Imprint molding template, mold, and method for manufacturing mold

Abstract

To provide a nano-imprint molding template that has a high gas permeability and high strength and can be used over a long period of time in an industrial production process, a mold using the same, and a method for manufacturing the mold.SOLUTION: A mold 3 fitted with an imprint molding template 8 made of an extremely stable composition comprising a combination of a silicon-containing monomer and a titanium-containing monomer has a gas-permeation functionally graded portion 10 formed by laminating a porous layer 6 and a lattice layer 7 on a truss layer 5. The truss layer 5, the porous layer 6 and the lattice layer 7 are made of a metal sintered material, and functions of each portion are realized by adjusting a sintering temperature and a sintering time. The sintering is continuously performed from the truss layer 5 to the porous layer 6 and the lattice layer 7.SELECTED DRAWING: Figure 4

Description

[Technical Field]

[0001] The present invention relates to a nanoimprint template having high gas permeability, a mold using the same, and a method for manufacturing the mold. [Background technology]

[0002] High-precision microfabrication using imprint molding in the micro- or nanometer range has already been put to practical use on compact discs, and is expected to be applied to electronic devices such as water-repellent and stain-resistant surface sheets for solar cell panels, light-scattering films for displays, light-emitting diodes (LEDs), semiconductors, hard disk recording devices, displays, solar cells, and biosensors.

[0003] Compared to conventional microfabrication using laser light, imprint molding has several advantages: (1) it reduces LER (line edge roughness) and LWR (line width roughness), which indicate manufacturing variations during processing using high-precision micro-molds; (2) because the resolution does not depend on the wavelength of the laser light source, it does not require expensive equipment such as laser exposure devices or electron beam lithography devices, thereby achieving low costs; (3) it is possible to process three-dimensional, spherical, and curved surfaces; (4) it is possible to process large areas on the order of meters; (5) it does not require a vacuum process; and (6) it enables direct patterning on biosubstrates and metal materials, which are difficult to etch after processing.

[0004] In imprint molding, the pattern-bearing surface of a template (metal mold or die) is pressed against a transfer agent applied to a substrate, and activation energy such as heat or light is applied to harden the transfer agent, resulting in the template being peeled off, thereby transferring the pattern. Templates are typically made of silicon-based materials such as quartz or polydimethylsiloxane (PDMS). However, with these conventional templates, gases such as air can become trapped between the transfer agent and the template during pressing, preventing the transfer agent from uniformly filling the minute recesses in the template and resulting in chips in the transferred pattern corresponding to the gas. Furthermore, depending on the transfer conditions, such as the pattern shape, pressing pressure, and heating temperature, the pattern on the expensive template itself can be damaged, preventing the formation of high-precision patterns over a long period of time. Furthermore, if the transfer agent contains volatile components such as diluents (or solvents), a similar phenomenon occurs due to the evaporation of these components, limiting the use of transfer agents such as highly viscous resin components.

[0005] Even if the pressure is applied without gas entrapment, depending on the pattern shape, the adhesion between the template and the transfer agent may be high, possibly due to an anchor effect, which may reduce releasability and result in damage to the template or the pattern of the hardened transfer agent. If the pattern of the transfer agent is damaged, part of the hardened transfer agent remains on the pattern-forming surface of the template as foreign matter, making subsequent transfer impossible and also making it extremely difficult to remove the foreign matter without damaging the fine pattern.

[0006] These phenomena become more pronounced as pattern shapes become more precise and finer, posing an obstacle to the expansion of the applications mentioned above. As a solution, the development of gas-permeable templates is being considered.

[0007] However, conventional gas-permeable templates do not have sufficient gas permeability, probably because they are made of quartz-based materials that have inherently low gas permeability. Therefore, further improvement of gas permeability is required for imprint molding in air or for using transfer agents containing organic solvents.

[0008] In view of the above, the present inventors have addressed the problem of providing a polymerizable compound capable of forming a cured product having high gas permeability (e.g., a template for imprint molding) in Patent Document 1, and have disclosed a compound in which the hydrogen atoms of at least some of the hydroxyl groups of a hydroxyl group-containing polysaccharide or a hydroxyl group-containing macrocyclic compound are substituted with at least one polymerizable substituent selected from specific groups.

[0009] Incidentally, the domestic market for antibacterial products has recently reached a scale of 1 trillion yen, and a graph showing the trend in the number of products registered with the SIAA mark for antibacterial / anti-fungal properties by SIAA (Society of International Standards for Antibacterial Articles) shows that the number of registered products is steadily increasing. As the social need for antibacterial products is extremely high, various attempts have been made to impart antibacterial properties to, for example, the field of air conditioners.

[0010] Patent Document 2 aims to provide an air conditioner that easily removes dust and dirt from the filter and also suppresses the growth of bacteria from the dust, and discloses an air conditioner that includes a heat exchanger, a filter arranged upstream of the heat exchanger, and a blower fan that blows air that has passed through the filter so that it exchanges heat in the heat exchanger, the filter comprising a metal plate on which a mesh is formed by photoetching, and an antibacterial and deodorizing resin coated with a charge transfer catalyst that is arranged downstream of the metal plate in the direction in which indoor air passes. Furthermore, Patent Document 3 aims to obtain a room air conditioner equipped with a blower fan having a coating film that is excellent in antifouling properties, removal of adhering water, and durability. The patent document 3 discloses an air conditioner in which a hydrophilic / hydrophobic water-based coating material containing first silica microparticles with an average particle size of 2 to 10 nm and fluororesin microparticles with an average particle size of 50 to 500 nm is applied to the blower fan, and further a water-repellent coating material is applied to the end of the positive pressure surface of the blower fan. [Prior art documents] [Patent documents]

[0011] [Patent Document 1] Patent Publication No. 2017-145320 [Patent Document 2] Japanese Patent Application Laid-Open No. 2010-19498 [Patent Document 3] Japanese Patent Application Laid-Open No. 2008-292069 Summary of the Invention [Problem to be solved by the invention]

[0012] As shown in Patent Documents 2 and 3, conventional methods for imparting antibacterial properties to air conditioners involve, for example, coating the resin surface with an antibacterial agent containing Ag ions or kneading the antibacterial agent into the resin material. However, the method of coating the resin surface with an antibacterial agent has the problem that the coating peels off over time, causing the antibacterial properties to be lost. Furthermore, the method of kneading an antibacterial agent into a resin material requires a large amount of antibacterial agent, which is costly, and also makes it difficult to recycle the resin into which the antibacterial agent has been kneaded, resulting in a problem of a large environmental load.

[0013] In view of the problems with the conventional technology described above, the present inventors have considered the application of the imprint molding template having high gas permeability, as disclosed in Patent Document 1, in order to provide a mold to be used in the manufacture of antibacterial resin molded products that are inexpensive, deteriorate little over time, and have a low environmental impact, as well as a method for manufacturing such a mold. However, the imprint molding template disclosed in Patent Document 1 has high gas permeability but lacks strength, making it difficult to use over long periods in industrial production processes. In particular, when using the template over long periods in industrial production processes, the releasability of the surface layer material, which is the imprint molding template, becomes an important factor. The releasability of the surface layer material is an issue for both the releasability between the surface layer material and plastic resin and the releasability between the surface layer material and metal (gas-permeable sintered metal body).

[0014] Therefore, an object of the present invention is to provide a nanoimprint molding template that has high gas permeability and high strength and can be used over a long period of time in industrial production processes, a mold using the same, and a method for manufacturing the mold. [Means for solving the problem]

[0015] As a result of extensive research to achieve the above-mentioned objectives, the inventors have found that a gas-permeable mold surface layer forming composition can be made extremely stable by combining a silicon-containing monomer and a titanium-containing monomer. Furthermore, the epoxy groups in the hydrolysis condensate of the silicon-containing monomer and the titanium-containing monomer react with the crosslinking agent to form a three-dimensional crosslinked structure. This makes the composition highly resistant to both organic solvents and water. Therefore, it does not intermix with injection-molded transfers, nor does it dissolve when melted during pattern formation on the transfer surface. By utilizing these properties, the inventors have found that the composition can be used as a gas-permeable mold surface layer forming composition in the injection molding process over a long period of time in industrial production, and have thus completed the present invention. The inventors also refer to Ivanova, EP, Hassan, J., Webb, HK, Truong, VK, Watson, GS, Watson, JA, Baulin, VA, Pogodin, S., Wang, JY, Tobin, MJ, Lobbe, C. and Crawford, RJ:Small ,8,2489(2012) and Ivanova, EP, Hassan, J., Webb, HK, Gervinskas, G., Juodkazis, S., Truong, VK, Wu, AHF, Lamb, RN, Baulin, VA, Watson, GS, Watson, JA, Mainwaring,DE and Crawford, RJ:Nature Commun., 4, 2838 (2013), nanostructures exhibit high mechanical bactericidal properties regardless of their chemical composition, and specifically, the present invention was conceived by noticing that nanostructure pillars destroy bacterial cell walls and physically kill bacteria.

[0016] That is, the imprint molding template of the present invention is characterized by having a structure represented by the following formula, which is formed from a cured product of a curable composition containing a polymerizable compound obtained by combining a silicon-containing monomer and a titanium-containing monomer: [ka]

[0017] That is, the imprint molding template of the present invention is characterized by having a structure represented by the following formula, which is formed from a cured product of a curable composition containing a polymerizable compound obtained by combining a silicon-containing monomer and a titanium-containing monomer: [ka]

[0018] That is, the imprint molding template of the present invention is characterized by having a structure represented by the following formula, which is formed from a cured product of a curable composition containing a polymerizable compound obtained by combining a silicon-containing monomer and a titanium-containing monomer: [ka]

[0019] That is, the imprint molding template of the present invention is characterized by having a structure represented by the following formula, which is formed from a cured product of a curable composition containing a polymerizable compound obtained by combining a silicon-containing monomer and a titanium-containing monomer: [ka]

[0020] The imprint molding template of the present invention is formed from a cured product of a curable composition containing a polymerizable compound formed by combining a silicon-containing monomer and a titanium-containing monomer, and the curable composition may further contain a thermal polymerization initiator and / or a photopolymerization initiator. The curable composition may also further contain a solvent.

[0021] The cured product may be a micro- or nano-imprint molding template. The micro- or nano-imprint molding template may have a pattern shape that is an inversion of the pattern shape of the master template. The cured product may have an oxygen gas permeability coefficient of about 10×10-12 to 2000×10-12 cm3·cm / (cm2·sec·cmHg) measured in accordance with JIS K7126-1 (2006).

[0022] Furthermore, the present invention also encompasses a method for forming the cured product by applying activation energy to the curable composition and curing it, and a method for transferring a pattern to a transfer-receiving material using the cured product as a template. The transfer-receiving material may contain a solvent.

[0023] The mold of the present invention comprises an imprint molding template laminated on a gas-permeable sintered metal layer, and is characterized in that the imprint molding template has a configuration of Chemical Formula 1 formed from a cured product of a curable composition containing a polymerizable compound formed by combining a silicon-containing monomer and a titanium-containing monomer.

[0024] The mold of the present invention is characterized in that it comprises an imprint molding template laminated on a gas-permeable sintered metal layer, and the imprint molding template has a configuration of Chemical Formula 2 formed from a cured product of a curable composition containing a polymerizable compound formed by combining a silicon-containing monomer and a titanium-containing monomer.

[0025] Furthermore, the mold of the present invention comprises an imprint molding template laminated on a gas-permeable sintered metal layer, and is characterized in that the imprint molding template has a structure represented by Chemical Formula 3, which is formed from a cured product of a curable composition containing a polymerizable compound formed by combining a silicon-containing monomer and a titanium-containing monomer.

[0026] Additionally, the mold of the present invention comprises an imprint molding template laminated on a gas-permeable sintered metal layer, and is characterized in that the imprint molding template has a configuration of Chemical Formula 4 formed from a cured product of a curable composition containing a polymerizable compound formed by combining a silicon-containing monomer and a titanium-containing monomer.

[0027] The gas-permeable sintered metal layer may be made of at least one of a gas-permeable truss layer, a gas-permeable porous layer, and a gas-permeable lattice layer.

[0028] Two or more of the gas permeable truss layer, the gas permeable porous layer and the gas permeable lattice layer may be continuous sintered layers.

[0029] The imprint molding template preferably has recesses formed therein with a depth of 250 to 1000 nm.

[0030] In this case, if the depth of the recesses is less than 250 nm, it is difficult to mold a resin molded product using this mold, and the antibacterial properties of the molded resin product will be reduced.On the other hand, if the depth exceeds 1000 nm, there is a possibility that the antibacterial properties of the resin molded product will be reduced.

[0031] The distance between the centers of adjacent recesses is preferably 250 to 800 nm. In this case, if the center-to-center distance between the recesses is less than 250 nm, it is difficult to mold a resin molded product using this mold, and the antibacterial activity of the molded resin product is not improved.On the other hand, if the distance exceeds 800 nm, the antibacterial activity of the resin molded product using this mold is reduced.

[0032] In addition, the method for manufacturing a mold of the present invention comprises the steps of: forming at least two or more of a gas permeable truss layer, a gas permeable porous layer, and a gas permeable lattice layer by continuous sintering; applying a gas permeable surface layer liquid to one of the gas permeable truss layer, the gas permeable porous layer, and the gas permeable lattice layer; placing an original plate with a fine nanostructure on the gas permeable surface layer liquid applied to the lattice layer; a photo-curing reaction step of irradiating ultraviolet light onto the gas permeable surface layer liquid on which the original plate with a fine nanostructure is placed; and removing the original plate with a fine nanostructure.

[0033] The original plate with a fine nanostructure has fine projections formed on its surface, and the projections on the surface preferably have a height of 250 to 1000 nm.

[0034] If the height of the convex portions is less than 250 nm, it will be difficult to mold the resin using the resulting mold, and the antibacterial activity will be reduced. Conversely, if the height exceeds 1000 nm, the antibacterial activity of the resin molded product using the resulting mold may be reduced.

[0035] The center-to-center distance between adjacent convex portions is preferably 250 to 800 nm. In this case, if the center-to-center spacing is less than 250 nm, molding using the resulting mold is difficult, and no improvement in the antibacterial properties of the molded resin article is observed, whereas if it exceeds 800 nm, a decrease in the antibacterial properties of the molded resin article using the resulting mold is observed. [Effect]

[0036] Figure 23 shows the published test results showing the viable bacteria rate against pillar height for samples prepared by creating a nanostructure on a silicon substrate, with the nanopillar pitch and width set to 200 nm and 150 nm, respectively, and varying only the height, for which antibacterial evaluation was conducted in accordance with the JIS-Z2801 film adhesion method. As shown in the figure, there is a tendency for the antibacterial rate to increase as the nanopillar height increases, indicating that a pillar height of approximately 200 nm or more is required to exhibit antibacterial properties. It is thought that when the nanopillar height is low, there is less damage to the cell membrane and antibacterial properties decrease, while when the pillar height is high, the number of bacteria that cause membrane damage increases. [Effects of the Invention]

[0037] The nanoimprint molding template of the present invention has high gas permeability and high strength, allowing it to be used for a long period of time in industrial production processes. Furthermore, a mold of the present invention using the template and a method for manufacturing the mold can be used to produce antibacterial resin molded products that are inexpensive, have little deterioration over time, and have a low environmental impact. [Brief explanation of the drawings]

[0038] [Figure 1] 1A and 1B are external perspective views of a resin molded product obtained using a mold according to the present invention, where A shows one embodiment, B shows another embodiment, C shows another embodiment, and D shows yet another embodiment. [Figure 2] 1 is a schematic cross-sectional view of an embodiment of a mold according to the present invention. [Figure 3]1A and 1B are partial external perspective views of one embodiment of a mold according to the present invention, where A shows one embodiment, B shows another embodiment, C shows another embodiment, and D shows yet another embodiment. [Figure 4] 1A and 1B are a partial schematic cross-sectional view and a partial schematic perspective view of one embodiment of a mold according to the present invention. [Figure 5] 1A and 1B are a partial schematic cross-sectional view and a partial schematic perspective view, respectively, of one embodiment of a mold according to the present invention. [Figure 6] 1A to 1C are explanatory diagrams of a method for manufacturing a mold according to the present invention. [Figure 7] FIG. 10 is a schematic cross-sectional view of another embodiment of a mold according to the present invention. [Figure 8] FIG. 10 is a schematic cross-sectional view of yet another embodiment of a mold according to the present invention. [Figure 9] FIG. 10 is a schematic cross-sectional view of another embodiment of a mold according to the present invention. [Figure 10] FIG. 10 is a schematic cross-sectional view of yet another embodiment of a mold according to the present invention. [Figure 11] FIG. 10 is a schematic cross-sectional view of yet another embodiment of a mold according to the present invention. [Figure 12] FIG. 1 is a perspective view of an embodiment of a mold according to the present invention. [Figure 13] FIG. 1 is a perspective view of an embodiment of a mold according to the present invention, and is an explanatory view showing parts of the mold. [Figure 14] FIG. 1 is a perspective view of a resin molded product obtained using a mold according to the present invention. [Figure 15] FIG. 1 is an explanatory diagram showing the details of an antibacterial evaluation test conducted using a resin molded product obtained using the mold according to the present invention and a normal resin molded product. [Figure 16] 1 is a graph showing the results of an antibacterial evaluation test carried out using a resin molded product obtained using a mold according to the present invention and a normal resin molded product. [Figure 17] FIG. 1 is an explanatory diagram showing the results of a water repellency evaluation performed using a resin molded product having a microstructure obtained using a mold according to the present invention and a normal resin molded product. [Figure 18]FIG. 1 is an explanatory diagram showing the results of a comparison of the transferability of a microstructure to a molded article with and without gas permeability using an injection molding die. [Figure 19] 19(a) shows a 3D image, 19(b) shows a 3D transmission image, 19(c) shows a horizontal cross-sectional image of each layer, and 19(d) shows a vertical cross-sectional image of each layer. [Figure 20] 1A and 1B are explanatory side and perspective views, respectively, of a gas permeation measurement test piece for conducting a gas permeation measurement test of a mold according to an embodiment of the present invention. [Figure 21] FIG. 2 is an explanatory diagram of a gas permeation measuring device used in a gas permeation measuring test. [Figure 22] FIG. 1 is an explanatory diagram of the results of a gas permeation measurement test. [Figure 23] FIG. 23 is a graph showing the published test results of antibacterial evaluation of nanostructures created on a silicon substrate, showing the viable bacteria rate versus pillar height. [Figure 24] 1A to 1C are explanatory diagrams relating to the demolding properties of a nanoimprint molding template according to an embodiment of the present invention. [Figure 25] FIG. 10 is another explanatory diagram relating to the demolding properties of the nanoimprint molding template according to the embodiment of the present invention. [Figure 26] FIG. 10 is still another explanatory diagram relating to the demolding properties of the nanoimprint molding template according to the embodiment of the present invention. [Figure 27] FIG. 10 is another explanatory diagram relating to the demolding properties of the nanoimprint molding template according to the embodiment of the present invention. [Figure 28] FIG. 10 is yet another explanatory diagram relating to the demolding properties of the nanoimprint molding template according to the embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0039] [Polymerizable compound] The imprint molding template of the present invention is an extremely stable composition comprising a combination of a silicon-containing monomer and a titanium-containing monomer. Furthermore, as shown in Chemical Formula 5, the epoxy groups in the hydrolysis condensation product of a combination of a silicon-containing monomer and a titanium-containing monomer react with the crosslinking agent to form a three-dimensional crosslinked structure. This makes the product less soluble in organic solvents and water, providing extremely high resistance. Therefore, intermixing with the injection-molded transfer product does not occur, and dissolution due to melting during pattern formation on the transfer product surface does not occur. [ka] [Curable composition] The curable composition of the present invention may further contain, as needed, a polymerization initiator which is a cationic ionic photoacid generator, a solvent, a rheology modifier, an adhesion aid, other polymerizable compounds (e.g., a reactive diluent, etc.), etc., as shown in Chemical Formula 6. [ka]

[0040] (Polymerization initiator) The curable composition of the present invention may contain a photopolymerization initiator. Examples of the photopolymerization initiator (or photoradical polymerization initiator) include benzoins (e.g., benzoin; benzoin alkyl ethers such as benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether); acetophenones (acetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, etc.); aminoacetophenones (2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone-1, etc.); anthraquinones (anthraquinone, anthraquinone-2-sulfonate, etc.); thioxanthones (e.g., thioxanthone, isopropoxychlorothioxanthone, etc.); and ketals. Examples of photopolymerization initiators include benzophenones (e.g., benzophenone, 4-hydroxybenzophenone); 2,4,5-triarylimidazole dimers (e.g., 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(2,4-dimethoxyphenyl)-4,5-diphenylimidazole dimer); xanthones; 2,4,6-trihalomethyltriazines; acridine derivatives (e.g., 9-phenylacridine, 1,7-bis(9,9′-acridinyl)heptane); and bisacylphosphine oxides (e.g., bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide). These photopolymerization initiators may be used alone or in combination of two or more.

[0041] The proportion of the polymerization initiator (thermal and / or photopolymerization initiator) may be, for example, 0.01 to 20 parts by weight, preferably 0.1 to 15 parts by weight (e.g., 0.5 to 10 parts by weight), and more preferably 1 to 9 parts by weight (e.g., 3 to 7 parts by weight) relative to 100 parts by weight of the total amount of (meth)acryloyl group-containing compounds in the curable composition (e.g., the total amount of the polymerizable compound of the present invention and other polymerizable compounds described below). If the amount of polymerization initiator is too large, the crosslink density of the cured product may increase, possibly resulting in a decrease in the gas permeability of the cured product.

[0042] The photopolymerization initiator may be combined with a photosensitizer. Examples of photosensitizers include conventional photosensitizers such as tertiary amines (e.g., trialkylamines, trialkanolamines (e.g., triethanolamine), dialkylaminobenzoic acid alkyl esters such as ethyl N,N-dimethylaminobenzoate (e.g., ethyl p-(dimethylamino)benzoate), amyl N,N-dimethylaminobenzoate (e.g., amyl p-(dimethylamino)benzoate), bis(dialkylamino)benzophenones such as 4,4-bis(dimethylamino)benzophenone and 4,4-bis(diethylamino)benzophenone, and dialkylaminobenzophenones such as 4-(dimethylamino)benzophenone and 4-methoxy-4'-dimethylaminobenzophenone). These photosensitizers may be used alone or in combination of two or more.

[0043] The proportion of the photosensitizer may be about 1 to 200 parts by weight, preferably 5 to 150 parts by weight, and more preferably 10 to 100 parts by weight, relative to 100 parts by weight of the photopolymerization initiator.

[0044] (solvent) The solvent (or dispersion medium) may be any solvent capable of dispersing or dissolving the polymerizable compound and preparing a uniform dispersion or solution, and examples thereof include water; glycols (e.g., (poly)C2-4 alkylene glycols such as ethylene glycol, propylene glycol, and diethylene glycol); (poly) alkylene glycol monoalkyl ethers [e.g., cellosolves such as ethylene glycol monomethyl ether (methyl cellosolve) and ethylene glycol monoethyl ether (ethyl cellosolve); carbitols such as diethylene glycol monomethyl ether (methyl carbitol) and diethylene glycol monoethyl ether (ethyl carbitol); C3-4 alkylene glycol mono-C1-4 alkyl ethers such as propylene glycol monomethyl ether and propylene glycol monobutyl ether]; (poly) alkylene glycol monoalkyl ether acetates [e.g., cellosolve acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; carbitol acetates such as methyl carbitol acetate and ethyl carbitol acetate]. acetates; (poly)C3-4 alkylene glycol monoC1-4 alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, etc.; ethers (e.g., dialkyl ethers such as diethyl ether; cyclic ethers such as tetrahydrofuran); ketones (e.g., chain ketones such as acetone and methyl ethyl ketone; cyclic ketones such as cyclopentanone and cyclohexanone, etc.) ); esters {for example, alkanoic acid esters (for example, C2-5 alkanoic acid C1-5 alkyl esters such as ethyl acetate, butyl acetate, etc.); alkoxyalkanoic acid esters (for example, C1-2 alkoxyC2-5 alkanoic acid C1-5 alkyl esters such as ethoxyethyl acetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.); hydroxyalkanoic acid esters [for example, hydroxyacetic acid esters such as hydroxyethyl acetate;Examples of suitable hydroxyalkanoates include lactate esters such as ethyl 2-hydroxypropionate (ethyl lactate) and butyl 2-hydroxypropionate (butyl lactate); C1-5 alkyl hydroxyalkanoates such as ethyl 2-hydroxy-2-methylpropionate and methyl 2-hydroxy-3-methylbutanoate; pyruvates (e.g., C1-5 alkyl pyruvates such as methyl pyruvate and ethyl pyruvate); amides (e.g., N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone); nitriles (e.g., acetonitrile); sulfoxides (e.g., dimethyl sulfoxide); hydrocarbons (e.g., aliphatic hydrocarbons such as hexane and heptane; alicyclic hydrocarbons such as cyclohexane; aromatic hydrocarbons such as toluene and xylene); and halogenated hydrocarbons (e.g., methylene chloride, chloroform, 1,2-dichloroethane, chlorobenzene).

[0045] These solvents can be used alone or in combination of two or more. Of these solvents, ketones such as methyl ethyl ketone are preferred. The proportion of the solvent (or dispersion medium) may be, for example, 10 to 1000 parts by weight, preferably 50 to 500 parts by weight, and more preferably about 100 to 200 parts by weight, relative to 100 parts by weight of the total amount of (meth)acryloyl group-containing compounds in the curable composition (for example, the total amount of the polymerizable compound of the present invention and other polymerizable compounds described below). If the proportion of the solvent is too low, it may be difficult to apply (or coat) the composition to a substrate, and further, storage stability may be reduced.

[0046] (Rheology modifier) The curable composition of the present invention may optionally contain a rheology modifier to adjust the flowability of the curable composition. Examples of the rheology modifier include dialkyl phthalates (e.g., dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dihexyl phthalate, butyl isodecyl phthalate, etc.); dialkyl adipates (e.g., di-n-butyl adipate, diisobutyl adipate, diisooctyl adipate, octyl decyl adipate, etc.); dialkyl maleates (e.g., di-n-butyl maleate, diethyl maleate, dinonyl maleate, etc.); oleates (e.g., alkyl oleates such as methyl oleate and butyl oleate; tetrahydrofurfuryl oleate, etc.); stearates (e.g., alkyl stearates such as n-butyl stearate; glyceryl stearate, etc.).

[0047] The proportion of the rheology modifier may be, for example, 0 to 100 parts by weight, preferably about 1 to 50 parts by weight, relative to 100 parts by weight of the total amount of (meth)acryloyl group-containing compounds in the curable composition (for example, the total amount of the polymerizable compound of the present invention and other polymerizable compounds described below). If the proportion of the rheology modifier is too high, the mechanical strength of the cured product may be reduced.

[0048] (adhesion aid) If necessary, an adhesion promoter may be added to the curable composition of the present invention to improve the adhesion between the substrate on which the curable composition is applied and the cured product. Examples of the adhesion promoter include silanes {e.g., chlorosilanes (e.g., trimethylchlorosilane, dimethylvinylchlorosilane, chloromethyldimethylchlorosilane, etc.); alkoxysilanes (e.g., monoalkoxysilanes such as trimethylmethoxysilane and dimethylvinylethoxysilane; dialkoxysilanes such as dimethyldiethoxysilane and diphenyldimethoxysilane; trialkoxysilanes (or silane coupling agents) such as phenyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidyloxypropyltrimethoxysilane, and γ-(meth)acryloyloxypropyltrimethoxysilane); silylamines (e.g., dimethyltrimethylsilylamine, etc.); silazanes (e.g., hexamethyldisilazane, etc.); silylimidazoles (e.g., trimethylsilylsilane, γ-chloropropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ-(meth)acryloyloxypropyltrimethoxysilane, etc.); silyl ureas (e.g., N,N'-bis(trimethylsilyl)urea, etc.); ureas [urea compounds (e.g., 1,1-dimethylurea (N,N-dimethylurea), 1,3-dimethylurea (N,N'-dimethylurea)]; thiourea compounds, etc.]; heterocycles [e.g., imidazoles (e.g., imidazole, benzimidazole, mercaptoimidazole, 2-mercaptobenzimidazole, etc.); triazoles (e.g., benzotriazole, etc.); indazoles (e.g., indazole, etc.); oxazoles (e.g., 2-mercaptobenzoxazole, etc.); thiazoles (e.g., 2-mercaptobenzothiazole, etc.); urazoles (e.g., urazole, etc.); thiouracils (e.g., 4-thiouracil, etc.); pyrimidines (e.g., mercaptopyrimidine, etc.)].

[0049] The proportion of the adhesion aid may be, for example, 0 to 10 parts by weight, preferably about 1 to 5 parts by weight, relative to 100 parts by weight of the total amount of (meth)acryloyl group-containing compounds in the curable composition (for example, the total amount of the polymerizable compound of the present invention and other polymerizable compounds described below).

[0050] (Other polymerizable compounds) The curable composition may further contain, in addition to the polymerizable cured product of the present invention, other polymerizable compounds (sometimes simply referred to as monomers) having one or more polymerizable groups in the molecule. The monomers are compounds having a polymerizable group (or polymerizable unsaturated bond) in the molecule [for example, an alkenyl group (e.g., a vinyl group, an allyl group, etc.), a (meth)acryloyl group, etc.]. Examples of the monomer include (meth)acrylic monomers.

[0051] The (meth)acrylic monomer may be monofunctional or polyfunctional having two or more (meth)acryloyl groups. Examples of the monofunctional (meth)acrylic monomer include (meth)acrylic acid, (meth)acrylamide, (meth)acrylonitrile, and the like, and may also be a monofunctional (meth)acrylate. These monomers may be used alone or in combination of two or more.

[0052] Examples of monofunctional (meth)acrylates include alkyl (meth)acrylates [e.g., C1-20 alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, and butyl (meth)acrylate]; cycloalkyl (meth)acrylates [e.g., monocyclic C5-10 cycloalkyl (meth)acrylates such as cyclohexyl (meth)acrylate; bridged cyclic C7-20 cycloalkyl (meth)acrylates such as isobornyl (meth)acrylate, norbornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and adamantyl (meth)acrylate]; aryl (meth)acrylates (e.g., phenyl (meth)acrylate); aralkyl (meth)acrylates (e.g., benzyl (meth)acrylate) etc.); aryloxyalkyl (meth)acrylates (e.g., phenoxyethyl (meth)acrylate, etc.); alkylaryloxyalkyl (meth)acrylates (e.g., nonylphenoxyethyl (meth)acrylate, etc.); hydroxyalkyl (meth)acrylates (e.g., 2-hydroxyethyl (meth)acrylate, etc.); alkoxyalkyl (meth)acrylates (e.g., methoxyethyl (meth)acrylate, etc.); epoxy group-containing (meth)acrylates (e.g., glycidyl (meth)acrylate, etc.); sulfur atom-containing (meth)acrylates (e.g., phenylthioethyl (meth)acrylate, etc.); N,N-dialkylaminoalkyl (meth)acrylates (e.g., N,N-dimethylaminoethyl (meth)acrylate, etc.). These monofunctional (meth)acrylates can be used alone or in combination of two or more.

[0053] The (meth)acrylic monomer may be polyfunctional, and examples of polyfunctional (meth)acrylates include difunctional (meth)acrylates [e.g., (poly)C2-4 alkylene glycol di(meth)acrylates such as ethylene glycol di(meth)acrylate and dipropylene glycol di(meth)acrylate; di(meth)acrylate of bisphenol A (or its C2-4 alkylene oxide adduct); glycerin di(meth)acrylate, etc.]; trifunctional or higher functional (meth)acrylates [e.g., glycerin tri(meth)acrylate, trimethylolpropanediol, etc.]; Examples of the polyfunctional (meth)acrylate include tri- or hexaol tri- or hexa(meth)acrylates such as ditrimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate; (meth)acrylate oligomers [e.g., urethane (meth)acrylate, epoxy (meth)acrylate, polyester (meth)acrylate, etc.]. These polyfunctional (meth)acrylates may be used alone or in combination of two or more.

[0054] The proportion of these other polymerizable compounds may be, for example, 0 to 100 parts by weight, preferably about 1 to 50 parts by weight, relative to 100 parts by weight of the polymerizable compound of the present invention. If the proportion of the other polymerizable compounds is too high, the gas permeability of the cured product may decrease.

[0055] (Other additives) The curable composition may further contain, as necessary, conventional additives such as colorants, stabilizers (heat stabilizers, antioxidants, ultraviolet absorbers, etc.), fillers, antistatic agents, flame retardants, surfactants, It may contain a plasticizer, a polymerization inhibitor, etc. These additives may be used alone or in combination of two or more.

[0056] [Characteristics of the cured product (template) and curing method] (Curing method) The curable composition of the present invention can be easily cured to form a cured product by undergoing a curing step in which active energy (active energy rays) is applied. The active energy used in the curing step can be thermal energy and / or light energy (ultraviolet rays, electron beams, X-rays, etc.).

[0057] When thermal energy is used, the heating temperature may be, for example, about 50 to 250° C., preferably about 80 to 200° C., and more preferably about 100 to 150° C. The heating time may be, for example, about 5 minutes to 12 hours, preferably about 10 minutes to 8 hours, and more preferably about 30 minutes to 4 hours.

[0058] Furthermore, when light energy (e.g., light irradiation such as ultraviolet irradiation) is used, the amount of light irradiation energy can be appropriately selected depending on the application and may be, for example, about 100 to 200,000 mJ / cm2, preferably 1,000 to 150,000 mJ / cm2, and more preferably 10,000 to 100,000 mJ / cm2 (e.g., 50,000 to 80,000 mJ / cm2). Examples of light sources that can be used include deep UV lamps, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, halogen lamps, and laser light sources (e.g., helium-cadmium lasers, excimer lasers, and other light sources). Even when curing by light irradiation, heat treatment (after-baking) may be performed to improve reactivity. The temperature and time of the heat treatment may be the same as those when using thermal energy. Furthermore, the reaction (or polymerization, crosslinking, or curing) may be carried out in an air atmosphere or an inert gas atmosphere (e.g., a nitrogen atmosphere; a rare gas atmosphere such as helium or argon), and may be carried out under normal pressure, elevated pressure, or reduced pressure.

[0059] (Characteristics of the cured product) The cured product of the present invention obtained by such a method has excellent gas permeability. For example, the gas permeability coefficient for oxygen measured in accordance with JIS K7126-1 (2006) can be selected from a range of about 10×10-12 to 2000×10-12 cm3·cm / (cm2·sec·cmHg), and may be, for example, about 50×10-12 to 1500×10-12 cm3·cm / (cm2·sec·cmHg), preferably about 80×10-12 to 1000×10-12 cm3·cm / (cm2·sec·cmHg), and more preferably about 100×10-12 to 700×10-12 cm3·cm / (cm2·sec·cmHg).

[0060] Furthermore, the cured product of the present invention is excellent not only in gas permeability but also in mechanical strength. For example, the Young's modulus (elastic modulus) measured in accordance with JIS K7161-1 (2014) can be selected from the range of about 0.5 to 10 GPa, and may be, for example, about 1 to 8 GPa, preferably about 2 to 6 GPa, and more preferably about 2.5 to 4 GPa.

[0061] Furthermore, the cured product of the present invention has high transparency (light transmittance). In a film-like cured product (thickness 10 μm), the light transmittance at a wavelength of 300 to 900 nm may be, for example, 50% or more (e.g., 70% or more), preferably 80% or more (e.g., 90% or more), and more preferably 95% or more (particularly about 98 to 100%). The light transmittance can be measured by the method described in the Examples below.

[0062] The cured product of the present invention also has excellent solvent resistance. Even when immersed in a solvent (for example, a polar solvent such as methyl ethyl ketone or N,N-dimethylformamide) at room temperature for 3 minutes, the film thickness of the cured product does not change at all and it does not swell.

[0063] The cured product (template) of the present invention has high gas permeability and can simultaneously achieve mechanical properties such as elastic modulus and various properties required in imprint molding (e.g., solvent resistance, low linear thermal expansion (or dimensional stability), transparency (light transmittance), etc.), and therefore can be suitably used as a template for imprint molding.

[0064] (Imprint template and its preparation method) The imprint template is formed from the cured product and has a pattern shape (a concave-convex pattern or a patterned surface) on at least a portion of the surface of the cured product. The pattern shape is not particularly limited and may be, for example, line and space, dot, pillar, V-groove, lattice, lens, honeycomb, pyramid, or a combination thereof. These pattern shapes may be micrometer-sized or nanometer-sized (for example, in line and space, the line width may be about 10 to 1,000 nm, preferably about 100 to 600 nm). The template of the present invention has high gas permeability and dimensional stability (low linear thermal expansion), and therefore can transfer finer or more complex pattern shapes with high accuracy in imprint molding.

[0065] Conventional methods can be used to form the pattern shape. For example, the pattern shape may be formed by transferring the pattern shape of a master template (i.e., imprint molding). In this method, for example, the curable composition of the present invention may be applied (or coated) to a substrate to form a curable composition layer, and the pattern surface of the master template may be pressed against this curable composition layer, thereby transferring the pattern shape through the curing step. In forming the curable composition layer, if the curable composition contains a volatile component such as a solvent, the volatile component may be removed from the curable composition layer by heating and / or reducing pressure before pressing against the master template, thereby improving productivity. Furthermore, pressing may be performed so as not to introduce air bubbles during contact with the master template. The method may further include a demolding step in which the cured product (template) obtained through the curing step is released from the master template. By such a method, a cured product (template) having a pattern shape (a shape that is the inverse of the pattern of the master template) can be easily prepared.

[0066] In this method, the master template may be formed from a material such as ceramics (e.g., quartz), metal, or resin, or may be formed from a material with low gas permeability (e.g., quartz). Even if the master template has low gas permeability, the cured product (template) of the present invention has high gas permeability and easily transmits ambient air (e.g., air), and therefore can be easily released from the master template in the demolding step. Therefore, even if the cured product and the master template are in close contact due to a fine pattern shape, damage to the pattern shape due to demolding can be prevented (or suppressed), and a pattern can be formed with high precision.

[0067] The substrate may be in the form of a plate or a flexible (or bendable) film. The substrate may be formed of, for example, an inorganic material (e.g., silicon, alumina, glass, etc.), a metal (e.g., brass, aluminum, etc.), a resin (e.g., a (meth)acrylic resin such as polymethyl methacrylate (PMMA), a polyester resin such as polyethylene terephthalate (PET), etc.), or a transparent substrate such as a glass substrate or a transparent resin substrate (e.g., a PET substrate) because the template of the present invention has excellent transparency and can be used for optical imprinting.

[0068] An adhesive layer made of an adhesive material (such as "GF" manufactured by Nissan Chemical Industries, Ltd.) may be laminated on the surface of the substrate to adhere the cured product (template). The thickness may be about 10 to 100 nm (for example, 30 to 70 nm).

[0069] (Method of transferring a pattern formed on a template) As a method for transferring a pattern to a transfer-receiving material using the template of the present invention, a method similar to the above-mentioned method for preparing the template (imprint molding) can be used.

[0070] The components of the transfer-receiving agent are not particularly limited and may be resin components such as thermoplastic resins and heat- or photo-curable resins. In particular, the template of the present invention has high transparency (light transmittance), so that the transfer-receiving agent can be irradiated with light through the template. Therefore, photo-curable resins, such as photo-radical curable resins and photo-cationic curable resins (e.g., epoxy resins, oxetane resins, vinyl ether resins, etc.), may be suitably used as the transfer-receiving agent. These photo-curable resins may be used alone or in combination of two or more. Of these photo-curable resins, photo-radical curable resins are preferred.

[0071] The photoradical curable resin may be any resin capable of forming a three-dimensional network-like cured product by polymerization, and examples thereof include the polyfunctional (meth)acrylates exemplified in the section on other polymerizable compounds. These polyfunctional (meth)acrylates may be used alone or in combination of two or more. Among these polyfunctional (meth)acrylates, bifunctional (meth)acrylates and (meth)acrylate oligomers are preferred, and bifunctional (meth)acrylates (particularly (poly)C2-4 alkylene glycol di(meth)acrylates such as ethylene glycol di(meth)acrylate) are particularly preferred.

[0072] Furthermore, the photoradical curable resin may further contain, as necessary, a monofunctional (meth)acrylate exemplified in the section on other polymerizable compounds. These monofunctional (meth)acrylates may be used alone or in combination of two or more. Among these monofunctional (meth)acrylates, alkyl (meth)acrylates, cycloalkyl (meth)acrylates, and the like are preferred, and C1-4 alkyl (meth)acrylates such as butyl (meth)acrylate, and C7-10 crosslinked cyclic (meth)acrylates such as isobornyl (meth)acrylate are particularly preferred. The proportion of the monofunctional (meth)acrylate may be, for example, 0 to 1,000 parts by weight, preferably 10 to 800 parts by weight, and more preferably about 100 to 500 parts by weight, relative to 100 parts by weight of the polyfunctional (meth)acrylate.

[0073] The transfer-receiving agent may further contain additives such as a thermal or photopolymerization initiator, a photosensitizer, a solvent, a rheology modifier, an adhesive aid, or other conventional additives. Examples of these additives include the components described in the section on the polymerizable composition, and preferred components and proportions may also be similar to those described above. Typically, when the transfer-receiving agent contains a solvent (or a volatile component, such as methyl ethyl ketone), evaporation of the solvent reduces transfer accuracy and increases transfer failure (or pattern defects). Therefore, in conventional methods, a good pattern shape cannot be transferred unless the solvent is removed before pressing the template. However, the method of the present invention allows efficient and highly accurate pattern transfer without removing the solvent from the transfer-receiving agent layer, and therefore, solvents can be suitably used. Therefore, resin components that were previously unusable as transfer-receiving agents (e.g., resin components that are highly viscous and therefore do not easily transfer patterns in the absence of a solvent) can now be used, expanding the range of applications for imprint molding.

[0074] The template of the present invention has high gas permeability, so that even if the transfer-receiving material (or transfer-receiving material layer) contains a large amount of solvent during imprint molding, the evaporated solvent vapor can pass through the template, and the solvent vapor can be efficiently diffused between the template and the transfer-receiving material. Therefore, a pattern can be transferred with high precision without removing the solvent from the transfer-receiving material layer, and transfer defects can be effectively reduced. For example, when the line width is 100 to 1000 nm (for example, 1 When transferring a line and space pattern having a width of about 50 to 600 nm (e.g., 100 to 1000 nm (e.g., 300 to 700 nm) and a line:space ratio of 1:1, the variation in the line width dimension of the transferred pattern exceeds ±10% with a conventional template such as polydimethylsiloxane (PDMS), whereas with the template of the present invention, this can be reduced to, for example, ±10% or less (e.g., ±8% or less), preferably ±5% or less (e.g., ±2% or less).

[0075] Furthermore, the template of the present invention has high gas permeability, which effectively prevents the inclusion of air bubbles between the template and the material to be imprinted (or the material layer to be imprinted) when the template is brought into contact with the material to be imprinted. Therefore, in imprint molding, a pattern can be easily and accurately transferred in the atmosphere without the need for a special method for suppressing the inclusion of air bubbles (for example, a method performed in a special environment such as a helium gas atmosphere or a reduced pressure environment).

[0076] Furthermore, since the template is easily permeable to external air (such as air), the template can be easily released in the demolding step, and damage to the pattern shape and the resulting contamination with foreign matter can be effectively prevented. Therefore, even when imprint molding is repeatedly performed using the template of the present invention, the pattern shape can be transferred satisfactorily, and the durability of the template can be improved.

[0077] Next, a resin molded product molded by a mold according to one embodiment of the present invention using the template of the present invention will be described with reference to the drawings. As shown in Fig. 1, the resin molded product 1 is a resin molded product having minute protrusions 2 on its surface, and the protrusions 2 on the surface have a height of 250 nm to 1000 nm and a pitch of 250 nm to 800 nm. Here, the pitch is the distance between the centers of adjacent protrusions 2.

[0078] Next, a method for manufacturing the above-described resin molded product 1 will be described with reference to the drawings. The method for manufacturing a resin molded product according to this embodiment uses a mold 3 shown in Fig. 2. The mold 3 is laminated on a base (not shown) and includes a truss layer 5 having gas flow passages 4 formed therein, a porous layer 6 laminated on the truss layer 5, a lattice layer 7 having a lattice-like structure laminated on the porous layer 6, and an imprint molding template 8 laminated on the lattice layer 7. The gas flow passages 4 are formed in an oblique manner as a result of the truss layer 5 having an internal structure in which triangular layers are stacked.

[0079] As shown in Fig. 3, recesses 9 are formed in the imprint molding template 8. The size of these recesses 9 can be set as needed, with a depth of 250 nm to 1000 nm and a pitch of 250 nm to 800 nm. Here, the pitch is the distance between the centers of adjacent recesses 9. In the method for manufacturing the resin molded product 1, resin is injected into a cavity formed by the mold 3 and then hardened.

[0080] As shown in FIGS. 4 and 5, a mold 3 according to an embodiment of the present invention has a gas permeable functionally graded portion 10 formed by laminating a porous layer 6 and a lattice layer 7 on a truss layer 5 . The truss layer 5, porous layer 6, and lattice layer 7 are made of sintered metal, and the functions of each part are realized by adjusting the sintering temperature and sintering time. Furthermore, the sintering is carried out continuously from the truss layer 5 to the porous layer 6 and the lattice layer 7, and the joint boundary between the truss layer 5 and the porous layer 6 and the joint boundary between the porous layer 6 and the lattice layer 7 are continuous layers formed by continuous sintering.

[0081] The gas flow passages 4 formed in the truss layer 5 are formed in an X-shaped configuration with multiple paths intersecting, which allows for the flow of large amounts of gas while maintaining the strength of the truss layer 5 and reducing its weight. The porous layer 6 laminated on the truss layer 5 has gas permeability due to its porosity. On the other hand, gas passages 11 having a width of 100 to 120 μm and a pitch of 2.0 to 3.0 mm are formed in the lattice layer 7. Here, the pitch is the distance between the centers of the gas permeation holes 11a. In this way, by laminating the porous layer 6 and the lattice layer 7 on the truss layer 5 to form the gas permeable functionally graded portion 10, it is possible to maintain strength while allowing gas to permeate.

[0082] Gas permeability is also ensured by providing numerous pores 8a in the imprint molding template 8. The size of the recesses 9 can be set as needed within the range of a diameter of 20 to 500 nm, a depth of 250 to 1000 nm, and a center-to-center distance between adjacent recesses 9 of 250 to 800 nm.

[0083] As described above, the truss layer 5 of the mold 3, the imprint molding template 8, and the gas-permeable gradient functional portion 10 are all gas-permeable, which makes it possible to exhaust gas from the cavity formed by the mold 3 during injection molding, and also makes it extremely easy to transfer the surface shape of the mold 3 to the molded object.

[0084] Next, one embodiment of the method for manufacturing a mold according to the present invention will be described. 6, the mold manufacturing method of this embodiment includes a step of applying a gas permeable surface layer liquid 8b to a gas permeable functionally gradient section 10 formed by laminating a porous layer 6 and a lattice layer 7 on a truss layer 5. Next, a step of placing an original plate 12 with a fine nanostructure on the gas permeable surface layer liquid 8b applied to the lattice layer 7 of the gas permeable functionally gradient section 10 is performed.

[0085] This original plate 12 with a fine nanostructure has fine protrusions 12a formed on its surface in advance, and these protrusions 12a on the surface have a diameter of 20 to 500 nm, a height of 250 to 1000 nm, and a center-to-center distance between adjacent protrusions of 250 to 800 nm.

[0086] Next, a photo-curing reaction step is carried out in which ultraviolet light is irradiated onto the gas-permeable surface layer liquid 8b on which the original plate 12 with fine nanostructures is placed. The photo-curing reaction process consists of a first irradiation step in which ultraviolet (UV) light is irradiated for 30 seconds using a Hamaphoto LC8, and a second irradiation step in which ultraviolet (UV) light is irradiated for 1 minute using a metal halide lamp. Pre-irradiation is performed in the first irradiation step, and main irradiation is performed in the second irradiation step. By dividing the process into two steps in this way, sufficient photo-curing can be achieved.

[0087] Next, by removing the original plate 12 with the fine nanostructure, a mold 3 can be obtained that is equipped with an imprint molding template 8 having recesses 9 to which fine protrusions 12a previously formed on the surface of the original plate 12 with the fine nanostructure have been transferred.

[0088] The resins that can be injection molded using mold 3 are thermoplastic resins such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polybutylene-ethylene terephthalate (PBT-PET copolymer resin), polyether ether ketone (PEEK resin), polyphenylene sulfide (PPS), polyetherimide (PEI), 6 nylon (PA6), 6-6 nylon (PA66), 6T nylon (PA6T), polyphthalamide (PPA), polystyrene (PS), ABS resin (ABS), polyvinyl chloride resin (PVC), polyacetal (POM), liquid crystal polymer (LCP), polysulfone (PSU), polypropylene (PP), polycarbonate (PC), etc. These can be used alone or in combination. Also included are thermosetting resins such as phenolic resin (PF), epoxy resin (EP), diallyl phthalate resin (PDAP), silicone resin (SI), polyimide resin (PI), melamine resin (MF), and urea resin (UF). These thermoplastic and thermosetting resins may be appropriately blended with inorganic fillers such as carbon fiber, glass fiber, glass beads, and talc to improve heat resistance and dimensional stability. Organic fillers such as cellulose nanofibers may also be appropriately blended.

[0089] 7 is a schematic cross-sectional view of another embodiment of a mold according to the present invention. The mold 3 of this embodiment has a two-layer structure in which an imprint molding template 8 is laminated on a porous layer 6. This two-layer structure can improve gas permeability. However, the resin injection pressure when using the mold 3 of this embodiment is set taking into account the strength obtained in this mode.

[0090] 8 is a schematic cross-sectional view of yet another embodiment of a mold according to the present invention. The mold 3 of this embodiment has a two-layer structure in which an imprint molding template 8 is laminated on a lattice layer 7. This two-layer structure can improve gas permeability. However, the resin injection pressure when using the mold 3 of this embodiment is set taking into account the strength obtained in this configuration.

[0091] 9 is a schematic cross-sectional view of another embodiment of a mold according to the present invention. The mold 3 of this embodiment has a three-layer structure in which a porous layer 6 is laminated on a lattice layer 7, and an imprint molding template 8 is laminated on the porous layer 6. This three-layer structure can improve gas permeability and strength. However, the resin injection pressure when using the mold 3 of this embodiment is set taking into account the strength obtained in this mode.

[0092] 10 is a schematic cross-sectional view of yet another embodiment of a mold according to the present invention. The mold 3 of this embodiment has a three-layer structure in which a lattice layer 7 is laminated on a porous layer 6, and an imprint molding template 8 is laminated on the lattice layer 7. This three-layer structure can improve gas permeability and strength. However, the resin injection pressure when using the mold 3 of this embodiment is set taking into account the strength obtained in this configuration.

[0093] 11 is a schematic cross-sectional view of yet another embodiment of a mold according to the present invention. The mold 3 of this embodiment has a four-layer structure in which a lattice layer 7 is laminated on a truss layer 5, a porous layer 6 is laminated on the lattice layer 7, and an imprint molding template 8 is laminated on the porous layer 6. This four-layer structure can improve strength while maintaining the necessary gas permeability. However, the resin injection pressure when using the mold 3 of this embodiment is set taking into account the strength obtained in this mode. [Example]

[0094] An embodiment of the imprint molding template 8 of the present invention will be described below. 35 parts by weight of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (Gelest), 35 parts by weight of methyltrimethoxysilane (Gelest), 5 parts by weight of 3-Aminopropyltriethoxysilane (Gelest), 10 parts by weight of tetraethoxysilane (Gelest), 10 parts by weight of tetraethyltitanate (Gelest), and 155 parts by weight of toluene (Tokyo Chemical Industry) were stirred with a magnetic stirrer in a reaction vessel filled with nitrogen and dissolved for 1 hour to obtain a mixed solution.

[0095] Next, 100 g of the resulting mixed solution was heated to 55°C, and 19.5 g of ion-exchanged water, 0.76 g of paratoluenesulfonic acid, and 0.42 g of hydrochloric acid were added. After reacting at 55°C for 2 hours, the resulting reaction solution was cooled to room temperature. An appropriate amount of anhydrous magnesium sulfate (Fujifilm Wako Pure Chemical Industries) was added to the reaction solution to dehydrate it and filter it. An appropriate amount of activated carbon (Tokyo Chemical Industry Co., Ltd.) was added to the filtrate, and it was similarly filtered. Excess toluene and ion-exchanged water were distilled off under reduced pressure to obtain a hydrolysis condensate combining a silicon-containing monomer and a titanium-containing monomer to be used in the gas-permeable mold surface layer.

[0096] <Solid content measurement> The solid content of the hydrolysis condensation product was calculated from the weight before and after heating after removing the solvent by heating. Specifically, the polymer solution (x g) was heated on a hot plate at 90°C for 30 minutes, and then heated on a hot plate at 120°C for 1 hour. The solid content was defined using the following formula based on the obtained solid content weight (y g). Solid content (%) = y / x x 100

[0097] 8.7 g (solids equivalent) of the hydrolysis condensate of the silicon-containing monomer and titanium-containing monomer obtained above, 1.0 g of TETRAKIS[(EPOXYCYCLOHEXYL)ETHYL]TETRAMETHYLCYCLOTETRASILOXANE,tech (manufactured by Gelest Co., Ltd.), and 0.30 g of CPI-100B (trade name) manufactured by San-Apro Co., Ltd. were added to prepare a solution of a gas-permeable mold surface layer forming composition.

[0098] (Evaluation of Solvent Resistance) A solution of the gas-permeable mold surface layer forming composition was applied to a silicon wafer by casting, irradiated for 2 minutes with a UV spotlight source (Lightning 358cure LC8, Hamamatsu Photonics), and then baked for 10 minutes on a hot plate at 120°C. The wafer was then immersed in toluene for 1 minute, and the change in the coating film thickness before and after was examined. A change in film thickness of 10 nm or less was considered good and marked with a circle, while a change in film thickness of more than 10 nm was considered bad and marked with an x. (Water resistance evaluation) A solution of the gas-permeable mold surface layer forming composition was applied to a silicon wafer by casting, irradiated for 2 minutes with a UV spotlight source (Lightning 358cure LC8, Hamamatsu Photonics), and then baked for 10 minutes on a hot plate at 120°C. The wafer was then immersed in ion-exchanged water for 1 minute, and the change in the coating film thickness before and after was examined. A change in film thickness of 10 nm or less was considered good and marked with a circle, while a change in film thickness of more than 10 nm was considered bad and marked with an x.

[0099] [Table 1] Solvent resistance test and developer resistance test ------------------------------------------------------------ Solvent resistance test: Yes (change in film thickness: 6.5 nm) Developer resistance test: Yes (film thickness change: 8.9 nm)

[0100] Next, an embodiment of the mold 3 of the present invention will be described. Fig. 12 is a perspective view of the mold 3 of the present invention described above. Also, the recesses shown in Fig. 3 are formed in parts A, B, C, and D of the mold 3 shown in Fig. 13, with different depths in the range of 250 to 1000 nm. Fig. 14 is a perspective view of a resin molded product obtained by injection molding using this mold 3. In parts A, B, C, and D of this resin molded product, protrusions corresponding to the recesses in parts A, B, C, and D of the mold 3 shown in Fig. 1 are formed with different heights in the range of 250 to 1000 nm. [Antibacterial evaluation test] FIG. 15 shows the details of an antibacterial evaluation test carried out using a resin molded product obtained using a mold according to an embodiment of the present invention and a normal resin molded product obtained using polypropylene (PP). The test method conformed to the revised JIS standard, and test bacteria solution (bacteria (E. coli)) was dropwise inoculated onto specimens (resin molded products molded using the molds of the examples of the present invention and ordinary resin molded products), and then polyethylene film was placed over them to prevent evaporation. The specimens were cultured for 24 hours at 37°C and 100% relative humidity. After that, the specimens were washed out immediately after inoculation and 24 hours after culture for the ordinary resin molded product specimens, and after 24 hours of culture for the resin molded product specimens of the examples of the present invention, and the viable bacteria count in the washout solution was measured to calculate the viable bacteria concentration in the specimens.

[0101] The results of the antibacterial evaluation test are shown in Figure 16. As shown in Figure 16, a 48% decrease in bacterial cell concentration was observed in the resin molded product test piece molded using the mold of the example of the present invention having a fine shape, compared to a regular resin molded product test piece without a fine shape.

[0102] Figure 17 shows the results of a water repellency evaluation conducted using a resin molded product having a microstructure molded using a mold according to an embodiment of the present invention obtained using polypropylene (PP) and a standard resin molded product. As shown in the figure, the resin molded product having a microstructure molded using a mold according to an embodiment of the present invention has a contact angle that is 45 degrees higher than that of the standard resin molded product. These results demonstrate that the resin molded product molded using a mold according to the present invention with a fine nano-surface structure has high water repellency, low wettability with water, and can inhibit mold growth.

[0103] Figure 18 shows the results of a comparison of the ability to transfer microstructures to molded articles with and without gas permeability, using an injection molding mold. As shown in the figure, polypropylene (PP) molded articles molded with a mold that has a convex surface structure with a microstructure height of 250 to 1000 nm and is not gas permeable showed no microstructure in the molded article, resulting in poor transfer. In contrast, polypropylene (PP) molded articles molded with a mold that has a concave surface structure with a microstructure depth of 250 to 1000 nm and is gas permeable showed a microstructure in the molded article and good transfer.

[0104] Figure 19 shows photographs of CT scans of mold 3 of the example. Figure 19(a) shows a 3D image, Figure 19(b) shows a 3D transmission image, Figure 19(c) shows horizontal cross-sectional images of each layer, and Figure 19(d) shows vertical cross-sectional images of each layer. As shown in the figure, at the joint boundary between the truss layer 5 and the porous layer 6 and at the joint boundary between the porous layer 6 and the lattice layer 7, each layer is continuously and firmly joined.

[0105] FIG. 20 shows a gas permeation measurement specimen 13 for carrying out a gas permeation measurement test. The gas permeation test piece 13 is made by laminating a porous layer 6 on a lattice layer 7, and has a variable thickness of 1.0, 2.0, 3.0, 5.0, or 7.0 mm, and has a gas-impermeable portion 13a of 40 mm diameter and a gas-permeable portion 13b of 20 mm diameter.

[0106] FIG. 21 shows a gas permeation measuring device 14 used in a gas permeation measuring test using the gas permeation measuring specimen 13. The gas permeation measurement device 14 has a jig (lower) 15 and a jig (upper) 16, and the gas permeation measurement test piece 13 is placed between the jig (lower) 15 and the jig (upper) 16. A pressure sensor (No. 2) 17 and a pressure sensor (No. 1) 18 are disposed near the jig (lower) 15 and the jig (upper) 16. The pressure sensor (No. 2) 17 detects the pressure inside the jig (upper) 16, and the pressure sensor (No. 1) 18 detects the pressure inside the jig (lower) 15. On the other hand, a flow meter (No. 1) 22 is connected to a compressor 20 via a regulator 21 in a gas flow upstream piping 19 of the jig (lower part) 15 so as to allow gas to flow. A flow meter (No. 2) 24 is disposed in the gas flow downstream pipe 23 of the jig (upper part) 16 .

[0107] FIG. 22 shows the results of a gas permeation measurement test carried out using a gas permeation measurement specimen 13 and a gas permeation measurement device 14. As shown in the figure, a gas permeation measurement test using a 1.0 mm thick gas permeation measurement test piece 13 showed effective gas permeability at 0.2 to 0.3 MPa, and a gas permeation measurement test using a 2.0 mm thick gas permeation measurement test piece 13 showed effective gas permeability at 0.4 to 0.7 MPa.

[0108] 24 to 28 show the results of investigating the releasability of the surface layer material that is the imprint molding template 8. FIG. As shown in Figure 24, the demoldability of the surface material 8 needs to be evaluated in terms of the demoldability between the surface material 8 and the plastic resin (e.g., PP, AS+GF, PMMA, etc.) that is the resin molded product 1, and the demoldability between the surface material 8 and the metal (gas permeable sintered metal body) of the gas permeable gradient functional part 10. As shown in Figure 25, in the conventional product, foreign matter 25 was found to be attached to the surface layer material 8 in the molded product after 10 shots, but as shown in Figure 26, in the surface layer material 8 of the present invention, no foreign matter was found to be attached to the surface layer material 8 even in the molded product after 1000 shots. In the conventional product shown in FIG. 25, the shape of the fine structure is 500 nm in diameter and 130 nm in height. On the other hand, in the surface layer material 8 of the present invention shown in FIG. 26, the shape of the fine structure was set to a diameter of 200 nm and a height of 290 nm.

[0109] Regarding the releasability of the surface layer material 8 from the metal (gas permeable sintered metal body), when the state of the surface layer material 8 being released from the metal (gas permeable sintered metal body) after 10 shots was examined, peeled areas 26 were present in the surface layer material 8 as shown in Figure 27. In contrast, in the surface layer material 8 of the present invention, there was no peeling of the surface layer material 8 as shown in Figure 28. Note that the arrows in Figures 27 and 28 indicate the flow direction of the resin. [Explanation of symbols]

[0110] 1···Resin molded product, 2···Convex part, 3···Mold, 4···Gas flow channel, 5···Base, 6···Porous layer, 7···Lattice layer, 8···Imprint molding template, 9···Concave part, 10···Gas permeable functionally graded part, 11···Gas channel, 12···Original plate with fine nanostructure.

Claims

1. An imprint molding template, characterized by having a structure according to the following formula, formed from a cured product of a curable composition containing a polymerizable compound obtained by combining a silicon-containing monomer and a titanium-containing monomer. 【Chemical 1】

2. 1. An imprint molding template comprising a silicon-containing monomer and a titanium-containing monomer in combination, the imprint molding template having the following formula: 【Chemistry 2】

3. 1. An imprint molding template comprising a silicon-containing monomer and a titanium-containing monomer in combination, the imprint molding template having the following formula: 【Chemistry 3】

4. 1. An imprint molding template comprising a silicon-containing monomer and a titanium-containing monomer in combination, the imprint molding template having the following formula: 【Chemistry 4】

5. 5. The imprint molding template according to claim 1, further comprising a thermal polymerization initiator and / or a photopolymerization initiator.

6. The imprint molding template according to any one of claims 1 to 5, further comprising a solvent.

7. 7. The imprint molding template according to claim 1, which is a micro- or nano-imprint molding template.

8. 8. The imprint molding template according to claim 1, wherein the pattern shape is an inverse of the pattern shape of the master template.

9. 9. The imprint molding template according to claim 1, wherein the oxygen gas permeability coefficient measured in accordance with JIS K7126-1 (2006) is 10×10 to 2000×10 cm cm / (cm sec cmHg).

10. A method for forming the imprint molding template according to any one of claims 1 to 9, comprising applying activation energy to the curable composition according to any one of claims 1 to 6 to cure it.

11. A method for transferring a pattern to a transfer-receiving material, using the imprint molding template according to any one of claims 1 to 9 as a template.

12. 12. The method of claim 11, wherein the receiver comprises a solvent.

13. A mold comprising an imprint molding template laminated on a gas-permeable sintered metal layer, wherein the imprint molding template has a structure shown in Chemical Formula 1 formed from a cured product of a curable composition containing a polymerizable compound formed by combining a silicon-containing monomer and a titanium-containing monomer.

14. A mold comprising an imprint molding template laminated on a gas-permeable sintered metal layer, wherein the imprint molding template has a structure shown in Chemical Formula 2 and is formed from a cured product of a curable composition containing a polymerizable compound formed by combining a silicon-containing monomer and a titanium-containing monomer.

15. A mold comprising an imprint molding template laminated on a gas-permeable sintered metal layer, wherein the imprint molding template has a structure shown in Chemical Formula 3 and is formed from a cured product of a curable composition containing a polymerizable compound formed by combining a silicon-containing monomer and a titanium-containing monomer.

16. A mold comprising an imprint molding template laminated on a gas-permeable sintered metal layer, wherein the imprint molding template has a structure shown in Chemical Formula 4 and is formed from a cured product of a curable composition containing a polymerizable compound formed by combining a silicon-containing monomer and a titanium-containing monomer.

17. 14. The mold according to claim 13, wherein the gas-permeable sintered metal layer comprises at least one of a gas-permeable truss layer, a gas-permeable porous layer, and a gas-permeable lattice layer.

18. 18. The mold of claim 17, wherein two or more of the gas permeable truss layer, the gas permeable porous layer, and the gas permeable lattice layer are continuous sintered layers.

19. The mold according to claim 13, wherein the imprint molding template has a recess formed therein with a depth of 250 to 1000 nm.

20. 20. The mold according to claim 19, wherein the center-to-center spacing of adjacent recesses is 250 to 800 nm.

21. A method for manufacturing a mold, comprising the steps of: forming at least two of a gas permeable truss layer, a gas permeable porous layer, and a gas permeable lattice layer by continuous sintering; applying a gas permeable surface layer liquid to one of the gas permeable truss layer, the gas permeable porous layer, and the gas permeable lattice layer; placing an original plate with a fine nanostructure on the gas permeable surface layer liquid applied to the lattice layer; a photo-curing reaction step of irradiating ultraviolet light onto the gas permeable surface layer liquid on which the original plate with a fine nanostructure is placed; and removing the original plate with a fine nanostructure.

22. The method for manufacturing a mold according to claim 21, wherein the original plate with a fine nanostructure has fine convex portions formed on the surface, and the convex portions on the surface have a height of 250 to 1000 nm.

23. The method for manufacturing a mold according to claim 22, wherein the center-to-center distance between adjacent convex portions is 250 to 800 nm.

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