Photocurable components

Abstract

The photocurable composition comprises a polymerizable material, a hindered stabilizer, and a photopolymerization initiator, wherein the polymerizable material comprises at least one polyfunctional aromatic vinyl monomer, and the hindered stabilizer is a hindered amine of formula (1) or a hindered phenol of formula (2). [Formula 1] TIFF2026515272000025.tif52136 Here, X is H, CH3, or YZ, Y is CH2, O, S, or N, Z is an organic substituent, R1 is H, CH3, OH, OR5, CO-CH3, or C(=O)R5, and R2, R3, R4, and R5 are organic substituents.

Description

[Technical Field]

[0001] This disclosure relates to a photocurable composition, and more particularly to a photocurable composition for inkjet-adaptive planarization suitable for forming a photocurable layer. [Background technology]

[0002] Inkjet adaptive planarization (IAP) is a process for planarizing the surface of a substrate, such as a wafer containing electrical circuits, by spraying droplets of a photocurable composition onto the substrate's surface and forming a flat liquid layer by bringing a flat superstraight into direct contact with the added liquid. The flat liquid layer is typically solidified under UV light exposure, and after removal of the superstraight, a flat polymer surface is obtained, which can be subjected to subsequent processing steps, such as baking, etching, and / or further deposition steps.

[0003] The subsequent baking of the formed photocured layer is often carried out at a temperature higher than its glass transition temperature and close to its melting point, requiring high thermal stability and low shrinkage.

[0004] There is a need for improved IAP materials that allow the photocurable composition to have a long shelf life and to form a flat photocurable layer with high thermal stability during subsequent processing. [Overview of the project]

[0005] In one embodiment, the photocurable composition may comprise a polymerizable material, a hindered stabilizer, and a photopolymerization initiator, wherein the polymerizable material comprises at least one polyfunctional aromatic vinyl monomer, and the hindered stabilizer may be a hindered amine of formula (1) or a hindered phenol of formula (2). [ka] Here, X is H, CH3, or YZ, Y is CH2, O, S, or N, Z is an organic substituent, R1 is H, CH3, OH, OR5, CO-CH3, or C(=O)R5, and R2, R3, R4, and R5 are organic substituents.

[0006] In one embodiment of the photocurable composition, the hindered stabilizer has the structure of formula (1), where X is YZ and Z comprises at least one reactive C=C group.

[0007] In a particular embodiment of the photocurable composition, the hinder stabilizer is [ka] It may be a hindered amine selected from the group.

[0008] In another embodiment, the hindered stabilizer may have a molecular weight of at least 600 g / mol.

[0009] In a further embodiment of the photocurable composition, the hinder stabilizer is [ka] It may be a hindered phenol selected from the group.

[0010] In one embodiment of the photocurable composition, the amount of the hindered stabilizer may be 0.5% by weight or more and 5% by weight or less.

[0011] In another embodiment, the at least one polyfunctional aromatic vinyl monomer of the polymerizable material may include divinylbiphenyl monomer (DVBPh), trivinylbiphenyl monomer (TVBPh), trivinylphenyl monomer (TVPh), or a combination thereof.

[0012] In one aspect, the at least one polyfunctional aromatic vinyl monomer may include at least one vinyl group and at least one acrylate group.

[0013] In certain aspects, the polyfunctional aromatic vinyl monomer of the polymeric material is

Chemical formula

[0014] In one aspect of the photocurable composition, the amount of the polyfunctional vinyl monomer can be at least 80% by weight based on the total weight of the polymeric material. In another aspect, the amount of the polyfunctional vinyl monomer can be at least 95% by weight based on the total weight of the polymeric material.

[0015] In a further embodiment of the photocurable composition, the amount of the polymeric material can be at least 90% by weight based on the total weight of the photocurable composition.

[0016] In one aspect, the carbon content of the photocurable composition after photocuring can be at least 71 percent.

[0017] In another aspect, the viscosity of the photocurable composition can be 30 mPa·s or less.

[0018] In certain aspects, the photocurable composition may be essentially free of solvents.

[0019] In one embodiment, the laminate can include a substrate and a photocurable layer overlapping the substrate, and the photocurable layer is formed from the photocurable composition of the present disclosure.

[0020] In one aspect of the laminate, the initial decomposition temperature T(X) of the photocurable layer can be at least 330°C.

[0021] In another embodiment, a method for forming a photocurable layer on a substrate comprises the step of coating a layer of a photocurable composition on the substrate, wherein the photocurable composition may include a polymerizable material, a hindered stabilizer, and a photopolymerization initiator, wherein the polymerizable material includes at least one polyfunctional aromatic vinyl monomer, and the hindered stabilizer is a hindered amine of formula (1) or a hindered phenol of formula (2). [ka] Here, X is H, CH3, or YZ, Y is CH2, O, S, or N, Z is an organic substituent, R1 is H, CH3, OH, OR5, CO-CH3, or COR5, and R2, R3, R4, and R5 are organic substituents. The process may include the steps of contacting the photocurable composition with a superstraight or imprint template, irradiating the photocurable composition with light to form a photocured layer, and removing the superstraight or imprint template from the photocured layer.

[0022] In one embodiment of the above method, the initial decomposition temperature T(X) of the photocured layer may be at least 330°C.

[0023] In a further embodiment, the method for manufacturing an article may include the steps of forming a photocurable layer on a substrate as described above, forming a pattern on the substrate, processing the substrate on which the pattern was formed in the forming step, and manufacturing the article from the substrate processed in the processing step. [Brief explanation of the drawing]

[0024] The embodiments are shown as examples and are not limited to the accompanying drawings.

[0025] [Figure 1] Figure 1 includes a graph showing the TGA curve obtained by dynamic thermogravimetric analysis of a photocurable material prepared from the photocurable composition of Example 1 according to the embodiment.

[0026] [Figure 2] Figure 2 includes a graph showing the TGA curve obtained by isothermal thermogravimetric analysis at 350°C for a photocurable material prepared from the photocurable composition of Example 1 according to the embodiment.

[0027] [Figure 3] Figure 3 includes a graph showing the TGA curve obtained by dynamic thermogravimetric analysis of the photocurable material prepared from the photocurable composition of Example 2 according to the embodiment.

[0028] [Figure 4] Figure 4 includes a graph showing the TGA curve obtained by isothermal thermogravimetric analysis at 400°C for a photocurable material prepared from the photocurable composition of Example 2 according to the embodiment. [Modes for carrying out the invention]

[0029] The following description is provided to help understand the teachings disclosed herein and focuses on specific implementations and embodiments of the teachings. This focus is provided to help illustrate the teachings and should not be construed as a limitation on the scope or applicability of the teachings.

[0030] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those skilled in the art to which this invention pertains. Materials, methods, and examples are illustrative and not intended to limit the scope. Much detail regarding specific materials and processing procedures not described herein is conventional and can be found in textbooks and other materials relating to imprint and lithography techniques.

[0031] As used herein, the terms “comprises,” “comprising,” “includes,” “including,” “has,” and “having,” or any other conjugations thereof, shall cover non-restrictive inclusion. For example, a process, method, article, or apparatus that includes a list of features is not necessarily limited to those features and may include other features not expressly listed or that are inherent to such process, method, article, or apparatus.

[0032] As used herein, and unless explicitly stated otherwise, “or” means inclusive OR and not exclusive OR. For example, condition A or B is satisfied by any one of the following: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); or both A and B are true (or exist).

[0033] Furthermore, the use of "a" or "an" is used to describe the elements and components described herein. This is used simply for convenience to indicate the general meaning of the scope of the invention. This specification should be read as including one or at least one, and singular forms include plural forms unless it is obvious that it is not intended to be plural.

[0034] This disclosure relates to a photocurable composition comprising a polymerizable material, a hindered stabilizer, and a photopolymerization initiator, wherein the polymerizable material may comprise at least one polyfunctional aromatic vinyl monomer, and the hindered stabilizer may be a hindered amine of formula (1) or a hindered phenol of formula (2). [ka] Here, X is H, CH3, or YZ, Y is CH2, O, S, or N, Z is an organic substituent, R1 is H, CH3, OH, OR5, CO-CH3, or C(=O)R5, and R2, R3, R4, and R5 are organic substituents. Here, each organic substituent may be different from the others, the same, or at least partially the same.

[0035] While not bound by theory, photocurable compositions comprising specific combinations of aromatic vinyl monomers having the structure of formula (1) or formula (2) and a hindered stabilizer may have the advantages of forming a photocurable layer during IAP treatment, which has a long shelf life, high thermal stability, and high etching resistance.

[0036]

[0036] In one embodiment, the hindered stabilizer may be the hindered amine of formula (1), where X is YZ and Z comprises at least one reactive C=C group.

[0037] In certain embodiments, the molecular weight of the hindered stabilizer may be at least 230 g / mol, or at least 250 g / mol, or at least 300 g / mol, or at least 400 g / mol, or at least 440 g / mol, or at least 500 g / mol, or at least 550 g / mol, or at least 600 g / mol. In other embodiments, the molecular weight of the hindered stabilizer may be 3000 g / mol or less, or 2500 g / mol or less, or 2000 g / mol or less, or 1000 g / mol or less, or 800 g / mol or less, or 500 g / mol or less.

[0038] Non-limiting examples of hindered amine stabilizers may be one or more stabilizers of structures (3) to (9). [ka]

[0039] In another embodiment, the hindered stabilizer may be a hindered phenol having the structure of formula (2). Non-limiting examples of hindered phenol stabilizers corresponding to the structure of formula (2) may be the following structures (11) to (14). [ka]

[0040] In one embodiment, the hindered stabilizer may be a combination of at least one hindered amine of formula (1) and at least one hindered phenol of formula (2).

[0041] In one embodiment, the amount of the hindered stabilizer in the photocurable composition of the present disclosure may be at least 0.1% by weight, or at least 0.3% by weight, or at least 0.5% by weight, or at least 1% by weight, or at least 2% by weight, or at least 3% by weight, or at least 4% by weight, or at least 5% by weight, based on the total weight of the photocurable composition. In another embodiment, the amount of the hindered stabilizer may be 10% by weight or less, or 8% by weight or less, or 5% by weight or less, or 3% by weight or less. In one embodiment, the amount of the hindered stabilizer may be at least 0.5% to 5% by weight, or at least 1.0% to 3% by weight, based on the total weight of the photocurable composition.

[0042] The polymerizable material of the photocurable composition of the present disclosure may comprise at least one polyfunctional aromatic vinyl monomer. In one embodiment, the polyfunctional aromatic vinyl monomer may comprise at least one aromatic ring and at least two vinyl groups. In another embodiment, the at least one polyfunctional aromatic vinyl monomer may comprise at least one aromatic ring, at least one vinyl group, and at least one acrylate group.

[0043] In certain embodiments, at least one polyfunctional aromatic vinyl monomer may include divinylbiphenyl monomer (DVBPh), trivinylbiphenyl monomer (TVBPh), trivinylphenyl monomer (TVPh), or a combination thereof.

[0044] Non-limiting examples of polyfunctional aromatic vinyl monomers may be one or more of the following monomers: [ka]

[0045] The amount of polyfunctional aromatic vinyl monomer may be at least 70% by weight, for example, at least 75%, at least 80%, at least 85%, at least 90%, or at least 95% by weight, relative to the total weight of the polymerizable material. In another embodiment, all of the polymerizable material may be one or more polyfunctional aromatic vinyl monomers (100% by weight), or 98% or less by weight, or 95% or less by weight, or 90% or less, relative to the total weight of the polymerizable material. In a particular embodiment, the amount of polyfunctional aromatic vinyl monomer may be in the range of at least 80% to 100% by weight, relative to the total weight of the polymerizable material.

[0046] In further embodiments, the polymerizable material of the photocurable composition of the present disclosure may further comprise at least one polymerizable monomer that does not contain an aromatic ring, or a polymerizable monomer that does not contain a vinyl group but contains other functional groups, such as one or more acrylate groups. As used herein, the term "acrylate monomer" refers to unsubstituted or alkyl-substituted acrylate monomers, such as methacrylate monomers.

[0047] The amount of polymerizable material in the photocurable composition may be at least 50% by weight, for example, at least 60%, at least 70%, at least 80%, at least 85%, at least 90%, or at least 95% by weight, relative to the total weight of the photocurable composition. In another embodiment, the amount of polymerizable material may be 99% or less by weight, for example, 98% or less by weight, or 97% or less by weight, or 95% or less by weight, or 90% or less by weight, relative to the total weight of the photocurable composition. The amount of polymerizable material may be a value between any of the above minimum and maximum values. In a particular embodiment, the amount of polymerizable material may be 80% or more and 97% or less by weight.

[0048] In another embodiment, the polymerizable material of the photocurable composition may include a certain amount of polymerizable oligomer or polymer.

[0049] The photocurable compositions disclosed herein can be adapted for use in inkjet adaptive planarization (IAP) or nanoimprint lithography (NIL).

[0050] IAP and NIL treatments typically use low-viscosity photocurable compositions. In one embodiment, the viscosity of the photocurable composition of the present invention may be 50 mPa·s or less, for example, 40 mPa·s or less, 30 mPa·s or less, 25 mPa·s or less, or 20 mPa·s or less. In other specific embodiments, the viscosity may be at least 2 mPa·s, or at least 3 mPa·s, or at least 5 mPa·s. As used herein, all viscosity values ​​relate to viscosity measured at a temperature of 23°C using the Brookfield method with a Brookfield viscometer.

[0051] The selection of polymerizable monomers can be done with the aim of producing a photocurable composition that can form a photocurable layer having a high carbon content. In one embodiment, the carbon content of the layer formed after photocuring may be at least 71% by weight, or at least 72% by weight, or at least 73% by weight, relative to the total weight of the photocurable layer.

[0052] In another embodiment, the photocured layer of the laminate may have an Ohnishi number of 3.2 or less, or 3.1 or less, or 3.0 or less, or 2.8 or less, or 2.7 or less, or 2.6 or less. In another embodiment, the Ohnishi number may be at least 1.8, for example, at least 1.9, at least 2.0, at least 2.1, at least 2.2, or at least 2.3.

[0053] In certain embodiments, the photocured layer may have a carbon content of at least 71% and an Onishi number of 3.1 or less.

[0054] The photocurable composition can be adapted so that the photocured layer formed from the photocurable composition has high thermal stability. In one embodiment, the onset temperature for the thermal degradation of the photocured layer may be at least 300°C, or at least 330°C, or at least 350°C, or at least 375°C, or at least 400°C. As used herein, “onset temperature for the thermal degradation” is also called “initial degradation temperature T(X)” and refers to the temperature at which the first deviation of the curve from a nearly linear plateau is observed in the TGA curve, immediately before the rapid degradation of the sample begins.

[0055] In one embodiment, the first photocurable composition of the present disclosure may be essentially solvent-free.

[0056] As used herein, unless otherwise indicated, the term solvent refers to a compound that can dissolve or disperse polymerizable monomers and hindered stabilizers but does not polymerize itself during the photocuring of the photocurable composition. The phrase “essentially solvent-free” means herein an amount of solvent of 5% by weight or less relative to the total weight of the photocurable composition. In certain embodiments, the amount of solvent may 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.

[0057] To initiate photocuring of the composition when exposed to light, one or more photopolymerization initiators may be included in the photocurable composition.

[0058] In one embodiment, curing may also be carried out by a combination of photocuring and thermal curing.

[0059] The photocurable composition may further contain one or more optional additives. Non-limiting examples of optional additives may be stabilizers, dispersants, solvents, surfactants, inhibitors, or any combination thereof.

[0060] In one embodiment, a photocurable composition can be applied to a substrate to form a photocurable layer. When used herein, the combination of a substrate and a photocurable layer superimposed on the substrate is referred to as a laminate.

[0061] The disclosure further relates to a method for forming a photocurable layer. The method may include the steps of: applying a layer of the above-mentioned photocurable composition onto a substrate; bringing the photocurable composition into contact with a template or superstraight; irradiating the photocurable composition with light to form a photocurable layer; and removing the template or superstraight from the photocurable layer.

[0062] The substrate and solidified layer may be subjected to additional processing, such as an etching process, to transfer an image corresponding to the pattern of one or both of the patterns in the solidified layer and / or the pattern layer beneath the solidified layer onto 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, moldable material removal, dicing, bonding, and packaging.

[0063] The photocurable layer may be used as an interlayer insulating film in semiconductor devices such as LSIs, system LSIs, DRAMs, SDRAMs, RDRAMs, and D-RDRAMs, or as a resist film used in semiconductor manufacturing processes.

[0064] As further demonstrated in the examples, it was surprisingly discovered that photocurable compositions containing specific combinations of polymerizable monomers and hindered stabilizers of formula (1) or formula (2) can have desired property profiles particularly suitable for IAP and NIL treatments. Examples

[0065] The following non-limiting embodiments illustrate the concepts described herein.

[0066] In the following examples, various photocurable compositions were prepared and tested with different hindered stabilizers. Table 1 includes a summary of the hindered stabilizers used in Examples 1-4.

[0067] [Table 1]

[0068] Example 1

[0069] Photocurable compositions were prepared by combining 100 parts of polymerizable monomer 5-ethenyl-1,3-benylate (VMXDA), 3 parts of photopolymerization initiator Irgacure 819, 1 part of surfactant FS3100, and various amounts of different types of hindered stabilizers. The following hindered stabilizers were used: hindered phenol HP1, hindered phenol HP2, hindered phenol HP3, hindered phenol HP4, and hindered amine HA1. Comparative photocurable composition C1 contained all components similar to compositions S1 to S8, except for the hindered stabilizers.

[0070] Table 2 summarizes the various types and amounts of hindered stabilizers used in photocurable compositions, along with the viscosity of the photocurable composition and the T(X) of the layer after photocuring.

[0071] [Table 2]

[0072] The photocured layer was prepared from a photocurable composition by filling the space between two glass slides with the respective composition, with a distance of 300 microns between the two glass slides. The photocurable composition was then photocured by applying a radiation energy of 5 J.

[0073] dynamic thermogravimetry

[0074] The thermal stability of the photocured layer was measured by dynamic thermogravimetric analysis (TGA) using a LINSEIS STA PT1000 instrument (Linseis Messgeraete GmbH, Germany). All measurements were performed under nitrogen at a rate of 5 liters per hour.

[0075] For TGA measurement, 25–35 mg of photocured sample was placed in a crucible and the initial weight was recorded. A reference crucible was used to monitor the weight change of the crucible due to temperature fluctuations. The sample was heated at a rate of 20°C / min, and the weight loss of the sample as the temperature increased was recorded at 1-second intervals. The relative weight change rate was calculated using the weight loss divided by the original total weight of the sample.

[0076] The TGA curves for samples S1-S8 and comparative sample C1 are very similar. Figure 1 illustrates the TGA curves for samples S2, S6, S8, and C1. The first phase up to the decomposition temperature has only a very small, almost linear weight loss, while the second phase, starting at the thermal decomposition temperature, is very steep until the complete decomposition of the sample (the curves are only shown up to 30% decomposition). The initial decomposition temperature T(X) for each curve was determined by determining the deflection point from the established baseline of phase 1 of the TGA curve and is listed in Table 2.

[0077] Isothermal Gravimetric Measurement

[0078] Furthermore, isothermal thermogravimetric analysis (TGA) was performed at a constant temperature of 350°C for at least 30 minutes. The measurements were performed using the same TGA apparatus as described above, and also under nitrogen. For each measurement, 25–35 mg of the photocured sample was placed in a crucible and the initial weight was recorded. The temperature was rapidly increased to 350°C (within 20 minutes), and once 350°C was reached, the weight loss was recorded over a 30-minute period. Figure 2 shows the relative weight loss of photocured samples S2, S6, S7, S8, and C1 over 30 minutes at a constant temperature of 350°C. It can be seen that sample C1 has a much faster weight loss than samples S2, S6, S7, and S8.

[0079] The rate of weight loss is characterized by converting the data curve recorded for each sample into a straight line and expressing the slope of that line in the form of a K value (Δweight-loss / minute), where a negative slope is represented as a positive number. The K value can be used as an indicator of the thermal stability of the sample; a higher K value indicates lower sample stability. As shown in Table 3, the comparison sample C1 had the highest K value, while samples S2, S6, S7, and S8 had lower K values. By normalizing the K values ​​so that the comparison sample is set to 1, it can be seen that sample S8 has approximately 28 percent better thermal stability than comparison sample C1.

[0080] [Table 3]

[0081] Thermal shrinkage

[0082] Thermal shrinkage was measured by exposing the photocured layer to a baking process on a hot plate at 350°C for 2 minutes.

[0083] For the thermal shrinkage test, the photocurable layer was prepared by coating a layer of liquid photocurable composition onto a blank fused silica wafer and photocuring the liquid layer with light radiation having a wavelength of 365 nm at a total dose of 5 J. This test was designed so that the thickness of the resulting photocurable film (before baking) would be approximately 500 nm. The baking treatment of the cured film was performed by placing it on a hot plate at a temperature of 350 °C for 2 minutes. To calculate the thermal shrinkage rate, the film thickness before and after baking was measured using a JA Woolam Spectroscopic Ellipsometer M-2000 X-210. b350 =[(T p -T c ) / T p Linear contraction rate (S) according to the formula ] × 100% b350 ) was calculated. Here, T p The liquid film thickness of the photocurable composition before baking is T c This is the photo-cured film thickness after baking.

[0084] The results of the thermal shrinkage measurements are summarized in Table 4. The highest shrinkage occurred in the comparative sample C1 (2.6%), while the lowest shrinkage was obtained in sample S4, which had 1.55% shrinkage and was prepared by including 1% by weight of the hindered phenol stabilizer HP4 (see Table 2), which corresponds to a reduction of approximately 30% shrinkage.

[0085] [Table 4]

[0086] Example 2

[0087] A photocurable composition was prepared containing 100 parts of 3,3'-divinylbiphenyl (DVBPH) as a polymerizable monomer, 3 parts each of the photopolymerization initiators OXE02 and Omnirad 1316, and 1 part of the surfactant FS3100. The photocurable compositions differed by using hindered phenol HP4 (Sample S9) and hindered amine HA2 (Sample S10) as hindered stabilizers. Comparative sample C2 did not contain a hindered stabilizer. An overview of the curable compositions is shown in Table 5.

[0088] [Table 5]

[0089] The photocurable layer was prepared from a curable composition and analyzed via dynamic TGA in the same manner as described in Example 1.

[0090] The TGA curve is shown in Figure 3. It can be seen that sample S10, which contains 1% by weight of hindered amine HA2, had a higher initial pyrolysis temperature T(X) than the comparative sample C2. The increase in T(X) was approximately 26°C.

[0091] Isothermal thermogravimetric analysis (TGA) was performed at 400°C on photocured sample S10 and comparative sample C2. As shown in Figure 4, it is clear that the addition of 1% by weight of the hindered amine stabilizer HA2 enhances thermal stability and slows down decomposition.

[0092] Example 3

[0093] 45 parts of 3,5-divinylbenzyl acrylate (DVBA); 30 parts of 5-ethenyl-1,3-benzenediyl acrylate (VMXDA); and 25 parts of 3,4’,5-trivinyl-1,1’-biphenyl (3VPH) were used as the polymerizable monomers to prepare a third set of photocurable compositions. All the curable compositions further contained 1 part of FS3100, 3 parts of Irgacure 819 and 3 parts of OXE02. This involved changing the type of hindered stabilizer, which was 3 wt% of the hindered amine HA1 for sample S11 and 3 wt% of the hindered phenol HP4 for sample S12. The comparative sample C3, similar to samples S11 and S12, did not contain a hindered stabilizer but contained all other components. The overview of the photocurable compositions is shown in Table 6.

[0094]

Table 6

[0095] A photocurable layer was prepared from the photocurable composition and analyzed via dynamic TGA in the same manner as described in Example 1. The TGA curve (not shown) was similar to that of the sample in Example 1. The increase in the initial decomposition temperature (T(X)) from C3 to S11 was about 21 °C.

[0096] Example 4

[0097] Investigation of Double Bond Conversion

[0098] Using Fourier transform infrared spectroscopy (FTIR), the double bond conversion under the specified UV curing conditions was measured for samples S1 - S8 (described in Example 1) and samples S11 and S12 (described in Example 3). For the measurement, the decrease in the peak of the C=C double bond at 1405 cm[[ID=2,5]] -1 in the infrared spectra before and after curing was measured, and at 71 cm[[ID=2,7]] -1The peak of the CH-benzene ring vibration was used as an internal reference. The FTIR spectrum was obtained using a Thermo Nicolet 6700 FTIR (with DTGS TEC detector) at 4000 cm⁻¹. -1 From 625cm -1 Recorded within the specified range.

[0099] For the measurement, a sample volume of 0.3–0.5 μl was dropped onto an NaCl window (25 mm × 25 mm), and then covered with another NaCl window of the same size. The intensity of the irradiated UV light was 38 mW / cm². 2 The irradiation time was 132 seconds, which corresponds to 5 J / cm². 2 This corresponds to the dose. The conversion rate of C=C bonds was calculated by the peak ratio of the cured sample (after exposure under curing conditions) to the uncured sample (at the start of measurement, before UV exposure).

[0100] Table 7 provides a summary of the C=C conversions measured for the test samples. It can be seen that when VMXDA is used as the polymerizable material, the addition of a hindered stabilizer did not adversely affect the conversion rate. When the combination of DVBA / VMXDA / 3VPH was used as the polymerizable material (samples S11, S12, and C3), the addition of the hindered stabilizer HA1 (sample S11) increased the C=C conversion rate by 7.4%, and the addition of the stabilizer HP4 (sample S12) increased it by 5.6% compared to the comparative sample C3.

[0101] [Table 7]

[0102] Example 5

[0103] Consideration of validity period

[0104] Storage life tests were performed to monitor the solution viscosity over time for the curable compositions S11, S12, and C3 (see also the detailed composition descriptions in Example 3). Monitoring was carried out over a period of 9 weeks, with the sample bottles opened once a week to allow oxygen to come into contact with the samples.

[0105] Table 8 summarizes the results. Compositions containing the hindered amine stabilizer HA1 or the hindered phenol stabilizer HP4 showed only a very slight viscosity change after 9 weeks, with a viscosity increase of 0.6 mPa·s or less. In contrast, comparative composition C3 of the present invention, which does not contain the hindered stabilizer, already showed a viscosity increase of 1 mPa·s after 6 weeks.

[0106] [Table 8]

[0107] Carbon content and Onishi number

[0108] Further important properties for developing photocurable compositions suitable for IAP and NIL treatments are carbon content and the Onishi number.

[0109] Table 9 summarizes the calculated carbon content (%) and Onishi number for representative photocurable compositions described in Examples 1, 2, and 3.

[0110] The Onishi number (ON) is known to be an empirical parameter, and is the total number of atoms (N) in the polymer repeating unit. t The ratio of ) to the number of C atoms in the unit (N c ) and the number of oxygen atoms (N o It is calculated by dividing by the difference between ) and ON=N t / (N C -N O ). For the calculation of the Onishi number, it was assumed that the cured material contains 100% by weight of polymer monomer units formed by addition polymerization (no atoms are lost during polymerization).

[0111] The carbon content was calculated as the percentage of carbon atoms based on the total molecular weight of the polymerizable material compounds contained in the photocurable composition.

[0112] Table 9 shows that the photocurable compositions S1 to S12 had a carbon content of 71 percent to 93 percent and an Onishi number of 3.0 or less.

[0113] [Table 9]

[0114] Viscosity measurement

[0115] Viscosity was measured using a Brookfield DV-11+Pro viscometer with spindle #18. For each viscosity measurement, 6–7 ml of sample was taken, added to the sample chamber, and allowed to equilibrate for 15–20 minutes until the target temperature of 23°C was reached. Viscosity was measured at a speed of 135 rpm using spindle #18. For each sample, the measurement was repeated three times, and the average value was calculated.

[0116] The description and examples of embodiments described herein are intended to provide a general understanding of the structures of various embodiments. This specification and examples do not exhaustively or comprehensively describe all elements and features of apparatus and systems that use the structures or methods described herein. Different embodiments may also be provided in combination in a single embodiment, and conversely, for the sake of 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 all values ​​within that range. Many other embodiments may become apparent to those skilled in the art only after reading this specification. Other embodiments derived from this disclosure may also be available, and structural substitutions, logical substitutions, or other modifications may be made without departing from the scope of this disclosure. Therefore, this disclosure should be considered illustrative rather than restrictive.

Claims

1. A photocurable composition comprising a polymerizable material, a hindered stabilizer, and a photopolymerization initiator, The polymerizable material comprises at least one polyfunctional aromatic vinyl monomer, The aforementioned hindered stabilizer is a hindered amine of formula (1) or a hindered phenol of formula (2). 【Chemistry 1】 Here, X is H, CH 3 , or Y-Z, where Y is CH 2 , O, S, or N, and Z is an organic substituent, and R 1 is H, CH 3 , OH, OR 5 , CO-CH 3 , or C(=O)R 5 and R 2 , R 3 , R 4 , R 5 are organic substituents. A photocurable composition characterized by the following features.

2. The photocurable composition according to claim 1, characterized in that the hindered stabilizer comprises the hindered amine of formula (1), where X is YZ and Z comprises at least one reactive C=C group.

3. The aforementioned hinder stabilizer is 【Chemistry 17】 The photocurable composition according to claim 1, characterized in that it is a hindered amine selected from the group.

4. The photocurable composition according to claim 1, characterized in that the hindered stabilizer has a molecular weight of at least 600 g / mol.

5. The aforementioned hinder stabilizer is 【Transformation 3】 The photocurable composition according to claim 1, characterized in that it is a hindered phenol selected from the group.

6. The photocurable composition according to claim 1, characterized in that the content of the hindered stabilizer is 0.5% by weight or more and 5% by weight or less with respect to the total weight of the photocurable composition.

7. The photocurable composition according to claim 1, characterized in that the at least one polyfunctional aromatic vinyl monomer includes divinylbiphenyl monomer (DVBPh), trivinylbiphenyl monomer (TVBPh), trivinylphenyl monomer (TVPh), or a combination thereof.

8. The photocurable composition according to claim 1, characterized in that the at least one polyfunctional aromatic vinyl monomer comprises at least one vinyl group and at least one acrylate group.

9. The aforementioned polyfunctional aromatic vinyl monomer is 【Chemistry 4】 A photocurable composition according to claim 8, characterized by being selected from the above.

10. The photocurable composition according to claim 1, characterized in that the amount of the polyfunctional vinyl monomer is at least 80% by weight relative to the total weight of the polymerizable material.

11. The photocurable composition according to claim 10, characterized in that the amount of the polyfunctional vinyl monomer is at least 95% by weight relative to the total weight of the polymerizable material.

12. The photocurable composition according to claim 1, characterized in that the amount of the polymerizable material is at least 90% by weight of the total weight of the photocurable composition.

13. The photocurable composition according to claim 1, characterized in that the carbon content of the photocurable composition after photocuring is at least 71 percent.

14. The photocurable composition according to claim 1, characterized in that the viscosity of the photocurable composition is 30 mPa·s or less.

15. The photocurable composition according to claim 1, characterized in that the photocurable composition is essentially solvent-free.

16. A laminate comprising a substrate and a photocurable layer superimposed on the substrate, wherein the photocurable layer is formed from the photocurable composition described in claim 1.

17. The laminate according to claim 16, wherein the initial decomposition temperature T(X) of the photocurable layer is at least 330°C.

18. A method for forming a photocurable layer on a substrate, A step of coating a layer of a photocurable composition onto the substrate, wherein the photocurable composition comprises a polymerizable material, a hindered stabilizer, and a photopolymerization initiator, wherein the polymerizable material comprises at least one polyfunctional aromatic vinyl monomer, and the hindered stabilizer is a hindered amine of formula (1) or a hindered phenol of formula (2). 【Chemistry 1】 Here, X is H, CH 3 , or YZ, where Y is CH 2 , O, S, or N, where Z is an organic substituent, R 1 H, CH 3 , OH, OR 5 CO-CH 3 , or COR 5 And R 2 , R 3 , R 4 , R 5 is an organic substituent, The steps include bringing the photocurable composition into contact with a SuperStraight or imprint template, The steps include irradiating the photocurable composition with light to form a photocurable layer, A step of removing the superstraight or the imprint template from the photocuring layer, A method characterized by having the following:

19. The method according to 18, characterized in that the initial decomposition temperature T(X) of the photocured layer is at least 330°C.

20. A method for manufacturing an article, A step of forming a photocurable layer on a substrate according to the method of claim 18, A step of forming a pattern on the substrate, The process of forming the pattern includes a step of processing the substrate on which the pattern has been formed, A step of manufacturing the article from the substrate processed in the processing step, A manufacturing method characterized by having the following features.

Images