Photocurable composition

Abstract

To provide an improved ink-jet adaptive planarization material that provides a planar cured layer having high thermal stability.SOLUTION: A photocurable composition can include a polymerizable material and at least one photoinitiator, wherein the polymerizable material includes at least one multifunctional vinylbenzene monomer in an amount of at least 30 wt -%, based on the total weight of the polymerizable material, and wherein the at least one photoinitiator includes an oxime ester compound. The photocurable composition can be adapted to have a UV shrinkage of 4.0% or less after forming a photocurable layer at 23 °C. and a thermal shrinkage of 3.5% or less after baking the photocurable layer at 350 °C.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to photocurable compositions, and in particular to photocurable compositions suitable for inkjet compatible planarization. [Background technology]

[0002] Inkjet adaptive planarization (IAP) is a process for planarizing the surface of a substrate (e.g., a wafer containing electronic circuits) by jetting droplets of a curable composition onto the surface and directly contacting a planar superstrate with the applied liquid to form a planar liquid layer. The planar liquid layer is typically solidified under exposure to UV light, and after removal of the superstrate, a planar surface is obtained that can be subjected to subsequent processing steps, such as baking, etching, and / or further deposition steps. Improved IAP materials that result in planar cured layers with high thermal stability are needed. Summary of the Invention

[0003] In one embodiment, the photocurable composition can include a polymerizable material and at least one photoinitiator, wherein the polymerizable material includes at least one multifunctional vinylbenzene monomer in an amount of at least 30 wt % based on the total weight of the polymerizable material, and the at least one photoinitiator includes an oxime ester compound, and the photocurable composition is adapted to have a UV shrinkage of 4.0% or less after forming a photocured layer at 23°C.

[0004] In another embodiment, the photocurable composition is adapted to enable the photocurable layer formed from the photocurable composition to have a thermal shrinkage of 3.5% or less after a baking process at 350°C, the baking process comprising baking the photocurable layer on a stainless steel plate at a temperature of 350°C under a N2 atmosphere for 2 minutes.

[0005] In one embodiment, the oxime ester compound can have the structure of formula (1): JPEG2026027400000001.jpg22170R1 is an aromatic ring system or a heteroaromatic ring system, R2 is H or C1-C8 alkyl, and R3 is H or C1-C8 alkyl.

[0006] In certain embodiments, the oxime ester compound can comprise the structure of formula (2). JPEG2026027400000002.jpg32170

[0007] In another embodiment, the oxime ester compound can comprise the structure of formula (3). JPEG2026027400000003.jpg50170

[0008] In one embodiment, the photocurable composition can further comprise at least 0.05 wt % 4-tert-butylcatechol (TBC).

[0009] In other embodiments of the photocurable composition, the amount of the oxime ester compound can be at least 1 wt % and no more than 7 wt %, based on the total weight of the photocurable composition.

[0010] In certain embodiments, the at least one photoinitiator can further include a photoinitiator that is not an oxime ester compound.

[0011] In another embodiment of the photocurable composition, the amount of polymerizable material can be at least 85% by weight, based on the total weight of the photocurable composition.

[0012] In one embodiment, the polyfunctional vinylbenzene monomer can include at least three vinyl groups. In one aspect, the polyfunctional vinylbenzene monomer can be a biphenyl compound containing three vinyl groups.

[0013] In other embodiments of the photocurable composition, the polymerizable material can further include at least one multifunctional acrylate monomer. In one particular aspect, the multifunctional acrylate monomer can include at least one acrylate group and at least one vinyl group.

[0014] In yet another embodiment of the photocurable composition, the total amount of the multifunctional vinylbenzene monomer and the multifunctional acrylate monomer can be at least 85 wt %, based on the total weight of the polymerizable material.

[0015] In a further embodiment, the polymerizable material of the photocurable composition can have a weight percent ratio of the multifunctional acrylate monomer to the multifunctional vinylbenzene monomer that can range from 2:1 to 1:2.

[0016] In a further embodiment, the viscosity of the photocurable composition can be 50 mPa·s or less.

[0017] In one embodiment, a method for forming a photocurable layer on a substrate includes applying a layer of a photocurable composition onto the substrate, the photocurable composition comprising a polymerizable material and at least one photoinitiator, the polymerizable material comprising at least one multifunctional vinylbenzene monomer in an amount of at least 30 wt %, based on the total weight of the polymerizable material, and the at least one photoinitiator comprising an oxime ester compound; contacting the photocurable composition with a template or superstrate; irradiating the photocurable composition with light to form a photocurable layer; and removing the template or superstrate from the photocurable layer.

[0018] In one embodiment of the method, the step of irradiating the photocurable composition may be performed with UV light, and the UV shrinkage rate after the photocurable layer is formed may be 4.0% or less.

[0019] In another aspect of the method, the photocurable layer can have a thermal shrinkage of 3.5% or less after a baking treatment at 350°C, the baking treatment comprising baking the photocurable layer on a stainless steel plate at a temperature of 350°C under a N2 atmosphere for 2 minutes.

[0020] In another embodiment, a method for making an article includes applying a layer of a photocurable composition onto a substrate, the photocurable composition comprising a polymerizable material and at least one photoinitiator, the polymerizable material comprising at least one multifunctional vinylbenzene monomer in an amount of at least 30 wt % based on the total weight of the polymerizable material, and the at least one photoinitiator comprising an oxime ester compound; contacting the photocurable composition with a template or superstrate; irradiating the photocurable composition with light to form a photocurable layer; removing the template or superstrate from the photocurable layer; forming a pattern on the substrate; processing the substrate with the pattern formed in the forming step; and manufacturing an article from the substrate processed in the processing step. DETAILED DESCRIPTION OF THE INVENTION

[0021] The following description is provided to aid in understanding the teachings disclosed herein and focuses on particular implementations and embodiments of the teachings. This focus is provided to help explain the teachings and should not be construed as a limitation on the scope or applicability of the teachings.

[0022] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which this invention belongs. The materials, methods, and examples are illustrative only and are not intended to be limiting. To the extent not described herein, many details regarding specific materials and processing operations are conventional and can be found in textbooks and other sources within imprint and lithography technology.

[0023] As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having," or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus comprising a list of features is not necessarily limited to only those features and may include other features not expressly listed or inherent in such process, method, article, or apparatus.

[0024] As used herein, unless expressly stated to the contrary, "or" refers to an inclusive or, not an exclusive or. For example, a condition A or B is satisfied by any one of: A being true (or existing) and B being false (or not existing), A being false (or not existing) and B being true (or existing), and both A and B being true (or existing).

[0025] Additionally, the use of "a" or "an" is used to describe elements and components described herein. This is used merely for convenience and to give a general sense of the scope of the invention. This specification should be read to include one or at least one, and the singular also includes the plural unless otherwise clearly intended.

[0026] The present disclosure is directed to a photocurable composition comprising a polymerizable material and a photoinitiator, wherein the photoinitiator can comprise an oxime ester compound, and the polymerizable material can comprise a multifunctional vinylbenzene monomer in an amount of at least 30% by weight.

[0027] The photocurable compositions of the present disclosure can have the advantage of being usable in inkjet adaptive planarization (IAP) processes by having low viscosity, low shrinkage during cure, and very high thermal stability.

[0028] In one embodiment, the photocurable composition of the present disclosure can be adapted such that the UV shrinkage after forming a photocured layer at 23°C can be 4.0% or less, or 3.5% or less, or 3.0% or less.

[0029] In another embodiment, a photocured layer formed from the photocurable composition can have a shrinkage of 3.5% or less after baking at 350° C., where the baking comprises baking the photocured layer for 2 minutes on a stainless steel plate having a temperature of 350° C. In further aspects, the linear shrinkage after baking at 350° C. can be 3.0% or less, 2.5% or less, 2.0% or less, 1.5% or less, or 1.0% or less, or 0.5% or less.

[0030] In one embodiment, the oxime ester compound of the photoinitiator can have the structure of formula (1): JPEG2026027400000004.jpg22170R1 is an aromatic ring system or a heteroaromatic ring system, R2 is H or C1-C8 alkyl, and R3 is H or C1-C8 alkyl.

[0031] In certain embodiments, the oxime ester compound may have the structure of formula (2): JPEG2026027400000005.jpg32170

[0032] In another particular embodiment, the oxime ester compound may have the structure of formula (3): JPEG2026027400000006.jpg50170

[0033] In further particular embodiments, the oxime ester can have the structure of formula (4): JPEG2026027400000007.jpg42170

[0034] The amount of the oxime ester compound of the photoinitiator can be at least 1.0 wt%, or at least 1.5 wt%, or at least 2.0 wt%, or at least 2.5 wt%, or at least 3.0 wt%, or at least 3.5 wt%, or at least 4.0 wt%, based on the total weight of the photocurable composition. In another embodiment, the amount of the oxime ester compound can be 10 wt% or less, or 8 wt% or less, or 7 wt% or less, or 6 wt% or less, or 5 wt% or less, or 4 wt% or less, based on the total weight of the photocurable composition. The amount of the oxime ester compound of the photoinitiator can be any value between any of the minimum and maximum numbers listed above.

[0035] In some embodiments, the photoinitiator of the photocurable composition can further include at least one photoinitiator that is not an oxime ester compound.

[0036] The polymerizable material of the photocurable composition can be a major amount of the composition, hi one embodiment, the amount of polymerizable material can be at least 60 wt%, or at least 70 wt%, or at least 80 wt%, or at least 90 wt%, or at least 92 wt%, or at least 95 wt%, based on the total weight of the photocurable composition.

[0037] As used herein, the term polyfunctional vinylbenzene of a polymerizable material refers to a polymerizable monomer containing one or more benzene rings and at least two vinyl groups directly bonded to the one or more benzene rings. In certain embodiments, the polyfunctional vinylbenzene can contain at least three vinyl groups or at least four vinyl groups. In some embodiments, the polyfunctional vinylbenzene monomer can contain two benzene rings and three vinyl groups bonded to the benzene rings. A non-limiting example of such a monomer can be 3,4',5-trivinyl-1,1'biphenyl (3VPH).

[0038] In one embodiment, the amount of multifunctional vinylbenzene monomer can be at least 30% by weight, e.g., at least 35%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, or at least 95% by weight, based on the total weight of the polymerizable material. In another aspect, the amount of multifunctional vinylbenzene monomer can be 98% by weight or less, or 95% by weight or less, or 90% by weight or less, or 80% by weight or less, or 70% by weight or less, or 60% by weight or less, or 50% by weight or less, based on the total weight of the polymerizable material. The amount of multifunctional vinylbenzene monomer can be any value between any of the minimum and maximum numbers listed above.

[0039] In another embodiment, the polymerizable material can further comprise a multifunctional acrylate monomer. In one aspect, the multifunctional acrylate monomer can comprise at least two acrylate groups, or at least three acrylate groups, or at least four acrylate groups. In another aspect, the multifunctional acrylate monomer can comprise at least one acrylate group and at least one vinyl group. As used herein, the term acrylic acid monomer refers to substituted and unsubstituted acrylic acid monomers. Non-limiting examples of substituted acrylate monomers can be C1-C8 alkyl acrylates, such as methacrylate or ethyl acrylate. Furthermore, as used herein, the term "vinyl group" does not refer to a vinyl group that is part of an acrylate group and is itself a functional group.

[0040] In certain embodiments, the multifunctional acrylate monomer can include one acrylate group, two vinyl groups, and an aromatic ring structure, such as one or more benzene rings.

[0041] The amount of multifunctional acrylate monomer can be at least 20 wt%, or at least 30 wt%, or at least 40 wt%, or at least 50 wt%, or at least 60 wt%, based on the total weight of the polymerizable material. In another embodiment, the amount of multifunctional acrylate monomer can be 70 wt% or less, or 60 wt% or less, or 50 wt% or less, based on the total weight of the polymerizable material. The amount of multifunctional acrylate monomer can be any value between any of the minimum and maximum numbers listed above.

[0042] In one embodiment, the polymerizable material can consist essentially of a multifunctional vinylbenzene monomer and a multifunctional acrylate monomer. In certain embodiments, the weight percent ratio of the multifunctional acrylate monomer to the multifunctional vinylbenzene monomer can range from 2:1 to 1:2, or from 1.5:1 to 1:1.5. As used herein, consisting essentially of a multifunctional vinylbenzene monomer and a multifunctional acrylate monomer means that 1% or less by weight of the polymerizable material contains other types of polymerizable monomers, oligomers, or polymers.

[0043] In other embodiments, the polymerizable material can include other types of polymerizable compounds, such as monofunctional monomers, polymerizable oligomers, or polymerizable polymers, in addition to the polyfunctional vinylbenzene monomer and the polyfunctional acrylate monomer. The amount of the other polymerizable compounds can be at least 1 wt. %, or at least 5 wt. %, or at least 10 wt. %, based on the total weight of the polymerizable material. In other embodiments, the amount of the other polymerizable compounds can be 30 wt. % or less, or 20 wt. % or less, or 15 wt. % or less, or 10 wt. % or less.

[0044] In certain embodiments, the photocurable composition may be essentially free of maleimide monomers. Essentially free of maleimide monomers, as used herein, means that 0.5% by weight or less of the polymerizable material may be maleimide monomers. In other embodiments, the photocurable composition may be free of maleimide monomers.

[0045] To stabilize the polyfunctional vinylbenzene monomer in the photocurable composition (to prevent undesired polymerization during storage), a suitable stabilizer can be added to the composition. In one embodiment, the photocurable composition can include 4-tert-butylcatechol (TBC) as a stabilizer in an amount of at least 0.05 wt %, based on the total weight of the photocurable composition. In certain embodiments, the amount of TBC can be at least 0.1 wt %, or at least 0.2 wt %, or at least 0.3 wt %, based on the total weight of the photocurable composition. In other embodiments, the amount of TBC can be 1 wt % or less, or 0.5 wt % or less, or 0.3 wt % or less, or 0.2 wt % or less, based on the total weight of the photocurable composition.

[0046] In some embodiments, the photocurable compositions of the present disclosure may be essentially solvent-free.

[0047] As used herein, unless otherwise indicated, the term "solvent" refers to a compound that can dissolve or disperse polymerizable monomers but does not itself polymerize during photocuring of the photocurable composition. The term "essentially solvent-free" as used herein means that the amount of solvent is 5% by weight or less, based on the total weight of the photocurable composition. In certain embodiments, the amount of solvent can be 3% by weight or less, 2% by weight or less, 1% by weight or less, or the photocurable composition may be solvent-free except for unavoidable impurities.

[0048] In another embodiment, the photocurable composition and the present disclosure can include a solvent in an amount greater than 5 wt. % based on the total weight of the photocurable composition. In certain embodiments, the amount of solvent can be at least 7 wt. %, or at least 10 wt. %, or at least 15 wt. %, or at least 20 wt. %, or at least 25 wt. % based on the total weight of the photocurable composition. In another embodiment, the amount of solvent can be 40 wt. % or less, or 30 wt. % or less, or 20 wt. % or less, or 10 wt. % or less based on the total weight of the photocurable composition.

[0049] In one embodiment, the curable compositions of the present disclosure can have low viscosities, which can enable the use of these compositions in IAP applications. In one aspect, the viscosity of the curable composition at a temperature of 23° C. can be 50 mPa·s or less, e.g., 40 mPa·s or less, or 30 mPa·s or less, 20 mPa·s or less, 15 mPa·s or less, or 10 mPa·s or less. In another aspect, the viscosity can be at least 5 mPa·s, or at least 7 mPa·s. As used herein, all viscosity values ​​refer to viscosities measured at a given temperature using the Brookfield method.

[0050] In a further embodiment, the photocurable composition can contain at least one optional additive, non-limiting examples of which can be a surfactant, a dispersant, a stabilizer, a cosolvent, an initiator, an inhibitor, a dye, or any combination thereof.

[0051] In another embodiment, the present disclosure is directed to a laminate including a substrate and a photocurable layer overlying the substrate, the photocurable layer may be formed from the photocurable composition described above.

[0052] In some embodiments, the laminate can further include one or more layers, such as an adhesive layer, between the substrate and the curable layer.

[0053] The present disclosure is further directed to a method of forming a photocurable layer, which may include applying the above-described photocurable composition onto a substrate, contacting the photocurable composition with a template or superstrate, irradiating the photocurable composition with light to form the photocurable layer, and removing the template or superstrate from the photocurable layer.

[0054] In one embodiment, the light irradiation can be carried out with light having a wavelength of 250 nm to 760 nm, and in a preferred embodiment, the light irradiation can be carried out with light having a wavelength of 300 nm to 450 nm.

[0055] The substrate and solidified (photocured) layer may be subjected to additional processing to form the desired article, for example, by including an etching process to transfer an image corresponding to the pattern in one or both of the solidified layer and / or the patterned layer underlying the solidified layer to the substrate. The substrate may be further subjected to known steps and processes for device (article) fabrication, including, for example, curing, oxidation, layering, deposition, doping, planarization, etching, moldable material removal, dicing, bonding, and packaging. In some embodiments, the substrate may be processed to fabricate multiple articles (devices).

[0056] The hardened layer may further be used as an interlayer insulating film for semiconductor elements such as LSI, system LSI, DRAM, SDRAM, RDRAM, and D-RDRAM, or as a resist film used in semiconductor manufacturing processes.

[0057] As further demonstrated in the examples, it was surprisingly discovered that photocurable compositions containing a specific combination of an oxime ester compound as a photoinitiator and a multifunctional vinylbenzene as part of the polymerizable material are highly suitable for IAP processing. For example, it was possible to balance parameters important for IAP processing, such as low viscosity, UV cure speed, low shrinkage during UV curing to obtain a smooth surface, and high thermal stability to enable downstream processing at temperatures such as 350°C, 400°C, or even 450°C.

[0058] Example The following non-limiting examples illustrate the concepts described herein.

[0059] Example 1

[0060] Preparation of light-curable IAP compositions

[0061] A first set of photocurable compositions was prepared containing 50 parts by weight of 3,3'-divinylbiphenyl (DVBP), 50 parts by weight of m-xylene diacrylate (MXDA), 1 part by weight of nonionic fluorosurfactant FS3100 (Dupont), 0.3 parts by weight of 4-tert-butylcatechol (TBC), and 1 or 2 parts by weight of a photoinitiator. The compositions were varied by using different types and amounts of oxime ester photoinitiators.

[0062] The following oxime ester photoinitiators were used: OXE01 (see Structure 4 above); OXE02 (see Structure 2 above); and OXE03 (see Structure 3 above). Comparative compositions C1 and C2 contain typical photoinitiators that are well known for photocurable compositions compatible with IAP processing and are not oxime esters: Irgacure 819 and 907.

[0063] A summary of the first set of photocurable compositions is shown in Table 1.

[0064] Table 1 JPEG2026027400000008.jpg97170

[0065] A second set of photocurable compositions was prepared by mixing the following components: 40 parts by weight of 3,4',5-trivinyl-1,1'-biphenyl (3VPH), 60 parts by weight of 3,5-divinylbenzyl acrylate (DVBA), 1 part by weight of nonionic fluorosurfactant FS3100 (Dupont), 0.5 parts by weight of TBC, and various types and amounts of photoinitiators. The types of photoinitiators were the same as those in the first set of photocurable compositions, except that Irgacure 907 was also used as a comparative example. The amount of photoinitiator was varied by using 2 parts, 4 parts, and 6 parts by weight of the photoinitiator based on the total weight of the photocurable composition.

[0066] A summary of the second set of photocurable compositions can be seen in Table 2.

[0067] Table 2 JPEG2026027400000009.jpg97170

[0068] A further set of comparative photocurable compositions was prepared by using a combination of 60 wt% MXDA, 35 wt% trimethylolpropane triacrylate, and 1 wt% surfactant FS2000M1 as the polymerizable monomer. As photoinitiators, OXE02 and Irgacure 907 were used in varying amounts of 2 wt% and 4 wt%. A summary of the compositions and test results can be seen in Table 3.

[0069] Table 3 JPEG2026027400000010.jpg49170

[0070] UV shrinkage rate

[0071] The photocurable compositions were cured using an Anton Paar MCR-301 rheometer connected to a UV curing system and heater. Samples were irradiated with a mercury UV lamp with a 365 nm band filter. The light intensity was 38 mW / cm. 2 The UV radiation was performed at room temperature (23°C).

[0072] Before the UV radiation was initiated, the distance between the glass plate and the measuring unit was narrowed to a gap of 0.1 mm. At the onset of UV radiation, the radicals generated by the photoinitiator were consumed by the inhibitors present in the resist, so the storage modulus did not increase until all the inhibitors were gone. This period was recorded as the induction time. The UV radiation exposure was 1 × 10 7 The test was continued until a storage modulus of 1 Pa was obtained.

[0073] The thickness of the photocurable composition layer before curing was 35 microns, and shrinkage was observed by tracking the change in thickness of the layer during UV curing. The UV shrinkage, also referred to herein as linear shrinkage, is S UV =(T p -T c ) / Tp Percent UV shrinkage (S) according to the formula UV [%]) and T p is the thickness of the liquid film of the photocurable composition before UV curing, and T c After hardening (1×10 7 is the thickness of the photocured film (when a storage modulus of 1000 Pa is reached).

[0074] As can be seen specifically for the photocurable compositions in Tables 1 and 2, the compositions made with photoinitiators OXE01, OXE02, and OXE03 all exhibited lower shrinkage during UV curing than the comparative compositions (C1-C8) using photoinitiators Irgacure 819 or Irgacure 907 at all photoinitiator concentrations.

[0075] It was further observed that comparative compositions C9, C10, and C11 (see Table 3), which do not contain a multifunctional vinyl monomer in combination with a multifunctional acrylate monomer, but do contain a combination of the difunctional acrylate MXDA and a trifunctional acrylate monomer, did not have the desired low UV shrinkage; the UV shrinkage of these samples was greater than 4.5%.

[0076] Induction time and hardening speed

[0077] Further comparisons shown in Tables 1 and 2 show the induction time (the time until the increase in storage modulus is measured) and the cure time (1 × 10 7 In particular, photocurable compositions containing the oxime ester photoinitiators OXE01 and OXE02 exhibited induction and cure times (1×10 7 It can be seen that the storage modulus (storage modulus) of the composition containing the photoinitiators Irgacure 819 and Irgacure 907 was comparable to that of the composition containing the photoinitiators Irgacure 819 and Irgacure 907.

[0078] Heat shrinkage rate

[0079] The heat shrinkage was determined according to the following procedure.

[0080] A UV-cured layer was prepared by first depositing a 500 nm thick liquid film of the photocurable composition onto a blank fused silica template. Measurements were performed using an AntonPaar MCR-301 rheometer coupled to the Hamamatsu Lightningcure LC8 UV power source described above. The liquid film was irradiated at 365 nm for 263 seconds at 38 mW / cm. 2 The light intensity is 10 J / cm 2 This corresponds to a curing energy dose of 1000 kJ / cm.

[0081] The photocured film was subjected to a high-temperature baking treatment by placing the UV-cured film on a hot plate at a temperature of 350°C under nitrogen for 2 minutes. The film thickness before and after baking was measured using a JA Woollam Spectroscopic Ellipsometer M-2000 X-210. The thermal shrinkage (St) was calculated using the formula: St = (T u -T b ) / T u is calculated according to T u is the thickness of the photocured film before baking, and T b is the thickness of the film after baking.

[0082] The measured heat shrinkage values ​​are summarized in Tables 1, 2, and 3. Notably, it can be seen that the second set of photocurable compositions summarized in Table 2 had very low heat shrinkage of less than 3% when photoinitiators OXE02 or OXE03 were used. However, photoinitiator OXE02 was unable to achieve a heat shrinkage of less than 4.5 percent when the monomer combination did not include a trifunctional vinyl monomer but instead included a trifunctional acrylate monomer (see C9, C10, and C11 in Table 3). However, the heat shrinkage values ​​using photoinitiator OXE02 in this set of experiments were also lower compared to using photoinitiator Irgacure 907.

[0083] The best results were obtained with the combination of a three-vinyl-group biphenyl-benzene monomer (3VPH) and the oxime photoinitiators OXE02 or OXE03, with thermal shrinkage consistently below 3 percent. Without wishing to be bound by theory, the advantages of the OXE02 and OXE03 oxime ester photoinitiators may be due to the formation of CO2 and CH3- radicals during photocuring. The small CH3 radicals can migrate into the formed polymer network and reach unreacted C=C groups hidden within the network. The released CO2 can trigger the formation of subnanopores, which may help prevent the polymer network from collapsing before it is fully solidified.

[0084] viscosity

[0085] The viscosity of the photocurable compositions was measured using a Brookfield Viscometer LVDV-II + Pro at 200 rpm with a spindle size of #18 and a spin speed of 135 rpm. For viscosity tests, approximately 6-7 mL of sample liquid, sufficient to cover the spindle head, was dispensed into the sample chamber. The sample contained within the chamber was allowed to equilibrate for approximately 20 minutes to reach the desired measurement temperature of 23°C before the actual measurement began. For all viscosity tests, at least three measurements were taken, and an average value was calculated.

[0086] The specification and drawings of the embodiments described herein are intended to provide a general understanding of the structures of various embodiments. The specification and drawings do not provide an exhaustive or comprehensive description of all of the elements and features of apparatus and systems that use the structures or methods described herein. Separate embodiments may also be provided in combination in a single embodiment, and conversely, various features that are described for brevity in the context of a single embodiment may also be provided separately or in any subcombination. Furthermore, references to values ​​described in ranges include each and every value within that range. Many other embodiments may be apparent to those skilled in the art only after reading this specification. Other embodiments may be utilized and derived from the present disclosure, such that structural substitutions, logical substitutions, or other changes may be made without departing from the scope of the present disclosure. Accordingly, the present disclosure should be considered illustrative and not restrictive.

Claims

1. 1. A photocurable composition comprising a polymerizable material and at least one photoinitiator, the polymerizable material comprises at least one multifunctional vinylbenzene monomer in an amount of at least 30 wt %, based on the total weight of the polymerizable material; the at least one photoinitiator comprises an oxime ester compound; The photocurable composition is adapted to have a UV shrinkage of 4.0% or less after forming a photocured layer at 23°C.

2. 2. The photocurable composition of claim 1, wherein the photocurable composition is adapted so that the photocured layer formed from the photocurable composition has a thermal shrinkage of 3.5% or less after baking at 350°C, and the baking comprises baking the photocured layer on a stainless steel plate at 350°C in an N2 atmosphere for 2 minutes.

3. The oxime ester compound has a structure of formula (1): R １ is an aromatic or heteroaromatic ring system, and R ２ is H or C １ -C ８ alkyl, and R ３ is H or C １ -C ８ The photocurable composition of claim 1 wherein the alkyl is alkyl.

4. The oxime ester compound comprises a structure of formula (2): The photocurable composition according to claim 3 .

5. The oxime ester compound comprises a structure of formula (3): The photocurable composition according to claim 3 .

6. The photocurable composition of claim 1 further comprising at least 0.05 wt. % 4-tert-butylcatechol (TBC).

7. 10. The photocurable composition of claim 1, wherein the amount of the oxime ester compound is at least 1 wt% and no more than 7 wt%, based on the total weight of the photocurable composition.

8. 10. The photocurable composition of claim 1, wherein the at least one photoinitiator further comprises a photoinitiator that is not an oxime ester compound.

9. The photocurable composition of claim 1 , wherein the amount of polymerizable material is at least 85% by weight, based on the total weight of the photocurable composition.

10. The photocurable composition of claim 1 , wherein the multifunctional vinylbenzene monomer comprises at least three vinyl groups.

11. 11. The photocurable composition of claim 10, wherein the multifunctional vinylbenzene monomer is a biphenyl compound containing three vinyl groups.

12. The photocurable composition of claim 1 , wherein the polymerizable material further comprises at least one multifunctional acrylate monomer.

13. The photocurable composition of claim 12, wherein the multifunctional acrylate monomer comprises at least one acrylate group and at least one vinyl group.

14. 13. The photocurable composition of claim 12, wherein the total amount of the multifunctional vinylbenzene monomer and the multifunctional acrylate monomer is at least 85% by weight, based on the total weight of the polymerizable material.

15. 13. The photocurable composition of claim 12, wherein the weight percent ratio of said multifunctional acrylate monomer to said multifunctional vinylbenzene monomer ranges from 2:1 to 1:

2.

16. The photocurable composition according to claim 1 , wherein the photocurable composition has a viscosity of 50 mPa·s or less.

17. 1. A method for forming a photocurable layer on a substrate, comprising: applying a layer of a photocurable composition onto the substrate, the photocurable composition comprising a polymerizable material and at least one photoinitiator, the polymerizable material comprising at least one multifunctional vinylbenzene monomer in an amount of at least 30 wt % based on the total weight of the polymerizable material, and the at least one photoinitiator comprising an oxime ester compound; contacting the photocurable composition with a template or superstrate; a step of irradiating the photocurable composition with light to form a photocured layer; removing the template or the superstrate from the photocurable layer; A method comprising:

18. The method of claim 17, wherein the step of irradiating the photocurable composition is performed with UV light, and the UV shrinkage rate after forming the photocured layer is 4.0% or less.

19. The photocurable layer has a thermal shrinkage of 3.5% or less after baking at 350°C, and the baking is performed on a stainless steel plate at a temperature of 350°C. ２ 18. The method of claim 17, comprising baking the photocurable layer under ambient conditions for 2 minutes.

20. 1. A method for manufacturing an article, comprising: applying a layer of a photocurable composition onto a substrate, the photocurable composition comprising a polymerizable material and at least one photoinitiator, the polymerizable material comprising at least one multifunctional vinylbenzene monomer in an amount of at least 30 wt % based on the total weight of the polymerizable material, and the at least one photoinitiator comprising an oxime ester compound; contacting the photocurable composition with a template or superstrate; a step of irradiating the photocurable composition with light to form a photocured layer; removing the template or the superstrate from the photocurable layer; forming a pattern on the substrate; a step of processing the substrate on which the pattern has been formed in the forming step; manufacturing an article from the substrate processed in the processing step; A method for manufacturing an article, comprising:

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