TW202414117A - Method for producing patterned base material, curable composition and method for producing component - Google Patents

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 parts

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

As a method for forming fine patterns on a substrate, photolithography or embossing is widely used. Compared with photolithography, embossing has advantages such as being able to form patterns at low cost, and has attracted attention in recent years (see Patent Document 1). [Prior Art Document] [Patent Document]

[Patent Document 1] Japanese Patent Publication No. 2014-3276

[The problem the invention is trying to solve]

In the above-mentioned lithography or embossing, when forming a pattern mask including a hardening layer, the hardening layer may remain in an unexpected position on the substrate. When the pattern mask is used as an etchant to etch the substrate after the pattern mask is formed, the desired pattern mask may not be transferred to the substrate due to the unexpected hardening layer.

In view of this situation, the subject of some aspects of the present invention is to provide a method for manufacturing a pattern substrate that maintains the required pattern mask and removes the unexpected hardening layer. In addition, the subject of some aspects of the present invention is to provide a curable composition used in the method for manufacturing the pattern substrate, and a method for manufacturing parts using the method for manufacturing the pattern substrate. [Technical means for solving the problem]

The inventors of the present invention have made great efforts to solve the above-mentioned problems and have found that by using the following removal steps (A) and (C) of a removal liquid to treat the pre-driving pattern mask of the hardening layer, the unexpected hardening layer can be removed and the desired pattern substrate can be obtained, thereby completing certain aspects of the present invention.

One aspect of the present invention is a method for manufacturing a (A) pattern substrate, which includes the following steps: a first removal step (A), in which a first removal liquid is used to treat the front-drive pattern mask in a hardening layer composite having a substrate and a hardening layer formed on the substrate and having a concave portion and a convex portion, and at least the hardening layer is removed by a thickness of the hardening layer corresponding to the concave portion, thereby obtaining a substrate having the substrate exposed in the concave portion. a surface treatment step (B), in which the surface treatment is performed on the above-mentioned anti-corrosion composite through the above-mentioned pattern mask to obtain a treated surface composite; and a second removal step (C), in which the above-mentioned specified pattern mask of the above-mentioned surface treatment composite is removed by a second removal liquid to obtain a pattern substrate; the removal conditions in the above-mentioned first removal step (A) are different from the removal conditions in the above-mentioned second removal step (C).

In the method for manufacturing the pattern substrate, the surface treatment step (B) may be etching of the substrate exposed through the specified pattern mask, and obtaining an etched composite as the etching step (B1) of the surface treatment composite. Furthermore, the surface treatment step (B) may also be a heterogeneous material configuration step (B2), which configures a material different from the hardening layer constituting the specified pattern mask on the surface of the anti-etching composite, and obtains a heterogeneous material composite having a material layer containing the above-mentioned different material disposed on the substrate through the specified pattern mask as the surface treatment composite. In any of the above-mentioned embodiments, the composition of the first removal liquid may be different from the composition of the second removal liquid, the temperature of the first removal liquid may be lower than the temperature of the second removal liquid, and the removal time of the hardened layer in the step (A) may be less than the removal time of the hardened layer in the step (C). In any of the above-mentioned embodiments, the front-drive pattern mask may be an embossed molded object. In any of the above-mentioned embodiments, steps (A) to (C) may be performed in a roll-to-roll process.

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, comprising a monomer and a polymerization initiator, wherein the content of the monofunctional monomer in the above monomer components is 95 mass % or more.

Another aspect of the present invention is a method for manufacturing a component, which includes a method for manufacturing a pattern substrate of any of the above aspects. [Effect of the invention]

The method for manufacturing a pattern substrate according to one aspect of the present invention can maintain the desired pattern mask and remove the unexpected hardening layer.

The present invention is described in detail below. In this specification, "(meth)acrylate" means both "acrylate" and "methacrylate". "(Meth)acryl" also means both "acryl" and "methacryl". "(Meth)acrylic acid" also means both "acrylic acid" and "methacrylic acid". In addition, "polymerizable group" means free radical polymerizable groups such as (meth)acryl, vinyl, allyl, homoallyl, propargyl and homopropargyl. Furthermore, groups such as epoxy and cyclobutyl also function in the same manner as the polymerizable groups in this specification and obtain the same effects.

<1> Method for manufacturing pattern substrate One aspect of the present invention is a method for manufacturing a pattern substrate including the above steps.

<1-1> Preparation step of hardening layer composite The manufacturing method of a pattern substrate of one aspect of the present invention may include a preparation step of hardening layer composite comprising a substrate and a hardening layer front-drive pattern mask formed on the substrate. Furthermore, the front-drive pattern mask is a pattern having concave and convex parts, which can be manufactured by known methods such as photolithography, injection molding and embossing. Furthermore, the hardening layer composite can be manufactured and used by such known methods, or a commercially available product can be used.

The imprinting method includes, for example, the following steps: applying a curable composition on a substrate to form a curable composition layer; bringing the curable composition layer into contact with a mold having a pattern; and curing the curable composition layer by heat or light; thereby forming a front-drive pattern mask having concave and convex portions. Furthermore, the curable composition used will be described below. Here, the concave portion of the front-drive pattern mask is a portion where the thickness of the curing layer is smaller than that of the convex portion. In the above steps, sometimes an unexpected curing layer (hereinafter also referred to as "residual film") originating from the gap between the substrate and the mold when forming the opening portion remains at the edge of the opening portion, etc., which is also set as the above-mentioned concave portion. Since such residual film is easily generated in the embossing method, the manufacturing method of the above-mentioned pattern substrate can be preferably used when the above-mentioned hardening layer is formed by the embossing method before the pattern mask is driven. Figure 1 (a) shows an example of a hardening layer composite. The hardening layer composite 10A includes a hardening layer (front-drive pattern mask) 1, a substrate 2, and a support 3, and a hardening layer 1 is formed on the substrate 2 disposed on the support 3. The hardening layer 1 preferably includes a concave portion 1a with a thinner film thickness and a convex portion 1b with a thicker film thickness, and the thickness (difference film thickness) obtained by subtracting the film thickness of the concave portion 1a from the thickness of the convex portion 1b becomes the pattern mask film thickness specified below. Furthermore, the concave portion 1a may be a residual film when the opening portion is formed, or the thickness of the central portion of the concave portion 1a may be thinner, or an opening may be formed in the central portion.

The shape and size of the front-drive pattern mask including the hardening layer can be appropriately selected according to the purpose of the pattern substrate obtained by the method for manufacturing the pattern substrate of one aspect of the present invention. Examples of the shape of the front-drive pattern mask include: hole pattern, column pattern, cone pattern, grid pattern, honeycomb pattern, and line and space pattern. Furthermore, the bottom surface of the hole pattern, column pattern, and cone pattern can be a circle, an ellipse, or a polygon such as a triangle or a quadrilateral. As the size of the front-drive pattern mask, in the case of a line and space pattern, the width of the line and/or space can be 20 nm to 100 μm, preferably 50 nm to 50 μm, more preferably 100 nm to 10 μm, and the film thickness can be 20 nm to 100 μm, preferably 50 nm to 50 μm, and more preferably 100 nm to 10 μm. In the case where the pattern mask is other than a line and space pattern, the side constituting the bottom surface of the pattern mask (the diameter in the case of a circle, the long axis in the case of an ellipse) can be 20 nm to 100 μm, preferably 50 nm to 50 μm, and more preferably 100 nm to 1 μm, and the film thickness can be 20 nm to 100 μm, preferably 50 nm to 50 μm, and more preferably 100 nm to 1 μm. Furthermore, the pitch of the front-drive pattern mask can be 20 nm to 100 μm, preferably 50 nm to 50 μm, and more preferably 100 nm to 1 μm. Furthermore, the film thickness of the front-drive pattern mask indicates the film thickness of the convex portion 1b. Furthermore, the aspect ratio of the front-drive pattern mask is preferably 0.5 to 100. Furthermore, the aspect ratio indicates the ratio of the differential film thickness to the smaller width of the concave portion 1a and the convex portion 1b.

The material of the mold 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, polyolefin, polyethylene, polypropylene, polyethylene, polyvinylene, polyurethane, polyester, polymethyl methacrylate, polyether sulfone, polydimethylsiloxane and polytetrafluoroethylene; etc. In addition, the mold can also be a replica mold made by hardening a thermosetting resin or a light-curing resin.

The material of the above-mentioned 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, polyethylene, polyvinylene, polyurethane, polyether sulfone and polytetrafluoroethylene; etc. The above-mentioned substrate can also be a substrate made by curing a thermosetting resin or a photocuring resin. Furthermore, "substrate" refers to the material that contacts the curing layer on the surface of the above-mentioned curing layer opposite to the front-drive pattern mask. In addition to the curing layer and the substrate, the above-mentioned curing layer composite can also have materials such as a support.

The thickness of the substrate can be appropriately selected according to the purpose 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. Furthermore, when the following steps (A) to (C) are performed by a roll-to-roll process, from the perspective of the ease of rolling up the hardened layer composite, the total thickness of the substrate and the support is preferably 1 μm to 300 μm, more preferably 10 μm to 100 μm.

The combination of the substrate and the support can be appropriately selected according to the purpose 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 the surface, a support having a metal vapor-deposited layer (substrate) on the surface, and the like.

<1-2> First Removal Step (A) FIG. 1(b) shows an example of an anti-corrosion composite after the first removal step. The method for manufacturing a pattern of one aspect of the present invention includes a first removal step (A), which removes the concave hardening layer (also referred to as a residual film) of the front-drive pattern mask 1 in the hardening layer composite 10A by a first removal liquid, thereby obtaining an anti-corrosion composite 20A having a prescribed pattern mask 1A in which the substrate 2 located in the concave portion 1a is exposed. In step (A), the hardening layer is removed in such a manner that only the substrate 2 opposite to the concave portion 1a of the front-drive pattern mask 1 is exposed, and the substrate 2 located in the convex portion 1b of the front-drive pattern mask 1 is not exposed. That is, at least the hardened layer equivalent to the thickness of the concave portion 1a is removed, and as a result, the concave portion 1a becomes the opening portion 1d, and the convex portion 1b becomes the convex portion 1c with reduced film thickness, and only the substrate 2 opposite to the opening portion 1d is exposed. The hardened layer of the concave portion 1a is preferably substantially completely removed. In addition, the amount of the hardened layer removed is preferably an amount equivalent to the thickness of the concave portion 1a, and as long as the required pattern substrate can be obtained, it can be more than the amount equivalent to the thickness of the concave portion 1a. That is, since the hardened layer is basically removed isotropically in two directions, namely, the thickness direction and the surface direction orthogonal to the thickness direction, it is sufficient to remove it until the size of the surface direction of the concave portion 1a becomes the specified size. Furthermore, in step (A), the hardened layer can also be strictly removed anisotropically. For example, since the film thickness of the composition layer forming the concave portion by curing is smaller than that of the composition layer forming the convex portion by curing, the light absorption of the photopolymerization initiator described below is smaller, and therefore, the curing degree of the concave portion hardened layer is sometimes lower. In this case, the concave portion hardened layer tends to be easier to remove than the convex portion hardened layer. On the other hand, due to the stirring conditions of the first removal liquid and the shape of the front-drive pattern mask, the concave portion hardened layer sometimes does not fully contact the first removal liquid. In this case, the concave portion hardened layer tends to be easier to remove than the convex portion hardened layer. Due to the above-mentioned various reasons, the removal speed of the concave portion hardened layer is sometimes different from the removal speed of the convex portion hardened layer, and the hardened layer in step (A) is removed anisotropically. Regarding the concave hardening layer, that is, the removal of the residual film can be in the form of the residual film being dissolved in the first removal liquid, or in the form of the residual film being peeled off from the surface of the substrate.

The thickness of the pattern mask film after the residual film is removed is preferably 10 nm to 100 μm, more preferably 100 nm to 50 μm. Furthermore, when the subsequent surface treatment step (B) is an etching step (B1), the thickness of the pattern mask film is preferably 10 nm to 50 μm, more preferably 100 nm to 10 μm. When the subsequent surface treatment step (B) is a heterogeneous material configuration step (B2), the thickness of the pattern mask film is preferably 100 nm to 100 μm, more preferably 500 nm to 10 μm.

The first removal liquid may be a solvent with a higher affinity to the hardened layer (hereinafter also referred to as a "good solvent"), or a mixed solvent of a solvent with a lower affinity to the hardened layer (hereinafter also referred to as a "bad solvent") and a good solvent. By using a good solvent as the first removal liquid, the residual film can be effectively removed. Furthermore, when only a good solvent is used, even the desired pattern mask is removed, it is better to use a mixed solvent of a bad solvent and a good solvent. The first removal liquid and the second removal liquid described below may further include additives such as a solubility adjuster, a surfactant, a defoaming agent, and a stabilizer. The content of the additive is preferably 10 parts by mass or less, and more preferably 5 parts by mass or less relative to 100 parts by mass of the removal liquid. The lower limit of the content of the additive can be set to 0.01 parts by mass, for example. Furthermore, the first removal liquid can be made substantially free of additives, which is preferred. Furthermore, in this specification, the "affinity" of the removal liquid and the hardened layer refers to the degree of interaction between the removal liquid and the hardened layer. When a solvent with a higher affinity comes into contact with the hardened layer, the hardened layer is dissolved or swelled and removed.

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, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether; 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, ethyl acetate, ethyl acetate, Ester solvents such as butyl acetate, amyl acetate, isoamyl acetate, ethyl lactate and γ-butyrolactone; ketone solvents such as cyclohexanone, methyl isobutyl ketone (MIBK), methyl ethyl 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, 1,3,5-trimethylbenzene; impurity atom-containing solvents such as acetonitrile, propionitrile, benzonitrile, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide and dimethyl sulfoxide; etc. These good solvents can be used alone or in combination of two or more. From the perspective of efficiently removing residual films, the above-mentioned good solvent is preferably a solvent containing glycol ether solvent, cyclic ether solvent, aromatic ether solvent or ketone solvent, and more preferably a solvent containing glycol ether solvent.

Examples of the poor solvent include: alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol (IPA), n-butanol, 2-butanol, 3-butanol, amyl alcohol, and diacetone alcohol; dialkyl ether solvents such as dibutyl ether, 3-butyl methyl ether, dipropyl ether, and diisopropyl ether; aliphatic hydrocarbon solvents such as n-hexane, n-heptane, n-octane, and cyclohexane; water; etc. These poor solvents may be used alone or in combination of two or more. In terms of safety or cost, alcohol solvents and water are preferred among the above poor solvents.

When a mixed solvent of a good solvent and a poor solvent is used as the first removing solution, the mixing ratio can be appropriately selected according to the affinity of each solvent to the hardened layer. As a mixing ratio (mass ratio), when water is used as the poor solvent, it is preferably good solvent: poor solvent = 99:1 to 50:50, more preferably 97:3 to 60:40, and further preferably 95:5 to 70:30. When an organic solvent is used as the poor solvent, it is preferably good solvent: poor solvent = 5:95 to 90:10, more preferably 10:90 to 80:20, and further preferably 20:80 to 70:30.

In the case where the removal of the residual film is insufficient in the following preliminary test step (P), it is preferred to prepare the first removal solution by increasing the ratio of the good solvent in the preliminary test step (P). On the contrary, in the case where even the desired pattern mask is removed, it is preferred to prepare the first removal solution by increasing the ratio of the bad solvent in the preliminary test step (P). Furthermore, in the case of using a mixed solvent of a bad solvent and a good solvent, the bad solvent and the good solvent are preferably uniformly mixed at the above-mentioned mixing ratio at room temperature (e.g., 25° C.).

The removal amount of the hardened layer per unit time of the first removal liquid is preferably below a certain value. With this first removal liquid, both the removal of the residual film and the maintenance of the required pattern mask can be taken into account. Furthermore, the above removal amount can be measured by preparing the hardened layer by the method described in the hardened layer composite preparation step, and by immersing the hardened layer in the removal liquid in the preparation step (preliminary test step (P)). That is, the processing conditions of step (A) and step (C) can be determined by the preliminary test step (P).

That is, another aspect of the present invention is a method for manufacturing a pattern substrate, which includes the following steps: a preliminary test step (P), in which a pre-hardened layer composite having a pre-hardened layer and a pre-hardened layer formed on the pre-hardened layer is treated under specified conditions to determine a first removal condition and a second removal condition; a first removal step (A), in which a pre-hardened layer having a pre-hardened layer and a pre-hardened layer formed on the pre-hardened layer is removed under the first removal condition. The hardened layer of the concave portion of the above-mentioned front-driven pattern mask in the hardened layer composite of the mask is obtained to obtain an anti-corrosion composite having a specified pattern mask with the above-mentioned substrate located in the concave portion exposed; a surface treatment step (B), which performs surface treatment on the above-mentioned anti-corrosion composite to obtain a treated surface composite; and a second removal step (C), which removes the hardened layer of the above-mentioned treated surface composite under the above-mentioned second removal condition to obtain a pattern substrate; the above-mentioned first removal condition is different from the above-mentioned second removal condition.

In the method for manufacturing the pattern substrate including the preliminary test step (P), the hardened layer composite of step (A) and the treatment conditions of steps (A) and (C) are preferably the same as the pre-hardened layer composite and the treatment conditions determined by the preliminary test step (P). Furthermore, the treatment conditions include the composition, temperature, stirring conditions, and treatment time of each removal solution.

From the viewpoint of taking into account both the residual film removal and the maintenance of the desired pattern mask, it is preferred that the composition of the first removal liquid is different from that of the second removal liquid. Specifically, it is preferred that the content ratio of the bad solvent in the first removal liquid is greater than the content ratio of the bad solvent in the second removal liquid. By setting the composition of the first removal liquid and the second removal liquid as described above, the removal amount in step (A) can be made smaller than the removal amount in step (C), and in step (A), both the residual film removal and the maintenance of the desired pattern mask can be taken into account.

From the perspective of balancing the removal of the residual film and the maintenance of the desired pattern mask, it is preferred that the temperature of the first removal liquid is lower than the temperature of the second removal liquid. By making the temperature of the first removal liquid lower than the temperature of the second removal liquid, the amount of removal in step (A) can be made smaller than the amount of removal in step (C), and the removal of the residual film in step (A) and the maintenance of the desired pattern mask can be balanced. The temperature of the first removal liquid is not particularly limited as long as it is a temperature below the boiling point of the first removal liquid, and can be set, for example, below 50°C, below room temperature (e.g., 25°C), below 15°C, or below 5°C. Furthermore, the lower limit of the temperature of the first removal liquid is not particularly limited as long as it is the temperature at which the first removal liquid is a liquid, and can be set, for example, above 0°C.

From the perspective of taking into account both the removal of residual film and the maintenance of a prescribed pattern mask, it is preferred 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 removal amount in step (A) can be made smaller than the removal amount in step (C), and both the removal of residual film in step (A) and the maintenance of a desired pattern mask can be taken into account. The removal time of the hardened layer in step (A) can be set, for example, to be less than 30 minutes, less than 20 minutes, less than 15 minutes, or less than 5 minutes. Furthermore, the lower limit of the time for removing the hardened layer in step (A) is not particularly limited as long as the residual film can be removed, and can be set to, for example, 10 seconds or more.

Furthermore, the above-mentioned 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 respectively, and the difference in thickness is calculated. The difference is divided by the removal time (minutes), thereby calculating the removal rate (nm/minute). Furthermore, as mentioned above, the removal amount (nm) represented by the difference is preferably an amount equivalent to the thickness of the recessed portion 1a. As long as the required pattern substrate can be obtained, the amount may be more than the amount equivalent to the thickness of the recessed portion 1a, and the size of the surface direction of the recessed portion 1a may be removed to a specified size. Furthermore, as mentioned above, the removal rate of the recessed hardened layer and the removal rate of the convex hardened layer are different due to various reasons, and sometimes the hardened layer in step (A) is removed anisotropically.

As described above, in the method for manufacturing the pattern substrate, the removal conditions in the first removal step (A) (hereinafter also referred to as the "first removal conditions") are different from the removal conditions in the second removal step (C) (hereinafter also referred to as the "second removal conditions"). The different conditions 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. As other conditions, for example, the convection velocity of the removal liquid in the removal step and the ultrasonic vibration time can be cited. Furthermore, the convection velocity of the removal liquid can be appropriately adjusted by the known method of controlling the fluid, such as the stirring speed of the removal liquid in the removal tank, the circulation volume of the circulation pump, etc.

The method of treating with the first removing liquid can be appropriately selected according to the thickness of the hardened layer, etc. Examples of the treating 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 (spraying method), a method of spraying the removing liquid onto the hardened layer composite (spraying method), and a method of allowing the removing liquid to overflow onto the hardened layer composite (liquid covering method).

<1-3> Surface treatment step (B) The method for manufacturing a pattern substrate of one aspect of the present invention includes a surface treatment step (B) of treating the above-mentioned anti-corrosion composite through the above-mentioned pattern mask to obtain a treated surface composite. Examples of the treated surface composite include etching composites and heterogeneous material composites. The details will be described below.

In one aspect of the present invention, the surface treatment step (B) is preferably an etching treatment of the substrate exposed through the above-mentioned pattern mask in the anti-etching composite, and the etching step (B1) of obtaining the etching composite as the above-mentioned surface treatment composite. The etching step (B1) can be dry etching or wet etching. In anisotropic dry etching, the side of the pattern mask may be unintentionally etched in the roll-to-roll process, and the affinity of the hardened layer treated by dry etching to the second removal solution described below may be reduced. Therefore, the etching step (B1) is preferably wet etching. FIG1(c) shows an example of an etching composite when the surface treatment step (B) is a wet etching step (B1). The substrate 2 of the etching composite 30A is processed by the pattern mask 1A to become a processed substrate 2A in which the substrate area opposite to the opening 1d is removed.

When the etching step (B1) is wet etching, the composition and temperature of the etching solution and the processing time and other conditions can be appropriately selected from known ones according to the material and thickness of the substrate. Examples of the etching solution include: an oxidizing solution containing an oxidizing agent such as hydrogen peroxide solution, perchloric acid, ammonium peroxydisulfate, and sodium peroxydisulfate; 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 (III) chloride, copper (II) chloride, chromium (IV) oxide, aluminum chloride, sodium cyanide, and ammonium nitrate; an alkaline solution containing an alkali such as tetramethylammonium hydroxide, hydroxylamine, hydrazine, ethylenediamine, sodium hydroxide, and potassium hydroxide; etc. The etching solution may further contain additives such as a surfactant, a stabilizer, and a defoaming agent.

The temperature of the etching solution is not particularly limited as long as it is below the boiling point of the etching solution, and can be set to, for example, 80°C or below, 60°C or below, or 50°C or below. The lower limit of the temperature of the etching solution is not particularly limited as long as it is the temperature of the etching solution in liquid form, and can be set to, for example, 0°C or above or above room temperature. The etching time can be appropriately set according to the thickness of the substrate, and can be set to, for example, 30 seconds to 30 minutes, 1 minute to 20 minutes, or 3 minutes to 10 minutes.

In another aspect of the present invention, the surface treatment step (B) is preferably a heterogeneous material placement step (B2), which places a material different from the hardened layer constituting the above-mentioned pattern mask on the surface of the anti-corrosion composite, and obtains a heterogeneous material composite in which a material layer including the above-mentioned different material is disposed on the above-mentioned substrate via the above-mentioned pattern mask as the above-mentioned treated surface composite. As a method for placing heterogeneous materials in the heterogeneous material placement step (B2), for example, sputtering, sol-gel method, direct coating method, electrolytic plating method and electroless plating method can be cited, and a known method can be appropriately selected according to the type of heterogeneous materials to be placed. These methods can be implemented by using known materials and sequences, except for using the above-mentioned anti-corrosion composite as the treated layer.

When the concavo-convex portions of the hardened layer are completely covered by the foreign material in the foreign material configuration step (B2), an exposing step of removing at least a portion of the configured foreign material and exposing at least a portion of the convex portions of the hardened layer may be performed as needed after the foreign material configuration step (B2) and before the second removal step (C). The convex portions of the hardened layer are exposed by the exposing step, so that the hardened layer can be removed efficiently in the second removal step (C). The method of exposing the convex portions of the hardened layer can be appropriately selected from known removal methods, such as the removal of foreign materials using a scraper, etching, and CMP (Chemical Mechanical Polishing). FIG2(c) shows an example of a heterogeneous material composite when the surface treatment step (B) is a heterogeneous material configuration step (B2). Here, since FIG2(a) and (b) are the same as FIG1(a) and (b) except that there is no support 1, repeated description is omitted. Furthermore, in the process of FIG2, a support 1 can of course also be provided. In the heterogeneous material composite 30B, a material layer 4 containing different materials is formed on a substrate 2 having a pattern mask 1A. At this time, since the material layer 4 is not provided on the side of the convex portion 1c of the pattern mask 1A, a partial removal step of the material layer 4 is not necessarily required, and a step of removing only the material layer 4 on the convex portion 1c can also be implemented.

When the heterogeneous material placement step (B2) is a sputtering step, the conditions such as the sputtering target, inert gas, current value and processing time can be appropriately selected from known ones according to the material and thickness of the substrate and the purpose of the pattern substrate. The heterogeneous material placed in the sputtering step can be appropriately selected according to the purpose of the pattern substrate, for example, known metal elements, alloys, metal oxides, etc. can be cited. Furthermore, the heterogeneous material placement step (B2) can be PVD (physical evaporation) other than sputtering, such as vacuum evaporation and ion plating, or CVD (chemical evaporation).

When the heterogeneous material configuration step (B2) is a step using a sol-gel method, for example, it is preferred to apply a pre-driver solution containing a metal compound to the surface of the above-mentioned anti-corrosion composite, and heat the coating to obtain a heterogeneous material composite having metal configured on the surface of the above-mentioned anti-corrosion composite. In the above sequence, additives such as acids, bases, and nucleophilic reagents may be used in combination to promote the gelation reaction. Specifically, for example, a pre-driver solution containing tetraethoxysilane is applied, and the coating is heated to obtain a heterogeneous material composite having silicon oxide configured on the surface of the above-mentioned anti-corrosion composite. The heterogeneous materials used in the sol-gel method can be appropriately selected according to the purpose of the pattern substrate, and examples thereof include oxides such as magnesium oxide, aluminum oxide, silicon dioxide, titanium dioxide, and zirconium oxide, and composite materials containing these oxides.

In the case where the heterogeneous material configuration step (B2) is a step using a direct coating method, for example, it is preferred to apply a dispersion containing microparticles of a metal or its oxide to the surface of the above-mentioned anti-corrosion composite, thereby obtaining a heterogeneous material composite having the metal configured on the surface of the above-mentioned anti-corrosion composite. In the above sequence, the coating may be heated to volatilize the dispersion medium. Specifically, for example, a dispersion containing silver nanoparticles is applied and the coating is heated to obtain a heterogeneous material composite having silver configured on the surface of the above-mentioned anti-corrosion composite. The heterogeneous material configured in the direct coating method using microparticles can be appropriately selected according to the purpose of the pattern substrate, for example, known metal elements, alloys, metal oxides, etc. can be cited.

As another example of the direct coating method of the heterogeneous material configuration step (B2), the following steps can also be cited: a curable composition is coated on the surface of the above-mentioned anti-corrosion composite, and the coating is cured by light or heat, thereby obtaining a heterogeneous material composite having a heterogeneous material hardened layer configured on the surface of the above-mentioned anti-corrosion composite. The heterogeneous material hardened 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 a hydride group as a photosensitive group is coated, and ultraviolet rays are irradiated to obtain a heterogeneous material composite having a heterogeneous material hardened layer configured on the surface of the above-mentioned anti-corrosion composite.

When the dissimilar material placement step (B2) is an electrolytic plating step, for example, it is preferred to immerse the anti-corrosion composite in a plating solution, immerse an anode containing a metal in the plating solution, and pass a current between the substrate and the anode, thereby obtaining a dissimilar material composite having the metal placed on the surface of the anti-corrosion composite. Furthermore, when the dissimilar material placement step (B2) is an electrolytic plating method, a conductive material is used as the substrate. In addition, a metal salt containing ions of the metal may be added to the plating solution.

When the heterogeneous material placement step (B2) is an electroless plating step, for example, it is preferred that a plating solution containing a metal salt containing metal ions is impregnated into the above-mentioned anti-corrosion composite to obtain a heterogeneous material composite having the metal placed on the surface of the above-mentioned anti-corrosion composite. In the above sequence, in order to promote plating, additives such as a pH adjuster, a reducing agent, and a catalyst may also be added to the plating solution.

The thickness of the foreign material arranged in the foreign material arrangement step (B2) can be within a range that does not hinder the removal of the hardened layer in the second removal step (C) described below, and can be appropriately selected according to the purpose of the pattern substrate to be formed and the type of step (B2). The thickness of the foreign material is preferably 1.0 or less, more preferably less than 1.0, relative to the depth of the concave portion of the pattern mask, for example. It can be set to 0.5 or less or 0.1 or less. In addition, relative to the depth of the concave portion, it can be set to, for example, 0.005 or more.

<1-4> Second Removal Step (C) The method for manufacturing a pattern substrate according to one aspect of the present invention includes removing the hardened layer of the treated surface composite by a second removal liquid to obtain the second removal step (C) of the pattern substrate. By treating the treated surface composite by the second removal step (C), the hardened layer on the substrate can be substantially completely removed. The removal of the hardened layer can be in the form of dissolving the hardened layer in the second removal liquid or in the form of peeling the hardened layer from the surface of the substrate. Figures 1(d) and 2(d) show examples of pattern substrates formed by the second removal step (C). The pattern substrate 40A of FIG. 1( d ) is formed by removing the pattern mask 1A including the hardening layer by an etching step ( B1 ), and includes a processed substrate 2A having a portion of a concave portion. On the other hand, the pattern substrate 40B of FIG. 2( d ) has a patterned material layer 4A formed on the substrate 2 by a heterogeneous material configuration step ( B2 ).

In the method for manufacturing a pattern substrate of one aspect of the present invention, the first removal condition is different from the second removal condition. By making the first removal condition different from the second removal condition, both the residual film removal and the required pattern mask maintenance can be taken into account in step (A), and the entire hardened layer can be substantially removed in the second removal step (C). As a method for setting a difference between the first removal condition and the second removal condition, it is preferably any one of the composition of the removal liquid, the temperature of the removal liquid, the removal time, and other conditions, and it can also be a combination of these conditions.

From the viewpoint of efficiently removing the hardened layer, the second removing liquid preferably contains a solvent having a high affinity with the hardened layer. Examples of such a solvent include the above-mentioned good solvents.

The composition of the first removal liquid and the composition of the second removal liquid may be the same or different. When the first removal liquid and the second removal liquid have the same composition, for example, it is preferable to make the temperature of the second removal liquid higher than the temperature of the first removal liquid, or to make the treatment time of the second removal liquid longer than the treatment time of the first removal liquid. It is preferable to make the removal amount in step (A) smaller than the removal amount in step (C) by these methods.

In the second removal step (C), the second removal liquid can be convected by a known convection method such as a stirring device and a circulation pump, and an ultrasonic vibration tank can also be used. In addition, when convection is also used in the first step (A), the convection speed of the second removal liquid can be higher than the convection speed of the first removal liquid. By such treatment, the removal speed of the hardened layer can be increased and the treatment time of step (C) can be shortened. Furthermore, the stirring speed when stirring can be set to, for example, 50 rpm to 500 rpm.

The above steps (A) to (C) are preferably performed in a roll-to-roll process. By performing the above steps in a roll-to-roll process, a large area of hardened layer composite, anti-corrosion composite and surface layer composite can be continuously processed, which is advantageous from the perspective of productivity and manufacturing cost. Furthermore, the rolls, take-up devices and unwinding devices used in the roll-to-roll process can be appropriately used.

<2> Curable composition One aspect of the present invention is a curable composition used in the method for manufacturing the pattern substrate, which contains a monomer and a polymerization initiator, wherein the monomer includes a monofunctional monomer, and the content of the monofunctional monomer in the monomer component is 95% by mass or more.

<2-1> Monofunctional monomer The above-mentioned curable composition contains a monofunctional monomer. A monofunctional monomer refers to a compound having one polymerizable group in one molecule. As monofunctional monomers, there can be cited: 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, isopentyl (meth)acrylate and isononyl (meth)acrylate; cyclohexyl (meth)acrylate, isobutyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate , cyclopentyloxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, and adamantyl (meth)acrylate, etc. cyclic aliphatic monofunctional (meth)acrylates; 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, etc. Monofunctional monomers may be used alone or in combination.

Furthermore, the aliphatic ring of the cyclic aliphatic monofunctional (meth)acrylate may be a monoaliphatic ring such as cyclopentane and cyclohexane, a condensed aliphatic ring such as decahydronaphthalene, tricyclodecane, adamantane and norethane, or a heteroaliphatic ring such as pyrrolidine, pyrrolidone and tetrahydrofuran. Furthermore, the aromatic ring of the above-mentioned aromatic monofunctional (meth)acrylate and the above-mentioned aromatic monofunctional vinyl compound may be a monoaromatic ring such as benzene, a condensed aromatic ring such as naphthalene, anthracene and fluorene, or a heteroaromatic ring such as furan, pyridine and thiophene.

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

At least one hydrogen atom of the monofunctional monomer may be substituted by 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, or a triarylsilyl group. Examples of the halogen include fluorine, chlorine, bromine, and iodine.

From the viewpoint of affinity between the hardened layer and the second removing liquid, the hardening composition preferably contains a cyclic aliphatic monofunctional (meth)acrylate as a monofunctional monomer.

The carbon number of the monofunctional monomer is preferably 3 to 50, more preferably 4 to 30, and further preferably 6 to 20. Furthermore, the double bond equivalent of the monofunctional monomer is preferably 50 to 500, more preferably 60 to 400, and further preferably 80 to 300. Furthermore, the above carbon number includes the carbon number of the above polymerizable group and the above 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 or the crosslinking density of the hardened layer can be controlled, so the affinity with the removal liquid can be controlled, and a pre-driven pattern mask with the required properties such as mechanical strength or flexibility can be obtained. Furthermore, in this specification, "double bond equivalent" means the mass of the monomer per 1 mol of polymerizable group, and the unit is g/mol.

The content of the monofunctional monomer in the monomer component of the curable composition is 95 mass % or more. From the viewpoint of affinity with the second removing liquid, the content of the monofunctional monomer is preferably 98 mass % or more, and more preferably 99 mass % or more. In addition, the monomer component may be substantially all monofunctional monomers.

<2-2> Polymerization initiator The curable composition contains a polymerization initiator. The polymerization initiator is not particularly limited as long as it can cure the curable composition by heat or energy rays, and can be appropriately selected from known materials. The polymerization initiator can be used alone or in combination. As the polymerization initiator, a photoradical polymerization initiator is preferred. Furthermore, as energy rays used in curing, for example, infrared rays, visible rays, ultraviolet rays, excimer lasers, extreme ultraviolet rays, electromagnetic waves such as X-rays and gamma rays, and particle beams such as electron beams and alpha rays can be cited, and can be appropriately selected according to the photoradical polymerization initiator used.

<2-3> Optional components The curable composition may further contain any components other than the monofunctional monomer and polymerization initiator as the above-mentioned monomer. Examples of the optional components include: polyfunctional monomers, polymers, solvents, additives, etc. as the above-mentioned monomers.

The curable composition may also contain a polyfunctional monomer. A polyfunctional monomer refers to 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, trihydroxymethylpropane tri(meth)acrylate, 1,4-cyclohexanediol di(meth)acrylate, and tricyclodecane dimethanol di(meth)acrylate; aromatic polyfunctional (meth)acrylates such as EO (ethylene oxide) modified bisphenol A di(meth)acrylate and 9,9-bis[(meth)acryloyloxyethoxyphenyl]fluorene; and aromatic polyfunctional vinyl compounds such as divinylbenzene and divinylnaphthalene; etc.

The number of polymerizable groups in the multifunctional 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 hardened layer can be adjusted, and the amount of removal in step (A) and step (C) can be adjusted. As the multifunctional monomer, multifunctional monomers having different numbers of polymerizable groups can be used in combination.

The carbon number of the multifunctional monomer is preferably 8 to 100, more preferably 10 to 50, and further preferably 15 to 30. Furthermore, the above carbon number includes the above polymerizable group carbon number. In addition, the double bond equivalent of the multifunctional monomer is preferably 50 to 1000, more preferably 60 to 800, and further preferably 80 to 500. By setting the carbon number or double bond equivalent of the multifunctional monomer within the above range, the curability of the curable composition or the crosslinking density of the hardened layer can be controlled, so the affinity with the removal liquid can be controlled, and a front-drive pattern mask with the required characteristics such as mechanical strength or flexibility can be obtained.

When the curable composition contains a multifunctional monomer, the content of the multifunctional monomer is preferably 5 mass % or less, more preferably 2 mass % or less, and further preferably 1 mass % or less in the monomer component. By setting the content of the multifunctional monomer within the above range, the affinity between the hardened layer and the second removing solution is improved.

The curable composition may contain a polymer. The polymer may be appropriately used for the curable composition. By containing a polymer in the curable composition, the time to obtain a hardened layer from the curable composition tends to be shortened. In addition, by adjusting the molecular weight of the polymer, the affinity between the hardened layer and the removal liquid can be adjusted. Specifically, by making the curable composition contain a polymer with a relatively small molecular weight, the removal rate of the hardened layer in step (A) and step (C) tends to increase. In addition, the glass transition temperature of the polymer is preferably above room temperature, and further preferably above the processing temperature of steps (A) to (C). In the case where the curable composition contains a polymer, the content of the polymer can be set to 10 to 300 parts by mass relative to 100 parts by mass of the total amount of the monomer component, the polymerization initiator and the additive. Furthermore, even when the curable composition contains a polymerization initiator and an additive in addition to the monomer component, the content of the polymer can be set to 10 to 300 parts by mass relative to 100 parts by mass of the monomer component.

The curable composition may also contain a solvent. The solvent may be appropriately used for the curable composition, and the same solvent as the good solvent in step (A) may be exemplified. When the curable composition contains a solvent, 1 to 10,000 parts by mass of the solvent may be used relative to 100 parts by mass of the total amount of the monomer component, polymerization initiator, polymer, and additive. Furthermore, in this specification, the solvent refers to a liquid compound having no polymerizable group other than the monofunctional monomer, the polymerization initiator, the multifunctional monomer, and the polymer. Reactive diluents having polymerizable groups are not included in the solvent and are regarded as the monofunctional monomer or the multifunctional monomer.

The curable composition may also contain additives. As additives, those commonly used in curable compositions may be appropriately used. Examples of additives include mold 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 additives, the content is preferably within a range that does not significantly affect the affinity of the composition with the removal liquid, the curability, and the filling property of the mold. 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 relative to 100 parts by mass of the total monomer components.

Furthermore, the above-mentioned additives are sometimes compounds having polymerizable groups such as (meth)acryl, vinyl and allyl groups together with functional groups (perfluoroalkyl, alkoxysilyl, oxyalkylene, phenolic hydroxyl and amino groups, etc.) that function as additives. In this specification, such compounds having both functional groups and polymerizable groups are not additives, but are regarded as the above-mentioned multifunctional monomers or the above-mentioned monofunctional monomers.

The glass transition temperature of the hardened layer obtained from the hardening composition is preferably above room temperature, and further preferably above the processing temperature of steps (A) to (C). By setting the glass transition temperature of the hardened layer within the above range, the softening of the hardened layer during processing is suppressed, and the desired pattern mask and pattern substrate can be obtained efficiently.

<3> Parts manufacturing method One aspect of the present invention is a parts manufacturing method using the above-mentioned pattern substrate manufacturing method.

The method for manufacturing the pattern substrate can be used in a method for manufacturing parts. The method for manufacturing the pattern substrate can remove the hardened layer by using a removal liquid in steps (A) and (C). Therefore, in the manufacturing of parts, compared with the known method of removing the residual film or the hardened layer by dry etching, it has advantages in terms of productivity, manufacturing equipment, and manufacturing cost.

As the above-mentioned parts, there is no particular limitation as long as they are parts using pattern substrates, and examples thereof include: components with fine wiring, wire grid polarizers, patterned media, flow paths, LEDs (Light Emitting Diodes), microlens arrays, light guide plates, various electrode substrate components, energy devices such as solar cells and fuel cells, biological devices such as biosensors and cell culture devices, microreactors, etc. In addition, as the above-mentioned parts, it is also preferred to use electrodes of batteries such as electrolytic capacitors, electric double layer capacitors, ceramic capacitors, lithium ion batteries, nickel hydrogen batteries, and lead batteries using aluminum, titanium, tantalum, conductive polymers, etc. In the manufacturing method of the present invention, the electrodes can obtain patterned electrode substrates by using electrode substrates including aluminum, titanium, tantalum, conductive polymers, etc. as the above-mentioned substrates. The electrodes manufactured by the manufacturing method of the present invention have the effects of increasing the surface area and improving the electrostatic capacitance due to the patterns on the surface. [Example]

Hereinafter, some aspects of the present invention will be described based on the embodiments, and the present invention can be implemented according to its purpose. Hereinafter, an example in which the surface treatment step is an etching step or a sputtering step will be described. The surface treatment in the method for manufacturing the pattern substrate of the present invention can be appropriately selected from the known surface treatments according to its purpose. In addition, the numbers of the components in the embodiments correspond to the reference numbers in the drawings. Furthermore, the drawings are schematic representations of the materials processed in each step, and the length, thickness and ratio of each component in the drawings are not limited to those shown in the drawings.

In the method for manufacturing a patterned substrate according to one aspect of the present invention, examples (Examples 1 to 17 and Comparative Examples 1 to 11) in which the surface treatment step is an etching step are shown below.

[Example 1] <Preparation of film mold> 96 parts by weight of perfluoropolyether urethane dimethacrylate (Fluorolink MD-700, manufactured by Solvay Specialty Polymers Japan Co., Ltd.) and 4 parts by weight of 1-hydroxycyclohexyl phenyl ketone (Omnirad184, manufactured by IGM Resins BV) 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 about 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., with a hole pattern and a depth of 1 μm and a diameter of 500 nm) pre-treated with a fluorine-based mold release agent (OPTOOL HD-1100TH, manufactured by Daikin Industries, Ltd.). In this state, the film mold composition layer was exposed to a UV-LED (ultraviolet) lamp (wavelength 365 nm, illumination 100 mW/cm ² ) for 200 seconds in a nitrogen atmosphere to cure. After curing, the film mold was demolded from the silicon mold to obtain a film mold.

<Preparation of curable composition sample> 96 parts by mass of FA-513AS (dicyclopentyl acrylate, manufactured by Showa Denko Materials Co., Ltd.) and 4 parts by mass of 2,4,6-trimethylbenzyl-diphenylphosphine oxide (Omnirad TPO, manufactured by IGM Resins B.V.) were mixed at room temperature to prepare a curable composition sample.

3-Methacryloyloxypropyltrimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) was dripped onto an aluminum vapor-deposited silicon wafer (the aluminum vapor-deposited layer had a thickness of about 350 nm and was 2 cm square, manufactured by Advantech Co., Ltd.) in a manner of spreading over the entire surface. The aluminum vapor-deposited layer was equivalent to substrate 2, and the silicon wafer was equivalent to support 3. The wafer was heated at 120°C for 15 minutes, cooled at room temperature, and washed with acetone to obtain a pre-treated substrate. Subsequently, the above-mentioned composition sample was dripped onto the substrate, and spin coating was performed using a spin coater (1H-DX2, manufactured by Mikasa Co., Ltd.) to form a composition layer with a film thickness of about 3.5 μm.

Using a vacuum pump, the film mold cut into a size of 1.5 cm square is pressed against the composition layer obtained above, while being in a decompressed state of 10 kPa. After standing for 1 minute under a load of 186 N applied to the film mold, the composition layer is exposed to a UV-LED lamp (wavelength 365 nm, illumination 100 mW/cm ² ) for 10 seconds to harden it. Furthermore, the thickness of the residual film 1A containing the composition layer above remaining in the concave portion of the front-drive pattern mask is 10 nm to 100 nm. Thereafter, the hardened layer is demolded from the film mold to obtain a hardened layer composite 10. The hardened layer composite obtained has a hole pattern (represented as "holes" in the table) originating from the film mold.

<First Removal Step> The hardened layer composite 10 obtained in the above was immersed in the first removal liquid (60 mL) at room temperature, removed from the removal liquid and dried, thereby obtaining an anti-corrosion composite 20. The type of the first removal liquid and the immersion time are shown in Table 1. In the above immersion, the hardened layer composite 10 was arranged in the removal liquid stirred at a speed of 50 rpm to 500 rpm by a magnetic stirrer (KF-82, manufactured by Yazawa Scientific Co., Ltd.) in a manner that it does not contact the stirring rod. In addition, the example of using the first removal liquid as described above in the first removal step is indicated as "wet type" in "First Removal Step" of the table.

<Evaluation of the first removal step> The anti-corrosion composite 20 obtained in the first removal step was cut along the thickness direction, and the cross section was observed and evaluated using an electron microscope (JSM-IT200, manufactured by JEOL Ltd.). The samples in which the molded pattern mask did not disappear were marked as "○" and shown in the following table. In addition, the samples in which the pattern mask disappeared due to excessive dissolution of the solvent in the first removal solution were marked as "×", and the samples in which the residual film 1A was confirmed after the removal step were marked as "××", and shown in the following table. Furthermore, in the evaluation of the first removal step, the samples in which the pattern mask disappeared due to excessive dissolution of the solvent, or the samples in which a thin film was confirmed after the first removal step were not evaluated for the surface treatment step (etching step) and the second removal step. This type of sample is indicated as "-" in the table.

<Surface treatment step (etching step)> Hydrochloric acid, nitric acid and water were mixed in a volume ratio of 3:1:2 to prepare a wet etching solution. 20 mL of the wet etching solution was transferred to a glass beaker, and the anti-etching composite was immersed in it at room temperature for 5 minutes to perform wet etching treatment on the aluminum vapor-deposited layer located in the concave part of the pattern mask. After the treatment, it was washed with water and dried to obtain a treated surface composite 30 (etching composite 30A).

<Evaluation of the surface treatment step (etching step)> The etched composite 30A obtained in the above surface treatment step (etching step) was cut along the thickness direction, and the cross section was observed and evaluated using an electron microscope (JSM-IT200, manufactured by JEOL Ltd.). Samples where the aluminum vapor deposition layer was observed to be dissolved were marked as "○", and samples where the aluminum vapor deposition layer was not observed to be dissolved were marked as "×", and are shown in the following table.

<Second Removal Step> The same operation as the first removal step is performed except that the etching composite 30A obtained above is used instead of the hardened layer composite 10 and the processing conditions are changed to the conditions shown in the table. The type, temperature and immersion time of the second removal solution are shown in Table 1. In the temperature of the second removal solution, "rt" represents room temperature.

<Evaluation of the second removal step> The samples obtained in the second removal step were visually observed and evaluated. Samples in which the hardened layer 1 was completely dissolved were marked as "○", samples with dissolved residues were marked as "×", and samples that were completely undissolved were marked as "××", and the results are shown in the following table.

[Examples 2 to 17] The monomers in the curable composition sample, the shape of the front-drive pattern mask, the composition of the removal liquid (the mixing ratio in the case of mixed solvents is the mass ratio), the temperature of the removal liquid, and the removal time were changed as described in Table 1, and the pattern substrate was formed and evaluated using the same steps as in Example 1. In addition, the monomer "IB-XA" in Table 1 represents isobutyl acrylate (manufactured by Kyoei Chemical Co., Ltd.). In addition, when lines and spaces (represented as "L/S" in the table) are used as the shape of the front-drive pattern mask, a nickel mold with a line and space pattern (manufactured by Kyoei High-Tech Co., Ltd., the depth and line width of the concave portion are 5 μm) is used instead of the above-mentioned silicon mold with a hole pattern. The evaluation results are shown in Table 1.

[Comparative Examples 1 to 11] Except that the method of the first removal step, the monomer of the curable composition sample, the shape of the front-driving pattern mask, the composition of the removal solution, the temperature of the removal solution, and the removal time are changed as described in Table 1, the pattern substrate formation and evaluation are performed using the same steps as in Example 1. In the first removal step of Comparative Examples 1 to 6, the curing layer composite 10 is treated by dry etching instead of the above-mentioned immersion. Specifically, a plasma dry cleaner (PDC210, manufactured by Yamato Scientific Co., Ltd.) was used to perform dry etching for 90 seconds under the conditions of an oxygen flow rate of 10 mL/min and an RF output of 350 W to remove the residual film 1A located in the concave portion of the front-drive pattern mask, and obtain an anti-etching composite 20 with the aluminum evaporated silicon wafer located in the concave portion exposed. The example of using dry etching in the first removal step as described above is indicated as "dry" in the "first removal step" of the table.

[Table 1] Removal Step 1 Etching steps Step 2 Removal Single Pattern Method (first removal liquid or etching gas) Time(minutes) result result Second removal solution temperature Time(minutes) result Embodiment 1 FA-513AS hole Wet formula (H ₂ O:PGME＝5:95) 5 ○ ○ THF rt 1 ○ Embodiment 2 FA-513AS hole Wet formula (H ₂ O:PGME＝5:95) 5 ○ ○ MEK rt 600 ○ Embodiment 3 FA-513AS hole Wet formula (H ₂ O:PGME＝5:95) 5 ○ ○ Toluene rt 1 ○ Embodiment 4 FA-513AS hole Wet formula (H ₂ O:PGME＝5:95) 5 ○ ○ Cyclohexanone rt 2 ○ Embodiment 5 FA-513AS hole Wet formula (H ₂ O:PGME＝5:95) 5 ○ ○ MIBK rt 5 ○ Embodiment 6 FA-513AS hole Wet formula (H ₂ O:PGME＝5:95) 5 ○ ○ Amyl acetate rt 1 ○ Embodiment 7 IB-XA hole Wet formula (H ₂ O:PGME＝5:95) 5 ○ ○ MEK rt 1 ○ Embodiment 8 FA-513AS hole Wet formula (H ₂ O:PGME＝5:95) 5 ○ ○ MEK 70℃ 10 ○ Embodiment 9 FA-513AS hole Wet formula (H ₂ O:PGME＝5:95) 5 ○ ○ MEK:THF＝50:50 rt 1 ○ Embodiment 10 FA-513AS L/S Wet (PGME) 15 ○ ○ MIBK rt 5 ○ Embodiment 11 IB-XA L/S Wet (PGME) 1 ○ ○ MIBK rt 1 ○ Embodiment 12 FA-513AS hole Wet formula (methanol:PGME=30:70) 5 ○ ○ MIBK rt 5 ○ Embodiment 13 FA-513AS hole Wet (IPA:PGME＝80:20) 5 ○ ○ MIBK rt 5 ○ Embodiment 14 FA-513AS hole Wet formula (methanol: diethylene glycol dimethyl ether = 70:30) 1 ○ ○ MIBK rt 5 ○ Embodiment 15 FA-513AS hole Wet formula (methanol:MIBK=80:20) 1 ○ ○ MIBK rt 5 ○ Embodiment 16 FA-513AS hole Wet formula (methanol:MIBK=80:20) 1 ○ ○ MIBK rt 5 ○ Embodiment 17 FA-513AS hole Wet formula (methanol:MIBK=80:20) 1 ○ ○ Methanol: MIBK = 10: 90 rt 180 ○ Comparison Example 1 FA-513AS hole Dry (O ₂ gas) 1.5 ○ ○ THF rt 600 ×× Comparison Example 2 FA-513AS hole Dry (O ₂ gas) 1.5 ○ ○ MEK rt 600 ×× Comparison Example 3 FA-513AS hole Dry (O ₂ gas) 1.5 ○ ○ Toluene rt 600 ×× Comparison Example 4 FA-513AS hole Dry (O ₂ gas) 1.5 ○ ○ Cyclohexanone rt 600 ×× Comparison Example 5 FA-513AS hole Dry (O ₂ gas) 1.5 ○ ○ MIBK rt 600 ×× Comparative Example 6 FA-513AS hole Dry (O ₂ gas) 1.5 ○ ○ Amyl acetate rt 600 ×× Comparative Example 7 FA-513AS hole Wet formula (H ₂ O:PGME＝5:95) 5 ○ ○ _H2O :PGME＝5：95 rt 5 × Comparative Example 8 FA-513AS L/S Wet (PGME) 15 ○ ○ PGME rt 15 × Comparative Example 9 FA-513AS hole Wet (THF) 1 × - - - - - Comparative Example 10 FA-513AS L/S Wet (THF) 1 × - - - - - Comparative Example 11 FA-513AS L/S Wet (H ₂ O) 600 ×× - - - - -

In the method for manufacturing a pattern substrate of one aspect of the present invention, the example (Examples 18 to 34 and Comparative Examples 12 to 22) in which the surface treatment step is a sputtering step is shown below. Furthermore, the hardened layer composite 10 used is the same as that in the above-mentioned etching step example. In addition, the first removal step, the second removal step, and the evaluation of the first removal step are performed in the same manner as in the above-mentioned etching step example. The conditions of the examples and comparative examples, as well as the evaluation results, are shown in Table 2.

<Surface treatment step (sputtering step)> The above-mentioned anti-corrosion composite 20 was sputtered for 60 seconds using Auto Fine Coater (JEC-3000FC, manufactured by JEOL Ltd.) at a sputtering current of 20 mA, so that platinum as a sputtering target was deposited on the above-mentioned anti-corrosion composite with a thickness of about 3 nm. The above-mentioned sputtering was repeated 15 times in total, and a treated surface composite 30 (heterogeneous material composite 30B) in which platinum was deposited on the surface with a thickness of about 45 nm was obtained.

<Evaluation of the second removal step after the surface treatment step (sputtering step)> The pattern substrate 40B obtained in the above-mentioned surface treatment step (sputtering step) and the second removal step was cut along the thickness direction, and the cross section was observed and evaluated using an electron microscope (JSM-IT200, manufactured by JEOL Ltd.). The sample in which the desired pattern substrate formed by platinum was obtained without leaving the hardened layer 1 was marked as "○", and the sample in which the desired pattern substrate formed by platinum was not obtained with the hardened layer 1 remaining was marked as "×", as shown in the following Table 2. Furthermore, in the evaluation of the first removal step, the sample patterns whose pattern mask disappeared due to excessive solvent dissolution, or the samples where residual film was confirmed after the first removal step, were not evaluated in the second removal step. Such samples are indicated as "-" in Table 2.

[Table 2] Removal Step 1 Second removal step after surface treatment step (sputtering step) Single Pattern Method (first removal liquid or etching gas) Time(minutes) result Second removal solution temperature Time(minutes) result Embodiment 18 FA-513AS hole Wet formula (H ₂ O:PGME＝5:95) 5 ○ THF rt 1 ○ Embodiment 19 FA-513AS hole Wet formula (H ₂ O:PGME＝5:95) 5 ○ MEK rt 600 ○ Embodiment 20 FA-513AS hole Wet formula (H ₂ O:PGME＝5:95) 5 ○ Toluene rt 1 ○ Embodiment 21 FA-513AS hole Wet formula (H ₂ O:PGME＝5:95) 5 ○ Cyclohexanone rt 2 ○ Embodiment 22 FA-513AS hole Wet formula (H ₂ O:PGME＝5:95) 5 ○ MIBK rt 5 ○ Embodiment 23 FA-513AS hole Wet formula (H ₂ O:PGME＝5:95) 5 ○ Amyl acetate rt 1 ○ Embodiment 24 IB-XA hole Wet formula (H ₂ O:PGME＝5:95) 5 ○ MEK rt 1 ○ Embodiment 25 FA-513AS hole Wet formula (H ₂ O:PGME＝5:95) 5 ○ MEK 70℃ 10 ○ Embodiment 26 FA-513AS hole Wet formula (H ₂ O:PGME＝5:95) 5 ○ MEK:THF＝50:50 rt 1 ○ Embodiment 27 FA-513AS L/S Wet (PGME) 15 ○ MIBK rt 5 ○ Embodiment 28 IB-XA L/S Wet (PGME) 1 ○ MIBK rt 1 ○ Embodiment 29 FA-513AS hole Wet formula (methanol:PGME=30:70) 5 ○ MIBK rt 5 ○ Embodiment 30 FA-513AS hole Wet (IPA:PGME＝80:20) 5 ○ MIBK rt 5 ○ Embodiment 31 FA-513AS hole Wet formula (methanol: diethylene glycol dimethyl ether = 70:30) 1 ○ MIBK rt 5 ○ Embodiment 32 FA-513AS hole Wet formula (methanol:MIBK=80:20) 1 ○ MIBK rt 5 ○ Embodiment 33 FA-513AS hole Wet formula (methanol:MIBK=80:20) 1 ○ MIBK rt 5 ○ Embodiment 34 FA-513AS hole Wet formula (methanol:MIBK=80:20) 1 ○ Methanol: MIBK = 10: 90 rt 180 ○ Comparative Example 12 FA-513AS hole Dry (O ₂ gas) 1.5 ○ THF rt 600 × Comparative Example 13 FA-513AS hole Dry (O ₂ gas) 1.5 ○ MEK rt 600 × Comparative Example 14 FA-513AS hole Dry (O ₂ gas) 1.5 ○ Toluene rt 600 × Comparative Example 15 FA-513AS hole Dry (O ₂ gas) 1.5 ○ Cyclohexanone rt 600 × Comparative Example 16 FA-513AS hole Dry (O ₂ gas) 1.5 ○ MIBK rt 600 × Comparative Example 17 FA-513AS hole Dry (O ₂ gas) 1.5 ○ Amyl acetate rt 600 × Comparative Example 18 FA-513AS hole Wet formula (H ₂ O:PGME＝5:95) 5 ○ _H2O :PGME＝5：95 rt 5 × Comparative Example 19 FA-513AS L/S Wet (PGME) 15 ○ PGME rt 15 × Comparative Example 20 FA-513AS hole Wet (THF) 1 × - - - - Comparative Example 21 FA-513AS L/S Wet (THF) 1 × - - - - Comparative Example 22 FA-513AS L/S Wet (H ₂ O) 600 ×× - - - -

As described above, it can be seen that the method for manufacturing a pattern substrate according to one aspect of the present invention can maintain the required pattern mask and remove the residual film. On the other hand, it can be seen that under the conditions of the comparative example, the residual film is not removed, or the formed pattern mask is removed, and the required pattern substrate is not obtained. In addition, when dry etching is used to remove the residual film, it takes a long time to remove the formed pattern mask. From the perspective of productivity, it is not suitable for industrial use. It is speculated that the reason is that the hardened layer deteriorates due to dry etching, and the affinity for the second removal liquid is significantly reduced.

Furthermore, the conditions used in the above-mentioned embodiments (hardening composition, front-drive pattern mask, first removal liquid and second removal liquid, etc.) can be appropriately adjusted. Moreover, even if the conditions are other than the conditions used in the above-mentioned embodiments, as long as they are variations based on the description of this specification, the same effect will be achieved. [Industrial Applicability]

The method for manufacturing a pattern substrate in one aspect of the present invention can maintain the desired pattern mask and remove the unexpected hardening layer by treating the hardening layer composite body in a specific method. Therefore, it is useful for manufacturing parts.

1: Hardening layer (front-drive pattern mask) 1A: Hardening layer (pattern mask) 1a: Concave part 1b: Convex part 1c: Convex part 1d: Opening part 2: Substrate 2A: Processing substrate 3: Support body 4: Dissimilar material layer 4A: Material layer 10: Hardening layer composite 10A: Hardening layer composite 20: Anti-etching composite 20A: Anti-etching composite 30A: Etching composite 30B: Dissimilar material composite 40A: Pattern substrate 40B: Pattern substrate

Figure 1 (a) to (d) are cross-sectional views showing a method for manufacturing a pattern substrate according to one example of an implementation method. Figure 2 (a) to (d) are cross-sectional views showing a method for manufacturing a pattern substrate according to another example of an implementation method.

1: Hardening layer (front-drive pattern mask)

1A: Hardening layer (pattern mask)

1a: Concave part

1b: convex part

1c: convex part

1d: Opening

2: Base material

2A: Processing substrate

3: Support body

10A: Hardening layer composite

20A: Anti-corrosion compound

30A: Etching complex

40A: Pattern substrate

Claims (11)

A method for manufacturing a pattern substrate, comprising the following steps: A first removal step (A), in which a hardening layer composite having a substrate and a hardening layer formed on the substrate and having a concave portion and a convex portion is treated with a first removal liquid, and at least the hardening layer is removed by a thickness corresponding to the hardening layer in the concave portion, thereby obtaining an anti-corrosion composite having a prescribed pattern mask with the substrate located in the concave portion exposed; A surface treatment step (B), in which a surface treatment is performed on the anti-corrosion composite through the prescribed pattern mask, thereby obtaining a treated surface composite; and The second removal step (C) is to remove the above-mentioned prescribed pattern mask of the above-mentioned treated surface composite by the second removal liquid to obtain the pattern substrate; The removal conditions in the above-mentioned first removal step (A) are different from the removal conditions in the above-mentioned second removal step (C). A method for manufacturing a patterned substrate as claimed in claim 1, wherein the surface treatment step (B) is an etching step of obtaining the treated surface composite by etching the exposed substrate through the prescribed pattern mask. A method for manufacturing a pattern substrate as claimed in claim 1, wherein the surface treatment step (B) is a heterogeneous material configuration step, wherein a material different from the hardened layer constituting the above-mentioned pattern mask is configured on the surface of the above-mentioned anti-corrosion composite, thereby obtaining the above-mentioned treated surface composite having a material layer comprising the above-mentioned different material disposed on the above-mentioned substrate through the above-mentioned pattern mask. A method for manufacturing a patterned substrate as claimed in any one of claims 1 to 3, wherein the composition of the first removing liquid is different from the composition of the second removing liquid. A method for manufacturing a patterned substrate as claimed in any one of claims 1 to 4, wherein the temperature of the first removing liquid is lower than the temperature of the second removing liquid. A method for manufacturing a patterned substrate as claimed in any one of claims 1 to 5, wherein the time for removing the hardened layer in the step (A) is shorter than the time for removing the hardened layer in the step (C). A method for manufacturing a pattern substrate as claimed in any one of claims 1 to 6, wherein the front-drive pattern mask is an embossed molded object. A method for manufacturing a patterned substrate as claimed in any one of claims 1 to 7, wherein the steps (A) to (C) are performed in a roll-to-roll process. The method for producing a pattern substrate according to any one of claims 1 to 8, wherein the curable layer of the curable layer composite is a cured product of a curable composition containing 95 mass % or more of a monofunctional monomer in its monomer components. A curable composition, which is used in a method for manufacturing a pattern substrate as in any one of claims 1 to 9, contains a monomer and a polymerization initiator, wherein the monomer includes a monofunctional monomer, and the content of the monofunctional monomer in the monomer component is 95% by mass or more. A method for manufacturing a part, which is a method for manufacturing a pattern substrate as described in any one of claims 1 to 9.