Method for manufacturing pattern substrate, curable composition for imprinting, and method for manufacturing parts

Abstract

The present invention provides a method for producing a patterned base material, the method being capable of removing an unintended cured layer, while maintaining a desired pattern mask.　The present invention provides a method for producing a patterned base material, the method comprising: a first removal step (A) in which a precursor pattern mask in cured layer composite body, which comprises a base material and the precursor pattern mask that is formed of a cured layer formed on the base material and has a recessed part and a projected part, is processed with a first remover liquid so as to remove at least a part of the cured layer corresponding to the thickness of the cured layer in the recessed part, thereby obtaining a resist composite body which has a specific pattern mask from which the base material positioned in the recessed part is exposed; a surface treatment step (B) in which a surface treatment is performed on the resist composite body via the specific pattern mask, thereby obtaining a surface-treated composite body; and a second removal step (C) in which the specific pattern mask of the surface-treated composite body is removed by means of a second remover liquid, thereby obtaining a patterned base material. With respect to this method for producing a patterned base material, the removal conditions in the first removal step (A) and the removal conditions in the second removal step (C) are different from each other.

Description

Method for manufacturing pattern substrate, curable composition, and method for manufacturing part

[0001] Some aspects of the present invention relate to a method for producing a pattern substrate. Some other aspects of the present invention relate to a curable composition used in the method for producing a pattern substrate. Some other aspects of the present invention relate to a method for producing a part using the method for producing a pattern substrate.

[0002] Photolithography and imprinting are widely used methods for forming fine patterns on a substrate. Imprinting has been attracting attention in recent years due to its advantages, such as the ability to form patterns at lower cost than photolithography (see Patent Document 1).

[0003] Japanese Patent Application Laid-Open No. 2014-3276

[0004] When a pattern mask made of a cured layer is formed in the above-described lithography or imprinting, the cured layer may remain in unintended locations on the substrate. When the substrate is etched using the pattern mask as a resist after the pattern mask is formed, such unintended cured layer may cause a problem that the desired pattern mask is not transferred to the substrate.

[0005] In view of the above circumstances, some aspects of the present invention aim to provide a method for manufacturing a pattern substrate that removes an unintended cured layer while maintaining a desired pattern mask. Also, some aspects of the present invention aim to provide a curable composition used in the method for manufacturing the pattern substrate, and a method for manufacturing a part using the method for manufacturing the pattern substrate.

[0006] As a result of intensive research to solve the above-mentioned problems, the present inventors have found that by treating a precursor pattern mask of a hardened layer with a removal solution in the removal steps (A) and (C) described below, an unintended hardened layer can be removed and a desired pattern substrate can be obtained, and have completed several aspects of the present invention.

[0007] One aspect of the present invention is a method for producing a patterned substrate (A), comprising: a first removal step (A) of treating a hardened layer composite having a substrate and a precursor pattern mask, the precursor pattern mask being made of a hardened layer formed on the substrate and having recesses and protrusions, with a first removal liquid to remove at least an amount of the hardened layer corresponding to the thickness of the hardened layer in the recesses, thereby obtaining a resist composite having a predetermined pattern mask in which the substrate located in the recesses is exposed; a surface layer treatment step (B) of performing a surface treatment on the resist composite through the predetermined pattern mask to obtain a treated surface layer composite; and a second removal step (C) of removing the predetermined pattern mask of the surface layer treatment composite with a second removal liquid to obtain a patterned substrate, wherein the removal conditions in the first removal step (A) and the second removal step (C) are different.

[0008] In the method for producing a patterned substrate, the surface layer treatment step (B) may be an etching step (B1) in which the substrate exposed through the predetermined pattern mask is etched to obtain an etched composite as the treated surface layer composite. Alternatively, the surface layer treatment step (B) may be a heterogeneous material arrangement step (B2) in which a material different from the cured layer constituting the predetermined pattern mask is arranged on the surface of the resist composite to obtain a heterogeneous material composite in which a material layer made of the different material is provided on the substrate through the predetermined pattern mask as the treated surface layer composite. In any of the above aspects, the composition of the first removing liquid and the composition of the second removing liquid may be different, the temperature of the first removing liquid may be lower than the temperature of the second removing liquid, and the removal time of the cured layer in step (A) may be shorter than the removal time of the cured layer in step (C). In any of the above aspects, the precursor pattern mask may be an imprint molded product. In any of the above aspects, steps (A) to (C) may be performed using a roll-to-roll process.

[0009] Another aspect of the present invention is a curable composition used in the method for producing a pattern substrate of any of the above aspects, which contains a monomer and a polymerization initiator, and in which the content of the monofunctional monomer in the monomer components is 95 mass% or more.

[0010] Another aspect of the present invention is a method for manufacturing a part, which includes the method for manufacturing a pattern substrate according to any one of the above aspects.

[0011] The method for producing a patterned substrate according to one embodiment of the present invention can remove an unintended hardened layer while maintaining a desired pattern mask.

[0012] 1A and 1B are cross-sectional views illustrating a method for manufacturing a pattern substrate according to an embodiment, and FIG. 2A and 2B are cross-sectional views illustrating a method for manufacturing a pattern substrate according to another embodiment.

[0013] The present invention will be described in detail below. In this specification, "(meth)acrylate" means both "acrylate" and "methacrylate". Similarly, "(meth)acryloyl" means both "acryloyl" and "methacryloyl". Similarly, "(meth)acrylic" means both "acrylic" and "methacrylic". Furthermore, "polymerizable group" represents a radically polymerizable group such as a (meth)acryloyl group, a vinyl group, an allyl group, a homoallyl group, a propargyl group, and a homopropargyl group. Note that groups such as an epoxy group and an oxetanyl group also act in the same manner as the polymerizable group in this specification and provide the same effects.

[0014] <1> Method for Producing Patterned Substrate One aspect of the present invention is a method for producing a patterned substrate, which includes the steps described above.

[0015] <1-1> Hardened Layer Composite Preparation Step A method for producing a patterned substrate according to one embodiment of the present invention may include a hardened layer composite preparation step of preparing a hardened layer composite having a substrate and a precursor pattern mask made of a hardened layer formed on the substrate. The precursor pattern mask is a pattern having recesses and protrusions, and can be produced by known methods such as photolithography, injection molding, and imprinting. The hardened layer composite may be produced by these known methods, or a commercially available product may be used.

[0016] The imprinting method includes, for example, the steps of applying a curable composition to a substrate to form a curable composition layer, contacting the curable composition layer with a mold having a pattern, and curing the curable composition layer with heat or light, thereby forming a precursor pattern mask having concave and convex portions. The curable composition used will be described later. The concave portions of the precursor pattern mask are areas where the thickness of the cured layer is smaller than that of the convex portions. In the above steps, an unintended cured layer (hereinafter also referred to as a "residual film") resulting from a gap between the substrate and the mold when forming the openings may remain on the edges of the openings, but this is also considered a concave portion. Since such residual film is likely to occur in the imprinting method, the above-mentioned method for manufacturing a pattern substrate can be suitably used when the precursor pattern mask for the cured layer is formed by the imprinting method. Figure 1(a) shows an example of a cured layer composite. The cured layer composite 10A comprises a cured layer (precursor pattern mask) 1, a substrate 2, and a support 3. The cured layer 1 is formed on the substrate 2 provided on the support 3. The cured layer 1 is composed of a thin recessed portion 1a and a thick protruding portion 1b, and it is preferable that the thickness obtained by subtracting the thickness of the recessed portion 1a from the thickness of the protruding portion 1b (differential thickness) is equal to a predetermined pattern mask thickness described later. Note that the recessed portion 1a may be a residual film when forming an opening, or the thickness of the central portion of the recessed portion 1a may be thin, or an opening may be formed in the central portion.

[0017] The shape and size of the precursor pattern mask comprising the cured layer are appropriately selected depending on the application of the pattern substrate obtained by the method for producing a pattern substrate according to one embodiment of the present invention. Examples of the shape of the precursor pattern mask include a hole pattern, a pillar pattern, a cone pattern, a lattice pattern, a honeycomb pattern, and a line-and-space pattern. The bottoms of the hole pattern, pillar pattern, and cone pattern may be circular, elliptical, or polygonal, such as triangular or rectangular. Regarding the size of the precursor pattern mask, in the case of a line-and-space pattern, the width of the lines and / or spaces may be 20 nm to 100 μm, preferably 50 nm to 50 μm, and more preferably 100 nm to 10 μm, and the film thickness may be 20 nm to 100 μm, preferably 50 nm to 50 μm, and more preferably 100 nm to 10 μm. When the pattern mask is other than a line-and-space pattern, the sides constituting the bottom surface of the pattern mask (diameter in the case of a circle, major axis in the case of an ellipse) may be 20 nm to 100 μm, preferably 50 nm to 50 μm, and more preferably 100 nm to 1 μm, and the film thickness may be 20 nm to 100 μm, preferably 50 nm to 50 μm, and more preferably 100 nm to 1 μm. The pitch of the precursor pattern mask may be 20 nm to 100 μm, preferably 50 nm to 50 μm, and more preferably 100 nm to 1 μm. The film thickness of the precursor pattern mask refers to the film thickness of the convex portions 1b. The aspect ratio of the precursor pattern mask is preferably 0.5 to 100. The aspect ratio refers to the ratio of the difference in film thickness between the width of the concave portions 1a and the width of the convex portions 1b, whichever is smaller, to the width 1.

[0018] The material of the mold can be appropriately selected from known materials, and examples thereof include metals such as nickel, chromium, titanium, iron, copper, aluminum, and stainless steel; non-metals such as glass, quartz, and silicon; and organic polymers such as polyethylene terephthalate, polyimide, polycarbonate, polycycloolefin, polyethylene, polypropylene, polyvinylidene, polyurethane, polyester, polymethyl methacrylate, polyethersulfone, polydimethylsiloxane, and polytetrafluoroethylene. Furthermore, the mold may be a replica mold produced by curing a thermosetting resin or a photocurable resin.

[0019] The material of the substrate can be appropriately selected from known materials, for example, metals such as nickel, chromium, titanium, iron, copper, aluminum, and stainless steel; non-metals such as glass, quartz, and silicon; and organic polymers such as polyethylene terephthalate, polyimide, polycarbonate, polycycloolefin, polyethylene, polypropylene, polyvinylidene, polyurethane, polyethersulfone, and polytetrafluoroethylene. The substrate may be a substrate prepared by curing a thermosetting resin or a photocurable resin. The term "substrate" refers to the material that contacts the cured layer on the surface of the cured layer facing the precursor pattern mask. The cured layer composite may further include a material such as a support in addition to the cured layer and the substrate.

[0020] The thickness of the substrate is appropriately selected depending on the application of the pattern substrate to be formed. The thickness of the substrate is preferably 50 nm to 10 mm, more preferably 500 nm to 1 mm. When steps (A) to (C) described below are performed by a roll-to-roll process, the total thickness of the substrate and support is preferably 1 μm to 300 μm, more preferably 10 μm to 100 μm, from the viewpoint of ease of winding up the cured layer composite.

[0021] The combination of the substrate and the support is appropriately selected depending on the application of the pattern substrate to be formed. Examples of the combination of the substrate and the support include a support having an organic polymer layer (substrate) on its surface, a support having a metal vapor deposition layer (substrate) on its surface, and the like.

[0022] <1-2> First Removal Step (A) An example of the resist composite after the first removal step is shown in FIG. 1(b). One embodiment of the pattern manufacturing method of the present invention includes a first removal step (A) in which the recessed hardened layer (also referred to as the residual film) of the precursor pattern mask 1 in the hardened layer composite 10A is removed with a first removal solution to obtain a resist composite 20A having a predetermined pattern mask 1A in which the substrate 2 located in the recessed portion 1a is exposed. In step (A), the hardened layer is removed so that only the substrate 2 facing the recessed portion 1a of the precursor pattern mask 1 is exposed, while the substrate 2 located in the protruding portion 1b of the precursor pattern mask 1 is not exposed. That is, the hardened layer is removed so that at least the thickness of the recessed portion 1a corresponds to the thickness of the hardened layer. As a result, the recessed portion 1a becomes an opening 1d, and the protruding portion 1b becomes a protruding portion 1c with a reduced film thickness, resulting in a predetermined pattern mask 1A in which only the substrate 2 facing the opening 1d is exposed. It is preferable that substantially all of the hardened layer in the recessed portion 1a is removed. Furthermore, the amount of the cured layer removed is preferably an amount corresponding to the thickness of the recesses 1a, but may be greater than the amount corresponding to the thickness of the recesses 1a as long as the desired pattern substrate is obtained. In other words, the cured layer is basically removed isotropically in both the thickness direction and the surface direction perpendicular to the thickness direction. Therefore, it is sufficient to remove the cured layer until the surface dimension of the recesses 1a reaches a predetermined dimension. In step (A), the cured layer may be removed anisotropically, strictly speaking. For example, the composition layer that becomes the recesses upon curing has a smaller film thickness than the composition layer that becomes the protrusions upon curing, and therefore the light absorption of the photopolymerization initiator described below may be lower, resulting in a lower degree of hardening of the recessed cured layer. In this case, the recessed cured layer tends to be more easily removed than the protruding cured layer. On the other hand, depending on the stirring conditions of the first removing liquid and the shape of the precursor pattern mask, the recessed cured layer may not fully contact the first removing liquid. In this case, the recessed cured layer tends to be more difficult to remove than the protruding cured layer. Due to these various factors, the removal rates of the recessed cured layer and the protruding cured layer may differ, and the cured layer in step (A) may be removed anisotropically. The cured layer in the recesses, i.e., the residual film, may be removed in a form in which the residual film is dissolved in the first removal liquid, or in a form in which the residual film is peeled off from the surface of the substrate.

[0023] The thickness of the pattern mask after removing the residual film is preferably 10 nm to 100 μm, more preferably 100 nm to 50 μm. When the subsequent surface layer treatment step (B) is an etching step (B1), the thickness of the pattern mask is preferably 10 nm to 50 μm, more preferably 100 nm to 10 μm. When the subsequent surface layer treatment step (B) is a different material arranging step (B2), the thickness of the pattern mask is preferably 100 nm to 100 μm, more preferably 500 nm to 10 μm.

[0024] The first removal liquid may be a solvent having a high affinity with the cured layer (hereinafter also referred to as a "good solvent"), or may be a mixed solvent of a good solvent and a solvent having a low affinity with the cured layer (hereinafter also referred to as a "poor solvent"). Using a good solvent as the first removal liquid allows for effective removal of the residual film. If the desired pattern mask is also removed using a good solvent alone, it is preferable to use a mixed solvent of a poor solvent and a good solvent. The first removal liquid and the second removal liquid described below may further contain additives such as a solubility adjuster, surfactant, antifoaming agent, and stabilizer. The content of the additive is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, per 100 parts by mass of the removal liquid. The lower limit of the additive content can be, for example, 0.01 parts by mass. The first removal liquid may also be, and is preferably, free of additives. In this specification, the "affinity" between the removal liquid and the cured layer refers to the degree of interaction between the removal liquid and the cured layer. When a solvent having a high affinity comes into contact with the cured layer, the cured layer dissolves or swells, and is removed.

[0025] Examples of good solvents include glycol ether solvents such as ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether acetate, dimethoxyethane, diglyme, and triglyme; cyclic ether solvents such as tetrahydrofuran (THF), tetrahydropyran, and dioxane; aromatic ether solvents such as anisole and ethoxybenzene; methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl β-methoxyisobutyrate, ethyl butyrate, propyl butyrate, cyclohexyl acetate, and acetic acid. Examples of good solvents include ester solvents such as ethyl acetate, butyl acetate, amyl acetate, isoamyl acetate, ethyl lactate, and γ-butyrolactone; ketone solvents such as cyclohexanone, methyl isobutyl ketone (MIBK), ethyl methyl ketone (MEK), 2-heptanone, and acetone; carbonate solvents such as dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate, and propylene carbonate; aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and mesitylene; and heteroatom-containing solvents such as acetonitrile, propionitrile, benzonitrile, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide. These good solvents may be used alone or in combination of two or more. From the viewpoint of efficiently removing the residual film, the good solvent is preferably a solvent containing a glycol ether solvent, a cyclic ether solvent, an aromatic ether solvent, or a ketone solvent, and more preferably a solvent containing a glycol ether solvent.

[0026] Examples of poor solvents include alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol (IPA), n-butanol, s-butanol, t-butanol, pentanol, and diacetone alcohol; dialkyl ether solvents such as dibutyl ether, t-butyl methyl ether, dipropyl ether, and diisopropyl ether; aliphatic hydrocarbon solvents such as n-hexane, n-heptane, n-octane, and cyclohexane; and water. These poor solvents may be used alone or in combination of two or more. From the viewpoints of safety and cost, alcohol solvents and water are preferred among the above poor solvents.

[0027] When a mixed solvent of a good solvent and a poor solvent is used as the first removal liquid, the mixing ratio can be appropriately selected depending on the affinity of each solvent with the cured layer. When water is used as the poor solvent, the mixing ratio (mass ratio) of good solvent:poor solvent is preferably 99:1 to 50:50, more preferably 97:3 to 60:40, and even more preferably 95:5 to 70:30. When an organic solvent is used as the poor solvent, the mixing ratio of good solvent:poor solvent is preferably 5:95 to 90:10, more preferably 10:90 to 80:20, and even more preferably 20:80 to 70:30.

[0028] If the removal of the residual film is insufficient in the preliminary test step (P) described below, it is preferable to prepare the first removal solution in the preliminary test step (P) so as to increase the ratio of the good solvent. Conversely, if the desired pattern mask is also removed, it is preferable to prepare the first removal solution in the preliminary test step (P) so as to increase the ratio of the poor solvent. Furthermore, when a mixed solvent of a poor solvent and a good solvent is used, it is preferable that the poor solvent and the good solvent are uniformly mixed at the above-mentioned mixing ratio at room temperature (e.g., 25°C).

[0029] It is preferable that the first removal liquid removes a certain amount of the hardened layer per unit time or less. This first removal liquid can achieve both removal of residual film and maintenance of the desired pattern mask. The removal amount can be measured by preparing a hardened layer using the method described in the hardened layer composite preparation step and immersing the hardened layer in a candidate removal liquid (preliminary test step (P)). In other words, the preliminary test step (P) can determine the processing conditions for steps (A) and (C).

[0030] That is, another embodiment of the present invention provides a method for producing a pattern substrate, comprising: a preliminary testing step (P) of treating a preliminary-cured layer composite having a preliminary substrate and a preliminary-cured layer formed on the preliminary substrate under predetermined conditions to determine first and second removal conditions; a first removal step (A) of removing the hardened layer in recesses of a precursor pattern mask in a hardened layer composite having a substrate and a precursor pattern mask consisting of a hardened layer formed on the substrate under the first removal conditions to obtain a resist composite having a predetermined pattern mask in which the substrate located in the recesses is exposed; a surface layer treatment step (B) of performing a surface layer treatment on the resist composite to obtain a treated surface layer composite; and a second removal step (C) of removing the hardened layer of the treated surface layer composite under the second removal conditions to obtain a pattern substrate, wherein the first removal conditions and the second removal conditions are different.

[0031] In the method for producing a pattern substrate including the preliminary test step (P), the cured layer composite of step (A) and the treatment conditions of steps (A) and (C) are preferably the same as the pre-cured layer composite and treatment conditions determined in the preliminary test step (P), respectively. The treatment conditions include the composition, temperature, and stirring conditions of each remover solution, as well as treatment time.

[0032] From the viewpoint of achieving both removal of residual films and maintenance of the desired pattern mask, it is preferable that the composition of the first removing liquid and the composition of the second removing liquid are different. Specifically, it is preferable that the content ratio of the poor solvent in the first removing liquid is greater than the content ratio of the poor solvent in the second removing liquid. By setting the compositions of the first removing liquid and the second removing liquid as described above, the amount of removal in step (A) can be made smaller than the amount of removal in step (C), and it is possible to achieve both removal of residual films and maintenance of the desired pattern mask in step (A).

[0033] From the viewpoint of achieving both residual film removal and maintaining the desired pattern mask, it is preferable that the temperature of the first removing liquid is lower than that of the second removing liquid. By lowering the temperature of the first removing liquid below that of the second removing liquid, the amount of removal in step (A) can be made smaller than the amount of removal in step (C), thereby achieving both residual film removal and maintaining the desired pattern mask in step (A). The temperature of the first removing liquid is not particularly limited as long as it is a temperature below the boiling point of the first removing liquid, and can be, for example, 50°C or lower, room temperature (e.g., 25°C) or lower, 15°C or lower, or 5°C or lower. The lower limit of the temperature of the first removing liquid is not particularly limited as long as it is a temperature at which the first removing liquid is liquid, and can be, for example, 0°C or higher.

[0034] From the viewpoint of achieving both the removal of residual film and the maintenance of a desired pattern mask, it is preferable that the removal time of the hardened layer in step (A) is shorter than the removal time of the hardened layer in step (C). By making the removal time of the hardened layer in step (A) shorter than the removal time of the hardened layer in step (C), the amount removed in step (A) can be made smaller than the amount removed in step (C), and both the removal of residual film and the maintenance of a desired pattern mask in step (A) can be achieved. The removal time of the hardened layer in step (A) can be, for example, 30 minutes or less, 20 minutes or less, 15 minutes or less, or 5 minutes or less. The lower limit of the removal time of the hardened layer in step (A) is not particularly limited as long as the residual film is removed, but can be, for example, 10 seconds or more.

[0035] The removal amount can be defined, for example, based on the thickness of the hardened layer removed per unit time. Specifically, the thickness (nm) of the hardened layer before and after the removal step is measured, the difference in thickness is calculated, and the difference is divided by the removal time (minutes) to calculate the removal rate (nm / min). As described above, the removal amount (nm) represented by the difference is preferably an amount corresponding to the thickness of the recess 1a. However, as long as the desired pattern substrate is obtained, it may be greater than the amount corresponding to the thickness of the recess 1a, and the removal may be performed until the dimension in the surface direction of the recess 1a reaches a predetermined dimension. As described above, the removal rate of the hardened layer in the recessed portion and the removal rate of the hardened layer in the protruding portion differ due to various factors, and the hardened layer in step (A) may be removed anisotropically.

[0036] As described above, in the method for producing a pattern substrate, the removal conditions in the first removal step (A) (hereinafter also referred to as "first removal conditions") are different from the removal conditions in the second removal step (C) (hereinafter also referred to as "second removal conditions"). The conditions that differ between step (A) and step (C) may be any one of the composition of the removal liquid, the temperature of the removal liquid, the removal time, and other conditions, or a combination of these conditions. Examples of other conditions include the convection velocity of the removal liquid in the removal step and the duration of ultrasonic vibration. The convection velocity of the removal liquid can be appropriately adjusted by a known method for controlling fluids, such as the stirring speed of the removal liquid in the removal tank and the circulation volume by a circulation pump.

[0037] The method for performing the treatment with the first removing liquid can be appropriately selected depending on the thickness of the hardened layer, etc. Examples of the treatment method include a method of immersing the hardened layer composite in the removing liquid (immersion method), a method of spraying the removing liquid onto the hardened layer composite (spray method), a method of showering the removing liquid onto the hardened layer composite (shower method), and a method of puddling the removing liquid onto the hardened layer composite (puddle method).

[0038] <1-3> Surface Layer Treatment Step (B) The method for producing a patterned substrate according to one embodiment of the present invention includes a surface layer treatment step (B) in which the resist composite is subjected to a surface layer treatment through the predetermined pattern mask to obtain a treated surface layer composite. Examples of treated surface layer composites include an etched composite and a heterogeneous material composite. Details will be described later.

[0039] In one embodiment of the present invention, the surface layer treatment step (B) is preferably an etching step (B1) in which the substrate exposed in the resist composite is etched through the predetermined pattern mask to obtain an etched composite as the treated surface layer composite. The etching step (B1) may be dry etching or wet etching. However, wet etching is preferred for the etching step (B1) because anisotropic dry etching can unintentionally etch the sides of the pattern mask in a roll-to-roll process, and the hardened layer surface-treated by dry etching can have a reduced affinity for the second removal solution described below. An example of an etched composite in which the surface layer treatment step (B) is a wet etching step (B1) is shown in FIG. 1(c). The substrate 2 of the etched composite 30A is treated through a pattern mask 1A, resulting in a treated substrate 2A in which the substrate in the region facing the opening 1d is removed.

[0040] When the etching step (B1) is wet etching, the conditions such as the composition, temperature, and treatment time of the etching solution are appropriately selected from known ones depending on the material and thickness of the substrate. Examples of the etching solution include: an oxidizing solution containing an oxidizing agent such as hydrogen peroxide, perchloric acid, ammonium peroxodisulfate, and sodium peroxodisulfate; an acidic solution containing an acid such as hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, phosphoric acid, oxalic acid, formic acid, and acetic acid; a metal salt solution containing a metal salt such as iron chloride (III), copper chloride (II), and chromium oxide (IV), aluminum chloride, sodium cyanide, and ammonium cerium nitrate; an alkaline solution containing an alkali such as tetramethylammonium hydroxide, hydroxylamine, hydrazine, ethylenediamine, sodium hydroxide, and potassium hydroxide; and the like. The etching solution may further contain additives such as a surfactant, a stabilizer, and an antifoaming agent.

[0041] The temperature of the etching solution is not particularly limited as long as it is equal to or lower than the boiling point of the etching solution, and can be, for example, 80°C or lower, 60°C or lower, or 50°C or lower. The lower limit of the temperature of the etching solution is not particularly limited as long as it is a temperature at which the etching solution is liquid, and can be, for example, 0°C or higher or room temperature or higher. The etching time can be set appropriately depending on the thickness of the substrate, and can be, for example, 30 seconds to 30 minutes, 1 minute to 20 minutes, or 3 minutes to 10 minutes.

[0042] In another aspect of the present invention, the surface layer treatment step (B) is preferably a heterogeneous material arrangement step (B2) in which a material different from the cured layer constituting the predetermined pattern mask is arranged on the surface of the resist composite, and a heterogeneous material composite is obtained as the treated surface layer composite by providing a material layer made of the different material on the substrate via the predetermined pattern mask. Examples of methods for arranging heterogeneous materials in the heterogeneous material arrangement step (B2) include sputtering, sol-gel methods, direct coating, electrolytic plating, and electroless plating, but known methods can be selected appropriately depending on the type of heterogeneous material to be arranged. These methods can be carried out using known materials and procedures, except that the resist composite is used as the treated layer.

[0043] When the unevenness of the hardened layer is completely covered with the different material in the different material disposition step (B2), an exposure step may be performed after the different material disposition step (B2) and before the second removal step (C), in which at least a portion of the disposed different material is removed to expose at least a portion of the convex portions of the hardened layer. By exposing the convex portions of the hardened layer in the exposure step, the hardened layer can be efficiently removed in the second removal step (C). The method for exposing the convex portions of the hardened layer can be appropriately selected from known removal methods, such as removal of the different material using a squeegee, etching, or CMP (chemical mechanical polishing). Figure 2(c) shows an example of a heterogeneous material composite in which the surface layer treatment step (B) is the different material disposition step (B2). Here, Figures 2(a) and (b) are identical to Figures 1(a) and (b) except for the absence of the support 1, so repeated explanations will be omitted. It goes without saying that a support 1 may be provided in the process of Figure 2. In the heterogeneous material composite 30B, a material layer 4 made of a different material is formed on the substrate 2 on which the pattern mask 1A is present. In this case, since the material layer 4 is not provided on the side surfaces of the convex portions 1c of the pattern mask 1A, the step of partially removing the material layer 4 is not necessarily required, but a step of removing only the material layer 4 on the convex portions 1c may be carried out.

[0044] When the dissimilar material disposing step (B2) is a sputtering step, conditions such as the sputtering target, inert gas, current value, and processing time are appropriately selected from known conditions depending on the material and thickness of the substrate and the use of the pattern substrate. The dissimilar material disposed in the sputtering step is appropriately selected depending on the use of the pattern substrate, and examples include known metal elements, alloys, metal oxides, etc. Note that the dissimilar material disposing step (B2) may be PVD (physical vapor deposition) other than sputtering, such as vacuum deposition and ion plating, or CVD (chemical vapor deposition).

[0045] When the heterogeneous material disposing step (B2) is a step using a sol-gel method, it is preferable to, for example, apply a precursor solution containing a metal compound to the surface of the resist composite and heat the coating to obtain a heterogeneous material composite in which a metal is disposed on the surface of the resist composite. In the above procedure, additives such as acids, bases, and nucleophiles may be used in combination to promote the gelation reaction. Specifically, for example, a precursor solution containing tetraethoxysilane is applied and the coating is heated to obtain a heterogeneous material composite in which silicon oxide is disposed on the surface of the resist composite. The heterogeneous material disposed in the sol-gel method is appropriately selected depending on the application of the pattern substrate, and examples thereof include oxides such as magnesia, alumina, silica, titania, and zirconia, as well as composite materials containing these oxides.

[0046] When the heterogeneous material disposing step (B2) is a step using a direct coating method, for example, a dispersion containing fine particles of a metal or its oxide is preferably applied to the surface of the resist composite to obtain a heterogeneous material composite in which the metal is disposed on the surface of the resist composite. In the above procedure, the coating film may be heated to volatilize the dispersion medium. Specifically, for example, a dispersion containing silver nanoparticles is applied and the coating film is heated to obtain a heterogeneous material composite in which silver is disposed on the surface of the resist composite. The heterogeneous material disposed in the direct coating method using fine particles is appropriately selected depending on the application of the pattern substrate, and examples thereof include known metal elements, alloys, metal oxides, etc.

[0047] Another example of the direct coating method for the heterogeneous material disposition step (B2) is to apply a curable composition to the surface of the resist composite and cure the coating film using light or heat to obtain a heterogeneous material composite having a heterogeneous material cured layer disposed on the surface of the resist composite. The heterogeneous material cured layer is not particularly limited as long as it is a material that cannot be removed by the second removal liquid described below. Specifically, for example, a water-soluble resin liquid having a polyvinyl alcohol skeleton as a main chain and an azide group as a photosensitive group is applied, and then ultraviolet light is irradiated to obtain a heterogeneous material composite having a heterogeneous material cured layer disposed on the surface of the resist composite.

[0048] When the dissimilar material disposing step (B2) is an electrolytic plating step, for example, the resist composite is immersed in a plating solution, a metal anode is immersed in the plating solution, and an electric current is passed between the substrate and the anode to obtain a dissimilar material composite in which the metal is disposed on the surface of the resist composite. Note that when the dissimilar material disposing step (B2) is an electrolytic plating method, a conductive material is used as the substrate. Furthermore, a metal salt containing ions of the metal may be added to the plating solution.

[0049] When the dissimilar material disposing step (B2) is an electroless plating step, it is preferable to obtain a dissimilar material composite in which a metal is disposed on the surface of the resist composite by, for example, immersing the resist composite in a plating solution containing a metal salt containing ions of the metal. In the above procedure, additives such as a pH adjuster, a reducing agent, and a catalyst may be added to the plating solution to promote plating.

[0050] The thickness of the different material disposed in the different material disposing step (B2) may be within a range that does not inhibit removal of the hardened layer in the second removal step (C) described below, and can be appropriately selected depending on the application of the pattern substrate to be formed and the type of step (B2). The thickness of the different material is, for example, preferably 1.0 or less, more preferably less than 1.0, relative to the depth of the recess of the pattern mask (1.0), and can be 0.5 or less or 0.1 or less. Furthermore, it can be, for example, 0.005 or more relative to the depth of the recess.

[0051] <1-4> Second Removal Step (C) One embodiment of the method for producing a patterned substrate of the present invention includes a second removal step (C) in which the hardened layer of the treated surface composite is removed with a second removal liquid to obtain a patterned substrate. By treating the treated surface composite in the second removal step (C), substantially all of the hardened layer on the substrate can be removed. The hardened layer may be dissolved in the second removal liquid or peeled off from the substrate surface. Examples of patterned substrates formed by the second removal step (C) are shown in FIGS. 1(d) and 2(d). The patterned substrate 40A in FIG. 1(d) is formed by removing the pattern mask 1A made of the hardened layer in the etching step (B1), and includes a treated substrate 2A with a partial recess. On the other hand, the patterned substrate 40B in FIG. 2(d) includes a patterned material layer 4A formed on the substrate 2 in the heterogeneous material disposition step (B2).

[0052] In one embodiment of the method for producing a patterned substrate according to the present invention, the first removal conditions are different from the second removal conditions. By making the first and second removal conditions different, it is possible to achieve both removal of the residual film and maintenance of the desired pattern mask in step (A), and to remove substantially all of the hardened layer in the second removal step (C). The method for providing a difference between the first and second removal conditions is preferably any one of the composition of the remover, the temperature and removal time of the remover, and other conditions, or a combination of these conditions.

[0053] From the viewpoint of efficiently removing the cured layer, the second removal liquid preferably contains a solvent having high affinity with the cured layer. Examples of such a solvent include the good solvents described above.

[0054] The composition of the first removing liquid and the composition of the second removing liquid may be the same or different. When the first removing liquid and the second removing liquid have the same composition, for example, a method of increasing the temperature of the second removing liquid to a temperature higher than that of the first removing liquid, or a method of extending the treatment time with the second removing liquid to a time longer than the treatment time with the first removing liquid, are desirable. By using these methods, it is preferable that the amount of removal in step (A) be smaller than the amount of removal in step (C).

[0055] In the second removal step (C), the second removal liquid may be convected by a known convection method such as a stirring device and a circulation pump, or an ultrasonic vibration tank may be used. When convection is also used in the first step (A), the convection speed of the second removal liquid may be set higher than the convection speed of the first removal liquid. These treatments increase the removal rate of the hardened layer and shorten the processing time of step (C). The stirring speed when stirring is performed may be, for example, 50 rpm to 500 rpm.

[0056] The above steps (A) to (C) are preferably performed by a roll-to-roll process. By performing the above steps by a roll-to-roll process, large-area hardened layer composites, resist composites, and treated surface layer composites can be continuously processed, which is advantageous in terms of throughput and manufacturing costs. Note that the rolls, winding devices, unwinding devices, etc. used in the roll-to-roll process can be those normally used in roll-to-roll processes, as appropriate.

[0057] <2> Curable Composition One aspect of the present invention is a curable composition used in the method for producing a pattern substrate, the curable composition comprising a monomer and a polymerization initiator, wherein the monomer includes a monofunctional monomer, and the content of the monofunctional monomer in the monomer components is 95 mass% or more.

[0058] <2-1> Monofunctional Monomer The curable composition contains a monofunctional monomer. A monofunctional monomer is a compound having one polymerizable group in one molecule. Examples of the monofunctional monomer include linear aliphatic monofunctional (meth)acrylates such as methyl (meth)acrylate, n-butyl (meth)acrylate, and lauryl (meth)acrylate; branched aliphatic monofunctional (meth)acrylates such as isobutyl (meth)acrylate, isoamyl (meth)acrylate, and isononyl (meth)acrylate; cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and dicyclopentenyl (meth)acrylate. Examples of the monofunctional monomer include cycloaliphatic monofunctional (meth)acrylates such as dicyclopentanyloxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, and adamantyl (meth)acrylate; aromatic monofunctional (meth)acrylates such as phenyl (meth)acrylate and phenoxyethyl (meth)acrylate; aromatic monofunctional vinyl compounds such as styrene and vinylnaphthalene; heterocyclic aliphatic monofunctional vinyl compounds such as N-vinylpyrrolidone; and (meth)acrylic acid. These monofunctional monomers may be used alone or in combination.

[0059] The alicyclic ring contained in the cycloaliphatic monofunctional (meth)acrylate may be a monoalicyclic ring such as cyclopentane or cyclohexane, a condensed alicyclic ring such as decalin, tricyclodecane, adamantane or norbornane, or a heteroalicyclic ring such as pyrrolidine, pyrrolidone or tetrahydrofuran. The aromatic ring contained in the aromatic monofunctional (meth)acrylate and the aromatic monofunctional vinyl compound may be a monoaromatic ring such as benzene, a condensed aromatic ring such as naphthalene, anthracene or fluorene, or a heteroaromatic ring such as furan, pyridine or thiophene.

[0060] At least one methylene group of the monofunctional monomer may be substituted with a divalent substituent such as a carbonyl group, an oxygen atom, etc. Examples of the monofunctional monomer in which the methylene group is substituted with an oxygen atom include monofunctional monomers having an alkylene oxide chain such as an ethylene oxide chain, a butylene oxide chain, and a perfluoroethylene oxide chain.

[0061] At least one hydrogen atom of the monofunctional monomer may be substituted with a substituent such as a hydroxyl group, a carboxyl group, a cyano group, a nitro group, a halogen atom, a halogenated alkyl group, a trialkylsilyl group, a triarylsilyl group, etc. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0062] From the viewpoint of affinity between the cured layer and the second removal liquid, the curable composition preferably contains a cyclic aliphatic monofunctional (meth)acrylate as the monofunctional monomer.

[0063] The number of carbon atoms in the monofunctional monomer is preferably 3 to 50, more preferably 4 to 30, and even more preferably 6 to 20. The double bond equivalent of the monofunctional monomer is preferably 50 to 500, more preferably 60 to 400, and even more preferably 80 to 300. The above carbon number includes the number of carbon atoms in the polymerizable group and the divalent substituent. By setting the carbon number or double bond equivalent of the monofunctional monomer within the above range, the curability of the curable composition and the crosslink density of the cured layer can be controlled, thereby controlling the affinity with the removal liquid and obtaining a precursor pattern mask with desired properties such as mechanical strength and flexibility. In this specification, the term "double bond equivalent" refers to the mass of the monomer per mole of polymerizable group, expressed in g / mol.

[0064] The content of the monofunctional monomer in the monomer components of the curable composition is 95% by mass or more. From the viewpoint of affinity with the second removal liquid, the content of the monofunctional monomer is preferably 98% by mass or more, more preferably 99% by mass or more. Furthermore, the monomer components may be substantially all monofunctional monomers.

[0065] <2-2> Polymerization Initiator The curable composition contains a polymerization initiator. The polymerization initiator is not particularly limited as long as it cures the curable composition by heat or energy rays, and can be appropriately selected from known materials. The polymerization initiators may be used alone or in combination. As the polymerization initiator, a photoradical polymerization initiator is preferred. Note that examples of energy rays used for curing include electromagnetic waves such as infrared rays, visible light, ultraviolet rays, excimer lasers, extreme ultraviolet rays, X-rays, and gamma rays, as well as particle rays such as electron beams and alpha rays, and can be appropriately selected depending on the photoradical polymerization initiator used.

[0066] <2-3> Optional Components The curable composition may further contain optional components other than the monofunctional monomer as the monomer and the polymerization initiator. Examples of the optional components include the polyfunctional monomer as the monomer, a polymer, a solvent, and additives.

[0067] The curable composition may contain a polyfunctional monomer. A polyfunctional monomer is a compound having two or more polymerizable groups in one molecule. Examples of the polyfunctional monomer include aliphatic polyfunctional (meth)acrylates such as ethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, 1,4-cyclohexanediol di(meth)acrylate, and tricyclodecane dimethanol di(meth)acrylate; aromatic polyfunctional (meth)acrylates such as EO-modified bisphenol A di(meth)acrylate and 9,9-bis[(meth)acryloyloxyethoxyphenyl]fluorene; and aromatic polyfunctional vinyl compounds such as divinylbenzene and divinylnaphthalene.

[0068] The number of polymerizable groups in the polyfunctional monomer is preferably 2 to 6, more preferably 2 to 4, and even more preferably 2 to 3. By setting the number of polymerizable groups within the above range, the degree of crosslinking of the cured layer can be adjusted, and the amount removed in steps (A) and (C) can be adjusted. As the polyfunctional monomer, a combination of polyfunctional monomers having different numbers of polymerizable groups may be used.

[0069] The number of carbon atoms in the polyfunctional monomer is preferably 8 to 100, more preferably 10 to 50, and even more preferably 15 to 30. The above number of carbon atoms includes the number of carbon atoms in the polymerizable group. The double bond equivalent of the polyfunctional monomer is preferably 50 to 1,000, more preferably 60 to 800, and even more preferably 80 to 500. By setting the number of carbon atoms or double bond equivalent of the polyfunctional monomer within the above ranges, it is possible to control the curability of the curable composition and the crosslink density of the cured layer, thereby controlling the affinity with the remover and obtaining a precursor pattern mask having desired properties such as mechanical strength and flexibility.

[0070] When the curable composition contains a polyfunctional monomer, the content of the polyfunctional monomer is preferably 5% by mass or less, more preferably 2% by mass or less, and even more preferably 1% by mass or less, based on the total weight of the monomer components. By setting the content of the polyfunctional monomer within this range, the affinity of the cured layer with the second removal liquid is improved.

[0071] The curable composition may contain a polymer. Polymers typically used in curable compositions can be used as appropriate. Inclusion of a polymer in the curable composition tends to shorten the time required to obtain a cured layer from the curable composition. Furthermore, adjusting the molecular weight of the polymer can adjust the affinity of the cured layer with the removal solution. Specifically, inclusion of a polymer with a relatively low molecular weight in the curable composition tends to increase the removal rate of the cured layer in steps (A) and (C). Furthermore, the glass transition temperature of the polymer is preferably room temperature or higher, and more preferably higher than the processing temperatures of steps (A) to (C). When the curable composition contains a polymer, the content of the polymer can be 10 to 300 parts by mass per 100 parts by mass of the total amount of the monomer components, polymerization initiator, and additives. Even when the curable composition contains a polymerization initiator and additives in addition to the monomer components, the content of the polymer can be 10 to 300 parts by mass per 100 parts by mass of the monomer components.

[0072] The curable composition may contain a solvent. Solvents typically used in curable compositions can be used as appropriate, and examples include the same solvents as the good solvents used in step (A). When the curable composition contains a solvent, 1 to 10,000 parts by mass of the solvent can be used per 100 parts by mass of the total amount of the monomer components, polymerization initiator, polymer, and additives. In this specification, the term "solvent" refers to a liquid compound that does not have a polymerizable group, excluding the monofunctional monomer, the polymerization initiator, the polyfunctional monomer, and the polymer. Reactive diluents and the like that have a polymerizable group are not included in the solvent and are considered to be the monofunctional monomer or the polyfunctional monomer.

[0073] The curable composition may contain an additive. Additives typically used in curable compositions can be used as appropriate. Examples of additives include release agents, adhesion promoters, antioxidants, polymerization inhibitors, colorants, plasticizers, surfactants, silane coupling agents, fillers, pigments, dyes, acidic compounds, and sensitizers. When the curable composition contains an additive, the content thereof is preferably within a range that does not significantly affect the composition's affinity with the removal liquid, curability, and mold fillability. The content of the additive is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass, and particularly preferably 0.05 to 3 parts by mass, per 100 parts by mass of the total amount of the monomer components.

[0074] In addition, the additive may be a compound having a functional group (such as a perfluoroalkyl group, an alkoxysilyl group, an oxyalkylene group, a phenolic hydroxyl group, or an amino group) that functions as an additive, as well as a polymerizable group such as a (meth)acryloyl group, a vinyl group, or an allyl group. In this specification, such a compound having both a functional group and a polymerizable group is considered to be the polyfunctional monomer or the monofunctional monomer, rather than an additive.

[0075] The cured layer obtained from the curable composition preferably has a glass transition temperature of room temperature or higher, and more preferably of the treatment temperatures of steps (A) to (C) or higher. By setting the glass transition temperature of the cured layer within the above range, softening of the cured layer during treatment is suppressed, and the desired pattern mask and pattern substrate can be efficiently obtained.

[0076] <3> Method for Manufacturing a Component One aspect of the present invention is a method for manufacturing a component using the above-described method for manufacturing a pattern substrate.

[0077] The method for manufacturing a pattern substrate can be used in manufacturing parts. The method for manufacturing a pattern substrate can remove a hardened layer by steps (A) and (C) using a remover. Therefore, in manufacturing parts, the method has advantages in terms of throughput, manufacturing equipment, and manufacturing costs compared to known methods in which residual film removal and hardened layer removal are performed by dry etching or the like.

[0078] The above-mentioned components are not particularly limited as long as they utilize a patterned substrate, and examples thereof include fine wiring, wire-grid polarizers, patterned media, flow channels, LEDs, microlens arrays, light guide plates, components having various electrode substrates, energy devices such as solar cells and fuel cells, biodevices such as biosensors and cell culture vessels, and microreactors. Also preferred as the above-mentioned components are electrodes for electrolytic capacitors, electric double-layer capacitors, ceramic capacitors, lithium-ion secondary batteries, nickel-metal hydride batteries, lead-acid batteries, and other batteries using aluminum, titanium, tantalum, conductive polymers, and the like. These electrodes can be obtained as patterned electrode substrates by using an electrode substrate made of aluminum, titanium, tantalum, conductive polymers, or the like as the substrate in the manufacturing method of the present invention. These electrodes manufactured by the manufacturing method of the present invention have the effect of increasing the surface area and improving the electrostatic capacitance due to the pattern on the surface.

[0079] Several aspects of the present invention will be described below based on examples, but the present invention can be implemented depending on the application. Below, examples will be described in which the surface layer treatment step is an etching step or a sputtering step, but the surface layer treatment in the method for producing a patterned substrate of the present invention can be appropriately selected from known surface layer treatments depending on the application. Furthermore, the numbers assigned to the components in the examples correspond to the reference numbers in the drawings. Note that the drawings are merely schematic illustrations of the materials treated in each step, and the length, thickness, ratio, etc. of each component in the drawings are not limited to those shown in the drawings.

[0080] In the method for producing a patterned substrate according to one embodiment of the present invention, examples (Examples 1 to 17 and Comparative Examples 1 to 11) in which the surface layer treatment step is an etching step will be described below.

[0081] Example 1 Preparation of Film Mold 96 parts by mass of perfluoropolyether urethane dimethacrylate (Fluorolink MD-700, manufactured by Solvay Specialty Polymers Japan Co., Ltd.) and 4 parts by mass of 1-hydroxycyclohexyl phenyl ketone (Omnirad 184, manufactured by IGM Resins B.V.) were mixed at room temperature to prepare a film mold composition. The film mold composition was dropped onto a PET film (Cosmoshine A4100, manufactured by Toyobo Co., Ltd., thickness 100 μm), and a film mold composition layer with a thickness of approximately 15 μm was formed using a bar coater. Next, the film mold composition layer was pressed against a silicon mold (DTM-7-2, manufactured by Kyodo International Co., Ltd., recess depth 1 μm, recess diameter 500 nm) with a hole pattern that had been pretreated with a fluorine-based mold release agent (Optoo HD-1100TH, manufactured by Daikin Industries, Ltd.). In this state, under a nitrogen atmosphere, a UV-LED lamp (wavelength 365 nm, illuminance 100 mW / cm ２ The film mold composition layer is exposed to light for 200 seconds using a photosensitive drum (photosensitive drum) to cure. After curing, the film mold composition layer is released from the silicon mold to obtain a film mold.

[0082] <Preparation of Curable Composition Sample> 96 parts by mass of FA-513AS (dicyclopentanyl acrylate, manufactured by Showa Denko Materials Inc.) and 4 parts by mass of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (Omnirad TPO, manufactured by IGM Resins B.V.) are mixed at room temperature to prepare a curable composition sample.

[0083] 3-Methacryloxypropyltrimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) is dropped onto an aluminum-deposited silicon wafer (aluminum-deposited layer approximately 350 nm thick, 2 cm square, manufactured by Advantec Co., Ltd.) so as to be spread over the entire surface. The aluminum-deposited layer corresponds to substrate 2, and the silicon wafer corresponds to support 3. This wafer is heated at 120°C for 15 minutes, then cooled to room temperature and washed with acetone to obtain a pretreated substrate. Next, the composition sample is dropped onto this substrate and spin-coated using a spin coater (1H-DX2, manufactured by Mikasa Co., Ltd.) to form a composition layer with a film thickness of approximately 3.5 μm.

[0084] A vacuum pump was used to reduce the pressure to 10 kPa, and the film mold cut into a 1.5 cm square was pressed against the composition layer obtained above. After leaving the film mold to stand for 1 minute with a load of 186 N, the film mold was irradiated with a UV-LED lamp (wavelength 365 nm, illuminance 100 mW / cm). ２ ) for 10 seconds to cure the composition layer. The thickness of the residual film 1A consisting of the composition layer remaining in the recesses of the precursor pattern mask is 10 nm to 100 nm. The cured layer is then released from the film mold to obtain a cured layer composite 10. The resulting cured layer composite has a hole pattern (represented as "Hole" in the table) derived from the film mold.

[0085] <First Removal Step> The hardened layer composite 10 obtained above is immersed in a first removal liquid (60 mL) at room temperature, removed from the removal liquid, and dried to obtain a resist composite 20. The type of first removal liquid and the immersion time are shown in Table 1. During the immersion, the hardened layer composite 10 is placed in the removal liquid being stirred at a rotation speed of 50 rpm to 500 rpm using a magnetic stirrer (KF-82, manufactured by Yazawa Scientific Co., Ltd.) so as not to come into contact with the stirrer. Examples in which the first removal liquid was used as described above in the first removal step are shown as "wet" in the "First Removal Step" section of the table.

[0086] <Evaluation of First Removal Step> The resist composite 20 obtained in the first removal step was cut in the thickness direction, and the cross section was observed and evaluated using an electron microscope (JSM-IT200, manufactured by JEOL Ltd.). Samples in which the molded pattern mask was not lost are indicated in the table below with "◯". In addition, samples in which the pattern mask was excessively dissolved and lost by the first removal solution with the solvent are indicated in the table below with "X", and samples in which a residual film 1A was observed even after the removal step are indicated in the table below with "XX". Note that samples in which the pattern mask was excessively dissolved and lost by the solvent in the evaluation of the first removal step, or samples in which a residual film was observed after the first removal step, were not evaluated in the surface layer treatment step (etching step) and the second removal step. Such samples are indicated in the table with "-".

[0087] <Surface Layer Treatment Step (Etching Step)> Hydrochloric acid, nitric acid, and water are mixed in a volume ratio of 3:1:2 to prepare a wet etching solution. 20 mL of the wet etching solution is transferred to a glass beaker, and the resist composite is immersed therein at room temperature for 5 minutes to wet-etch the aluminum vapor deposition layer located in the recesses of the pattern mask. After the treatment, the aluminum vapor deposition layer is washed with water and dried to obtain a treated surface layer composite 30 (etched composite 30A).

[0088] <Evaluation of Surface Layer Treatment Step (Etching Step)> The etched composite 30A obtained in the surface layer treatment step (etching step) was cut in the thickness direction, and the cross section was observed and evaluated using an electron microscope (JSM-IT200, manufactured by JEOL Ltd.) The results are shown in the table below, with samples in which dissolution of the aluminum vapor-deposited layer was observed marked with "O" and samples in which dissolution was not observed marked with "X."

[0089] <Second Removal Step> The same operations as in the first removal step were performed, except that the etched composite 30A obtained above was used instead of the cured layer composite 10, and the processing conditions were changed to those shown in Table 1. The type, temperature, and immersion time of the second removal solution are shown in Table 1. Note that, in the temperature of the second removal solution, "rt" represents room temperature.

[0090] <Evaluation of Second Removal Step> The samples obtained in the second removal step were visually observed and evaluated. The results are shown in the table below, with a sample in which the cured layer 1 was completely dissolved being marked "Good", a sample with some residual cured layer 1 being marked "Poor", and a sample in which the cured layer 1 was not dissolved at all being marked "XX".

[0091] Examples 2 to 17 Pattern substrates were formed and evaluated using the same steps as in Example 1, except that the monomers in the curable composition sample, the shape of the precursor pattern mask, the composition of the remover (mixing ratio by mass in the case of a mixed solvent), the temperature of the remover, and the removal time were changed as shown in Table 1. The monomer "IB-XA" in Table 1 represents isobornyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd.). When a line-and-space (denoted as "L / S" in the table) precursor pattern mask shape was used, a nickel mold with a line-and-space pattern (manufactured by Kyoei Engineering Co., Ltd., recess depth and line width 5 μm) was used instead of the silicon mold with a hole pattern. The evaluation results are shown in Table 1.

[0092] Comparative Examples 1 to 11: Pattern substrate formation and evaluation were performed in the same manner as in Example 1, except that the method of the first removal step, the monomer of the curable composition sample, the shape of the precursor pattern mask, the composition of the removal solution, the temperature of the removal solution, and the removal time were changed as shown in Table 1. In the first removal step of Comparative Examples 1 to 6, the cured layer composite 10 was treated by dry etching instead of the immersion. Specifically, a plasma dry cleaner (PDC210, manufactured by Yamato Scientific Co., Ltd.) was used to perform dry etching for 90 seconds under conditions of an oxygen flow rate of 10 mL / min and an RF output of 350 W, removing the residual film 1A located in the recesses of the precursor pattern mask, thereby obtaining a resist composite 20 in which the aluminum-deposited silicon wafer located in the recesses is exposed. Examples in which dry etching was used in the first removal step as described above are indicated as "dry" in the "First Removal Step" column in the table.

[0093]

[0094] In one embodiment of the method for producing a patterned substrate according to the present invention, examples (Examples 18 to 34 and Comparative Examples 12 to 22) in which the surface layer treatment step is a sputtering step are shown below. The same cured layer composite 10 as in the etching step example above is used. The first removal step, second removal step, and evaluation of the first removal step are performed in the same manner as in the etching step example above. The conditions and evaluation results for the examples and comparative examples are shown in Table 2.

[0095] <Surface Layer Treatment Step (Sputtering Step)> The resist composite 20 is subjected to sputtering for 60 seconds at a sputtering current of 20 mA using an Auto Fine Coater (JEC-3000FC, manufactured by JEOL Ltd.), and a platinum sputtering target is deposited on the resist composite to a thickness of about 3 nm. The sputtering is repeated 15 times to obtain a treated surface layer composite 30 (heterogeneous material composite 30B) having platinum laminated on the surface to a thickness of about 45 nm.

[0096] <Evaluation of the Second Removal Step After the Surface Layer Treatment Step (Sputtering Step)> The pattern substrate 40B obtained in the surface layer treatment step (sputtering step) and the second removal step was cut in the thickness direction, and the cross section was observed and evaluated using an electron microscope (JSM-IT200, manufactured by JEOL Ltd.). Samples in which the hardened layer 1 did not remain and the desired platinum pattern substrate was obtained were marked with "Good," and samples in which the hardened layer 1 remained and the desired platinum pattern substrate was not obtained were marked with "Poor." In the evaluation of the first removal step, sample patterns in which the pattern mask was excessively dissolved and disappeared by the solvent, or samples in which a residual film was observed after the first removal step, were not evaluated in the second removal step. Such samples are marked with "-" in Table 2.

[0097]

[0098] As described above, it can be seen that, according to one embodiment of the method for producing a pattern substrate of the present invention, the residual film is removed while maintaining the desired pattern mask. On the other hand, under the conditions of the comparative example, it can be seen that the residual film is not removed, or the formed pattern mask is removed, and the desired pattern substrate cannot be obtained. Furthermore, when dry etching is used to remove the residual film, it takes a long time to remove the formed pattern mask, and it is not suitable for industrial use from the perspective of throughput. This is presumably because the hardened layer is altered by dry etching, significantly reducing its affinity for the second remover.

[0099] The conditions used in the above examples (such as the curable composition, precursor pattern mask, first removal liquid, and second removal liquid) can be adjusted as appropriate. Even if conditions other than those used in the above examples are used, similar effects can be achieved as long as they are modified based on the description in this specification.

[0100] The method for producing a pattern substrate according to one embodiment of the present invention has the advantage that it is possible to remove an unintended cured layer while maintaining a desired pattern mask by treating the cured layer composite in a specific manner, and is therefore useful for manufacturing parts.

[0101] 1 Hardened layer (precursor pattern mask), 1A Hardened layer (pattern mask), 1a Convex portion, 1b Convex portion, 1c Convex portion, 1d Opening, 2 Substrate, 3 Support, 4 Heterogeneous material layer, 10 Hardened layer composite, 20 Resist composite, 30A Etched composite, 30B Heterogeneous material composite 40A, 40B Pattern substrate

Claims

1. A method for manufacturing a pattern substrate, A first removal step (A) is performed to treat the precursor pattern mask of a cured layer composite having a substrate and a cured layer formed on the substrate and having recesses and protrusions with a first removal solution to remove the cured layer corresponding to at least the thickness of the cured layer in the recess, thereby obtaining a resist composite having a predetermined pattern mask in which the substrate located in the recess is exposed. A surface treatment step (B) is performed on the resist composite via the predetermined pattern mask to obtain a treated surface composite, The process includes a second removal step (C) in which the predetermined pattern mask of the treated surface composite is removed with a second removal solution to obtain a pattern substrate, A method for manufacturing a patterned substrate, wherein the removal conditions in the first removal step (A) and the removal conditions in the second removal step (C) are different.

2. The method for manufacturing a patterned substrate according to claim 1, wherein the surface treatment step (B) is an etching step in which the substrate exposed through the predetermined pattern mask is etched to obtain the treated surface composite.

3. The method for manufacturing a pattern substrate according to claim 1, wherein the surface treatment step (B) is a heterogeneous material placement step, in which a material different from the cured layer constituting the predetermined pattern mask is placed on the surface of the resist composite, and a material layer made of the different material is provided on the substrate via the predetermined pattern mask to obtain the treated surface composite.

4. A method for producing a patterned substrate according to claim 1, wherein the composition of the first removal solution and the composition of the second removal solution are different.

5. The method for manufacturing a patterned substrate according to claim 1, wherein the temperature of the first removal solution is lower than the temperature of the second removal solution.

6. The method for manufacturing a patterned substrate according to claim 1, wherein the removal time of the hardened layer in the first removal step (A) is shorter than the removal time of the hardened layer in the second removal step (C).

7. The method for manufacturing a pattern substrate according to claim 1, wherein the precursor pattern mask is an imprinted molded product.

8. A method for manufacturing a patterned substrate according to claim 1, wherein steps (A) to (C) are performed in a roll-to-roll process.

9. The method for producing a pattern substrate according to claim 1, wherein the cured layer of the cured layer composite is a cured product of a curable composition containing 95% by mass or more of monofunctional monomers in the monomer components.

10. Monomers and, It contains a polymerization initiator and The monomers include monofunctional monomers and optionally polyfunctional monomers. A curable imprint composition for use in a method for producing a pattern substrate according to any one of claims 1 to 9, wherein the content of the polyfunctional monomer is less than 1% by mass of the monomer component.

11. A method for manufacturing parts using a pattern substrate, A method for manufacturing a component, wherein the pattern substrate is manufactured using the method for manufacturing a pattern substrate described in any one of claims 1 to 9.