Photocurable composition

Abstract

In one embodiment, the photocurable composition may include a polymerizable material and a photopolymerization initiator, and when R1 includes a carbon-carbon double bond and R2 is a substituted or unsubstituted alkyl, aryl, or alkylaryl, the polymerizable material includes an isocyanate group-containing compound of formula (1): R1-R2-N=C=O(1). An amount of 1wt% to 10wt% of the isocyanate group-containing compound causes strong adhesion strength of the photocurable composition to the silicon substrate after curing, and an adhesion layer between the substrate and the photocurable layer can be omitted.

Description

[Technical field]

[0001] The present disclosure relates to photocurable compositions adapted for use in nanoimprint lithography (NIL) or inkjet adaptive planarization (IAP) processes. The photocurable compositions include a polymerizable material that includes an isocyanate group-containing compound. [Background technology]

[0002] Inkjet adaptive planarization (IAP) uses a flowable liquid (resist) to fill trenches, gaps, or other topographical variations on a substrate. The applied liquid resist is then contacted by a superstrate and cured under the superstrate to form a planar layer. In nanoimprint lithography (NIL), a template is filled with liquid resist, and after curing and further processing, the pattern of the template is transferred to the underlying substrate. During IAP and NIL processing, an adhesion layer is typically applied between the substrate and the resist to enhance adhesion of the resist to the substrate.

[0003] There is a need to develop a photocurable composition that can be directly applied onto a substrate and has strong adhesion to the substrate, so that no adhesion layer is required between the substrate and the resist. If the adhesion layer between the substrate and the resist can be omitted, processing time and costs can be reduced, and product quality can be further improved. Summary of the Invention

[0004] In one embodiment, the photocurable composition may include a polymerizable material and a photopolymerization initiator, the polymerizable material including at least one first monomer and at least one second monomer, where R1 includes a carbon-carbon double bond and R2 is a substituted or unsubstituted alkyl, aryl, or alkylaryl, the at least one first monomer includes an isocyanate group-containing compound of formula (1): R1-R2-N=C=O(1), and the amount of the isocyanate group-containing compound may be 1 wt% or more and 10 wt% or less based on the total weight of the photocurable composition.

[0005] In one embodiment of the photocurable resin, R1 in formula (1) above may be selected from an acrylate group, a methacrylate group, or a vinyl group.

[0006] In another embodiment, R2 in formula (1) is phenyl, or C1-C 10 It may be alkyl, or (C1-C6-alkyl)phenyl.

[0007] In certain embodiments of the photocurable composition, the isocyanate group-containing compound of formula (1) may be selected from 2-isocyanatoethyl acrylate, 3-isopropenyl-α,α-dimethylbenzyl isocyanate, 2-isocyanatoethyl methacrylate, allyl isocyanate, or any combination thereof.

[0008] In a particular embodiment, the isocyanate group-containing compound may be selected from 2-isocyanatoethyl acrylate or 3-isopropenyl-α,α-dimethylbenzyl isocyanate.

[0009] In a further embodiment of the photocurable composition, the amount of the polymerizable material can be 90 wt % or more, based on the total weight of the photocurable composition.

[0010] In another embodiment of the photocurable composition, the at least one second monomer of the polymerizable material can include an acrylate monomer, a maleimide monomer, an epoxide monomer, or a vinyl benzene.

[0011] In yet another embodiment, the at least one second monomer of the photocurable composition can include at least one monofunctional acrylate monomer and at least one multifunctional acrylate monomer. In certain embodiments, the amount of the multifunctional acrylate monomer can be 20 wt% or more, based on the total weight of the photocurable composition. In certain embodiments, the amount of the multifunctional acrylate monomer can be 40 wt% or more, based on the total weight of the photocurable composition.

[0012] In another embodiment, the viscosity of the photocurable composition at 23° C. can be 30 mPa·s or less. In a particular embodiment, the viscosity of the curable composition at 23° C. can be 15 mPa·s or less.

[0013] In a further embodiment, the photocurable composition may be essentially free of solvent.

[0014] In one embodiment, a laminate includes a substrate and a photocurable layer directly overlying the substrate, the photocurable layer being formed from the photocurable composition of claim 1 .

[0015] In one embodiment of the laminate, the adhesion strength of the photocurable layer according to ASTM D 4541 may be 6.5 MPa or more.

[0016] In another embodiment, a method of forming a photocurable layer on a substrate may include directly applying a layer of a photocurable composition onto the substrate, the photocurable composition comprising a polymerizable material and a photoinitiator, the polymerizable material comprising at least one first monomer and at least one second monomer, the at least one first monomer comprising from 1 wt % to 10 wt % of an isocyanate group-containing compound of formula (1): R1-R2-N=C=O(1), where R1 comprises a carbon-carbon double bond and R2 is a substituted or unsubstituted alkyl, aryl, or alkylaryl, contacting the photocurable composition with an imprint template or superstrate, irradiating the photocurable composition with light to form a photocurable layer, and removing the imprint template or superstrate from the photocurable layer.

[0017] In one embodiment of the method, the isocyanate group-containing compound of formula (1) may be selected from 2-isocyanatoethyl acrylate, 3-isopropenyl-α,α-dimethylbenzyl isocyanate, 2-isocyanatoethyl methacrylate, allyl isocyanate, or any combination thereof.

[0018] In another aspect of the method, the at least one second monomer of the polymerizable material can include at least one monofunctional acrylate monomer and at least one multifunctional acrylate monomer.

[0019] In a further embodiment of the method, the amount of the polymerizable material can be 90 wt % or more, based on the total weight of the curable composition.

[0020] In another embodiment, a method of manufacturing an article may include applying a layer of a photocurable composition onto a substrate, the photocurable composition comprising a polymerizable material and a photoinitiator, the polymerizable material comprising at least one first monomer and at least one second monomer, wherein R1 comprises a carbon-carbon double bond and R2 is a substituted or unsubstituted alkyl, aryl, or alkylaryl, the at least one first monomer comprising from 1 wt % to 10 wt % of an isocyanate group-containing compound of formula (1): R1-R2-N=C=O (1), contacting the photocurable composition with an imprint template or superstrate, irradiating the photocurable composition with light to form an at least partially photocured layer, removing the imprint template or superstrate from the at least partially photocured layer, forming a pattern on the substrate, treating the substrate having the pattern formed in the forming step, and manufacturing an article from the substrate treated in the treating step. [Brief description of the drawings]

[0021] Embodiments are illustrated by way of example and not limitation in the accompanying figures.

[0022] [Figure 1] FIG. 1 includes a diagram illustrating a laminate according to one embodiment. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0023] The following description is provided to aid in understanding the teachings disclosed herein and focuses on specific 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.

[0024] 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 imprint and lithography technology textbooks and other sources.

[0025] As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having," or any other variations thereof, are intended to cover non-exclusive inclusion. For example, a process, method, article, or apparatus that includes a list of features is not necessarily limited to only those features and may include other features that are not expressly recited or that are inherent to such process, method, article, or apparatus.

[0026] As used herein, and unless expressly stated to the contrary, "or" refers to an inclusive OR and not to an exclusive OR. For example, a condition A or B is satisfied by one of: A is true (or present) and B is false (or absent), A is false (or absent) and B is true (or present), and both A and B are true (or present).

[0027] Additionally, the use of "a" or "an" is used to describe elements and components described herein. This is used merely for convenience to give a general sense of the scope of the invention. The specification should be read to include one or at least one, and the singular also includes the plural, unless it is clear that no plural is intended.

[0028] The present disclosure relates to a photocurable composition including a polymerizable material and a photopolymerization initiator, and the polymerizable material may include at least one first monomer and at least one second monomer. When R1 includes a carbon-carbon double bond and R2 is a substituted or unsubstituted alkyl, aryl, or alkylaryl, the at least one first monomer includes an isocyanate group-containing compound of formula (1): R1-R2-N=C=O(1). Also, the amount of the isocyanate group-containing compound may be 1 wt% or more and 10 wt% or less based on the total weight of the photocurable composition.

[0029] In one embodiment, R1 of formula (1) may be selected from an acrylate group, a methacrylate group, or a vinyl group. In a further embodiment, R2 of formula (1) may be selected from phenyl, or C1-C 10 alkyl, or (C1-C6 alkyl)-phenyl. As used herein, the term "alkyl" can include straight or branched chain alkyl structures.

[0030] In further embodiments, the isocyanate group-containing compound of formula (1) can be a small molecule having a molecular weight of 1000 g / mol or less, such as 500 g / mol or less, 400 g / mol or less, 300 g / mol or less, or 200 g / mol or less.

[0031] In one embodiment, the isocyanate group-containing compound of formula (1) is i) 2-Isocyanatoethyl acrylate (ICA): TIFF2024516479000002.tif3596; ii) 3-Isopropenyl-α,α-dimethylbenzyl isocyanate (IDI): TIFF2024516479000003.tif8382; iii) 2-Isocyanatoethyl methacrylate (ICM): TIFF2024516479000004.tif7765; iv) Allyl Isocyanate (AIC): TIFF2024516479000005.tif2370; or any combination thereof, can be selected from:

[0032] In one particular embodiment, the isocyanate group-containing compound can be 2-isocyanatoethyl acrylate (ICA). In another particular embodiment, the isocyanate group-containing compound can be 3-isopropenyl-α,α-dimethylbenzyl isocyanate (IDI).

[0033] The at least one second monomer of the polymerizable material may be different from the at least one first monomer and may be polymerized together with the at least one first monomer. Non-limiting examples of the at least one second monomer may be an acrylate monomer, a maleimide monomer, an epoxide monomer, a vinyl benzene (e.g., divinyl benzene), or any combination thereof.

[0034] In certain embodiments, the at least one second monomer may include at least one acrylate monomer. In one embodiment, the at least one acrylate monomer may be a combination of at least one monofunctional acrylate monomer and at least one multifunctional acrylate monomer. As used herein, the term acrylate monomer refers to any monomer structure that includes an acrylate unit or a substituted acrylate unit, such as a methacrylate unit.

[0035] The amount of monofunctional acrylate monomer can be 20 wt% or more, or 30 wt% or more, or 40 wt% or more, or 50 wt% or more, based on the total weight of the photocurable composition. In another embodiment, the amount of monofunctional acrylate monomer can be 70 wt% or less, or 60 wt% or less, or 50 wt% or less, or 45 wt% or less.

[0036] In some embodiments, the multifunctional acrylate monomer can be a difunctional acrylate monomer. In other embodiments, the multifunctional acrylate monomer can be a trifunctional or tetrafunctional acrylate monomer. The amount of the multifunctional acrylate monomer can be 10 wt% or more, or 15 wt% or more, or 20 wt% or more, or 30 wt% or more, or 40 wt% or more, or 50 wt% or more, based on the total weight of the photocurable composition. In other embodiments, the amount of the multifunctional acrylate monomer can be 70 wt% or less, or 60 wt% or less, or 50 wt% or less, or 40 wt% or less.

[0037] In certain embodiments, the polymerizable material can include at least two monofunctional acrylate monomers and at least one difunctional acrylate monomer.

[0038] Non-limiting examples of acrylate monomers can be benzyl acrylate (BA), 1-naphthyl acrylate (1-NA), isobornyl acrylate (IBOA), benzyl methacrylate (BMA), 1-naphthyl methacrylate (1-NMA), tetrahydrofurfuryl acrylate, isobornyl acrylate (IBOA), dicyclopentanyl acrylate, pentafluorobenzyl acrylate, 1-adamantyl methacrylate, 2-adamantyl acrylate, trimethylcyclohexyl acrylate, or neopentyl glycol diacrylate, or bisphenol A dimethacrylate (BPADMA).

[0039] In further embodiments, the amount of polymerizable material contained in the photocurable composition can be 60 wt% or more, for example, 70 wt% or more, 80 wt% or more, 85 wt% or more, 90 wt% or more, or 95 wt% or more, based on the total weight of the photocurable composition. In another embodiment, the amount of polymerizable material can be 99.5 wt% or less, for example, 99 wt% or less, or 98 wt% or less, or 97 wt% or less, or 95 wt% or less, or 93 wt% or less, or 90 wt% or less. Furthermore, the amount of polymerizable material can be within a range including any of the minimum and maximum values ​​above. In a particular embodiment, the amount of polymerizable material can be 85 wt% or more and 98 wt% or less, based on the total weight of the photocurable composition.

[0040] In a further aspect, the photocurable composition of the present disclosure may be solvent-free. As used herein, unless otherwise indicated, the term "solvent" refers to a liquid compound in which a polymerizable material can be dissolved, but which is not itself polymerizable.

[0041] In one embodiment, the monomers contained in the polymerizable material may be selected to obtain a low viscosity of the curable composition before curing. In one embodiment, the viscosity of the photocurable composition may be 30 mPa·s or less, or 25 mPa·s or less, or 20 mPa·s or less, or 15 mPa·s or less, or 12 mPa·s or less, or 10 mPa·s or less, or 8 mPa·s or less. In another embodiment, the viscosity may be 2 mPa·s or more, such as 3 mPa·s or more, or 4 mPa·s or more, or 5 mPa·s or more. In a particular embodiment, the curable composition may have a viscosity of 10 mPa·s or less. As used herein, all viscosity values ​​refer to viscosities measured at a temperature of 23° C. using the Brookfield method.

[0042] One or more photoinitiators may be included in the photocurable composition to initiate photocuring of the composition when exposed to light.

[0043] In another particular embodiment, the curing can be done by a combination of light curing and heat curing, with an additional heat cure to improve thermal stability. In one particular embodiment, the heat cure after the light initiated cure can be done at a temperature between 60°C and 250°C. In a particular embodiment, the heat cure can be done at 190°C to 230°C.

[0044] In further embodiments, the photocurable composition may contain at least one optional additive. Non-limiting examples of the optional additive may be a surfactant, a dispersant, a stabilizer, a co-solvent, an initiator, an inhibitor, a dye, or any combination thereof.

[0045] Surprisingly, it has been found that by selecting a specific combination of the isocyanate group-containing compound of formula (1) and at least one second monomer, a photocurable composition can be made that can have strong adhesion to the underlying substrate after curing without the presence of an adhesion layer, and can be used for IAP or NIL processing. Without being bound by theory, it is hypothesized that the isocyanate group of the isocyanate group-containing compound can react with functional groups, such as hydroxyl groups, amine groups, or carboxyl groups, contained in the surface of the substrate, thereby forming covalent bonds that contribute to the strong adhesion strength of the photocurable layer to the substrate. Furthermore, the isocyanate group-containing compound can participate in polymerization and crosslinking reactions through carbon-carbon double bonds during photocuring, and can be covalently incorporated into the polymer matrix formed during photocuring.

[0046] In one embodiment, the photocurable layer formed from the photocurable composition of the present disclosure is part of a laminate (10), which may include a substrate (11) and a photocurable layer (12) directly overlying the substrate (11) (see FIG. 1).

[0047] There is no limitation on the material of the substrate of the laminate. Non-limiting examples of the substrate can be ceramic, silicon, metal, metal alloy, polycarbonate, or organic polymers such as polyimide, polyurethane, PTFE, PVDF, or polyamide.

[0048] In one embodiment, the adhesion strength (also referred to herein as peel strength) of the photocured layer to the silicon substrate at 23° C. according to ASTM D 4541 can be 6.5 MPa or more, e.g., 7.0 MPa or more, 7.5 MPa or more, 8.0 MPa or more, or 8.5 MPa or more. In another embodiment, the adhesion strength can be 20 MPa or less, e.g., 15 MPa or less, or 10 MPa or less. Without being bound by theory, it is hypothesized that the outer surface of the silicon substrate contains a thin silicon oxide layer that generates hydroxyl groups when exposed to moisture in the air, and that the isocyanate groups of the isocyanate group-containing compound react with the hydroxyl groups on the substrate surface to form covalent bonds.

[0049] In certain embodiments, the photocurable compositions of the present disclosure are adapted to be liquid resist compositions for use in IAP and NIL processes to form photocured resist layers.

[0050] The present disclosure further relates to a method of forming a photocurable layer, which may include applying the above-described photocurable composition directly to an outer surface of a substrate, contacting the photocurable composition with a superstrate, irradiating the photocurable composition with light to form a photocurable layer, and removing the superstrate from the photocurable layer. As used herein, the term photocurable layer refers to the photocurable composition being converted from a liquid stage to a solid stage, where solid stage refers to the photocurable composition being at least partially cured or fully cured.

[0051] In one embodiment, the light irradiation may be performed with light having a wavelength of 250 nm to 760 nm. In a preferred embodiment, the light irradiation may be performed with light having a wavelength of 320 nm to 450 nm.

[0052] The substrate and solidified (cured) layer may be subjected to additional processing to form a 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) manufacturing, including, for example, curing, oxidation, layering, deposition, doping, planarization, etching, formable material removal, dicing, bonding, and packaging. In some embodiments, the substrate may be processed to manufacture multiple articles (devices).

[0053] The hardened layer may further be used as an interlayer insulating film for semiconductor devices such as LSI, system LSI, DRAM, SDRAM, RDRAM, and D-RDRAM, or may be used as a resist film used in the semiconductor manufacturing process.

[0054] example

[0055] The following non-limiting examples illustrate the concepts described herein.

[0056] Example 1

[0057] Preparation of photocurable resist composition

[0058] A photocurable base composition was prepared containing the following components: 10 wt% isobornyl acrylate (IBOA), 35 wt% benzyl acrylate (BA), 50 wt% neopentyl glycol diacrylate (SR247), 2 wt% photoinitiator Irgacure® TPO 4265, BASF (diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide), and 3 wt% photoinitiator Irgacure® 4265, BASF (50:50 blend of 2-hydroxy-2-methyl-1-phenyl-1-propanone and diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide). All wt% amounts are relative to the total weight of the photocurable base composition. The photocurable base composition is referred to in the following sample C2.

[0059] Various photocurable compositions (S1-S6) were prepared by adding an isocyanate group-containing compound to the base composition in an amount of 1 wt%-10 wt%, based on the total weight of the photocurable composition. As the isocyanate group-containing compound, 2-isocyanatoethyl acrylate and 3-isopropenyl-α,α-dimethylbenzyl isocyanate were used, both of which contain carbon-carbon double bonds as either acrylate or vinyl groups in addition to isocyanate groups.

[0060] A summary of all photocurable compositions is given in Table 1.

[0061] [Table 1]

[0062] A comparative photocurable composition (C1) was prepared by adding 3-chlorophenyl isocyanate, a compound that contains an isocyanate group but no carbon-carbon double bond, to the base composition.

[0063] It can be seen that the addition of the selected isocyanate group-containing compounds to the photocurable base composition did not result in an increase in viscosity, even when the isocyanate group-containing compounds were added in an amount of 10 wt %. All samples had viscosities below 10 mPa·s and were suitable for NIL or IAP processing.

[0064] Preparation of laminates and adhesion strength test

[0065] To measure the adhesion strength of the photocurable resist to the silicon wafer, the following assembly was constructed and tested.

[0066] Virgin grade silicon wafers (double-sided polished, Advantive Technologies) with a size of 200 mm in diameter were cut into square pieces of 25 mm x 25 mm. 2 μl of liquid resist sample was dropped by pipette onto the center of the silicon wafer pieces of 25 mm x 25 mm size, and a glass rod with a diameter of 5 mm and a length of 10 mm was placed at one end in the liquid resist and oriented in a length direction (z) perpendicular to the wafer surface (xy). The glass rod contained a solid adhesion layer coating made from TranSpin BT20-10 (see also U.S. Patent Application Publication No. 2007 / 0212494). The adhesion layer of the glass rod was selected to ensure a stronger adhesion strength of the glass rod to the photocurable resist than that of the photocurable resist to the silicon wafer.

[0067] At room temperature (23°C), 16mW / cm 2 The liquid resist placed on the silicon wafer was photocured by exposing it to ultraviolet light of 1000 nm for 18.8 seconds, which corresponds to a curing energy of 300 mJ.

[0068] After light curing, an aluminum plate was attached to the backside (uncoated side of the wafer) of the silicon wafer using an epoxy adhesive (Gorilla Epoxy Adhesive Clear from Gorilla Glue Company, not shown). The aluminum plate had a size of 25 mm x 50 mm and a thickness of 1 / 8 inch, and covered the finished silicon wafer. The epoxy adhesive was selected such that the adhesion strength of the aluminum plate to the silicon wafer was stronger than the adhesion strength of the photocured resist layer to the silicon wafer.

[0069] The actual adhesion test (pull-off strength measurement) was performed according to ASTM D 4541 using an Instron Model 5542 tensile tester. A silicon wafer containing a glass rod attached to an aluminum plate and fixed at one end to a silicon substrate via a light-cured resist was placed in a fixed position in the tensile tester. The moving head from the Instron tensile tester was adjusted so that it moved towards the glass rod at a rate of 0.5 mm per minute and on its side hit the glass rod 1.5 mm away from the end of the glass rod attached to the resist, and the force was recorded, whereupon the glass rod with the attached resist layer was separated from the silicon substrate. The adhesion strength (i.e., the pull-off strength of the resist to the silicon wafer) was measured in pounds and expressed as pounds / mm. 2 (19.62 mm at the end of the glass rod) 2 The force required to pull the resist layer away from the silicon wafer via the glass rod was measured, where the weakest interface was the interface between the silicon wafer and the cured resist layer, and the force required to pull the resist layer away from the silicon wafer via the glass rod was measured.

[0070] For each sample, the test was repeated eight times and the average value was calculated.

[0071] As a further comparative sample (C3), a silicon substrate was used containing an adhesion promoter layer coated with the above-mentioned photocurable base composition consisting of acryloxymethyltrimethoxysilane and not containing an isocyanate group-containing compound.

[0072] A summary of the results of the adhesion strength test is also shown in Table 1. It can be seen that the base composition (C2) applied directly onto the silicon wafer without an adhesion layer between the silicon substrate and the base layer had almost no adhesion. When only 1 wt% of the isocyanate group-containing compound 2-isocyanatoethyl acrylate (ICA) (see S1) or 3-isopropenyl-α,α-dimethylbenzyl isocyanate (IDI) (see S4) was added, the adhesion strength increased significantly, such as from 0.95 MPa (C2) to 8.1 MPa (S1) and from 0.95 MPa (C2) to 7.0 MPa (S4). When the amount of the isocyanate group-containing compound was further increased from 1 wt% to 10 wt%, the adhesion strength of compound ICA further increased from 8.1 MPa (S1) to 8.96 MPa (S3), whereas only a slight further increase in the pull-off strength from 7.0 MPa (S4) to 7.37 MPa (S6) was observed for compound IDI.

[0073] When an isocyanate group-containing compound containing only isocyanate groups and no carbon-carbon double bonds (see C1) was added to the base composition, a certain increase in peel strength was observed compared to the photocured base composition (C2), but the peel strength was much lower than the peel strength required to remove a photocured layer made with a composition containing an isocyanate group-containing compound containing a carbon-carbon double bond and corresponding to formula (1) above. The adhesion strength of the photocured samples S1 to S6 was comparable to the adhesion strength obtained when the base composition was attached to a substrate with a typical adhesion layer (see comparative sample C3).

[0074] The results of the adhesion strength test show that by directly adding an isocyanate group-containing compound corresponding to formula (1) to the photocurable resist composition, it is possible to obtain approximately the same adhesion strength (measured as pull-off strength) as when an additional adhesion layer is used. The experimental data demonstrates that the photocurable composition of the present disclosure is suitable for use in NIL or IAP processing without the inclusion of an additional adhesion layer.

[0075] The viscosity of the samples was measured using a Brookfield Viscometer LVDV-II+ Pro at 200 rpm, spindle size #18, and 23°C. For the viscosity tests, approximately 6-7 mL of sample liquid was added to the sample chamber, enough to cover the spindle head. For all viscosity tests, at least three measurements were taken and the average value was calculated.

[0076] The specification and description of the embodiments described herein are intended to provide a general understanding of the structure of the various embodiments. The specification and description are not intended to be exhaustive and comprehensive in describing all of the elements and features of the apparatus and systems that use the structures or methods described herein. Other embodiments may be provided in combination with other embodiments in a single embodiment, and conversely, for brevity, various features described in the context of a single embodiment may 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 used and derived from this disclosure, such that structural substitutions, logical substitutions, or other changes may be made without departing from the scope of this disclosure. Thus, this disclosure should be considered illustrative and not limiting.

Claims

1. A photocurable composition comprising a polymerizable material and a photopolymerization initiator, The polymerizable material includes at least one first monomer and at least one second monomer, R 1 contains a carbon-carbon double bond, and R 2 R is a substituted or unsubstituted alkyl, aryl, or alkylaryl, the at least one first monomer having the formula (1): 1 -R 2 -Contains an isocyanate group-containing compound of N=C=O(1), The amount of the isocyanate group-containing compound is 1 wt % or more and 10 wt % or less based on the total weight of the photocurable composition. A photocurable composition comprising:

2. R in the above formula (1) 1 2. The photocurable composition of claim 1, wherein is selected from an acrylate group, a methacrylate group, or a vinyl group.

3. R 2 is phenyl, or C 1 -C 10 Alkyl, or C 1 -C 6 2. The photocurable composition of claim 1, wherein the alkyl group is alkyl-phenyl.

4. 2. The photocurable composition of claim 1, wherein the isocyanate group-containing compound of formula (1) is selected from 2-isocyanatoethyl acrylate, 3-isopropenyl-α,α-dimethylbenzyl isocyanate, 2-isocyanatoethyl methacrylate, allyl isocyanate, or any combination thereof.

5. 2. The photocurable composition according to claim 1, wherein the isocyanate group-containing compound of formula (1) is selected from 2-isocyanatoethyl acrylate or 3-isopropenyl-α,α-dimethylbenzyl isocyanate.

6. 2. The photocurable composition of claim 1, wherein the amount of the polymerizable material is 90 wt % or more, based on the total weight of the photocurable composition.

7. 10. The photocurable composition of claim 1, wherein the at least one second monomer of the polymerizable material comprises an acrylate monomer, a maleimide monomer, an epoxide monomer, a vinylbenzene, or any combination thereof.

8. 10. The photocurable composition of claim 1, wherein the at least one second monomer comprises at least one monofunctional acrylate monomer and at least one multifunctional acrylate monomer.

9. 9. The photocurable composition of claim 8, wherein the amount of the multifunctional acrylate monomer is 20 wt% or more, based on the total weight of the photocurable composition.

10. 9. The photocurable composition of claim 8, wherein the amount of the multifunctional acrylate monomer is 40 wt% or more, based on the total weight of the photocurable composition.

11. 2. The photocurable composition according to claim 1, wherein the photocurable composition has a viscosity at 23° C. of 30 mPa·s or less.

12. 8. The photocurable composition according to claim 7, wherein the photocurable composition has a viscosity of 15 mPa·s or less at 23°C.

13. 10. The photocurable composition of claim 1, wherein the photocurable composition is essentially free of solvent.

14. 13. A laminate comprising a substrate and a photocurable layer directly overlying the substrate, the photocurable layer being formed from the photocurable composition of claim 1.

15. 15. The laminate of claim 14, wherein the adhesion strength of the photocurable layer to a silicon substrate at 23° C. according to ASTM D 4541 is 6.5 MPa or more.

16. 1. A method for forming a photocurable layer on a substrate, comprising: applying a layer of a photocurable composition directly onto the substrate, wherein the photocurable composition comprises a polymerizable material and a photoinitiator, the polymerizable material comprising at least one first monomer and at least one second monomer, R 1 contains a carbon-carbon double bond, and R 2 R is a substituted or unsubstituted alkyl, aryl, or alkylaryl, and the at least one first monomer is 1 wt % or more and 10 wt % or less of a compound represented by formula (1): 1 -R 2 -N=C=O(1) isocyanate group-containing compounds, contacting the photocurable composition with an imprint template or superstrate; A step of irradiating the photocurable composition with light to form a photocured layer; removing the imprint template or the superstrate from the photocurable layer; 23. The method of claim 22, further comprising:

17. 17. The method of claim 16, wherein the isocyanate group-containing compound of formula (1) is selected from 2-isocyanatoethyl acrylate, 3-isopropenyl-α,α-dimethylbenzyl isocyanate, 2-isocyanatoethyl methacrylate, allyl isocyanate, or any combination thereof.

18. 17. The method of claim 16, wherein the at least one second monomer of the polymerizable material comprises at least one monofunctional acrylate monomer and at least one multifunctional acrylate monomer.

19. 17. The method of claim 16, wherein the amount of the polymerizable material is 90 wt% or more, based on the total weight of the photocurable composition.

20. applying a layer of a photocurable composition onto a substrate, wherein the photocurable composition comprises a polymerizable material and a photoinitiator, the polymerizable material comprising at least one first monomer and at least one second monomer; R 1 contains a carbon-carbon double bond, and R 2 R is a substituted or unsubstituted alkyl, aryl, or alkylaryl, and the at least one first monomer is 1 wt % or more and 10 wt % or less of a compound represented by formula (1): 1 -R 2 -Contains an isocyanate group-containing compound of N=C=O(1), contacting the photocurable composition with an imprint template or superstrate; irradiating the photocurable composition with light to at least partially form a photocured layer; removing the imprint template or the superstrate from the at least partially photocured layer; forming a pattern on the substrate; processing the substrate on which the pattern is 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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