JP2013208846A - Resin mold for nanoimprint and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin-made mold for nanoimprint having excellent abrasion resistance, and a method for manufacturing the same.SOLUTION: A resin mold 10 for nanoimprint has a plurality of columns 12 on a surface of a resin substrate 11. In the resin mold for nanoimprint, an area of the bottom of the column 12 is 0.001-1 μm; a ratio of the height h to the diameter D (height D/diameter h) of the column 12 is 2 or larger; and an area of a cut surface when the column 12 is horizontally cut at a half position of the height thereof is 80% or larger with respect to the area of the bottom of the column. The column 12 includes a column body 13 formed of resin and a coating layer 14 containing a metal oxide.

Description

  The present invention relates to a resin mold for nanoimprint and a method for producing the same.

In recent years, a new micromachining technology called nanoimprint has attracted attention as an inexpensive micromachining technology with high resolution.
This nanoimprint technology can realize a finer structure than conventional press technology, and a technology for forming a desired circuit pattern on a silicon substrate using various molds has been developed. It's getting on.

  For example, Patent Document 1 states that “a method for producing a nanostructure, in which a layered body is formed by laminating two or more layers made of a material in which holes are formed by anodic oxidation on a substrate or a base. A step of anodizing the laminate to form a through-hole, a step of filling an inclusion in the hole, and an inclusion by selectively removing an upper layer of the anodized laminate A method for producing a nanostructure, comprising the step of forming a protrusion comprising: a method for producing a nanostructure ([Claim 1]), and a nanoimprint mold using the nanostructure. ([Claim 8]).

  Similarly, Patent Document 2 states that “a method for producing a nanostructure, in which a layered body is formed by laminating two or more layers made of a material in which holes are formed by anodic oxidation on a substrate or a base. A step of anodizing the laminate to form holes, a step of filling inclusions in the holes, and selectively dissolving and removing the upper layer of the anodized laminate, A method for producing a nanostructure having a nanowire characterized by comprising a step of forming a nanowire made of inclusions ([Claim 1]). The nanoimprint mold used is described ([Claim 7]).

  Patent Document 3 discloses that “a negative type made of anodized porous alumina or another material made using it as a mold for a mask forming layer provided on the surface of a substrate made of a semiconductor material or a metal material, or A mask layer having a shape obtained by transferring the concavo-convex structure of the mold is formed on the surface of the substrate by a nanoimprint method using a positive mold as a mold having a regular concavo-convex structure, and a mask portion or non-mask by the mask layer of the substrate is formed. The substrate manufacturing method is characterized in that a regular concavo-convex structure is formed on the surface of the substrate by performing chemical etching on the portion. "(Claim 1).

JP 2006-326723 A JP 2006-326724 A JP 2012-48030 A

  As a result of studying conventionally known molds described in Patent Documents 1 to 3 and the like, the present inventors have found that there are restrictions on the etchant that can be used or the mold is pressed against when a metal is used as a forming material. It turns out that there is a problem that the tip part is broken depending on the kind of the object, and when resin is used as the forming material, if it is pressed against an inorganic material such as a silicon substrate, the number of times of use may be reduced due to wear or the like. It turns out that there is a problem of being limited.

  Then, an object of this invention is to provide the mold for resin nanoimprint excellent in abrasion resistance, and its manufacturing method.

As a result of diligent research to achieve the above object, the present inventor has found that a resin mold having a columnar portion having a specific shape whose surface is coated with a metal oxide is excellent in wear resistance, and has completed the present invention. .
That is, the present invention provides the following (1) to (5).

(1) A resin mold for nanoimprinting having a plurality of columnar portions on the surface of a resin substrate,
The area of the bottom of the columnar part is 0.001 to 1 μm ² ,
The ratio of the height to the diameter of the bottom of the columnar part (height / diameter) is 2 or more,
The area of the cut surface when horizontally cut at half the height of the columnar part is 80% or more with respect to the area of the bottom of the columnar part,
A resin mold for nanoimprinting, wherein the columnar part is composed of a columnar part body made of a resin and a coating layer containing a metal oxide.

(2) Furthermore, the surface of the resin substrate has an anodized film of valve metal,
The resin mold for nanoimprints according to (1), wherein the thickness of the anodic oxide film is smaller than the height of the columnar part.

  (3) The resin mold for nanoimprints according to (1) or (2), wherein an area occupation ratio of the cut surface with respect to the surface of the resin substrate is 10% or more.

  (4) The resin mold for nanoimprints according to any one of (1) to (3), wherein the metal oxide includes at least one element selected from the group consisting of aluminum, silicon, and zirconium.

(5) A method for producing a resin mold for nanoimprints, which produces the resin mold for nanoimprints according to any one of (1) to (4) above,
Anodizing treatment for forming an anodized film having pores by anodizing the valve metal substrate;
A coating layer forming step of forming a coating layer containing a metal oxide on the pore inner wall of the pore;
A filling step of filling the pores in which the coating layer is formed with a resin, and
The manufacturing method of the resin mold for nanoimprint which has a columnar part formation process which melt | dissolves at least one part of the said anodic oxide film, and forms a columnar part in this order.

  As described below, according to the present invention, it is possible to provide a resin-made nanoimprint mold excellent in wear resistance and a method for producing the same.

It is sectional drawing which shows typically an example of the suitable embodiment of the mold for nanoimprint of this invention, (A) is sectional drawing which shows a 1st aspect, (B) is sectional drawing which shows a 2nd aspect. It is. It is a perspective view which shows an example when it cut | disconnects horizontally in the half position of the height of the columnar part of the mold for nanoimprint shown in FIG. 1 (A). It is sectional drawing which illustrates typically each process of the manufacturing method of the mold for nanoimprint of this invention.

[Resin mold for nanoimprint]
The nanoimprint mold of the present invention (hereinafter referred to as “the mold of the present invention”) has a plurality of columnar portions on the surface of a resin substrate, and the area (bottom area) of the bottom of the columnar portions is 0.001 to 1 μm. ² and the ratio of the height (height / diameter) (hereinafter also referred to as “aspect ratio”) to the diameter (bottom diameter) of the bottom of the columnar part is 2 or more, and the height of the columnar part is The area of the cut surface (hereinafter also simply referred to as “cross-sectional area”) when horizontally cut at a half position is 80% or more with respect to the bottom area of the columnar portion, and the columnar portion is made of resin. It is the resin mold for nanoimprints comprised by the part main body and the coating layer containing a metal oxide.
Next, the characteristic shape of the mold of this invention is demonstrated using FIG. 1 and FIG.

As shown in FIGS. 1 and 2, the mold 10 of the present invention has a plurality of columnar portions 12 on the surface of a resin substrate 11, and the columnar portion 12 includes a columnar portion main body 13 made of resin and a metal oxide. And a coating layer 14 including
In FIG. 1, the entire surface of the columnar body 13 is covered with the coating layer 14, but it is sufficient that the surface including at least the tip of the columnar body 13 is covered with the coating layer 14.

In the present invention, the bottom area S ₀ of the columnar section 12 is 0.001 to 1 μm ² , and the cross-sectional area S of the columnar section 12 is 80% or more with respect to the bottom area S ₀ of the columnar section 12. It is.
When the bottom area S ₀ and the cross-sectional area S of the columnar part 12 are in the above-described ranges, the tip density of the columnar part 12 can be maintained high.
Because these effects are more improved, the bottom area S ₀ of the columnar portion 12 is preferably a 0.001～0.05Myuemu ^2, and more preferably 0.005~0.01μm ^2.
For the same reason, the cross-sectional area S of the columnar portion 12 preferably has a with respect to the bottom area S ₀ of the columnar portion 12 to 90% or more, more preferably 95% or more.
Here, the “bottom area of the columnar part” is obtained by observing the cross section of the mold with a scanning electron microscope (SEM), measuring the radius of the bottom of any ten columnar parts, and calculating from the average value of these. It refers to the area.
In addition, the “cross-sectional area of the columnar part” means that the cut surface when horizontally cut at a position half the height of the columnar part is observed with a scanning electron microscope (SEM), and any 10 cut surfaces are obtained. This is the area calculated from the average of these radii.

In the present invention, the ratio (aspect ratio) of the height h to the bottom diameter D of the columnar portion 12 is 2 or more, preferably 5 or more, and more preferably 10 or more.
When the aspect ratio is 2 or more, reproducibility in transferring transfer holes and etchants formed when the mold of the present invention is pressed against an object is improved.
Here, the “bottom diameter of the columnar part” means that the cross section of the mold is observed with a scanning electron microscope (SEM), the diameters of the bottoms of any ten columnar parts are measured, and these values are averaged. Say.
“Columnar height” refers to the cross section of the mold observed with a scanning electron microscope (SEM), and the vertical distance from the bottom to the tip of any 10 columnar sections is measured. Means the average.

  In the present invention, in order to maintain the tip density of the columnar portion, the valve metal having a thickness smaller than the height of the columnar portion 12 is formed on the surface of the resin substrate 11 as shown in FIG. It is preferable to have the anodic oxide film 22.

Further, in the present invention, the wear resistance of the mold of the present invention is further improved, the uprightness of the columnar portion is also improved, and there is little change in shape even when the molds of the present invention are stacked and stored. For this reason, the area occupation ratio of the cut surface to the surface of the resin substrate when horizontally cut at a position half the height of the columnar portion 12 is preferably 10% or more, more preferably 15% or more. More preferably, it is more preferably 20% or more.
Here, the “area occupation ratio” is a ratio of the total area of the cross-sectional areas (areas of the cut surfaces) of all the columnar portions to the surface of the resin substrate (that is, on the surface of the mold of the present invention).
Next, materials, dimensions, etc. will be described for each configuration of the mold of the present invention.

[Resin substrate]
The material for forming the resin substrate included in the mold of the present invention is not particularly limited, and for example, a thermosetting resin, a photocurable resin, or the like can be used.
Specific examples of the thermosetting resin include phenol resin, melamine resin, urea resin, epoxy resin, unsaturated polyester resin, silicone resin, polyimide resin, diallyl phthalate resin, and the like. You may use independently and may use 2 or more types together.
On the other hand, specific examples of the photo-curable resin include acrylic resins and azide resins.

  Further, the thickness of the resin substrate is not particularly limited because it can be appropriately designed depending on the object using the mold of the present invention, but is preferably about 0.5 to 10 mm from the viewpoint of handleability and the like. .

(Columnar part)
The bottom diameter of the columnar part of the mold of the present invention is not particularly limited because it can be appropriately designed depending on the object using the mold of the present invention, but is preferably 40 to 300 nm, and preferably 60 to 100 nm. Is more preferable.
Similarly, the height of the columnar part is not particularly limited, but is preferably 1 to 100 μm, and more preferably 5 to 20 μm.
In addition, as above-mentioned, the ratio (aspect ratio) of the height with respect to the bottom part diameter of the said columnar part is 2 or more, it is preferable that it is 5 or more, and it is more preferable that it is 10 or more.

Further, the density of the columnar portion on the surface of the resin substrate is not particularly limited because it can be appropriately designed depending on the object using the mold of the present invention, but is preferably ² million pieces / mm ² or more, More preferably, it is 10 million pieces / mm ² or more.
Similarly, the distance between the centers of adjacent columnar portions is not particularly limited, but is preferably 60 to 500 nm, and more preferably 100 to 300 nm.

<Columnar body>
The material forming the columnar part main body in the columnar part is not particularly limited as long as it is a resin material, and for example, the same material as that of the resin substrate can be used. In addition, it is preferable to form the said columnar part main body integrally with the said resin substrate, as shown in the manufacturing method mentioned later.
Of the above-described resin materials, it is preferable to use a thermosetting resin because the wear resistance of the mold of the present invention becomes better and the heat resistance and durability are also good. More preferably, it is a silicone resin.

<Coating layer>
The coating layer in the columnar part is not particularly limited as long as it is a coating layer containing a metal oxide.
Here, examples of the metal oxide include those containing at least one element selected from the group consisting of aluminum, silicon, and zirconium. Specifically, aluminum oxide (alumina), silicon oxide, Zirconium oxide (zirconia) etc. are mentioned.
In the present invention, by having such a coating layer, the wear resistance when pressed against an inorganic material such as a silicon substrate is improved.

[Anodized film]
The anodized film that the mold of the present invention may have is not particularly limited as long as it is an anodized film of a valve metal.
Here, the valve metal has a characteristic that the metal surface is covered with an oxide film of the metal by anodic oxidation, and the oxide film flows only in one direction and flows very much in the reverse direction. It is a metal having difficult characteristics, and specific examples thereof include aluminum, tantalum, niobium, titanium, hafnium, zirconium, zinc, tungsten, bismuth, antimony and the like.

  In the present invention, the thickness of the anodized film is not particularly limited as long as it is smaller than the value of the height of the columnar part, but it is preferably 1 to 100 μm, more preferably 5 to 20 μm.

[Method for producing resin mold for nanoimprint]
The method for producing a resin mold for nanoimprinting of the present invention (hereinafter referred to as “the mold manufacturing method of the present invention”) includes at least anodizing a valve metal substrate to form an anodized film having pores. A treatment step, a coating layer forming step of forming a coating layer containing a metal oxide on the inner wall of the pores, a filling step of filling the pores formed with the coating layer with a resin, and the anodized film It is a manufacturing method which melt | dissolves at least one part and forms the columnar part in this order.
Next, the outline | summary of each process of the mold manufacturing method of this invention is demonstrated using FIG.

As shown in FIG. 3, the mold manufacturing method of the present invention comprises:
Anodizing the valve metal substrate 20 to form an anodized film 22 having pores 21 (see FIGS. 3A and 3B);
A coating layer forming step (see FIGS. 3B and 3C) for forming a coating layer 14 containing a metal oxide having a different solubility from the anodic oxide film 22 on the inner wall of the pore 21;
A filling step (see FIGS. 3C and 3D) for filling the resin 13 in the pores 21 in which the coating layer 14 is formed;
It is a manufacturing method which has a columnar part formation process (refer to Drawing 3 (D)-(F)) which melts at least a part of anodic oxide film 22 with the remainder of valve metal substrate 20, and forms a columnar part.
Next, materials used, processing conditions, etc. will be described for each step of the mold manufacturing method of the present invention.

[Anodizing treatment process]
The anodic acid treatment step is a step of subjecting the valve metal substrate to an anodic oxidation treatment to form an anodized film having pores.

<Valve metal substrate>
The valve metal substrate is a substrate made of a valve metal.
Here, as a valve metal, the thing similar to what was demonstrated in the mold of this invention mentioned above is mentioned.
Among these, the aluminum substrate described in detail below is preferable because of excellent workability and strength.

As the aluminum substrate suitably used for the anodizing treatment step, a known aluminum substrate can be used. In addition to a pure aluminum substrate, an alloy plate containing aluminum as a main component and a trace amount of foreign elements; low-purity aluminum (for example, Further, a substrate in which high-purity aluminum is vapor-deposited on a recycled material); a substrate in which high-purity aluminum is coated on the surface of a silicon wafer, quartz, glass or the like by a method such as vapor deposition or sputtering;
Here, the foreign elements that may be included in the alloy plate include silicon, iron, copper, manganese, magnesium, chromium, zinc, bismuth, nickel, titanium, etc., and the content of the foreign elements in the alloy is It is preferably 10% by mass or less.
In addition, a conventionally well-known composition, a preparation method (for example, casting method etc.), etc. can be suitably employ | adopted for such an aluminum substrate.

  In the present invention, the thickness of the valve metal substrate is not particularly limited, and is about 0.1 to 2.0 mm, preferably 0.15 to 1.5 mm, and 0.2 to 1.0 mm. More preferably. This thickness can be appropriately changed according to the user's wishes or the like.

<Anodizing treatment>
The anodizing treatment is not particularly limited, and can be performed by a conventionally performed method.
Specific examples of the solution used for the anodizing treatment include sulfuric acid, phosphoric acid, chromic acid, oxalic acid, sulfamic acid, benzenesulfonic acid, amidosulfonic acid, malonic acid, citric acid, tartaric acid, and boric acid. , Etc. can be used alone or in combination of two or more.

In addition, the conditions of the anodizing treatment vary depending on the electrolyte used, and thus cannot be determined unconditionally. In general, the electrolyte concentration is 1 to 80% by mass, the solution temperature is 5 to 70 ° C., and the current density. 0.5 to 60 A / dm ² , a voltage of 1 to 100 V, and an electrolysis time of 15 seconds to 50 minutes are appropriate and adjusted so as to obtain a desired anodic oxide film layer amount.

In the present invention, the film thickness of the anodized film formed by the anodizing treatment is preferably 1 to 100 μm, and more preferably 5 to 20 μm.
Further, the pore diameter of the pores in the anodized film formed by the anodizing treatment is preferably 40 to 300 nm, and more preferably 60 to 100 nm.
Furthermore, the density of the pores is preferably ² million pieces / mm ² or more, more preferably 10 million pieces / mm ² or more.

[Coating layer forming step]
The coating layer forming step is a step of forming a coating layer containing a metal oxide on the pore inner walls of the pores, and is a step of forming the coating layer in the mold of the present invention described above.

<Coating layer>
The coating layer is not particularly limited as long as it is a coating layer containing a metal oxide, but in the production method of the present invention, considering the workability when dissolving the anodized film in the columnar part forming step described later, The anodic oxide film is preferably a coating layer made of a metal oxide (for example, silicon oxide, zirconium oxide, etc.) having different solubility.

<Formation method>
The method for forming the coating layer is not particularly limited, and examples thereof include a method of applying (penetrating) a sodium silicate aqueous solution or a sodium fluorozirconate aqueous solution into the pores.

[Filling process]
The filling step is a step of filling the pores in which the coating layer is formed with a resin, and is a step of forming the columnar body in the mold of the present invention described above.
In the present invention, as shown in FIGS. 3C and 3D, it is preferable to form not only the columnar body 13 but also the resin substrate 11 at the same time when filling the resin in the pores (C). .
Moreover, as said resin, the thing similar to what was demonstrated in the mold of this invention mentioned above is mentioned.

<Filling method>
The method of filling the resin is not particularly limited. For example, a curable composition containing a polymerization initiator or a curing agent together with (meth) acrylate, an epoxy compound, a silicone compound, or the like is filled in pores under reduced pressure or pressure. And a method of curing after curing.

[Columnar forming step]
The columnar part forming step is a step of forming a columnar part by dissolving at least a part of the anodic oxide film.
In the present invention, it may be a step of dissolving a part of the anodized film (see FIG. 3E) or a step of dissolving the whole of the anodized film (see FIG. 3F). ).

<Dissolution method>
As the solution used for dissolution, it is preferable to use an aqueous solution capable of removing only the anodized film without dissolving the coating layer (metal oxide).
Here, the anodic oxide film does not dissolve in a neutral aqueous solution of pH 6.5 to 7.5, but slowly dissolves in a weak acid of pH 4 to 6.5 or a weak alkali of pH 7.5 to 10, and a strong acid or Dissolves in strong alkali.
Therefore, the solution used for dissolution is preferably a weakly acidic or weakly alkaline aqueous solution.
Moreover, it is preferable that the temperature range at the time of melt | dissolution is 5-60 degreeC, and it is more preferable that it is 15-45 degreeC.
Furthermore, the dissolution treatment time is preferably 10 minutes to 60 hours, and more preferably 30 minutes to 12 hours.

<Example 1>
(1) Anodizing treatment step An aluminum substrate (manufactured by Nippon Light Metal Co., Ltd.) having a purity of 99.99% was previously subjected to electropolishing treatment in a phosphoric acid solution, and the surface was removed by 20 μm.
Then, 0.5 M / l oxalic acid (15 ° C.) was used as the electrolytic solution, and an anodic oxidation treatment was performed in which a voltage of 40 V was applied between the SUS plate and the aluminum substrate as an anode for 1 hour.
As a result, an aluminum substrate on which an anodized film having straight tubular pores (density: 30 million pieces / mm ² , pore diameter: 60 nm, depth: 10 μm) was formed was obtained.

(2) Coating layer forming step Next, the aluminum substrate on which the anodized film was formed was immersed for 14 seconds in an aqueous solution of 2.5% by mass of No. 3 sodium silicate (manufactured by Fuji Chemical) heated to 70 ° C. Thereafter, a water-washing treatment was performed to form a coating layer containing silicon oxide on the pore inner walls.

(3) Filling Step After drying the substrate, the substrate was placed under reduced pressure, and an epoxy resin solution (SU-8 3000, Nippon Kayaku Co., Ltd.) was dropped and allowed to stand for 10 minutes.
Then, the epoxy resin was filled in the pores by heating and curing under the same reduced pressure.

(4) Columnar part forming step Using a potassium hydroxide aqueous solution (pH: 13), the remainder of the aluminum substrate and the whole of the anodized film are dissolved, and the resin mold for nanoimprinting has a plurality of columnar parts on the surface of the resin substrate. Was made.

<Example 2>
In the filling step, nanoimprinting was performed in the same manner as in Example 1 except that the silicone resin was filled with a silicone resin solution [silicone coating agent (KR-400), manufactured by Shin-Etsu Silicone Co., Ltd.] instead of the epoxy resin solution. A resin mold was prepared.

<Example 3>
A resin mold for nanoimprinting was produced in the same manner as in Example 1 except that the application time was 10 hours in the anodizing process.
In addition, an aluminum substrate on which an anodized film having pores (density: 30 million pieces / mm ² , pore diameter: 60 nm, depth: 100 μm) was formed by the anodizing treatment step was obtained.

<Example 4>
In the coating layer forming step, a mixed aqueous solution containing 1% by mass of sodium dihydrogen phosphate (manufactured by Wako Pure Chemical Industries) and 0.1% by mass of sodium fluoride zirconate (manufactured by Morita Chemical Co., Ltd.) was used. A resin mold for nanoimprinting was produced in the same manner as in Example 1 except that the coating layer containing zirconium oxide was formed on the inner walls of the pores by dipping at 10 ° C. for 10 seconds.

<Example 5>
In the filling step, the fluorine-based silicone resin was filled using a fluorine-based silicone resin solution [perfluoroalkylsilane, KBM7803 (heptadecatrifluorodecyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.] instead of the epoxy resin solution. Except for the above, a resin mold for nanoimprinting was produced in the same manner as in Example 4.

<Example 6>
A resin mold for nanoimprinting was produced in the same manner as in Example 1 except that the remaining part of the aluminum substrate and a part of the anodized film were dissolved in the columnar part forming step.
As shown in FIG. 1B, the produced mold was confirmed to have an anodized aluminum film (thickness: 10 nm) on the surface of the resin substrate.
In Table 1 below, the height and aspect ratio of the columnar portion formed in Example 6 are described in parentheses because they are described without considering the film thickness (10 nm) of the anodized film. However, it is clear that the columnar portion formed in Example 6 satisfies the columnar portion having a specific shape defined in the present invention.

<Comparative Example 1>
A resin mold for nanoimprinting was produced in the same manner as in Example 1 except that the coating layer forming step was not performed.

<Comparative example 2>
A resin mold for nanoimprinting was produced in the same manner as in Example 3 except that the coating layer forming step was not performed.

<Comparative Example 3>
A resin mold for nanoimprinting was produced in the same manner as in Example 1 except that in the columnar part forming step, the remaining part of the aluminum substrate and the entire anodized film were peeled off.
Note that the columnar part of the produced mold was broken during peeling.

<Comparative example 4>
Resin mold for nanoimprinting by the same method as in Example 1 except that the anodizing process was performed in the anodizing process and the remaining part of the aluminum substrate and the entire anodized film were peeled off in the columnar part forming process. Was made.
(Anodizing method)
In advance, an aluminum substrate having a purity of 99.99% (manufactured by Nippon Light Metal Co., Ltd.) was subjected to an electropolishing treatment in a phosphoric acid solution to remove 20 μm of the surface.
Thereafter, 0.5 M / l oxalic acid (15 ° C.) was used as the electrolytic solution, the SUS plate was used as the counter electrode, the aluminum plate was used as the anode, and a voltage of 40 V was applied between them for 4 hours to perform electrolysis (first oxide film Forming step).
Next, the formed first oxide film is once dissolved and removed in a 6% by mass phosphoric acid and 2% by mass chromic acid mixed aqueous solution (oxide film removing step), and then again the first oxide film forming step. Under the same conditions, anodization was performed for 30 seconds to form a second oxide film (second oxide film forming step).
Subsequently, it was immersed in 5 mass% phosphoric acid aqueous solution (30 degreeC) for 8 minutes, and the hole diameter expansion process which expands the pore of an oxide film was performed (pore diameter expansion process process).
Next, the second oxide film forming step and the above pore diameter expansion treatment step are repeated, and these are added five times in total, and tapered pores [pore diameter (opening portion): 100 nm, pore diameter (bottom portion): An aluminum substrate on which an anodized film having a thickness of 40 nm and a depth of 220 nm was formed was obtained.

The shape of the columnar part (bottom area, height, bottom diameter, aspect ratio, cross-sectional area / bottom area, area occupancy of the cut surface) in each mold was measured by the method described above. These results are shown in Table 1 below. Each shape was observed with a field emission scanning electron microscope (FE-SEM) at a magnification of 50,000 times or more, and the cut surface cut horizontally at half the height of the columnar part is a filling step. After being filled with the resin, mechanically polished to a position half the thickness of the anodized film measured in advance using an interference type film thickness meter (Phototal P-900, manufactured by Otsuka Electronics Co., Ltd.) A horizontal section was observed.
Further, the wear resistance and uprightness (sagging) were evaluated by the following evaluation methods, and the results are shown in Table 1 below.

<Abrasion resistance>
After pressing the columnar part of each manufactured mold onto a silicon wafer (6 inches) rotating (100 rpm) and applying a load of 50 g for 1 minute, the tip of the columnar part was observed with a scanning electron microscope.
As a result, when the tip shape was maintained in the initial state, it was evaluated as “1” as being extremely excellent in wear resistance, and those having a burr shape were evaluated as being excellent in wear resistance. It was evaluated as “2”, and the flattened one was evaluated as “3” as being inferior in wear resistance.

<Uprightness>
Each produced mold was observed with a scanning electron microscope from the thickness direction, and the uprightness of the columnar part with respect to the substrate was evaluated.
As a result, when the inclination of the columnar portion is within 10 degrees, the uprightness is evaluated as “1” as being extremely excellent, and when the inclination is 10 degrees or more and less than 45 degrees as “2” as being excellent in uprightness. Evaluation was made, and 45 ° or more was evaluated as “3” as inferior uprightness.

From the results shown in Table 1, it was found that the mold having no coating layer was inferior in wear resistance even when the columnar part had a specific shape (Comparative Examples 1 and 2).
Further, it was found that when the anodized film was peeled when forming the columnar part, the columnar part was broken, the aspect ratio was low, and the wear resistance was inferior (Comparative Example 3).
Further, it was found that a mold having a columnar portion having a cross-sectional area smaller than a predetermined range with respect to the bottom area is inferior in wear resistance even if it has a coating layer (Comparative Example 4).

On the other hand, it turned out that the mold which has the columnar part of the specific shape which has a coating layer becomes favorable in abrasion resistance, and is also favorable also in uprightness (hanging) (Examples 1-6).
In particular, the mold produced in Example 6 having an aluminum anodized film on the surface of the resin substrate is extremely good in wear resistance and uprightness (sag), and the molds are stacked and stored. It was found that no change in shape was observed, and it was found that handling was excellent.

DESCRIPTION OF SYMBOLS 10 Mold 11 Resin board | substrate 12 Columnar part 13 Columnar part main body 14 Coating layer 20 Valve metal substrate 21 Pore 22 Anodized film

Claims (5)

A resin mold for nanoimprinting having a plurality of columnar portions on the surface of a resin substrate,
The area of the bottom of the columnar part is 0.001 to 1 μm ² ;
The ratio of the height to the diameter of the bottom of the columnar part (height / diameter) is 2 or more,
The area of the cut surface when horizontally cut at a position half the height of the columnar part is 80% or more with respect to the area of the bottom of the columnar part,
A resin mold for nanoimprinting, wherein the columnar part is composed of a columnar part body made of resin and a coating layer containing a metal oxide. Furthermore, the surface of the resin substrate has an anodized film of valve metal,
The resin mold for nanoimprint according to claim 1, wherein the thickness of the anodic oxide film is smaller than the height of the columnar part.   The resin mold for nanoimprints according to claim 1 or 2, wherein an area occupation ratio of the cut surface to the surface of the resin substrate is 10% or more.   The resin mold for nanoimprints according to any one of claims 1 to 3, wherein the metal oxide contains at least one element selected from the group consisting of aluminum, silicon, and zirconium. It is a manufacturing method of the resin mold for nanoimprints which manufactures the resin mold for nanoimprints in any one of Claims 1-4, Comprising:
Anodizing treatment for forming an anodized film having pores by anodizing the valve metal substrate;
A coating layer forming step of forming a coating layer containing a metal oxide on the inner wall of the pore;
A filling step of filling the pores formed with the coating layer with a resin; and
The manufacturing method of the resin mold for nanoimprint which has the columnar part formation process which melt | dissolves at least one part of the said anodic oxide film, and forms a columnar part in this order.