WO2017130888A1 - Structure - Google Patents

Abstract

Provided is a structure having a fine pattern, in which there is less difference in height between regions having different heights in the fine pattern. According to the present invention, there is provided a structure having an elastic layer and a resin layer provided on the upper side of the elastic layer, wherein the resin layer is provided with a fine pattern on the surface on the opposite side from the elastic layer, the fine pattern is provided with a plurality of regions of different height, and the structure is provided with either of configurations (1) or (2): (1) the Young's modulus of the elastic layer is 1 GPa or less; (2) the Young's modulus of the elastic layer is less than the Young's modulus of a substrate supporting the elastic layer.

Description

Structure

The present invention relates to a structure used for imprint technology.

The imprint technique is a fine processing technique that obtains a fine structure by pressing a mold having a fine pattern against a resin layer such as a liquid resin on a transparent substrate, thereby transferring the mold pattern to the resin layer. The fine pattern exists from a nanoscale pattern of 10 nm level to a pattern of about 100 μm. The obtained microstructures are used in various fields such as semiconductor materials, optical materials, storage media, micromachines, biotechnology, and the environment.

For example, in Patent Document 1, in a nanoimprint apparatus that performs pattern transfer by pressing a mold against a workpiece, control is performed such that the pressing direction of the mold is maintained perpendicular to the pattern forming surface of the mold. There is disclosed a nanoimprint apparatus characterized by having a control means.

JP 2005-10201 A

Incidentally, a fine pattern formed in a fine structure may have a plurality of regions having different heights. For example, Japanese Patent Application No. 2014-152190, which is an earlier application of the applicant of the present application, describes a first transferred resin layer obtained by applying a first photocurable resin composition on a transparent substrate having a light shielding pattern. The first cured resin layer to which the first pattern is transferred is formed by irradiating the first transferred resin layer with active energy rays through the first mold while the first pattern of the first mold is pressed. The second light-shielding pattern is used as a mask while the second pattern of the second mold is pressed against the second transferred resin layer obtained by applying the second photocurable resin composition on the cured resin layer. A second cured resin layer having a stepped shape including a low step portion and a high step portion is formed by irradiating the transferred resin layer with an active energy ray to cure a part of the second transferred resin layer. Comprising the step of And at least one of the second pattern has a fine shape, manufacturing method of the fine structure is disclosed.

In such a technique, there are a plurality of regions having different heights in a fine pattern, but it may be desired to reduce the difference in height.

The present invention has been made in view of such circumstances, and provides a structure having a fine pattern and having a small difference in height between regions having different heights in the fine pattern.

According to the present invention, there is provided a structure having an elastic layer and a resin layer provided on the elastic layer, the resin layer having a fine pattern on a surface opposite to the elastic layer, and the fine pattern includes: A plurality of regions having different heights are provided, and the following configuration (1) or (2) is provided; (1) Young's modulus of the elastic layer is 1 GPa or less (2) Young's modulus of the elastic layer is the elasticity A structure is provided that is less than the Young's modulus of the substrate that supports the layer.

The point of the present invention is that an elastic layer is provided on the side opposite to the surface having a fine pattern including a plurality of regions having different heights. Such an elastic layer has the characteristics that (1) the Young's modulus of the elastic layer is 1 GPa or less, or (2) the Young's modulus of the elastic layer is smaller than the Young's modulus of the base material supporting the elastic layer. Such a structure can be suitably used as a mold in the nanoimprint method, and the structure (mold) is pressed against the transferred layer to form a fine pattern on the transferred layer, and the elastic layer is formed by pressing with the mold. By deforming, the difference in height between regions having different heights in the fine pattern can be reduced.

Hereinafter, various embodiments of the present invention will be exemplified. The embodiments described below can be combined with each other.
Preferably, the ratio of the Young's modulus of the base material to the Young's modulus of the elastic layer is 10 or more.
Preferably, the fine pattern includes a plurality of convex portions and a plurality of concave portions, and the plurality of regions having different heights of the fine pattern include a high step portion and a low step portion having a lower height than the high step portion. And a distance between a virtual line connecting the upper surfaces of the plurality of convex portions of the high step portion and a virtual line connecting the upper surfaces of the plurality of convex portions of the low step portion is 500 μm or less.
Preferably, the thickness of the thinnest part of the resin layer in the region where the fine pattern is provided is 100 nm or less.
Preferably, the value of the ratio of the thickness of the elastic layer to the thickness of the resin layer is 10 or more.
Preferably, the elastic layer has a uniform thickness.

(A) is a schematic diagram showing the structure 2 which concerns on one Embodiment of this invention, (b) is the elements on larger scale of the area | region X in (a). It is a schematic diagram which shows the composite mold 1, the transferred layer 21, the elastic layer 22, and the base material 23 used when manufacturing the structure 2 which concerns on one Embodiment of this invention. It is a figure explaining the manufacturing method of the structure 2 which concerns on one Embodiment of this invention, (a) is before pressing of the composite mold 1, (b) is hardening of the to-be-transferred layer 21, (c) is the composite mold 1. It is a figure shown about separation of. For convenience of explanation, the scales in the height direction of the high step portion 11h and the low step portion 11l included in the composite mold 1, and the transferred layer 21 and the elastic layer 22 are changed. The base material 23 is not shown. FIG. 4 is an enlarged view of FIG. 3C, illustrating a mechanism in which a difference between the height of the high step portion 21 h and the height of the low step portion 21 l included in the structure 2 is reduced. It is a figure showing a mode that other structures 3 are manufactured using structure 2 concerning one embodiment of the present invention. It is a figure explaining the manufacturing method of the structure 3 which concerns on one Embodiment of this invention, (a) is before the structure 2 is pressed, (b) is hardening of the to-be-transferred layer 31, (c) is the structure 2 It is a figure shown about separation of. For convenience of explanation, the scale in the height direction of the high step portion 21 h and the low step portion 21 l, the transfer layer 31 and the base material 33 included in the structure 2 is changed. The base material 23 is not shown. FIG. 4 is a diagram showing another embodiment of the present invention, in which (a) shows an example in which the substrate 2 is omitted and the structure 2 is manufactured, and (b) shows an intermediate layer between the transferred layer 21 and the elastic layer 22. An example in which 25 is provided is shown.

Hereinafter, embodiments of the present invention will be described. The following embodiments are exemplifications, and the scope of the present invention is not limited to those shown in the following embodiments.

1. Structure 2
Hereinafter, the structure 2 according to the embodiment of the present invention will be described with reference to FIG. Various characteristic items shown in the following embodiments can be combined with each other. In addition, the invention is independently established for each feature.

<Structure 2>
Fig.1 (a) is a schematic diagram showing the structure 2 which concerns on one Embodiment of this invention, FIG.1 (b) is the elements on larger scale of the area | region X in Fig.1 (a). The structure 2 includes a base material 23, an elastic layer 22, and a resin layer 24. The resin layer 24 includes a fine pattern 26 on the surface opposite to the elastic layer 22. The fine pattern 26 is a resin layer made of, for example, a resin composition.

<Resin layer 24 and fine pattern 26>
The fine pattern 26 is, for example, a transparent resin layer, and has a thickness d1 (the distance from the surface 24b having the fine pattern 26 to the upper surface of the convex portion of the high step portion 21h, which is also the thickness of the resin layer 24). 1 nm to 1 mm is preferable. More preferably, it is 5 nm to 200 nm. More preferably, it is 10 nm to 100 nm. With such a thickness, imprinting is easy to perform.

FIG.1 (b) is the elements on larger scale of the area | region X in Fig.1 (a). The fine pattern 26 according to an embodiment of the present invention is a concavo-convex fine pattern that repeats at a constant cycle. The fine pattern 26 includes a plurality of convex portions and a plurality of concave portions. The fine pattern 26 includes a high step portion 21h and a low step portion 21l. The low step portion 21l is a region having a lower height than the high step portion 21h. As shown in FIG. 1, the distance from the elastic layer 22 to the convex portion of the low step portion 21 l is shorter than the distance from the elastic layer 22 to the convex portion of the high step portion 21 h. A distance D1 between an imaginary line connecting the upper surfaces of the plurality of convex portions constituting the high step portion 21h and an imaginary line connecting the upper surfaces of the plurality of convex portions constituting the low step portion 21l is 0.5 nm to 500 μm. Is preferred. More preferably, the thickness is 5 nm to 50 μm. More preferably, it is 5 nm to 5 μm. Specifically, 5, 6, 7, 8, 9, 10, 15, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 35, 40, 41, 42, 43 , 44, 45, 50, 60, 70, 80 nm, and may be within a range between any two of the numerical values exemplified here. Note that since the heights of the plurality of convex portions are strictly different, the average height of the plurality of convex portions may be used as a virtual line. Here, the fine pattern 26 preferably has a period of 10 nm to 2 mm and a transfer surface of 1.0 mm ² to 1.0 × 10 ⁶ mm ² . More preferably, the period is 20 nm to 20 μm, and the transfer surface is 1.0 × 10 mm ² to 0.25 × 10 ⁶ mm ² . Here, the depth of the high step portion 21h and the low step portion 21l may be substantially the same or different from each other. Specific examples of the unevenness include moth eye, line, cylinder, monolith, cone, polygonal pyramid, and microlens. Further, the fine pattern 26 may be a fine shape pattern with irregularities randomly, or a regular fine shape pattern with a plurality of irregularities.

Further, it is preferable that the thickness H of the thinnest portion of the resin layer 24 in the region where the fine pattern 26 is provided is 100 nm or less.

<Elastic layer 22>
The elastic layer 22 is a layer provided on the placement surface side of the fine pattern 26. The elastic layer 22 can be made of resin, for example. The elastic layer 22 is characterized in that (1) the Young's modulus of the elastic layer 22 is 1 GPa or less, or (2) the Young's modulus of the elastic layer 22 is smaller than the Young's modulus of the base material 23 that supports the elastic layer 22. Have Here, the Young's modulus is a proportional constant of strain and stress in the coaxial direction in an elastic range where Hooke's law is established. In a linear elastic body, if the Young's modulus is E, the strain is x, and the stress is F, “F = Ex” is established. From this, it can be seen that when the magnitude of the strain is the same, the restoring force from the distorted state increases as the material has a higher Young's modulus. The upper limit of the Young's modulus of the elastic layer 22 is preferably 1 GPa or less. More preferably, it is 500 MPa or less. More preferably, it is 200MP or less. The lower limit of the Young's modulus of the elastic layer 22 is preferably 0.5 MPa or more. More preferably, it is 1 MPa or more. More preferably, it is 5 MPa. Particularly preferably, it is 10 MPa or more. The Young's modulus of the elastic layer 22 is, for example, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60 MPa, even if it is within the range between any two of the numerical values exemplified here. Good.

Further, the ratio of the Young's modulus of the base material 23 to the Young's modulus of the elastic layer 22 is preferably 10 or more. More preferably, it is 100 or more. More preferably, it is 500 or more. The ratio of the Young's modulus of the base material 23 to the Young's modulus of the elastic layer 22 is, for example, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 150, 200, 250, 300, 350. , 400, 450, 500, 550, 600, 650, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 2000, and within the range between any two of the numerical values exemplified here. There may be.

The thickness d2 of the elastic layer 22 is preferably 10 nm to 1 cm. More preferably, the thickness is 100 nm to 500 μm. More preferably, it is 1 μm to 100 μm. Furthermore, the value of the ratio of the thickness d1 of the resin layer 24 and the thickness d2 of the elastic layer 22 is preferably 10 or more. Specifically, the ratio value of the thickness d1 of the resin layer 24 and the thickness d2 of the elastic layer 22 is 10, 15, 20, 30, 40, 50, 100, 150, 200, 250, 300. It is preferable. Further, it may be within a range between any two of the numerical values exemplified here.

In this embodiment, as shown in FIG. 1, the elastic layer 22 has a uniform thickness d2, but is not limited thereto. For example, the thickness d2 may not be uniform and may be spatially displaced. Moreover, a hole may be provided periodically or aperiodically, and it is good also as a periodic or aperiodic pillar structure.

<Substrate 23>
The base material 23 supports the elastic layer 22. The material of the base material 23 is not specifically limited, A well-known resin, quartz, a metal, etc. can be used. Moreover, the same kind or different kind of base materials may be laminated, or the resin composition may be laminated on the base material in a film form. The base material 23 is formed of a transparent material such as a resin base material or a quartz base material.

The Young's modulus of the base material 23 is larger than the Young's modulus of the elastic layer 22. The upper limit of the Young's modulus of the substrate 23 is preferably 100 GPa or less. More preferably, it is 50 GPa or less. More preferably, it is 30 GPa or less. The lower limit of the Young's modulus of the substrate 23 is preferably 1.1 MPa or more. More preferably, it is 10 MPa or more. More preferably, it is 20 MPa or more.

The thickness d3 of the base material 23 is preferably 200 nm to 20 cm. More preferably, it is 2 μm to 1 cm. More preferably, it is 20 μm to 2 mm.

In the present embodiment, the elastic layer 22 is provided on the base material 23, but the invention is not limited to this, and the base material 23 may be omitted. In this case, the elastic layer 22 is directly placed on the placement surface.

2. Method for Manufacturing Structure 2 Next, a method for manufacturing the structure 2 will be described with reference to FIGS. As a manufacturing method according to the present invention, a transferred layer forming step of forming a transferred layer on the upper side of the elastic layer, and a mold having a fine pattern are pressed against the transferred layer, and the fine pattern is applied to the transferred layer. A transfer step for transferring, and a curing step for hardening the transferred layer, comprising the following configuration (1) or (2): (1) Young's modulus of the elastic layer is 1 GPa or less (2) A method for producing a structure in which the Young's modulus of the elastic layer is smaller than the Young's modulus of the substrate that supports the elastic layer can be used. (1) is a condition when the elastic layer 22 is directly placed on the placement surface without using the base material 23. (2) is a condition when the base material 23 is provided below the elastic layer 22. The method for adjusting the Young's modulus is not particularly limited. For example, the Young's modulus can be adjusted by changing the blending ratio of a plurality of resins.

Furthermore, another structure 3 can be manufactured using the structure 2. In this case, the structure includes an elastic layer and a resin layer provided above the elastic layer, and the resin layer includes a fine pattern on a surface opposite to the elastic layer, and the fine pattern has a height. A plurality of different regions and having the following configuration (1) or (2): (1) the Young's modulus of the elastic layer is 1 GPa or less (2) the Young's modulus of the elastic layer supports the elastic layer Production of a structure comprising a transfer step of pressing a structure smaller than the Young's modulus of a material against a transfer layer to transfer the fine pattern to the transfer layer and a curing step of curing the transfer layer You can use the method.

<Preparation>
<Composite mold 1>
FIG. 2 is a schematic view showing the composite mold 1, the transferred layer 21, the elastic layer 22, and the base material 23 used when the structure 2 according to the embodiment of the present invention is manufactured. The composite mold 1 is a mold having a fine pattern in which a plurality of regions having different heights are present on the base material 13. The fine pattern of the present embodiment is a concavo-convex fine pattern that repeats at a constant cycle. The fine pattern is composed of a plurality of convex portions and a plurality of concave portions. The fine pattern includes a high step portion 11h and a low step portion 11l. The low step portion 11l is a region having a height lower than that of the high step portion 11h. As shown in FIG. 2, the distance from the base material 13 to the convex portion of the low step portion 11l is shorter than the distance from the base material 13 to the convex portion of the high step portion 11h. A distance D between an imaginary line connecting the upper surfaces of the plurality of convex portions constituting the high step portion 11h and an imaginary line connecting the upper surfaces of the plurality of convex portions constituting the low step portion 11l is 0.5 nm to 500 μm. Is preferred. Note that since the heights of the plurality of convex portions are strictly different, the average height of the plurality of convex portions may be used as a virtual line. Here, the period of the fine pattern and the transfer surface can be set to the same conditions as those of the fine pattern 26 described above. Further, the depth of the high step portion 11h and the low step portion 11l may be substantially the same or different from each other. By setting in this way, a sufficient fine pattern can be transferred to the transfer layer 21 described later. Specific examples of the unevenness include moth eye, line, cylinder, monolith, cone, polygonal pyramid, and microlens. In addition, the fine pattern may be a fine shape pattern with irregularities randomly, or a fine shape pattern with a plurality of irregularities.

The material of the base material 13 and the fine patterns 11h and 11l constituting the composite mold 1 is not particularly limited, and a known resin, quartz, metal, or the like can be used. Moreover, the same kind or different kinds of base materials may be laminated, or the resin composition may be laminated on the base material in the form of a film, and it is preferable to laminate a release layer on the fine patterns 11h and 11l. The thickness of the substrate is preferably 200 nm to 20 cm. More preferably, it is 2 μm to 1 cm. More preferably, it is 20 μm to 2 mm.

<Transfer layer 21>
The transferred layer 21 is a layer to which a fine pattern of the composite mold 1 is transferred. The transferred layer 21 forms the fine pattern 26 and is made of, for example, a photocurable resin composition. The transferred layer 21 is, for example, a transparent resin layer, and the thickness d1 is preferably 1 nm to 1 mm. More preferably, it is 5 nm to 200 nm. More preferably, it is 10 nm to 100 nm. With such a thickness, imprinting is easy to perform. In this embodiment, a photocurable resin composition containing a monomer and a photoinitiator and having a property of being cured by irradiation with active energy rays is used.

Monomers include photopolymerizable monomers for forming (meth) acrylic resins, styrene resins, olefin resins, polycarbonate resins, polyester resins, epoxy resins, silicone resins, etc., and photopolymerizable (meth) acrylic. System monomers are preferred. In the present specification, (meth) acryl means methacryl and / or acryl, and (meth) acrylate means methacrylate and / or acrylate.

The photoinitiator is a component added to promote the polymerization of the monomer, and is preferably contained in an amount of 0.1 part by mass or more with respect to 100 parts by mass of the monomer. Although the upper limit of content of a photoinitiator is not prescribed | regulated in particular, For example, it is 20 mass parts with respect to 100 mass parts of monomers.

Moreover, the photocurable resin composition which comprises the to-be-transferred layer 21 can be manufactured by mixing the said component by a well-known method. The photocurable resin composition is applied on the elastic layer 22 described later by a method such as spin coating, spray coating, bar coating, dip coating, die coating, and slit coating, and the fine pattern 26 is formed by a manufacturing method described later. Is possible.
<Elastic layer 22>

The elastic layer 22 can be made of resin, for example. In this embodiment, a mixture of (meth) acrylate and urethane (meth) acrylate is used. Examples of the (meth) acrylate include bifunctional or lower (meth) acrylate, trifunctional (meth) acrylate, and tetrafunctional or higher (meth) acrylate.

The bifunctional or lower (meth) acrylate compound is a (meth) acrylate compound having 2 or less (meth) acrylate groups, and examples thereof include a bifunctional (meth) acrylate compound and a monofunctional (meth) acrylate compound. Bifunctional (meth) acrylate compounds include tripropylene glycol di (meth) acrylate, ethylene oxide modified bisphenol A di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (Meth) acrylate, 1,9-nonanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, neopentylglycol di (meth) acrylate , Pentaerythritol di (meth) acrylate, trimethylolpropane di (meth) acrylate, and the like. Monofunctional (meth) acrylate compounds include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl ( (Meth) acrylates having linear alkyl groups such as (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate and stearyl (meth) acrylate ;
(Meth) acrylic acid having a branched alkyl group such as iso-propyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and isooctyl (meth) acrylate Alkyl esters;
(Meth) acrylic acid alkyl esters having a cyclic alkyl group such as isobornyl (meth) acrylate and cyclohexyl (meth) acrylate;
Examples thereof include (meth) acrylic acid esters having an aromatic ring group such as benzyl (meth) acrylate and phenoxyethyl (meth) acrylate.

The trifunctional (meth) acrylate compound is a (meth) acrylate compound having three (meth) acrylate groups, such as trimethylolpropane tri (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, pentaerythritol tris. And (meth) acrylate.

The tetrafunctional or higher (meth) acrylate compound is a (meth) acrylate compound having four or more (meth) acrylate groups, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate monopropionate, Examples include dipentaerythritol hexa (meth) acrylate, tetramethylolethane tetra (meth) acrylate, and oligoester tetra (meth) acrylate.

As the urethane (meth) acrylate, a known compound can be used. Urethane (meth) acrylate is a reaction product of a polyisocyanate compound having a molecular terminal isocyanate group and a hydroxyl group-containing (meth) acrylate compound. The polyisocyanate compound is a known polyol comprising a polyol such as polyester polyol, polyether polyol, polycarbonate polyol or low molecular weight glycol, and a compound having two or more isocyanate groups in the molecule such as hexamethylene diisocyanate or tolylene diisocyanate. It can be obtained by reaction. The hydroxyl group-containing (meth) acrylate compound is not limited as long as it is a (meth) acrylate compound containing one or more hydroxyl groups. Specifically, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acryloyl phosphate 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, glycerin di (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol Examples include penta (meth) acrylate and caprolactone-modified 2-hydroxyethyl (meth) acrylate.
In addition, as the urethane (meth) acrylate of the present invention, commercially available products such as “purple light” series manufactured by Nippon Synthetic Chemical Industry Co., Ltd. and “UNIDIC” series manufactured by DIC Corporation can be used.

The elastic layer 22 can be formed on the base material 23 in the same manner as the transferred layer 21. The upper limit of the Young's modulus of the elastic layer 22 is preferably 1 GPa or less. Further, the lower limit of the Young's modulus of the elastic layer 22 is preferably 1 MPa or more. Further, the ratio of the Young's modulus of the base material 23 to the Young's modulus of the elastic layer 22 is preferably 10 or more. The thickness d2 of the elastic layer 22 is preferably 10 nm to 1 cm. Thus, by adjusting the thickness d2 and Young's modulus of the elastic layer 22 appropriately, the fine pattern 26 is formed on the transferred layer 21 by pressing the composite mold 1 against the transferred layer 21 in the manufacturing method described later. When the composite mold 1 is formed and separated from the fine pattern 26, the elastic layer 22 that has followed the pressing by the composite mold 1 is restored, so that a difference in height between regions having different heights in the fine pattern 26 can be obtained. Can be small. This will be described later with reference to FIG.

<Substrate 23>
Although the material of the base material 23 is not specifically limited, It is preferable to form with transparent materials, such as a resin base material, a silicone base material, and a quartz base material. As a resin constituting the resin substrate, polycarbonate, polyester (polyethylene terephthalate (PET)), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN)) Polyolefin, cyclic polyolefin, polyimide, polysulfone, polyethersulfone and the like can be used. Moreover, when using a resin base material, the same kind or different kind of base material may be laminated | stacked, or the resin composition may be laminated | stacked on the resin base material in the form of a film.
<Transfer process and curing process>
Next, each process of the manufacturing method of the structure 2 is demonstrated. 3A and 3B are diagrams for explaining a method of manufacturing the structure 2 according to the present embodiment, where FIG. 3A is a state before pressing the composite mold 1, FIG. 3B is a curing of the transferred layer 21, and FIG. 3C is a composite mold. It is a figure shown about 1 separation. For convenience of explanation, the scales in the height direction of the high step portion 11h and the low step portion 11l included in the composite mold 1, and the transferred layer 21 and the elastic layer 22 are changed. The base material 23 is not shown.

First, as shown in FIG. 3A, the composite mold 1 is positioned on the transferred layer 21. Then, the composite mold 1 is lowered until the high step portion 11 h and the low step portion 11 l of the composite mold 1 are pressed against the transferred layer 21.

As shown in FIG. 3B, when the high step portion 11h and the low step portion 11l of the composite mold 1 are pressed against the transfer layer 21, the elastic layer 22 is deformed by the pressure applied to the composite mold 1. Here, the composite mold 1 is laminated by a rubber roller having a weight of 1 kg to 20 kg. The weight of the rubber roller is preferably 2 to 15 kg. As shown in FIG. 3B, the pressure applied to the transferred layer 21 has a difference (D) in the height between the high step portion 11h and the low step portion 11l. A larger pressure is applied to the portion where 11h is pressed than to the portion where the low step portion 11l is pressed. Thereby, in the elastic layer 22, the portion corresponding to the portion where the high step portion 11 h in the transferred layer 21 is pressed is deformed more than the portion corresponding to the portion where the low step portion 11 l in the transferred layer 21 is pressed. To do. Strictly speaking, the portion of the transferred layer 21 corresponding to the portion to which the low step portion 11l is pressed is also deformed, but the deformation amount of the portion corresponding to the portion of the transferred layer 21 to which the high step portion 11h is pressed is It is small enough to be ignored. Therefore, in FIG. 3, the deformation of the elastic layer 22 corresponding to the portion where the low step portion 11 l of the transferred layer 21 is pressed is omitted.

Then, the active energy ray 5 is irradiated to the transferred layer 21 through the composite mold 1. The active energy ray 5 may be irradiated with an integrated light amount sufficient to sufficiently cure the transferred layer 21. The integrated light amount is, for example, 100 to 10,000 mJ / cm ² . By irradiating the active energy ray 5, the transferred layer 21 is cured to become a cured resin, and as shown in FIG. 3C, the fine pattern 26 (which is a cured resin) is a pattern obtained by inverting the fine pattern of the composite mold 1. The resin layer to be formed is formed on the resin layer 24.

3. FIG. 4 is an enlarged view of FIG. 3 (c), and shows the height of the high step portion 21h included in the structure 2 and the mechanism in which the difference in height between regions having different heights in the fine pattern 26 of the structure 2 is reduced. It is a figure explaining the mechanism in which the difference in the height of the low step part 21l becomes small. The position indicated by the broken line below the lower arrow is the position before the elastic layer 22 is restored, and the position indicated by the dotted line above the lower arrow is the position after the elastic layer 22 is restored. The position indicated by the broken line below the upper arrow is the position of the tip of the convex portion of the low step portion 21l before the elastic layer 22 is restored, and the position indicated by the dotted line above the upper arrow is the elastic layer 22. This is the position of the tip of the convex portion of the low step portion 21l after restoration. As the elastic layer 22 is restored by the amount indicated by the arrow, the lower step portion 21l of the fine pattern 26 supported by the elastic layer 22 is also raised by the amount indicated by the arrow. Thereby, the distance between the virtual line connecting the upper surfaces of the convex portions of the low step portion 21l and the virtual line connecting the upper surfaces of the convex portions of the high step portion 21h is changed from D before the elastic layer 22 is restored to the elastic layer. After restoration of 22, it changes to D1. Here, before the elastic layer 22 is restored, the distance between the imaginary line connecting the upper surfaces of the convex portions of the low step portion 21l and the imaginary line connecting the upper surfaces of the convex portions of the high step portion 21h is as follows. A virtual line connecting the upper surfaces of the plurality of convex portions constituting the high step portion 11h in the fine pattern of the composite mold 1 transferred to the transferred layer 21 and a virtual line connecting the upper surfaces of the plurality of convex portions constituting the low step portion 11l. It was assumed that it was equal to the distance D between the lines. Actually, the distance D in the structure 2 and the distance D in the composite mold 1 may not be equal, but for the convenience of explanation, these distances are approximated as being equal. Note that since the heights of the plurality of convex portions are strictly different, the average height of the plurality of convex portions may be used as a virtual line.

Further, it is preferable that the thickness H of the thinnest portion of the resin layer 24 in the region where the fine pattern 26 is provided is 100 nm or less. This is because if the thickness H is too large, the resistance force increases when the elastic layer 22 is restored, and the elastic layer 22 cannot be restored properly.

Furthermore, the ratio value of the thickness d1 of the resin layer 24 and the thickness d2 of the elastic layer 22 is preferably 10 or more. This is because the thickness d2 of the elastic layer 22 is preferably sufficiently larger than the thickness d1 of the resin layer in order for the elastic layer 22 to sufficiently recover.

When manufacturing the structure 2 by such a manufacturing method, the following are mentioned as characteristics required for the elastic layer 22.
(1) Adhesion with the substrate 23 (irrelevant when the substrate 23 is not used)
Adhesiveness to such an extent that the base material 23 and the elastic layer 22 do not peel off is required. For this purpose, for example, it is conceivable to adjust the elastic layer 22 to a desired characteristic by primer treatment or easy adhesion treatment.
(2) Resistance and adhesion to transferred layer 21 Adhesiveness to the extent that transferred layer 21 does not peel from elastic layer 22 is required. Further, when the transfer layer 21 is a liquid UV curable resin, it is necessary that the elastic layer 22 does not expand or dissolve with respect to the transfer layer 21 beyond a certain threshold value.
(3) Moderate elasticity From the examples described later, it can be seen that as the Young's modulus of the elastic layer 22 decreases, the height difference D1 of the fine pattern 26 of the structure 2 decreases. However, if the Young's modulus of the elastic layer 22 is too small, the restoring force of the elastic layer becomes too low, and the height difference D1 of the fine pattern 26 of the structure 2 is difficult to decrease.

4). Method for Manufacturing Other Structure 3 Using Structure 2 Next, a method for manufacturing another structure 3 using the structure 2 as the composite mold 1 will be described with reference to FIG. The structure 2 in FIG. 5 corresponds to the composite mold 1 in FIG. The composite mold 1 has no elastic layer, but the structure 2 is different in that the elastic layer 22 is provided. Further, the transferred layer 31 and the base material 33 in FIG. 5 correspond to the transferred layer 21 and the base material 23 in FIG. Since these functions are the same, description thereof is omitted. Thus, the manufacturing of the structure 3 is started from the state in which the structure 2 is positioned on the transferred layer 31.

6A and 6B are diagrams for explaining a method for manufacturing the structure 3 according to an embodiment of the present invention. FIG. 6A shows a state before the structure 2 is pressed, and FIG. FIG. 6C is a diagram showing the separation of the structure 2. For convenience of explanation, the scale in the height direction of the high step portion 21 h and the low step portion 21 l, the transfer layer 31 and the base material 33 included in the structure 2 is changed. The base material 23 is not shown.

First, as shown in FIG. 6A, the structure 2 is positioned on the transfer layer 31. Then, the structure 2 is lowered until the high step portion 21 h and the low step portion 21 l of the structure 2 are pressed against the transfer layer 31. At this time, the distance between the imaginary line connecting the upper surfaces of the plurality of convex parts constituting the high step portion 21h of the structure 2 and the virtual line connecting the upper surfaces of the plurality of convex parts constituting the low step portion 21l is D1.

As shown in FIG. 6B, when the high step portion 21h and the low step portion 21l of the structure 2 are pressed against the transfer layer 31, the elastic layer 22 is deformed by the pressure applied to the structure 2. Since the pressure applied to the elastic layer 22 has a difference (D1) between the height of the high step portion 21h and the low step portion 21l, the portion of the elastic layer 22 where the high step portion 21h is pressed is lower. A larger pressure is applied than the portion where is pressed. As a result, the portion of the elastic layer 22 corresponding to the portion to which the high step portion 21h is pressed deforms more than the portion corresponding to the portion to which the low step portion 21l is pressed. Strictly speaking, the portion of the elastic layer 22 corresponding to the portion to which the low step portion 21l is pressed is also deformed, but compared with the amount of deformation of the portion of the elastic layer 22 corresponding to the portion to which the high step portion 21h is pressed. Small enough to be ignored. For this reason, in FIG. 6, the deformation | transformation of the part corresponding to the part where the low step part 21l in the elastic layer 22 is pressed was abbreviate | omitted.

The position indicated by the broken line below the upper arrow is the position before the elastic layer 22 is deformed, and the position indicated by the dotted line above the upper arrow is the position after the elastic layer 22 is deformed. Further, the position indicated by the broken line below the downward arrow is the position of the tip of the convex portion of the high step portion 21h when the elastic layer 22 is not deformed, and the position indicated by the dotted line above the downward arrow. Is the position of the tip of the convex portion of the high step portion 21h when the elastic layer 22 is deformed. Thus, as the elastic layer 22 is deformed by the arrow, the high step portion 21h of the fine pattern 26 supported by the elastic layer 22 is also raised by the arrow. As a result, the distance between the imaginary line connecting the upper surfaces of the convex portions of the low step portion 21l and the imaginary line connecting the upper surfaces of the convex portions of the high step portion 21h is from D1 before deformation of the elastic layer 22 to the elastic layer. After the deformation of 22, it changes to D2 (D2 <D1).

Then, the active energy ray 5 is irradiated to the transfer layer 31 through the structure 2. By being irradiated with the active energy ray 5, the transferred layer 31 is cured to become a cured resin, and as shown in FIG. 6C, a fine pattern 36 (cured resin) which is a pattern obtained by inverting the fine pattern 26 of the structure 2 Is formed on the resin layer 34. The fine pattern 36 has a high step portion 31h and a low step portion 31l. And the distance between the virtual line which connects the upper surface of the convex part of the low step part 31l and the virtual line which connects the upper surface of the convex part of the high step part 31h becomes D2. Actually, the distance D2 in the structure 2 and the distance D2 in the structure 3 may not be equal, but for the convenience of explanation, these distances are approximated to be equal. Note that since the heights of the plurality of convex portions are strictly different, the average height of the plurality of convex portions may be used as a virtual line.

Thus, when the structure 3 is manufactured using the structure 2, it is not necessary to provide an elastic layer below the transfer layer 31. This is because the elastic layer 22 is provided on the structure 2 on the pressing side, so that the elastic layer 22 functions in the same manner as the elastic layer 22 in FIGS. Even in such a case, an elastic layer may be provided below the transfer layer 31. In this case, since two elastic layers in total act, a structure with a smaller difference in height between the high step portion and the low step portion can be obtained. Moreover, by repeating this method, the difference in height between the high step portion and the low step portion of the structure is further reduced.

In the present embodiment, the method of irradiating the active energy ray 5 to cure the transferred layer 21 (so-called “UV nanoimprint”) has been described, but the present invention is not limited to this. For example, a thermoplastic resin such as polymethyl methacrylate (PMMA) is applied to the base material, heated to a temperature higher than the glass transition temperature of the resin, the mold is pressed, and after cooling, the mold and the base material are separated, It can also be applied to a method of transferring a pattern to a resin (so-called “thermal nanoimprint”). In this case, the PMMA after cooling is lifted by the restoration of the elastic layer 22, and a structure having a fine pattern with a small difference in height between regions having different heights can be obtained.

5). Other Embodiments Next, other embodiments will be described with reference to FIG. As shown in FIG. 7A, the elastic layer 22 may be directly placed on the placement surface without providing the base material 23 below the elastic layer 22. In this case, the Young's modulus of the elastic layer 22 is adjusted so that the elastic layer 22 can stand upright with respect to the mounting surface. The method for adjusting the Young's modulus is not particularly limited. For example, the Young's modulus can be adjusted by changing the blending ratio of a plurality of resins.

Further, as shown in FIG. 7B, an intermediate layer 25 may be provided between the transferred layer 21 and the elastic layer 22. In this case, the restoring force of the elastic layer 22 is transmitted to the transferred layer 21 through the intermediate layer 25. The elastic layer 22 can be formed of, for example, a resin.

6). Example Next, specific manufacturing conditions of the structure 2 will be described. Although such manufacturing conditions can be adjusted as appropriate, a case where the structure 2 is manufactured under the following manufacturing conditions will be described as an example. In particular, Examples 1 to 5 in which the Young's modulus of the elastic layer 22 is changed will be described.

6-1: Manufacturing conditions <Composite mold 1>
The manufacturing conditions of the structure 2 are as follows. First, a composite mold 1 was prepared in which a fine pattern in which a resin layer made of an acrylic resin and a release layer were laminated on a PET substrate having a thickness of 200 μm and a Young's modulus of 5 GPa was prepared. Note that the height difference (D) between the high step portion 11h and the low step portion 11l of the fine pattern is 100 nm.
<Structure 2>

Then, a photocurable resin composition is applied onto a PET substrate having a thickness of 200 μm and a Young's modulus of 3 GPa, and the photocurable resin composition is cured by irradiating active energy rays 5, and has a thickness of 10 μm and a Young's modulus of 30 MPa. The elastic layer 22 was formed. Here, what mixed urethane acrylate and bifunctional acrylate was used as a photocurable resin composition apply | coated on PET base material. Here, the Young's modulus was gradually decreased from Example 1 to Example 4 by utilizing the property that the Young's modulus decreased as the blending ratio of the bifunctional acrylate was reduced. The respective compounding ratios are 3: 7, 4: 6, 5: 5, 6: 4 in the order of Examples 1 to 5. And the photocurable resin composition was apply | coated on the cured elastic layer 22, and the to-be-transferred layer 21 with a thickness of 100 nm was formed. Here, as the photocurable resin composition applied on the elastic layer 22, a composition obtained by adding 100 parts by weight of a bifunctional acrylate and 5 parts by weight of a photoinitiator was used.

The Young's modulus was calculated by applying a tensile load to the PET substrate or the elastic layer 22 and obtaining the displacement.

Thereafter, the composite mold 1 is pressed against the layer to be transferred 21 by laminating with a 5 kg rubber roller, UV irradiation is performed with an integrated light quantity of 500 mJ / cm ² , and the layer to be transferred 21 in which the fine pattern of the composite mold 1 is reversed is obtained. The structure 2 was obtained by curing.

6-2: Results Under the above manufacturing conditions, the Young's modulus of the elastic layer 22 is changed by changing the blending ratio of urethane acrylate and bifunctional acrylate, and the change in the height difference D1 (see FIG. 4) in the structure 2 is changed. Is shown in the table below.

As shown in Table 1, D1 decreases as the Young's modulus of the elastic layer 22 decreases. And when the Young's modulus of the elastic layer 22 is 5 MPa, the value of D1 takes the minimum value.

Next, the structure 2 having a height difference D1 of 30 nm obtained when the Young's modulus of the elastic layer 22 is 5 MPa is immersed in a container containing a release agent for 1 hour, and rinsed with a solvent after immersion. A release layer was laminated on the fine pattern of the structure 2. The height difference D1 of the structure pattern after release layer lamination was 30 nm. The structure 2 is pressed against a transferred layer having a thickness of 200 μm and a Young's modulus of 3 GPa on a 100 nm-thick transfer layer, and UV irradiation is performed with an integrated light amount of 500 mJ / cm ² to make the structure 2 fine. The transferred layer with the pattern 26 inverted was cured to obtain the structure 3. Here, the transferred layer was produced under the same conditions as described above. The structure 2 was pressed by laminating with a 5 kg rubber roller. At this time, D2 (see FIG. 6) of the structure 3 was 10 nm. As described above, the difference in height is determined by the manufacturing process described above, such as “D of composite mold 1: 100 nm” → “D1: 30 nm of structure 2” → “D2 of structure 3: 10 nm”. Each time it repeats, it decreases by about 1/3.

6-3: Comparative example (when the elastic layer 22 is not provided)
Next, a case where the elastic layer 22 is not provided will be described.
<Comparative Example 1>
A composite mold 1 having a difference in height (D) between the high step portion 11h and the low step portion 11l of the fine pattern of 100 nm on the acrylic plate substrate having a thickness of 200 μm and a Young's modulus of 3 MPa under the same manufacturing conditions as above. The formed layer to be transferred having a thickness of 100 nm was pressed and irradiated with UV light with an integrated light amount of 500 mJ / cm ² to cure the layer to be transferred in which the fine pattern of the composite mold 1 was inverted, whereby a transfer product X was obtained. Here, the transferred layer was produced under the same conditions as described above. The composite mold 1 was pressed by laminating with a 5 kg rubber roller. At this time, Dx of the transcript X (corresponding to D1 of the structure 2) was 100 nm. This is presumably because D of the composite mold 1 was almost transferred directly to the transfer layer 21 because there was no elastic layer 22.

<Comparative Example 2>
Next, using the composite mold 1 in which the height difference (D) between the high step portion 11h and the low step portion 11l of the fine pattern is 30 nm under the same conditions as in Comparative Example 1, the transfer product Y (structure having a fine pattern) ) Was manufactured. At this time, Dy of the transcript Y (corresponding to D1 of the structure 2) was 30 nm. This is presumably because D of the composite mold 1 was almost transferred directly to the transfer layer 21 because there was no elastic layer 22.

As described above, in the present invention, by appropriately adjusting the Young's modulus of the elastic layer 22, the structure has a fine pattern, and the difference in height between regions having different heights in the fine pattern is small. It became possible to get a body.

1: Composite mold, 11l, 21l, 31l: Low step, 11h, 21h, 31h: High step, 13, 23, 33: Base material, 21, 31: Transfer layer, 22, 32: Elastic layer, 24 34: Resin layer, 26, 36: Fine pattern, 24b: Surface having fine pattern, 25: Intermediate layer, 5: Active energy ray

Claims (6)

A structure having an elastic layer and a resin layer provided on the elastic layer,
The resin layer has a fine pattern on the surface opposite to the elastic layer,
The fine pattern includes a plurality of regions having different heights,
The following (1) or (2) is provided;
(1) The Young's modulus of the elastic layer is 1 GPa or less. (2) The Young's modulus of the elastic layer is smaller than the Young's modulus of the substrate that supports the elastic layer. The ratio of the Young's modulus of the substrate to the Young's modulus of the elastic layer is 10 or more.
The structure according to claim 1. The fine pattern includes a plurality of convex portions and a plurality of concave portions,
The plurality of regions having different heights of the fine pattern include a high step portion and a low step portion having a lower height than the high step portion,
The distance between the virtual line connecting the upper surfaces of the plurality of convex portions of the high step portion and the virtual line connecting the upper surfaces of the plurality of convex portions of the low step portion is 500 μm or less.
The structure according to claim 1 or 2. The thickness of the thinnest portion of the resin layer in the region where the fine pattern is provided is 100 nm or less.
The structure according to any one of claims 1 to 2. The value of the ratio of the thickness of the elastic layer to the thickness of the resin layer is 10 or more,
The structure according to any one of claims 1 to 4. The elastic layer has a uniform thickness;
The structure according to any one of claims 1 to 5.

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