Imprint molding template, mold, and method for manufacturing mold

Abstract

[Problem] To provide: a nano-imprint molding template that has high gas permeability, and that has high strength and can be used for a long period of time in an industrial production process; a mold using the template; and a method for manufacturing the mold. [Solution] A mold 3 has attached thereto an imprint molding template 8 that is an extremely stable composition obtained by combining a silicon-containing monomer and a titanium-containing monomer. The mold 3 has a gas permeation gradient function part 10 formed by laminating a porous layer 6 and a lattice layer 7 on a truss layer 5. The materials of the truss layer 5, the porous layer 6, and the lattice layer 7 are each a sintered metal material, and functions of respective parts thereof are realized by adjusting the sintering temperature and the sintering time. The sintering is continuously performed starting from the truss layer 5 to the porous layer 6 and the lattice layer 7.

Description

Imprint molding template, mold, and method for manufacturing the mold

[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.

[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 put to practical use in 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, including: (1) reduced 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, a pattern is transferred by pressing the pattern-forming surface of a template (metal mold or die) against a transfer agent applied to a substrate, applying active energy such as heat or light to harden the transfer agent, and then peeling off the template. The template is 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 high-precision pattern formation over a long period of time. Furthermore, if the transfer agent contains a volatile component such as a diluent (or solvent), a similar phenomenon occurs due to the evaporation of the component, limiting its use with 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 disclosed in Patent Document 1 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 have been substituted with at least one polymerizable substituent selected from specific groups, with the objective of providing a polymerizable compound capable of forming a cured product having high gas permeability (for example, a template for imprint molding).

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

[0010] Patent Document 2, which aims to provide an air conditioner that easily removes dust and dirt from a filter and also suppresses the growth of bacteria from the dust, 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 including a metal plate with a mesh formed by photoetching, and an antibacterial and deodorizing resin coated with a charge transfer catalyst, arranged downstream of the metal plate in the direction of indoor air passage. Patent Document 3, which aims to provide a room air conditioner with a blower fan that has a coating film formed thereon that is excellent in antifouling properties, water removal, and durability, 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 a water-repellent coating material is further applied to the end of the positive pressure surface of the blower fan.

[0011] JP 2017-145320 JP 2010-19498 JP 2008-292069

[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. This 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 the antibacterial agent into the resin material not only requires a large amount of antibacterial agent, which is costly, but also makes it difficult to recycle the resin kneaded with the antibacterial agent, resulting in a significant environmental impact.

[0013] In view of the above-mentioned problems in the prior art, the present inventors have investigated the application of the highly gas-permeable imprint molding template disclosed in Patent Document 1 in order to provide a mold for producing antibacterial resin molded products that is inexpensive, has little deterioration over time, and has a low environmental impact, as well as a method for manufacturing such a mold. However, although the imprint molding template disclosed in Patent Document 1 has high gas permeability, it 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 that forms the imprint molding template is an important factor. The releasability of the surface layer material concerns 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.

[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 present 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:

[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:

[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:

[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:

[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 a master template. Furthermore, the cured product may have an oxygen gas permeability coefficient measured in accordance with JIS K7126-1 (2006) of approximately 10×10 to 2000×10 cm / (cm sec cmHg).

[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 shown in Chemical Formula 2, 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.

[0025] Furthermore, 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 shown in Chemical Formula 3 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 shown in Chemical Formula 4, 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.

[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] Furthermore, it is preferable that the center-to-center distance between adjacent recesses is 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 performance of the molded resin product is not improved. On the other hand, if the distance exceeds 800 nm, the antibacterial performance 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, resin molding using the resulting mold is difficult and the antibacterial performance is reduced. Conversely, if the height exceeds 1000 nm, the antibacterial performance of the resin molded product using the resulting mold may be reduced.

[0035] It is also preferable that the center-to-center distance between adjacent convex portions is 250 to 800 nm. In this case, if the center-to-center distance 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. Conversely, if the distance exceeds 800 nm, a decrease in the antibacterial properties of the molded resin article using the resulting mold is observed. [Action]

[0036] Figure 23 shows the published test results of the viable bacteria rate versus pillar height for samples fabricated by creating a nanostructure on a silicon substrate, with nanopillars at a pitch and width of 200 nm and 150 nm, respectively, and varying only in height, and performing antibacterial evaluations 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 nanopillars become taller, 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, resulting in reduced antibacterial properties, while when the pillar height is high, the number of bacteria that cause membrane damage increases.

[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.

[0038] 1 is an external perspective view 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. FIG. 1 is a schematic cross-sectional view of an embodiment of a mold according to the present invention. FIG. 2 is a partial external perspective view of an 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. FIG. 3 is a partial schematic cross-sectional view of an embodiment of a mold according to the present invention and its partial schematic oblique view. FIG. 4 is another partial schematic cross-sectional view of an embodiment of a mold according to the present invention and its partial schematic oblique view. FIG. 5 is an explanatory diagram of a manufacturing method of a mold according to the present invention. FIG. 6 is a schematic cross-sectional view of another embodiment of a mold according to the present invention. FIG. 7 is a schematic cross-sectional view of yet another embodiment of a mold according to the present invention. FIG. 8 is a schematic cross-sectional view of yet another embodiment of a mold according to the present invention. FIG. 9 is a schematic cross-sectional view of yet another embodiment of a mold according to the present invention. FIG. 10 is a perspective view of an example of a mold according to the present invention, and is an explanatory view showing parts of the mold. FIG. 11 is a perspective view of an example of a mold according to the present invention, and is an explanatory view showing parts of the mold. FIG. 12 is a perspective view of a resin molded product obtained using a mold according to the present invention. FIG. 13 is an explanatory view showing the contents of an antibacterial evaluation test conducted using a resin molded product obtained using a mold according to the present invention and a normal resin molded product. 19(a) and 19(b) are side and perspective views, respectively, of a gas permeation measurement specimen for a mold according to an embodiment of the present invention, showing a 3D image, a 3D transmission image, a horizontal cross-sectional image of each layer, and a vertical cross-sectional image of each layer.

[0041] FIG. 19(a) is a side view of a gas permeation measurement specimen for a mold according to an embodiment of the present invention, and FIG. 19(b) is a perspective view of a gas permeation measurement specimen for a gas permeation measurement test of a mold according to an embodiment of the present invention, showing a 3D image, a 3D transmission image, a horizontal cross-sectional image of each layer, and a vertical cross-sectional image of each layer.

[0042] FIG. 19(b) is a side view of a gas permeation measurement specimen for a gas permeation measurement test of a mold according to an embodiment of the present invention, showing a 3D image, a 3D transmission image, a horizontal cross-sectional image of each layer, and a vertical cross-sectional image of each layer.

[0043] FIG. 19(c) is a side view of a gas permeation measurement specimen for a gas permeation measurement test of a mold according to an embodiment of the present invention, showing a 3D image, a 3D transmission image, a horizontal cross-sectional image of each layer, and a vertical cross-sectional image of each layer.

[0044] FIG. 19(d) is a side view of a gas permeation measurement specimen for a gas permeation measurement test of a mold according to an embodiment of the present invention, showing a 3D image, a 3D transmission image, a horizontal cross-sectional image of each layer, and a vertical cross-sectional image of each layer.

[0045] FIG. 19(b) is a perspective view of a gas permeation measurement specimen for a gas permeation measurement test of a mold according to an embodiment of the present invention, showing a 3D image, a 3D transmission image, a horizontal cross-sectional image of each layer, and a vertical cross-sectional imageFig. 1 is an explanatory diagram relating to the demolding properties of a nanoimprint molding template according to an embodiment of the present invention; Fig. 2 is another explanatory diagram relating to the demolding properties of a nanoimprint molding template according to an embodiment of the present invention; Fig. 3 is yet another explanatory diagram relating to the demolding properties of a nanoimprint molding template according to an embodiment of the present invention; Fig. 4 is yet another explanatory diagram relating to the demolding properties of a nanoimprint molding template according to an embodiment of the present 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 the combination 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 imprint molding template highly resistant to solubility in organic solvents and water. 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. [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 (for example, a reactive diluent, etc.), and the like, as shown in Chemical Formula 6.

[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); 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 photopolymerization initiators (e.g., acetophenone dimethyl ketal, benzyl dimethyl ketal, etc.); benzophenones (e.g., benzophenone, 4-hydroxybenzophenone, etc.); 2,4,5-triarylimidazole dimers (e.g., 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(2,4-dimethoxyphenyl)-4,5-diphenylimidazole dimer, etc.); xanthones; 2,4,6-trihalomethyltriazines; acridine derivatives (e.g., 9-phenylacridine, 1,7-bis(9,9'-acridinyl)heptane, etc.); bisacylphosphine oxides (e.g., bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, etc.). 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, and the gas permeability of the cured product may decrease.

[0042] The photopolymerization initiator may be combined with a photosensitizer. Examples of the photosensitizer include conventional photosensitizers such as tertiary amines (e.g., trialkylamines, trialkanolamines (triethanolamine, etc.), dialkylaminobenzoic acid alkyl esters such as ethyl N,N-dimethylaminobenzoate (ethyl p-(dimethylamino)benzoate, etc.) and amyl N,N-dimethylaminobenzoate (amyl p-(dimethylamino)benzoate, etc.), 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 mono-C1-4 alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, etc.; ethers (for example, dialkyl ethers such as diethyl ether; cyclic ethers such as tetrahydrofuran, etc.); ketones (for example, 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 alkoxy C2-5 alkanoic acid C1-5 alkyl esters such as ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.); hydroxyalkanoic acid esters [for example, hydroxyacetic acid esters such as ethyl hydroxyacetate;Examples of the hydroxyalkanoic acid ester include lactate esters such as ethyl 2-hydroxypropionate (ethyl lactate) and butyl 2-hydroxypropionate (butyl lactate); C1-5 alkyl hydroxy C2-5 alkanoate esters such as alkyl hydroxyalkanoate esters such as ethyl 2-hydroxy-2-methylpropionate and methyl 2-hydroxy-3-methylbutanoate; pyruvic acid esters (e.g., C1-5 alkyl pyruvic acid esters 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); 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 1,000 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 (e.g., 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, application (or coating) to a substrate may be difficult, and storage stability may also be reduced.

[0046] (Rheology Adjuster) If necessary, a rheology adjuster may be added to the curable composition of the present invention to adjust the fluidity of the curable composition. Examples of the rheology adjuster 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, octyldecyl 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 aid may be added to the curable composition of the present invention to improve the adhesion between a substrate onto which the curable composition is applied and the cured product. Examples of the adhesion aid 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, dimethylvinylethoxysilane, etc.); silyl ureas (for example, N,N'-bis(trimethylsilyl)urea, etc.); ureas [urea compounds (for example, 1,1-dimethylurea (N,N-dimethylurea), 1,3-dimethylurea (N,N'-dimethylurea), etc.]; thiourea compounds, etc.]; heterocycles [for example, imidazoles (for example, imidazole, benzimidazole, mercaptoimidazole, 2-mercaptobenzimidazoline, triazoles (for example, benzotriazole, etc.); indazoles (for example, indazole, etc.); oxazoles (for example, 2-mercaptobenzoxazole, etc.); thiazoles (for example, 2-mercaptobenzothiazole, etc.); urazoles (for example, urazole, etc.); thiouracils (for example, 4-thiouracil, etc.); pyrimidines (for example, mercaptopyrimidine, etc.), and the like.

[0049] The proportion of the adhesion aid may be, for example, about 0 to 10 parts by weight, and 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 later).

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

[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; crosslinked 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) and the like); 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 the polyfunctional (meth)acrylate 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, plasticizers, polymerization inhibitors, etc. These additives may be used alone or in combination of two or more.

[0056] [Characteristics of 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. Useful active energy in the curing step includes 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 / cm, preferably 1,000 to 150,000 mJ / cm, and more preferably 10,000 to 100,000 mJ / cm (e.g., 50,000 to 80,000 mJ / cm). 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 used when thermal energy is used. 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), or 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 of oxygen measured in accordance with JIS K7126-1 (2006) can be selected from a range of about 10×10 to 2000×10 cm / (cm sec cmHg), and may be, for example, about 50×10 to 1500×10 cm / (cm sec cmHg), preferably about 80×10 to 1000×10 cm / (cm sec cmHg), and more preferably about 100×10 to 700×10 cm / (cm 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. For example, even when a 1.1 μm thick cured product is immersed in a solvent (e.g., a polar solvent such as methyl ethyl ketone or N,N-dimethylformamide) at room temperature for 3 minutes, the thickness of the cured product remains unchanged 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 (for example, 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 Preparation Method Thereof) The imprint template is formed from the cured product, and it is sufficient that at least a portion of the surface of the cured product has a pattern shape (a concave-convex pattern or a patterned surface). The pattern shape is not particularly limited and may be, for example, lines and spaces, dots, pillars, V-grooves, lattices, lenses, honeycombs, pyramids, or combinations thereof. These pattern shapes may be micrometer-sized or nanometer-sized (for example, in lines and spaces, 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 be transferred with high accuracy in imprint molding even if it has a finer or more complex pattern shape.

[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 the curable composition layer, thereby transferring the pattern shape through the curing step. When 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 decompression before pressing the master template, thereby improving productivity. Furthermore, pressing may be performed so as not to introduce air bubbles during contact with the master template. Furthermore, the method may also include a demolding step in which the cured product (template) obtained through the curing step is released from the master template. This method allows for easy preparation of a cured product (template) having a pattern shape (a shape that is the inverse of the pattern of the master template).

[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 external 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 the like. Because the template of the present invention has excellent transparency and can be used for optical imprinting, the substrate may be a transparent substrate such as a glass substrate or a transparent resin substrate (e.g., a PET substrate).

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

[0069] (Method of Transferring a Pattern Formed on a Template) As a method of transferring a pattern to a transfer-receiving material using the template of the present invention, the same method as the above-described method of 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), allowing light to be irradiated onto the transfer-receiving agent 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 of imprint molding.

[0074] The template of the present invention has high gas permeability, so that even if the transfer agent (or transfer agent layer) contains a large amount of solvent during imprint molding, the evaporated solvent vapor can pass through the template, allowing efficient diffusion of the solvent vapor between the template and the transfer agent. This allows for highly accurate pattern transfer without removing the solvent from the transfer agent layer, effectively reducing transfer defects. For example, in the case of a line-and-space pattern transfer having a line width of approximately 100 to 1,000 nm (e.g., 150 to 600 nm), a height of approximately 100 to 1,000 nm (e.g., 300 to 700 nm), and a line:space ratio of 1:1, the variation in line width dimension of the transferred pattern exceeds ±10% with conventional templates such as polydimethylsiloxane (PDMS). However, with the template of the present invention, the variation 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, due to its high gas permeability, the template of the present invention can effectively prevent the inclusion of air bubbles between the template and the transfer material (or transfer material layer) when the template is brought into contact with the transfer material. Therefore, in imprint molding, a pattern can be easily transferred with high accuracy in the atmosphere without applying 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 ambient 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 Figure 1, the resin molded product 1 has minute protrusions 2 on its surface, each having 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 in this embodiment uses a mold 3 shown in Figure 2. The mold 3 is laminated on a substrate (not shown) and includes a truss layer 5 having gas flow channels 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 channels 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 Figure 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 manufacturing method for the resin molded product 1, resin is injected into a cavity formed by the mold 3 and cured.

[0080] As shown in Figures 4 and 5, a mold 3 according to one 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 materials, and the functions of each portion are realized by adjusting the sintering temperature and sintering time. Sintering is performed continuously from the truss layer 5 to the porous layer 6 and lattice layer 7, and the junction boundary between the truss layer 5 and the porous layer 6 and the junction boundary between the porous layer 6 and the lattice layer 7 are continuous layers formed by continuous sintering.

[0081] The gas flow channels 4 formed in the truss layer 5 are formed in an X-shaped configuration with multiple paths intersecting, allowing for the flow of large volumes 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. Meanwhile, the lattice layer 7 has gas channels 11 formed therein with a width of 100 to 120 μm and a pitch of 2.0 to 3.0 mm. Here, the pitch is the center-to-center spacing of the gas permeation openings 11a. By laminating the porous layer 6 and the lattice layer 7 on the truss layer 5 in this way to form a gas permeable functionally graded portion 10, it is possible to maintain strength while allowing gas to pass through.

[0082] Gas permeability is ensured by providing a large number of 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 of the present invention will be described. As shown in Figure 6, the method for manufacturing a mold of this embodiment involves a step of applying a gas permeable surface layer liquid 8b to a gas permeable functionally gradient portion 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 portion 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 process is performed 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-stage irradiation process in which ultraviolet (UV) light is irradiated for 30 seconds using Hamaphoto LC8, and a second-stage irradiation process in which ultraviolet (UV) light is irradiated for 1 minute using a metal halide lamp. Pre-irradiation is performed in the first-stage irradiation process, and main irradiation is performed in the second-stage irradiation process. By dividing the process into two stages 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 injection molded using the mold 3 include 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), nylon 6 (PA6), nylon 6-6 (PA66), nylon 6T (PA6T), polyphthalamide (PPA), polystyrene (PS), ABS resin (ABS), polyvinyl chloride resin (PVC), polyacetal (POM), liquid crystal polymer (LCP), polysulfone (PSU), polypropylene (PP), and polycarbonate (PC). These resins can be used alone or in combination. Thermosetting resins include 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 resins and thermosetting resins may be appropriately blended with inorganic fillers such as carbon fibers, glass fibers, glass beads, and talc, or with organic fillers such as cellulose nanofibers, in order to improve heat resistance and dimensional stability.

[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 configuration.

[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 configuration.

[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 improves 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 configuration.

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

[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 filtered in the same manner. Excess toluene and ion-exchanged water were distilled off under reduced pressure to obtain a hydrolysis condensate of a silicon-containing monomer and a titanium-containing monomer used in the gas-permeable mold surface layer.

[0096] <Solid content measurement> The solid content of the hydrolysis condensate 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 obtained solid content weight (y g) by the following formula: Solid content (%) = y / 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) 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 onto a silicon wafer by casting, irradiated for 2 minutes with a UV spotlight source (Lightning358cureLC8, Hamamatsu Photonics), and then baked on a hot plate at 120°C for 10 minutes. The wafer was then immersed in toluene for 1 minute, and the change in the coating film thickness before and after the application was examined. A change in film thickness of 10 nm or less was considered good and marked with a circle, and a change in film thickness of more than 10 nm was considered poor and marked with an x. (Evaluation of Water Resistance) A solution of the gas-permeable mold surface layer forming composition was applied onto a silicon wafer by casting, irradiated for 2 minutes with a UV spotlight source (Lightning358cureLC8, Hamamatsu Photonics), and then baked on a hot plate at 120°C for 10 minutes. The wafer was then immersed in ion-exchanged water for 1 minute, and the change in the coating film thickness before and after the application was examined. When the change in film thickness was 10 nm or less, it was considered to be good and marked with a symbol ◯, and when the change in film thickness exceeded 10 nm, it was considered to be bad and marked with a symbol x.

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

[0100] Next, an embodiment of the mold 3 of the present invention will be described. Figure 12 shows a perspective view of the mold 3 of the present invention described above. Also, in Figure 13, the recesses shown in Figure 3 are formed in the A, B, C, and D portions of the mold 3, with depths ranging from 250 to 1000 nm. Figure 14 is a perspective view of a resin molded product obtained by injection molding using the mold 3. The A, B, C, and D portions of the resin molded product have protrusions corresponding to the recesses in the A, B, C, and D portions of the mold 3, as shown in Figure 1, with heights ranging from 250 to 1000 nm. [Antibacterial Evaluation Test] Figure 15 shows the details of an antibacterial evaluation test conducted using a resin molded product molded using the mold of the present invention obtained using polypropylene (PP) and a standard resin molded product. The test method conformed to the revised JIS standard. Test bacteria solution (bacterial cells (E. coli)) was inoculated dropwise onto specimens (resin molded products molded using the mold of the present invention and a standard resin molded product) and then covered with a polyethylene film to prevent evaporation. The specimens were incubated at 37°C and 100% relative humidity for 24 hours. Thereafter, the specimens were washed out immediately after inoculation and 24 hours after incubation for the normal resin molded product test pieces, and after 24 hours of incubation for the resin molded product test pieces of the examples of the present invention, and the viable bacterial counts in the washed out liquid were measured to calculate the viable bacterial concentration of 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 normal resin molded product test piece without a fine shape.

[0102] 17 shows the results of a water repellency evaluation performed on 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 the mold according to the present invention, which has 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 transferability of microstructures to molded articles using injection molding molds with and without gas permeability. As shown in the figure, polypropylene (PP) molded articles molded using a mold with a convex surface structure and a microstructure height of 250 to 1000 nm that was not gas permeable did not have a microstructure formed in the molded article, resulting in poor transfer. In contrast, polypropylene (PP) molded articles molded using a mold with a concave surface structure and a microstructure depth of 250 to 1000 nm that was gas permeable formed a microstructure in the molded article and transfer was good.

[0104] Figure 19 shows CT scan images 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 a horizontal cross-sectional image of each layer, and Figure 19(d) shows a vertical cross-sectional image of each layer. As shown in the figure, each layer is continuously and firmly bonded at the joint boundary between truss layer 5 and porous layer 6 and at the joint boundary between porous layer 6 and lattice layer 7.

[0105] 20 shows a gas permeation test piece 13 for use in a gas permeation 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 includes a 40φ gas-impermeable portion 13a and a 20φ gas-permeable portion 13b.

[0106] FIG. 21 shows the gas permeation measurement device 14 used in the gas permeation measurement test using the gas permeation measurement specimen 13. The gas permeation measurement device 14 has a jig (lower) 15 and a jig (upper) 16, and the gas permeation measurement specimen 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. Meanwhile, a flow meter (No. 1) 22 is disposed in the gas flow upstream piping 19 of the jig (lower) 15, and is connected to a compressor 20 via a regulator 21 so as to allow gas to flow. A flow meter (No. 2) 24 is disposed in the gas flow downstream piping 23 of the jig (upper) 16.

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

[0108] Figures 24 to 28 show the results of an investigation into the demolding properties of the surface layer material, which is the imprint molding template 8. As shown in Figure 24, the demolding properties of the surface layer material 8 must be evaluated in terms of the demolding properties between the surface layer material 8 and the plastic resin (e.g., PP, AS+GF, PMMA, etc.) that constitutes the resin molded product 1, as well as the demolding properties between the surface layer material 8 and the metal (gas permeable sintered metal) of the gas permeable functionally graded portion 10. As shown in Figure 25, in the conventional product, foreign matter 25 was observed on the surface layer material 8 after 10 shots. However, as shown in Figure 26, in the surface layer material 8 of the present invention, no foreign matter was observed on the surface layer material 8 even after 1,000 shots. In the conventional product shown in Figure 25, the microstructure had a diameter of 500 nm and a height of 130 nm. In contrast, in the surface layer material 8 of the present invention shown in Figure 26, the microstructure had 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, with 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 direction of resin flow.

[0110] 1: resin molded product, 2: convex portion, 3: mold, 4: gas flow path, 5: base, 6: porous layer, 7: lattice layer, 8: imprint molding template, 9: concave portion, 10: gas permeable functionally graded portion, 11: gas path, 12: original plate with fine nanostructure

Claims

1. An imprint molding template having the following formula, 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:

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

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

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

5. The imprint molding template according to any one of claims 1 to 4, which contains a thermal polymerization initiator and / or a photopolymerization initiator.

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

7. The imprint molding template according to any one of claims 1 to 6, which is a micro- or nano-imprint molding template.

8. The imprint molding template according to any one of claims 1 to 7, which has a pattern shape that is the inverse of the pattern shape of the master template.

9. The imprint molding template according to any one of claims 1 to 8, wherein the oxygen gas permeability coefficient measured in accordance with JIS K7126-1 (2006) is 10 x 10-12 to 2000 x 10-12 cm3·cm / (cm2·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 target material using the imprint molding template according to any one of claims 1 to 9 as a template.

12. The method of claim 11, wherein the transfer agent 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 the structure 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.

14. A mold comprising an imprint molding template laminated on a gas-permeable sintered metal layer, wherein the imprint molding template has the structure of Chemical 2 formed from a hardened 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 the 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 the 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. The mold according to claim 13, wherein said 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. 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. The mold according to claim 19, wherein the center-to-center spacing between 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 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 liquid applied to the lattice layer; a photo-curing reaction step of irradiating ultraviolet light onto the gas permeable surface liquid on which the original plate with a fine nanostructure has been placed; and removing the original plate with a fine nanostructure.

22. A method for manufacturing a mold according to claim 21, wherein the original plate with a fine nanostructure has fine projections formed on its surface, the projections having 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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