer, comprising at least the following steps (i a ) and (i b ): (i a The composition of any one of claims 1 to 8 is provided onto a substrate, preferably by printing, more preferably by spin coating or inkjet printing; (i d Optionally, the composition may be brought into contact with the upper substrate; (i b The composition is cured by heating and / or by irradiating it with light to form a cured layer; (i e Optionally, the upper substrate can be removed from the cured layer.

11. The method according to claim 10, further comprising step (i) b The following steps are included (i) c ); (i c Bake the cured layer at a temperature ranging from 180°C to 450°C for a time ranging from 0.5 minutes to 10 minutes.

12. A cured layer, preferably a light-cured layer obtained by the method of any one of the preceding claims, or a light-cured layer obtainable by the method.

13. A cured layer, preferably a light-cured layer formed from the composition of any one of claims 1 to 8.

14. A stack layer comprising a substrate and a cured layer according to claim 12 or 13 covering at least partially over the substrate.

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