JP2019206180A - Resin mold, method of producing replica mold, and method of producing optical device - Google Patents

Abstract

To provide a resin mold in which uneven patterns are connected so that joint portions of unit molds cannot be visually observed.SOLUTION: A resin mold 100 comprises: a transcription uneven pattern region 1A; a transcription uneven pattern region 1B; uneven patterns; and transcription boundary portion 20, in which in one side transcription uneven pattern region 1A and another side transcription uneven pattern region 1B, heights of planes 10A and 10B formed by convex portions of the transcription uneven pattern regions are the same, and the uneven patterns are located between one side transcription uneven pattern region 1A and another side transcription uneven pattern region 1B being adjacent thereto, and the transcription boundary portion 20 has a height of the plane formed by the convex portion lower than the height of the plane formed by the convex portion of the transcription uneven pattern region. A width 21 of the transcription boundary portion 20 is within 2 μm, and a lowest convex portion 22 in which a height of the convex portion in the transcription boundary portion 20 is lowest is located closer to one of the transcription uneven pattern regions than a center 23 in a width direction.SELECTED DRAWING: Figure 2

Description

  Embodiments of the present disclosure relate to a resin mold, a replica mold manufacturing method, and an optical element manufacturing method.

In recent years, a fine processing technique for transferring a fine structure on a mold to a workpiece such as resin or metal has been developed and attracts attention.
In this imprint technology, an original mold (mold) on which a pattern to be transferred is formed is pressed against a material to be transferred such as a liquid resin on a substrate and cured while applying light, or a thermoplastic material to be transferred. In this method, the pattern of the mold is transferred to the material to be transferred by being pressed against the material. Fine concavo-convex patterns exist from nano-scales of 10 nm level to about 100 μm, and are used in various fields such as semiconductor materials, electronic / optical devices, recording media, biotechnology, environment, micromachines, etc. .

  On the other hand, in recent years, for example, display devices such as liquid crystal display devices and light-emitting display devices have been desired to have a large area and high performance. Various optical elements having a fine structure in which a fine concavo-convex pattern is transferred to the surface thereof are used in the display device. Therefore, a technique for forming a large-area fine uneven pattern is desired.

  However, a mold having a nano-order fine concavo-convex pattern on the surface is very expensive because it takes a long time to form the pattern, and in many cases, only a small-area original can be produced due to restrictions on the manufacturing method and apparatus.

Thus, a large-area microstructure having a plurality of individual microstructures (basic microstructures) arranged side by side on a substrate is disclosed.
For example, in Patent Document 1, in a fine structure in which a plurality of basic fine structures having a fine uneven pattern formed on the surface are arranged side by side on a substrate, the uneven patterns of the basic fine structures that are adjacent to each other are arranged. The ends of the basic microstructures are shaped so that the distances between the ends satisfy a specific range so that the basic microstructures can be arranged with each other. Is disclosed. It is described that the fine structure in Patent Document 1 is a fine structure in which the basic fine structures are placed as close as possible and the basic fine structures are positioned with high accuracy. However, a large-area fine structure in which a plurality of fine structures (basic fine structures) are arranged side by side is used as a mold to emboss a resist film formed on the surface of a transfer target. Then, resist enters the space existing between adjacent basic microstructures, and protrusions that differ greatly in height from the inverted pattern of the microstructure are formed. It becomes impossible to peel off the mold, and various problems occur.

Therefore, a method has been proposed that enables imprinting with a large area by repeating imprinting using a unit mold with a small area while shifting the position of the mold so that the processing regions do not overlap (step and repeat). Law).
However, according to the method of repeatedly performing while shifting the position of the unit mold so that the conventional processing region does not overlap, the portion where the pattern is not formed between the transferred patterns occurs in a size that can be visually observed, There existed a subject that the case where the joint part in which the said pattern was not formed does not satisfy | fill desired performance occurred.

  In Patent Document 2, when a large area mold is formed from one resin mold, a mold on one side is provided for the purpose of providing a resin mold in which the joined portion does not separate or impair the appearance. There is a connecting portion between the component and the mold component on the other side, the connecting portion is formed of an inclined surface, the height of the connecting portion is in the range of 100 nm to 100 μm, and the inclined surface is Resin that is inclined with respect to the plane including the mold component on the one side, and the plane including the mold component on the one side and the plane including the mold component on the other side are parallel to each other A mold is disclosed.

  In patent document 3, in order to eliminate the joint part in which the pattern is not formed, as a manufacturing method of a fine structure pattern aggregate that can join a plurality of basic fine structure patterns with high accuracy, A first step of dropping a photocurable resin into a second step, a second step of pressing and spreading a fine structure mold on the photocurable resin, and irradiating the photocurable resin with light to expose and harden it, A basic microstructure pattern forming unit step comprising a third step of forming a circular basic microstructure pattern and a release movement fourth step of releasing the microstructure from the basic microstructure pattern and raising it Is repeated a plurality of times to produce a fine structure pattern aggregate, which is a new method adjacent to the already formed basic fine structure pattern. When forming the basic fine structure pattern, the outer peripheral portion of the new basic fine structure pattern is partially overlapped with the outer peripheral portion of the already formed basic fine structure pattern. A featured method for producing a microstructured pattern assembly is described.

JP 2010-80670 A Japanese Patent No. 6100651 JP2013-161997A

  However, what is actually manufactured by the technique of Patent Document 2 includes a mold component on the one side having a width of the joint portion of the resin mold of about 30 μm as shown in FIG. 7 of Patent Document 2. The level difference between the flat surface and the flat surface including the mold component on the other side becomes as large as about 10 μm, and there is a problem that the joint portion can be visually observed.

Further, according to the technique of Patent Document 3, as described in FIG. 5 of Patent Document 3 (FIG. 10 of the present application), the uneven pattern 102 transferred next to the uneven pattern portion 101 which has already been transferred. Therefore, a level difference of about the height of the convex portion of the concave-convex pattern or more is formed at the joint between 101 and 102.
Applying a resin mold with a step of about the height of the convex part at or above the joint to imprint patterning on an etching resist film, as will be described in detail later, also applies to the resist of the material to be transferred. Similarly, an uneven pattern having a step is transferred. Then, when etching the residual film of the concave portion of the resist, if the residual film of the concave portion on the elevated portion is tried to be etched, the concave / convex pattern itself that has been lowered and relatively lowered in height is etched. The problem of being lost. In FIG. 5 of Patent Document 3 (FIG. 10 of the present application), it is schematically shown that one convex part of the pattern rides on. However, when the technique of Patent Document 3 is used, it is actually connected. It is difficult to adjust the width to be ridden by eyes to 10 μm or less. In the technology of Patent Document 3, the width of the stepped difference is increased, or the height of the resin layer height between the concavo-convex pattern already transferred and the next transferred concavo-convex pattern can be increased. The eye part becomes a size that can be visually observed, and the uneven pattern that is not etched becomes a size that can be visually observed, which adversely affects various performances exhibited by the uneven pattern.
Therefore, there has been a demand for a large-area resin mold in which the concavo-convex pattern is connected so that the joint portion of the small-area unit mold cannot be visually observed.

  The present disclosure has been made in view of the above circumstances, and a resin mold in which a concavo-convex pattern is connected so that a joint portion of unit molds cannot be visually observed, a method for manufacturing a replica mold using the resin mold, And it aims at providing the manufacturing method of the optical element using the said resin mold or replica mold.

In one embodiment of the present disclosure, in a resin mold in which a concave and convex pattern of a unit mold is transferred to a surface a plurality of times,
One transfer concavo-convex pattern region and the other transfer concavo-convex pattern region adjacent to the transfer concavo-convex pattern region have the same plane height formed by the convex portions of the transfer concavo-convex pattern region,
There is a concavo-convex pattern between the one transfer concavo-convex pattern region and the other adjacent transfer concavo-convex pattern region, and the height of the surface formed by the convex portion is the plane formed by the convex portion of the transfer concavo-convex pattern region. Having a transfer boundary lower than the height of
The width of the transfer boundary is within 2 μm,
The lowest convex part having the lowest convex part in the transfer boundary part is located in the width direction of the transfer boundary part and is located closer to one of the transfer uneven pattern areas than the center in the width direction. I will provide a.

  In one embodiment of the present disclosure, the surface formed by the convex portion in the transfer boundary portion is a gently inclined surface with the lowest convex portion having the lowest height in the width direction of the transfer boundary portion as a boundary. There is provided a resin mold having a surface having a larger inclination with respect to a plane formed by a convex portion of the transfer concavo-convex pattern region than the gently inclined surface.

  In an embodiment of the present disclosure, a difference in height between the lowest convex portion and a plane formed by the convex portion of the transfer concavo-convex pattern region is 90% or less of an average height of the convex portions of the transfer concavo-convex pattern region. A resin mold is provided.

  In one embodiment of the present disclosure, a difference in height from a plane formed by the convex portions of the transfer concave / convex pattern region with respect to the entire number of convex portions included in the width direction of the transfer boundary portion may be Provided is a resin mold in which convex portions that are 30% or less of the average height of the convex portions are 50% by number or more.

  In one embodiment of the present disclosure, a resin mold is provided in which the static contact angle of pure water in the transfer concavo-convex pattern region of the resin mold is 105 ° or more by the θ / 2 method.

  In one embodiment of the present disclosure, a resin mold having a reversal pattern of the resin mold of one embodiment of the present disclosure is provided.

  In one embodiment of the present disclosure, a method for manufacturing a replica mold is provided, which includes a step of transferring a concavo-convex pattern of the resin mold according to one embodiment of the present disclosure.

  In one embodiment of the present disclosure, a concavo-convex pattern is formed using the resin mold of the one embodiment of the present disclosure or the replica mold manufactured by the method of manufacturing the resin mold of the one embodiment of the present disclosure. The manufacturing method of an optical element which has the process to perform is provided.

  The embodiment of the present disclosure uses a resin mold in which a concavo-convex pattern is connected so that a joint part of unit molds cannot be visually observed, a method for manufacturing a replica mold using the resin mold, and the resin mold. It is possible to provide a method for manufacturing an optical element.

FIG. 1 is a schematic plan view schematically illustrating an example of a resin mold according to the present disclosure. 2A and 2B are diagrams schematically illustrating an example of a resin mold according to the present disclosure, in which FIG. 2A is a schematic cross-sectional view taken along the line AA ′ in FIG. 1, and FIG. It is a partially expanded sectional view. FIG. 3 is a partially enlarged cross-sectional view of FIG. 4A to 4E are schematic cross-sectional views illustrating a process of manufacturing the resin mold of the present disclosure in (A) to (E). FIG. 5: is typical sectional drawing explaining the process of manufacturing the resin mold of this indication in (F)-(J). FIG. 6 is a photograph of a part of the resin mold of the present disclosure including a transfer boundary portion taken with a scanning electron microscope. FIG. 7 is a photograph of a part including a transfer boundary portion of a cross section of a resin mold of a comparative example manufactured by the method described in the prior art (Patent Document 3) taken with a scanning electron microscope. FIG. 8 is a photograph obtained by photographing a part including a transfer boundary portion of a cross section of the resin mold according to the second embodiment of the present disclosure with a scanning electron microscope. FIG. 9 is a schematic perspective view for schematically explaining an example of the partial heating apparatus. FIG. 10 is a diagram showing a state in which the basic fine structure patterns obtained by the embodiment of the prior art (Patent Document 3) are overlaid.

Hereinafter, a resin mold, a replica mold manufacturing method, and an optical element manufacturing method according to the present disclosure will be described in detail.
In addition, as used in this specification, the shape and geometric conditions and the degree thereof are specified, for example, terms such as “parallel”, “orthogonal”, “identical”, length and angle values, etc. are strictly Without being bound by meaning, it should be interpreted including the extent to which similar functions can be expected.
Moreover, in this specification, (meth) acryl represents each of acrylic and methacryl.
Further, in this specification, “light” means actinic rays or radiation, and examples thereof include an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams, and the like. It is included.

I. Resin mold (1) First embodiment The resin mold according to the first embodiment of the present disclosure is a resin mold in which the concave / convex pattern of the unit mold is transferred to the surface a plurality of times.
One transfer concavo-convex pattern region and the other transfer concavo-convex pattern region adjacent to the transfer concavo-convex pattern region have the same plane height formed by the convex portions of the transfer concavo-convex pattern region,
There is a concavo-convex pattern between the one transfer concavo-convex pattern region and the other adjacent transfer concavo-convex pattern region, and the height of the surface formed by the convex portion is the plane formed by the convex portion of the transfer concavo-convex pattern region. Having a transfer boundary lower than the height of
The width of the transfer boundary is within 2 μm,
The lowest convex part having the lowest convex part in the transfer boundary part is located in the width direction of the transfer boundary part and is located closer to one of the transfer uneven pattern areas than the center in the width direction. It is.

Hereinafter, an embodiment of the present disclosure will be described with reference to the drawings. In the drawings attached to the present specification, for convenience of illustration and easy understanding, the scale and the vertical / horizontal dimension ratio may be appropriately changed and exaggerated from those of the actual ones.
FIG. 1 is a schematic plan view schematically illustrating an example of a resin mold according to the present disclosure. 2A is a schematic cross-sectional view in the direction of the line AA ′ of FIG. 1, and FIG. 2B is a partially enlarged cross-sectional view of FIG. 2A. Further, FIG. 3 is a partially enlarged cross-sectional view of FIG.

The resin mold 100 of the present disclosure is a resin mold having a plurality of transfer concavo-convex pattern regions (1A, 1B, 1C, 1D) formed on the surface by transferring the concavo-convex pattern of the unit mold a plurality of times. As shown in FIG. 2A, the resin mold 100 is a resin having a concavo-convex pattern (1A, 1B,...) On the surface of a support 50 that may be peeled off from the resin layer 40 if necessary. Layer 40 is provided.
In FIG. 1, four transfer patterns 1A, 1B, 1C, and 1D are shown as a plurality of transfer concavo-convex pattern areas for convenience, but the number of transfer pattern areas formed by transferring a plurality of times is appropriately adjusted. What is necessary is not limited.

  In the resin mold 100 of the present disclosure, one transfer uneven pattern region (1A) and the other transfer uneven pattern region (1B) adjacent to the transfer uneven pattern region (1A) are convex portions of the transfer uneven pattern region. The planes (10A and 10B) formed by have the same height. Here, the surface or plane formed by the convex portions refers to a virtual surface or a virtual plane connecting the tops of the respective convex portions. When the plane formed by the convex portion of one transfer uneven pattern region (1A) is the reference plane 11, the plane formed by the convex portion of the other transfer uneven pattern region (1B) has no difference in height from the reference plane 11. , Located on the same plane. In the present disclosure, when a virtual plane connecting the tops of the convex portions of the transfer concavo-convex pattern region is used as a virtual plane, or the height of the plane formed by the convex portions of the transfer concavo-convex pattern region is the same, or low The range in which there is no difference includes an error range within 5% of the average height of the convex portions of the transferred concave / convex pattern region.

The resin mold 100 of the present disclosure has a concavo-convex pattern between the one transfer concavo-convex pattern region (1A) and the other transfer concavo-convex pattern region (1B) adjacent to the surface of the surface formed by the convex portion. The transfer boundary portion 20 is lower than the height of the plane (10A, 10B) formed by the convex portions of the transfer uneven pattern region. The height of the surface formed by the convex portion of the transfer boundary portion 20 is lower than the reference plane 11 which is the plane formed by the convex portion of the one transfer concave / convex pattern region (1A).
The width 21 of the transfer boundary 20 is within 2 μm. Here, the width of the transfer boundary 20 is the shortest of the point 24 at the end of the one transfer uneven pattern region (1A) and the end of the other adjacent transfer uneven pattern region (1B). The distance from the point 25 in the distance is said.
The width 21 of the transfer boundary 20 is more preferably within 1.5 μm, and even more preferably within 1 μm.
The width 21 of the transfer boundary 20 is preferably small, but is preferably 0.5 μm or more from the effect of a resin adjustment region by the transfer boundary described later.

In the prior art, there is originally no difference in height between one transfer uneven pattern region and the other adjacent transfer uneven pattern region, or no difference in height between one transfer uneven pattern region and the other adjacent transfer uneven pattern region. Therefore, the joint portion of the unit mold can be visually observed, and the defects of the concave / convex pattern can be visually observed, which adversely affects various performances exhibited by the concave / convex pattern.
As described above, in the resin mold 100 of the present disclosure, one transfer concavo-convex pattern region (1A) and the other adjacent transfer concavo-convex pattern region (1B) are planes (10A) formed by the convex portions of the transfer concavo-convex pattern region. 10B), and the width 21 of the transfer boundary portion 20 having a difference in height is within 2 μm, the joint portion of the unit mold cannot be visually observed. Therefore, when a concavo-convex pattern is formed using the resin mold of the present disclosure, defects in the concavo-convex pattern become invisible and the adverse effects on various performances exhibited by the concavo-convex pattern can be suppressed.

The lowest convex part 22 having the lowest convex part in the transfer boundary part 20 has one transfer concave / convex pattern region (in the width 21 direction of the transfer boundary part 20) than the center 23 in the width direction. 1A) Located near the side. That is, in the direction of the width 21 of the transfer boundary portion 20, the number of convex portions from the position of the lowest convex portion 22 to the height of the reference plane 11 is small on one transfer concave / convex pattern region (1A) side, while the other There are more on the transfer unevenness pattern region (1B) side.
In this case, in the width 21 direction of the transfer boundary portion 20, the surface formed by the convex portions on the transfer concave / convex pattern region (1 </ b> B) side that returns to the height of the reference plane 11 with more convex portions from the position of the lowest convex portion 22. Is a surface formed by a convex portion on the transfer concave / convex pattern area (1A) side, which has a relatively gentle inclination with respect to the reference plane 11 and has fewer convex portions from the position of the lowest convex portion 22 and returns to the height of the reference plane 11. Is relatively steep with respect to the reference plane 11.
Thus, in the resin mold 100 of the present disclosure, the surface formed by the convex portion in the transfer boundary portion 20 is bordered by the lowest convex portion where the height of the convex portion is the lowest in the width direction of the transfer boundary portion. Since it has a surface having a relatively gentle inclination with respect to the reference plane 11 (hereinafter referred to as a gently inclined surface) and a surface having a relatively steep inclination (hereinafter referred to as a steeply inclined surface), an uneven pattern is formed on the transfer target. It is possible to further suppress the occurrence of defects in the concavo-convex pattern when transferring.
That is, when transferring the concavo-convex pattern using the resin mold, the transfer boundary portion 20 becomes a resin amount adjustment region of the transferred body, and the excess resin of the transferred body is blocked on the steeply inclined surface side. It is possible to stop, and pattern transfer can be carried out well even for the concavo-convex part in the transfer boundary part 20, and on the other hand, bubbles can be removed, and the occurrence of defects in the concavo-convex pattern can be further suppressed. .

  In the resin mold 100 of the present disclosure, the surface formed by the convex portion in the transfer boundary portion is a gently inclined surface (in the width direction of the transfer boundary portion, with the lowest convex portion 22 having the lowest height of the convex portion as a boundary. 30) and a surface (31) having a larger inclination with respect to the plane formed by the convex portions of the transfer concavo-convex pattern region than the gently inclined surface (30) (see FIG. 3). This embodiment is a preferred embodiment because the occurrence of defects in the concavo-convex pattern can be further suppressed.

A plane (reference plane 11) formed by the convex portion of the transfer concavo-convex pattern region of the gently inclined surface (30) with the lowest convex portion 22 having the lowest convex height as a boundary in the width 21 direction of the transfer boundary portion. Is preferably more than 0 °, less than 10 °, preferably more than 0 °, less than 5 °, more preferably more than 0 °, less than 3 °, more than 0 °, It is still more preferable that it is below °.
On the other hand, in the direction of the width 21 of the transfer boundary portion, the inclination with respect to the plane formed by the convex portion of the transfer concavo-convex pattern region is less than the gentle slope (30) bounded by the lowest convex portion 22 having the lowest convex portion height. The inclination angle of the large surface (31) with respect to the plane (reference plane 11) formed by the convex portions of the transfer concavo-convex pattern region is preferably 10 ° to 80 °, and preferably 15 ° to 80 °. More preferably, it is 20 ° or more and 80 ° or less.

  In the resin mold 100 of the present disclosure, the lowest convex portion 22 is in a range of 0.5 μm or less from the end portion of one of the transfer concavo-convex pattern regions in the width 21 direction of the transfer boundary portion 20. It is preferable that it is in the range of 0.4 μm or less.

In the resin mold 100 according to the present disclosure, the difference in height (32) between the lowest convex portion 22 and the plane (reference plane 11) formed by the convex portion of the transfer concave / convex pattern region is the convex portion of the transfer concave / convex pattern region. It is preferably 90% or less of the average height (10h) from the point that generation of defects in the uneven pattern can be further suppressed, more preferably 80% or less, and 70% or less. Is even more preferable (see FIG. 3).
Here, the average height (10h) of the convex portions is measured by measuring the height of the convex portions of ten convex portions that are in contact with the plane (reference plane 11) formed by the convex portions of the transfer concavo-convex pattern region. Further, an average value of 10 heights is calculated and obtained. In addition, the height of a convex part measures the height difference between the vertex of the convex part of an adjacent unevenness | corrugation, and the bottom point of a recessed part.

  In the resin mold 100 of the present disclosure, the height difference (32) between the lowest convex portion 22 and the plane (reference plane 11) formed by the convex portion of the transfer concave / convex pattern region appropriately varies depending on the size of the concave / convex pattern. However, for example, when the average height of the protrusions is about 100 nm, the average height can be less than 100 nm, 90 nm or less, 80 nm or less, or 70 nm or less.

  Further, in the resin mold 100 of the present disclosure, the height difference between the total number of convex portions included in the width 21 direction of the transfer boundary portion 20 and the plane formed by the convex portions of the transfer concavo-convex pattern region is as described above. It is preferable from the point that it is possible to further suppress the occurrence of defects in the concavo-convex pattern, that the convex part which is 30% or less of the average height (10h) of the convex part of the transfer concavo-convex pattern region is 50% by number or more Further, it is more preferably 60% by number or more (see FIG. 3).

  Further, in the resin mold 100 of the present disclosure, the height difference between the total number of convex portions included in the width 21 direction of the transfer boundary portion 20 and the plane formed by the convex portions of the transfer concavo-convex pattern region is as described above. It is preferable that the number of protrusions that are 25% or less of the average height (10h) of the protrusions in the transfer uneven pattern region is 50% by number or more from the point that the occurrence of defects in the uneven pattern can be further suppressed. Further, it is more preferably 60% by number or more (see FIG. 3).

Further, in the resin mold 100 of the present disclosure, the height difference between the total number of convex portions included in the width 21 direction of the transfer boundary portion 20 and the plane formed by the convex portions of the transfer concavo-convex pattern region is as described above. The number of protrusions exceeding 90% of the average height (10h) of the protrusions in the transferred uneven pattern area is 15% or less, more preferably 10% or less, and even more preferably 0%, more preferably 50% or more and 90%. The following convex portions are preferably 40% by number or less from the viewpoint of further suppressing the occurrence of defects in the uneven pattern, and more preferably 30% by number or less (see FIG. 3).
Note that the number% of each convex portion relative to the total number of convex portions included in the width 21 direction of the transfer boundary portion 20 is to observe a cross section including the transfer boundary portion using a scanning electron microscope, as will be described later. Can be obtained.

Further, in the resin mold 100 of the present disclosure, it is preferable from the viewpoint of releasability that the static contact angle of pure water in the transfer concavo-convex pattern region of the resin mold is 105 ° or more by the θ / 2 method. On the other hand, the upper limit of the static contact angle of the pure water may be 180 ° or less from the viewpoint of mold entry (transferability).
The static contact angle of pure water in the transferred concavo-convex pattern region is determined by dropping 1 μL of pure water onto the sample using an automatic contact angle meter (for example, model number: DM-SA manufactured by Kyowa Interface Science Co., Ltd.) It can be determined by measuring the contact angle after 500 milliseconds.

Further, in the resin mold 100 of the present disclosure, the Martens hardness of the surface of the transfer concavo-convex pattern region of the resin mold is 5 N / mm ² or more and 300 N / mm ² or less, and further 15 N / mm ² or more and 200 N / mm ^2. The following is preferable from the viewpoints of releasability, chipping of the shape, and entering the mold (transferability).
The Martens hardness of the surface of the transfer concavo-convex pattern region of the resin mold is maximum when the convex portion of the transfer concavo-convex pattern region is nano-indented (for example, model number: Picodenter HM-500, manufactured by Fisher Sinstrument Co., Ltd.). It can obtain | require by measuring on the conditions of load 0.2mN.

Examples of the resin that forms the resin layer 40 of the resin mold of the present disclosure include at least one selected from the group consisting of a thermoplastic resin, a thermosetting resin, and a photocurable resin. Is, for example, poly (meth) acrylic resin, polyester resin, polyolefin resin, polyurethane resin, polyamide resin, polycarbonate resin, epoxy resin, oxetane resin, phenol resin, cellulose resin, diallyl phthalate Resin, silicone resin, polyarylate resin, polyacetal resin, (meth) acrylic resin, and mixtures thereof.
The resin forming the resin layer 40 has a softening temperature of preferably 40 ° C. or higher and more preferably 50 ° C. or higher from the viewpoint of handling and storage at room temperature. On the other hand, if the softening temperature is too high, there is a risk of damage to the already-transferred part or damage to the support during concavo-convex pattern transfer, so the softening temperature is preferably 150 ° C. or lower, and more preferably 100 ° C. or lower. Is preferred.
The softening temperature of the resin layer can be measured according to JIS K7196: 2012 using a TMA (thermomechanical analysis) apparatus.

Moreover, you may make the material of a resin layer contain additives, such as a polymerization initiator and a mold release agent, suitably.
From the point that the release agent is contained in the resin layer, and when the uneven pattern of the resin mold is transferred, the resin plate is suppressed and the mold can be used continuously for a long period of time. preferable.

Examples of the release agent include conventionally known release agents such as solid waxes such as polyethylene wax, amide wax, and Teflon powder (Teflon is a registered trademark), fluorine-based and phosphate-based surfactants, and silicone. It can be used.
Particularly preferred is a silicone release agent, and the static contact angle of the pure water can be 90 ° or more, further 105 ° or more. Examples of the silicone release agent include polysiloxane, modified silicone oil, polysiloxane containing trimethylsiloxysilicic acid, silicone acrylic resin, and the like.

  The thickness of the resin layer 40 may be appropriately selected and is not particularly limited. Examples thereof include 50 nm to 100 μm, and further include 100 nm to 2 μm.

  Further, the surface of the resin layer 40 may be subjected to a mold release treatment for preventing adhesion with the transfer target. As the mold release treatment on the surface of the resin mold, the resin layer 40 surface may further have a mold release layer. The thickness of the release layer is preferably in the range of 0.5 nm to 10 nm, more preferably 0.5 nm to 5 nm. For the release treatment or the formation of the release layer, the release agent can be appropriately selected and used.

The shape of the uneven pattern on the surface of the resin mold of the present disclosure is not particularly limited. Examples of the shape of the convex portion include a linear shape, a cylindrical shape, a moth eye, a cone, a polygonal pyramid, and a microlens.
As a magnitude | size of the uneven | corrugated pattern on the surface of the resin mold of this indication, a period is 10 nm-5 micrometers, and the height of a convex part (depth of a recessed part) is 10 nm-3 micrometers. A so-called micro uneven pattern can be adopted as the uneven pattern on the surface of the resin mold of the present disclosure. Among them, an uneven pattern having a period of 50 nm to 250 nm and a height of the convex part (depth of the concave part) of 50 nm to 200 nm. A pattern is preferably used.

The size of the unit mold used for the transfer of the resin mold of the present disclosure is usually in the range of 5 mm × 5 mm to 200 mm × 200 mm.
As the size of the region in which the uneven pattern of the resin layer of the resin mold of the present disclosure is formed, the length of one side can be 200 mm or more, further 300 mm or more, and further 1000 mm or more. . The resin mold of the present disclosure is not particularly limited in size, and the area can be expanded to a desired size, and can be connected to an arbitrary shape.

The support 50 that may be peeled off from the resin layer 40 as long as it has a function of supporting the resin layer 40 is not particularly limited and is appropriately selected according to the use of the resin mold. It ’s fine.
Examples of the support material include acetylcellulose resin, polyethylene terephthalate, polyester resin, polyolefin resin, poly (meth) acrylic resin, polyurethane resin, polyamide resin, polyimide resin, polycarbonate resin, and polyresin. Examples of the resin material include (meth) acrylonitrile-based resins and cycloolefin (co) polymers. When the support is peeled off, glass such as soda glass, potassium glass, alkali-free glass, lead glass, ceramics such as lead lanthanum zirconate titanate (PLZT), transparent inorganic materials such as quartz and fluorite, etc. Paper, cloth, wood, ceramics, metal, stone, and a composite material obtained by laminating and mixing two or more of these, and these resin materials, Or a composite material or the like.
In addition, the support may be a sheet or a film, and may be any of those that can be wound, those that do not bend enough to be wound, but that can be bent by applying a load, or those that do not bend completely. Also good. The thickness of the support can be appropriately selected depending on the application and is not particularly limited, but is usually in the range of about 10 μm to 1000 μm.

The resin mold of the present disclosure may be manufactured by any method and is not particularly limited. The resin mold of the present disclosure can be manufactured as follows, for example. 4 and 5 are diagrams schematically illustrating an example of a process for manufacturing the resin mold of the present disclosure.
First, as shown in FIG. 4A, an uneven pattern forming substrate having a resin layer 41 over the entire region where a pattern is to be formed and a unit mold 70 are prepared on a support 51. The resin layer 41 in FIG. 4A is a thermoplastic resin layer and is provided so as to have a uniform height in the entire region where the pattern is formed. By providing the resin layer 41 so as to have a uniform height in the entire pattern formation region, after the pattern formation, one transfer concavo-convex pattern region and the other transfer concavo-convex pattern region adjacent to the transfer concavo-convex pattern region And the height of the plane formed by the convex portions of the transfer concave / convex pattern region is the same. The height of the resin layer is preferably provided so that the variation is less than 5 nm in the range in which the cross section is observed with the SEM (observation width: 5 μm).
As a method of providing the resin layer 41 so as to have a uniform height, the resin layer forming composition is usually prepared in a coating solution state using a diluting solvent, and then the composition is applied to the surface of the support. A resin layer is formed by uniformly applying and heating (appropriately) the diluted solvent from the coating film of the composition after application to remove (dry) the diluted solvent. The coating method may be any method that can form a film with a desired thickness with high accuracy, and may be appropriately selected. For example, gravure coating method, reverse coating method, knife coating method, dip coating method, spray coating method, air knife coating method, spin coating method, roll coating method, printing method, dip pulling method, curtain coating method, die coating method, casting Method, bar coat method, extrusion coat method and the like.
The resin layer 41 is a resin layer having thermoplasticity, and may have a property of being softened by heating at a predetermined shaping temperature. When heating at a predetermined shaping temperature, a part of the unit mold 70 to which the concavo-convex pattern is transferred may be partially heated 60, and a part adjacent to the heated part may be cooled 61.

As the unit mold 70, one having a reverse pattern of a desired concavo-convex pattern on the surface of a large-area resin mold to be manufactured is prepared. The unit mold 70 may be a quartz mold formed by electron beam lithography, a Si mold formed by photolithography, or a die by cutting. Further, a Ni electroforming mold manufactured from these molds or a resin mold may be used. As the resin mold as the unit mold 70, the resin mold of the present invention may be used.
The concave / convex pattern on the surface of the unit mold 70 is constant in the depth of the concave portion (the height of the convex portion) so that the height of the convex portion of the reverse pattern after transferring the concave / convex pattern to the resin layer 41 is constant. Preferably there is.
Further, the indentation hardness at the predetermined shaping temperature by the nanoindenter of the concavo-convex pattern of the unit mold 70 is higher than the indentation hardness at the predetermined shaping temperature by the nanoindenter of the resin layer 41 after the drying. Adjust to be larger.
The indentation hardness by the nanoindenter can be measured by indentation measurement with a load of 100 μN using a Barcovic indenter with a microindentation tester (for example, TI950 Tribodenter (manufactured by HYSITRON)).

Next, as shown in FIG. 4B, the concave / convex pattern of the unit mold 70 is transferred to a part of the resin layer 41 by pressing the unit mold 70 against the softened resin layer 41.
Next, by cooling 61 the heated resin layer 41 in a state where the unit mold 70 is pressure-bonded, the resin layer 41 is cured, and a region having a concavo-convex pattern is formed in a part of the resin layer 41. Thereafter, as shown in FIG. 4C, the unit mold 70 is peeled off. In the case where the heated resin layer 41 is cooled 61 with the unit mold 70 being pressure-bonded, the uneven pattern forming substrate may be allowed to cool at room temperature.
Next, as shown in FIG. 4D, among the region (Y) where the uneven pattern is to be formed next and the region (X) having the uneven pattern, the region where the uneven pattern is to be formed next. The partial heating 60 of the resin layer 41 is performed including (Y) and a part of the adjacent side. By the partial heating 60, as shown in FIG. 4E, a concavo-convex pattern is formed next in a region (Y) where a concavo-convex pattern is to be formed next and a region (X) having the concavo-convex pattern. The resin layer on a part (X ′) on the side adjacent to the planned region (Y) is softened and becomes an uncured or semi-cured state. In the case of the partial heating 60, it is preferable that the portion adjacent to the heated portion is cooled 61 so that the resin layer is not softened.
For example, the partial heating can be performed by using a partial heating device 95 in which a cooling unit 90 is arranged around the heating unit 80 and a portion adjacent to the heating portion can be forcibly cooled as shown in FIG. it can.
For example, a hot plate or the like can be used as the heating unit. As a cooling part, a cooling plate, a Peltier element, etc. can be used, for example.
The boundary part for performing partial heating is controlled by the boundary distance between the heating part and the cooling part.

Next, as shown in FIG. 5F, the concave / convex pattern of the unit mold 70 is transferred to a part of the resin layer 41 by pressing the unit mold 70 against the softened resin layer 41. A part (X ′) of the region (X) having the concavo-convex pattern can overwrite the concavo-convex pattern of the unit mold 70 because the resin layer is softened. By superimposing the unit mold 70 on a part (X ′) of the region (X) and transferring the pattern of the unit mold, there is no occurrence of a portion where no pattern is formed between the transferred patterns. It is possible to connect patterns formed by unit molds having a small area and suppress a step difference in the joints of the unit molds. By introducing a mechanism for forcibly cooling the portion adjacent to the heated portion and controlling the temperature gradient propagating from the heated portion to the non-heated portion to a minimum, the width of the transfer boundary portion is suppressed to within 2 μm. When the unit mold 70 is overlaid on a part (X ′) of the region (X), the influence of the uneven pattern originally formed on the part (X ′) of the region (X) Due to the influence of the portion of the region (X), only the end portion on a part (X ′) of the region (X) of the unit mold 70 is compared with the region (Y) where the uneven pattern is to be formed next. In some cases, the resin layer cannot be sufficiently pressed. Even in such a case, the unit mold is preferably flexible and is preferably made of a resin so that other portions of the unit mold 70 can be sufficiently pressed so that the uneven pattern can be transferred.
As shown in FIG. 5 (F), only the end portion on the part (X ′) of the region (X) of the unit mold 70 is sufficiently larger than the region (Y) where the uneven pattern is to be formed next. When the unit mold 70 cannot be pressed, the unit mold 70 is pressed with a surface slightly inclined in the region (Y) direction where the uneven pattern is to be formed next, and the end on (X ′) is sufficiently pressed. A softened resin layer may enter a portion where it cannot be done.
Next, by cooling 61 the heated resin layer 41 in a state where the unit mold 70 is pressure-bonded, the resin layer 41 is cured, and a region having a concavo-convex pattern is formed in a part of the resin layer 41. Thereafter, as shown in FIG. 5G, the unit mold 70 is peeled off.
In this way, as shown in FIG. 5 (H), a resin mold 101 having a resin layer 45 formed on the surface by transferring the concave / convex pattern of the unit mold 70 a plurality of times on the support 51 is provided. It is formed. Only the end on a part (X ′) of the region (X) of the unit mold 70 cannot be sufficiently pressed against the resin layer as compared with the region (Y) where the uneven pattern is to be formed next. When the pressing of the unit mold 70 is performed on a surface slightly inclined in the area (Y) direction where the uneven pattern is to be formed next, the resin mold 101 has one transfer uneven pattern area and the other transfer uneven pattern. The pattern region has the same height of the plane formed by the convex portions of the transfer concavo-convex pattern region, and has a concavo-convex pattern between the one transfer concavo-convex pattern region and the other adjacent transfer concavo-convex pattern region. The height of the surface formed by the convex portion has a transfer boundary portion higher than the height of the plane formed by the convex portion of the transfer concavo-convex pattern region. In the resin mold 101, one transfer concavo-convex pattern region and the other transfer concavo-convex pattern region have the same plane height formed by the concave portions of the transfer concavo-convex pattern region, and are adjacent to the one transfer concavo-convex pattern region. And a transfer boundary portion having a concavo-convex pattern between the other transfer concavo-convex pattern region and the height of the surface formed by the concave portion being higher than the height of the plane formed by the concave portion of the transfer concavo-convex pattern region. In that case, as shown in FIG. 5 (I), the uneven pattern on the surface of the resin mold 101 is transferred to another resin layer 42, and as shown in FIG. 5 (J), the reverse pattern of the resin mold 101 is transferred. A resin mold 100 having the following is obtained. In this way, the concavo-convex pattern of the unit mold is formed on the surface by being transferred a plurality of times. One transfer concavo-convex pattern region and the other transfer concavo-convex pattern region are planes formed by the convex portions of the transfer concavo-convex pattern region. The height of the surface formed by the convex part is the convex and concave pattern between the one transfer concave and convex pattern area adjacent to the other transfer concave and convex pattern area. The resin mold 100 of the present disclosure including the resin layer 40 having the transfer boundary portion lower than the plane height formed by the convex portions of the pattern region on the support 50 can be obtained.

  When the unit mold 70 is overlaid on a part (X ′) of the region (X), the unit mold 70 is influenced by the influence of the uneven pattern originally formed on a part (X ′) of the region (X). When only the end portion on a part (X ′) of the region (X) is pressed against the resin layer more strongly than on the region (Y) where the uneven pattern is to be formed next, that portion The height of the surface formed by the convex portion is lower than the height of the plane formed by the convex portion of the transfer concavo-convex pattern region (not shown). In this case, the resin layer 41 is cooled 61 in a state in which the unit mold 70 is pressure-bonded, the resin layer 41 is cured, and a region having a concavo-convex pattern is formed in a part of the resin layer 41. By removing the pattern, one transfer uneven pattern region and the other transfer uneven pattern region have the same plane height formed by the convex portions of the transfer uneven pattern region and are adjacent to the one transfer uneven pattern region. A transfer boundary portion having a concavo-convex pattern with the other transfer concavo-convex pattern region, wherein the height of the surface formed by the convex portion is lower than the height of the plane formed by the convex portion of the transfer concavo-convex pattern region. The resin mold 100 of the present disclosure including the resin layer 40 having the support 50 on the support 50 can be obtained.

6 is a photograph of a part including the transfer boundary portion 20 of the cross section of the resin mold of the present disclosure taken with a scanning electron microscope, and corresponds to the cross sectional view of FIG.
In the example of the resin mold of the present disclosure shown in FIG. 6, one of the transfer concavo-convex pattern region (10A) and the other transfer concavo-convex pattern region (10B) are high in the plane formed by the convex portions of the transfer concavo-convex pattern region. Between the one transfer uneven pattern region (10A) and the other transfer uneven pattern region (10B) adjacent to the other transfer uneven pattern region (10B). The transfer boundary portion 20 is lower than the height of the plane formed by the convex portions of the transfer concavo-convex pattern region, and the width 21 of the transfer boundary portion is 1.7 μm, which is within 2 μm. The lowest convex portion 22 having the lowest height is located closer to one of the transfer concavo-convex pattern regions than the center 23 in the width direction in the width direction of the transfer boundary portion.
The resin mold of the present disclosure shown in FIG. 6 is such that the joint portion of the unit mold cannot be visually observed. When the concavo-convex pattern is transferred using the resin mold of the present disclosure shown in FIG. 6, defects in the concavo-convex pattern become invisible so that adverse effects on various performances exhibited by the concavo-convex pattern can be suppressed.

In the example of FIG. 6, the height difference between the lowest convex portion 22 and the plane formed by the convex portion of the transfer concavo-convex pattern region is 64 nm, and 65% of the average height of the convex portion of the transfer concavo-convex pattern region is 99 nm. It is.
In the example of FIG. 6, the difference in height from the plane formed by the convex portions of the transfer concave / convex pattern region with respect to the total number of convex portions included in the width 21 direction of the transfer boundary portion 20 is the transfer concave / convex pattern. The number of convex portions that is 30% or less of the average height (10 h) of the convex portions in the region is 68% by number.
In the example of FIG. 6, the difference in height from the plane formed by the convex portions of the transfer concave / convex pattern region with respect to the total number of convex portions included in the width 21 direction of the transfer boundary portion 20 is the transfer concave / convex pattern. There are no more than 90% of the average height (10h) of the convex portions in the region, and the number of convex portions that are 50% or more and 90% or less is 11% by number.
Further, in the example of FIG. 6, in the width 21 direction of the transfer boundary part, the convex part of the transfer concave / convex pattern area of the gently inclined surface (30) with the lowest convex part 22 having the lowest height as the boundary. The inclination angle with respect to the plane formed by (reference plane 11) is 2.0 °, and the inclination with respect to the plane formed by the convex portions of the transfer concavo-convex pattern region is less than the gentle slope (30) with the lowest convex portion 22 as a boundary. The inclination angle of the large surface (31) with respect to the plane (reference plane 11) formed by the convex portions of the transfer concavo-convex pattern region is 13 °.

On the other hand, FIG. 7 is a photograph of a part including a transfer boundary portion of a cross section of a resin mold of a comparative example manufactured by the method described in Patent Document 3 (Japanese Patent Laid-Open No. 2013-161997) taken with a scanning electron microscope. . When the photocurable resin is dropped and spread by pressing the mold as in Patent Document 3, the unit mold is transferred to the end of the concavo-convex pattern after curing and the concavo-convex pattern is transferred. A level difference of approximately the height of the convex portion or more occurs in the portion, and one transfer concave / convex pattern region and the other transfer concave / convex pattern region are located at the height of the plane formed by the convex portion of the transfer concave / convex pattern region. A height difference of about the height or higher is possible. If the width of the transfer boundary is within 2 μm, the height of one transfer uneven pattern region and the other transfer uneven pattern region are not the same.
In the resin mold of the comparative example of FIG. 7, the joint portion of the unit mold can be visually observed. When the concave / convex pattern is transferred using the resin mold of the comparative example of FIG. 7, defects in the concave / convex pattern also become a size that can be visually observed, which adversely affects various performances exhibited by the concave / convex pattern.

In addition, about the cross section containing the uneven | corrugated pattern surface of a resin mold, and a transfer boundary part (joint part), for example, a scanning electron microscope (SEM, for example, Hitachi High-Technologies Corporation make: scanning electron microscope SU-8000). Can be observed. The cross-sectional photograph including the transfer boundary part (joint part) is the transfer boundary part (joint part) in the resin mold, where the height of the surface formed by the convex part is different from the height of the plane formed by the convex part of the transfer uneven pattern area. ), A cross section cut in a direction perpendicular to the surface of the support and in a direction perpendicular to the extending direction of the linear protrusions, for example, is observed. It is preferable to photograph and observe such that the lateral direction of the cross-sectional photograph is horizontal with respect to the surface of the support and the joint portion of the uneven pattern is substantially in the center.
Observation with a scanning electron microscope (SEM) can be performed, for example, at an acceleration voltage of 1 to 15 kV and an imaging magnification of 25000 times.

(2) Second embodiment The resin mold of the second embodiment of the present disclosure is a resin mold having a reversal pattern of the resin mold of the first embodiment of the present disclosure.
That is, the resin mold of the second embodiment of the present disclosure is a resin mold in which the concave / convex pattern of the unit mold is transferred to the surface a plurality of times.
One transfer concavo-convex pattern region and the other transfer concavo-convex pattern region adjacent to the transfer concavo-convex pattern region have the same plane height formed by the concave portions of the transfer concavo-convex pattern region,
There is a concavo-convex pattern between the one transfer concavo-convex pattern region and the other adjacent transfer concavo-convex pattern region, and the height of the surface formed by the concave portion is the height of the plane formed by the concave portion of the transfer concavo-convex pattern region. Has a higher transfer boundary,
The width of the transfer boundary is within 2 μm,
The highest concave portion in which the height of the concave portion in the transfer boundary portion is the highest is a resin mold located in the width direction of the transfer boundary portion and closer to one of the transfer uneven pattern regions than the center in the width direction. .

  The resin mold of the first embodiment of the present disclosure has a remarkable effect as described above with respect to the prior art. Since the resin mold of the second embodiment of the present disclosure is a resin mold (for example, 101 in FIG. 5H) having a reverse pattern of the resin mold of the first embodiment of the present disclosure. The resin mold of the first embodiment of the present disclosure can be manufactured by transferring the uneven pattern of the resin mold of the second embodiment (for example, FIG. 5 (I), FIG. 5 (J)). . Thus, the resin mold of the second embodiment of the present disclosure is useful as an intermediate plate for creating a replica mold of the resin mold of the first embodiment of the present disclosure.

FIG. 8 is a photograph of a part of the cross section of the resin mold 101 according to the second embodiment of the present disclosure including a transfer boundary 20 ′ taken with a scanning electron microscope.
In the example of the resin mold of the present disclosure shown in FIG. 8, one transfer concavo-convex pattern region (1A ′) and the other transfer concavo-convex pattern region (1B ′) are planes formed by the concave portions of the transfer concavo-convex pattern region. The height of the surface which has the same height and has a concavo-convex pattern between the one transfer concavo-convex pattern region (1A ′) and the other adjacent transfer concavo-convex pattern region (1B ′), and which is formed by the concave portion. Has a transfer boundary 20 ′ higher than the height (10A ′, 10B ′) of the plane formed by the recess of the transfer uneven pattern region, and the width 21 ′ of the transfer boundary is 1.8 μm, The highest concave portion 22 ′ within 2 μm and having the highest concave portion in the transfer boundary portion is closer to any one of the transfer concavo-convex pattern regions than the center 23 ′ in the width direction in the width direction of the transfer boundary portion. Is located. In FIG. 8, a reference plane 11 ′ is a plane formed by a recess of the one transfer uneven pattern region (10A ′).
The resin mold of the present disclosure in FIG. 8 is one in which the joint portion of the unit mold cannot be visually observed. When the concavo-convex pattern is transferred using the resin mold of the present disclosure shown in FIG. 8, defects in the concavo-convex pattern become invisible, and adverse effects on various performances exhibited by the concavo-convex pattern can be suppressed.

In the example of FIG. 8, the height difference between the highest concave portion 22 ′ and the plane (reference plane 11 ′) formed by the concave portion of the transferred concave / convex pattern region is 58 nm, and the average height of the convex portions of the transferred concave / convex pattern region is It is 56% of 104 nm.
Further, in the example of FIG. 8, the difference in height from the plane formed by the concave portions of the transfer concave / convex pattern region with respect to the total number of concave portions included in the width 21 ′ direction of the transfer boundary portion 20 ′ is the transfer concave / convex pattern. The number of concave portions that is 30% or less of the average height (10 h) of the convex portions in the region is 59% by number.
Further, in the example of FIG. 8, the difference in height from the plane formed by the concave portions of the transfer concave / convex pattern region with respect to the total number of concave portions included in the width 21 ′ direction of the transfer boundary portion 20 ′ is the transfer concave / convex pattern. The number of concave portions exceeding 90% of the average height (10 h) of the convex portions in the region is 0% by number, and the number of convex portions being 50% to 90% is 12% by number.
Further, in the example of FIG. 8, in the width 21 ′ direction of the transfer boundary portion, the transfer of the gently inclined surface (30 ′) among the surfaces formed by the recesses with the highest recess 22 ′ having the highest height as the boundary. The inclination angle with respect to the plane (reference plane 11 ′) formed by the concave portion of the concave / convex pattern region is 2.2 °, and the concave portion of the transferred concave / convex pattern region is more than the gentle slope (30 ′) with the highest concave portion 22 ′ as a boundary. The inclination angle of the surface (31 ′) having a large inclination with respect to the plane formed by the angle with respect to the plane (reference plane 11 ′) formed by the convex portions of the transfer concavo-convex pattern region is 12.1 °.

As the size of the resin mold of the present disclosure, the length of one side can be 200 mm or more, further 300 mm or more, and further 1000 mm or more. The size is not particularly limited, and a desired size. Since the area can be expanded further and it is possible to connect to an arbitrary shape, the resin mold of the present disclosure can be applied to various applications.
The resin mold of the present disclosure is required to form a concavo-convex pattern, the field of semiconductor materials, the field of electronic and optical devices such as optical elements as described later, the field of display, the field of recording media such as magnetic recording media and optical disks, It can be applied to various fields such as μ-TAS such as DNA chip, protein chip and separation chip, regenerative medical member such as cell culture sheet, chemical bio field such as μ reactor and micromixer, and MEMS.

(3) Method of manufacturing replica mold The method of manufacturing the replica mold of the present disclosure is a process of transferring the uneven pattern of the resin mold of the first embodiment of the present disclosure or the resin mold of the second embodiment. It is characterized by having.
As a method for transferring the concavo-convex pattern in the replica mold manufacturing method, a conventionally known method can be appropriately selected and used.
In the replica mold manufacturing method, as the resin layer for transferring the uneven pattern of the resin mold of the first embodiment of the present disclosure or the resin mold of the second embodiment, a photocurable resin layer or a heat A curable resin layer is preferable from the viewpoint of the durability of the resin mold. As in the resin layer of the resin mold of the first embodiment of the present disclosure, it is preferable to appropriately select and use an additive such as a release agent for the resin layer to which the uneven pattern is transferred. It is preferable to perform surface treatment such as.

II. Manufacturing method of optical element The manufacturing method of the optical element of the present disclosure is a process of forming a concavo-convex pattern using the resin mold of the present disclosure or the replica mold manufactured by the method of manufacturing the resin mold of the present disclosure. Have
Since the optical element manufactured using the method for manufacturing an optical element of the present disclosure forms a concavo-convex pattern using the resin mold of the present disclosure or a replica mold thereof, the joint portion is not visible. Since the concavo-convex pattern is connected and there is no portion where the concavo-convex pattern is not present in the joint portion, and the patterns are connected to each other, it is possible to manufacture an optical element in which defects due to the transfer boundary portion are suppressed. it can.

  Examples of the optical element include any element selected from the group consisting of a wire grid polarizer, an antireflection plate, a light diffusion plate, a light collecting plate, a contact prevention plate, an optical diffraction grating, a light guide plate, and a hologram.

  Hereinafter, a method for manufacturing a wire grid polarizer using the resin mold of the present disclosure as a mold will be described as an embodiment of a method for manufacturing an optical element of the present disclosure. However, the method is not limited to this method. Absent.

First, the resin mold of the present disclosure is prepared.
On the other hand, a laminate in which an aluminum layer and a silica layer are laminated on a glass substrate is prepared.
A photosensitive composition (resist) is applied on the silica layer of the laminate in which an aluminum layer and a silica layer are laminated on the glass substrate to form a resist layer.
Next, a resin mold is pressed against the resist layer, the resin mold is exposed while pressing the resin mold, the resist layer is cured, and the uneven pattern of the resin mold is transferred to the resist layer.
Next, the resin mold is peeled off to obtain a laminate having a resist uneven pattern formed on the surface.
Next, after removing the remaining film of the concave portion of the resist concave / convex pattern by etching, the silica layer of the concave portion is further etched until the aluminum layer is exposed in the concave portion.
Here, according to the manufacturing method of the present disclosure, since the concavo-convex pattern is connected so that the joint portion cannot be seen in the resin mold, the joint portion cannot be seen in the resist of the transfer material as well. The uneven pattern is transferred. Therefore, when etching the remaining film of the concave portion of the resist concave / convex pattern, even if there is a problem that the pattern of the convex portion of the lower portion disappears when it is aligned with the concave portion of the high portion, the width is not visible and the defect is A suppressed optical element can be manufactured.
As the etching, dry etching is used. As the dry etching, reactive ion etching (RIE) mainly involving ions, plasma etching (PE) mainly involving radicals, or the like can be used. As the etchant gas used in the dry etching, an etchant gas appropriately selected according to the material of the film to be dry etched is used.
Next, by using the silica layer of the convex portion as a mask, the aluminum layer exposed in the concave portion is etched to form a concave / convex pattern having the convex portion of the aluminum layer on the glass substrate. The convex silica layer used as a mask is appropriately removed by peeling treatment or etching.
The method for manufacturing the wire grid polarizer may include other conventionally known processes.

  In addition, this invention is not limited to the said embodiment. The above-described embodiment is an exemplification, and the present invention has any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits the same effects. Are included in the technical scope.

(Example 1: Production of resin mold)
(1) Preparation of a unit mold 150 mm × 150 mm, a synthetic quartz having a thickness of 6.35 mm, a pattern area of 100 mm × 100 mm, a linear recess having a width of 50 nm and a depth of 100 nm, and a pitch of 100 nm (linear A mold formed by dry etching with a protrusion width of 50 nm was prepared as an original plate.
A photocurable resin is dropped on the uneven surface of the original synthetic quartz mold, and an easy-adhesive PET (polyethylene terephthalate) film having a thickness of 100 μm is overlaid thereon. Cured.
By peeling the PET film from the synthetic quartz mold, a resin unit mold in which the uneven pattern of the uneven surface of the original mold was reproduced on the surface of the cured photocurable resin was obtained.

(2) Preparation of substrate for forming concavo-convex pattern After the thermoplastic resin (polyacrylic resin, softening temperature 50 ° C.) is bar coated on the easy-adhesion surface of 100 μm thick easy-adhesion PET film, it is 110 ° C. with a constant temperature dryer. By drying for 30 seconds, a coating film having a coating amount of 1.7 g / m ² was formed, and an uneven pattern forming substrate having a resin layer on a PET film substrate was obtained.

(3) Concavity and convexity pattern transfer molding device A partial heating device is installed on the pressure stage of the heat roll transfer device (Navitas RH-150), heating at 70 ° C by the heating unit and cooling at 23 ° C by the cooling unit, A substrate for forming a concavo-convex pattern was placed on the heating portion so that the resin layer was on the upper surface, and partial heating was performed. As a partial heating device, as shown in FIG. 9, a cooling unit 90 (water cooling pipe on an acrylic resin plate) around a heating unit 80 (a hot plate with a heater and a thermocouple temperature sensor on an aluminum flat plate, manufactured in-house). A partial heating device 95 was used, in which a portion adjacent to the heating portion was forcibly cooled. In the partial heating device 95, the front surface makes the heating unit 80 and the cooling unit 90 contact with each other so that there is no step and no gap, and the rear surface keeps the heating unit 80 and the cooling unit 90 apart to increase cooling efficiency. The heating unit 80 and the cooling unit 90 were installed.
As shown in FIG. 4 (B), the unit mold is placed on the resin layer of the heated concavo-convex pattern forming substrate so that the concavo-convex pattern surface is in contact with the resin layer, and the pressure roll of the transfer device is used. The resin layer and the unit mold were integrated by pressing against a hot plate and applying heat and pressure. (Pressure roll linear pressure: 10 kg / 150 mm width, roll speed: 5 mm / sec)
In the state where the unit mold is pressure-bonded, the substrate for forming an uneven pattern is removed from the partial heating apparatus and allowed to cool at room temperature (23 ° C.), thereby cooling the resin layer to room temperature (23 ° C.), and FIG. As shown in (C), the unit mold was peeled to obtain a resin layer in which a region (X) having an uneven pattern of the unit mold was formed on the surface.

(4) Next-surface concavo-convex pattern transfer As shown in FIG. 4D, among the region (Y) where the concavo-convex pattern is to be formed next and the region (X) having the concavo-convex pattern, the concavo-convex pattern is next. The resin layer was partially heated including the region (Y) to be formed and a part on the adjacent side.
Forming device The partial heating device is installed on the pressure stage of a heat roll transfer device (Navitas RH-150), and heating is performed at 70 ° C. and cooling at 23 ° C., thereby performing partial heating. As shown in (E), among the region (Y) where the uneven pattern is to be formed next and the region (X) having the uneven pattern, it is adjacent to the region (Y) where the uneven pattern is to be formed next. A part (X ′) of the resin layer on the side to be softened was softened.
Next, as shown in FIG. 5F, the region (X) is formed on the resin layer in which a part (X ′) on the side adjacent to the region (Y) where the uneven pattern is to be formed next is softened. The unit mold was placed over the softened part (X ′), pressed against a hot plate with a pressure roll of a transfer device, and heated and pressed to integrate the resin layer and the unit mold.
In a state where the unit mold is pressure-bonded, the concave / convex pattern forming substrate is removed from the partial heating device and allowed to cool at room temperature (23 ° C.), thereby curing the resin layer and forming the concave / convex pattern on a part of the resin layer. Then, as shown in FIG. 5G, the unit mold was peeled off.
Thereafter, in the same manner as the above-described next surface unevenness pattern transfer step, by repeating the partial heating of the resin layer, the unit mold pressure, the cooling of the resin layer, and the unit mold peeling step sequentially, the unevenness of the unit mold on the resin layer is performed. A resin mold with multiple patterns was produced.
As shown in FIG. 8, the resin mold of Example 1 obtained in this way has one transfer concavo-convex pattern area and the other transfer concavo-convex pattern area adjacent to the transfer concavo-convex pattern area. The height of the plane formed by the concave portions of the concave / convex pattern region is the same, and there is a concave / convex pattern between the one transfer concave / convex pattern region and the other adjacent transfer concave / convex pattern region, and the surface of the concave portion is formed. The transfer boundary portion has a height that is higher than the height of the plane formed by the recess of the transfer unevenness pattern region, the width of the transfer boundary portion is within 2 μm, and the height of the recess in the transfer boundary portion is the largest. The highest highest concave portion was located closer to one of the transfer concavo-convex pattern regions than the center in the width direction in the width direction of the transfer boundary portion. In the resin mold of Example 1, the joint portion of the unit mold was not visible.

(Example 2: Production of resin mold)
In the same manner as in Example 1, as shown in FIG. 8, one transfer uneven pattern region and the other transfer uneven pattern region adjacent to the transfer uneven pattern region are planes formed by recesses in the transfer uneven pattern region. The height of the surface formed by the concave portion is the height of the surface having the concave / convex pattern between the one transfer concave / convex pattern region adjacent to the other transfer concave / convex pattern region. A transfer boundary portion having a height higher than the height of a plane formed by the concave portion of the region, the width of the transfer boundary portion is within 2 μm, and the highest concave portion having the highest height in the transfer boundary portion is the transfer boundary portion In the width direction of the part, a resin mold was manufactured that was positioned closer to one of the transfer concavo-convex pattern regions than the center in the width direction.
Using the resin mold, the uneven pattern on the surface of the resin mold was transferred to another resin layer as shown in FIG. Specifically, a photocurable resin is dropped on the uneven surface of the resin mold, and an easy-adhesive PET film with a thickness of 100 μm is superimposed thereon, and then irradiated with ultraviolet rays to cure the photocurable resin. I let you. By peeling the PET film from the resin mold, a resin mold was obtained in which the reverse pattern of the uneven pattern on the surface of the resin mold was reproduced on the surface of the cured photocurable resin.
As shown in FIG. 6, the resin mold of Example 2 obtained in this way is formed by transferring the concavo-convex pattern of the unit mold a plurality of times on the surface, and one transfer concavo-convex pattern region, The other transfer concavo-convex pattern region has the same height of the plane formed by the convex portions of the transfer concavo-convex pattern region, and concavo-convex between the one transfer concavo-convex pattern region and the other transfer concavo-convex pattern region adjacent A transfer boundary portion having a pattern, wherein the height of the surface formed by the convex portion is lower than the height of the plane formed by the convex portion of the transfer concavo-convex pattern region, and the width of the transfer boundary portion is within 2 μm And the lowest convex part having the lowest convex part in the transfer boundary part is located closer to one of the transfer concavo-convex pattern areas than the center in the width direction in the width direction of the transfer boundary part. . In the resin mold of Example 2, the joint portion of the unit mold was not visible.

(Comparative Example 1: Production of comparative resin mold)
Using the same unit mold as that of Example 1, a comparative resin mold of Comparative Example 1 manufactured by the method described in Patent Document 3 (Japanese Patent Application Laid-Open No. 2013-161997) was manufactured. As described in Patent Document 3, in the manufacturing method in which a photocurable resin is dropped and a mold is pressed and spread, the unit mold is transferred to the end of the concavo-convex pattern after curing, and the concavo-convex pattern is transferred. As the resin rides on, a level difference of approximately the height of the convex portion is formed at the joint portion, and one transfer concave / convex pattern region and the other transfer concave / convex pattern region are planes formed by the convex portions of the transfer concave / convex pattern region. A height difference of about the height of the convex portion or more was made. When the width of the transfer boundary portion was within 2 μm, the height of one transfer concavo-convex pattern region and the other transfer concavo-convex pattern region were not the same (FIG. 7). In the resin mold of the comparative example, the joint portion of the unit mold can be visually observed.

[Evaluation of concavo-convex pattern transfer using resin mold]
Using the resin molds of Examples 1 and 2 and the comparative resin mold of Comparative Example 1, the evaluation of transferring the concavo-convex pattern was performed.
Specifically, a photocurable resin is dropped on the uneven surface of the resin mold, and an easy-adhesive PET film with a thickness of 100 μm is superimposed thereon, and then irradiated with ultraviolet rays to cure the photocurable resin. I let you. By detaching the PET film from the resin mold, a reverse pattern of the concavo-convex pattern on the surface of the resin mold was transferred to the surface of the cured photocurable resin.
In the concavo-convex pattern formed by transferring the concavo-convex pattern using the comparative resin mold of Comparative Example 1, an unshaped area was generated at a position corresponding to the boundary portion of the unit mold, and the defect was visually observed. This is thought to be because part of the uneven pattern of the comparative resin mold was not shaped into the photocurable resin due to air bubbles caused by the level difference in the portion corresponding to the boundary of the unit mold in the comparative resin mold. It was.
On the other hand, the concavo-convex pattern formed by transferring the concavo-convex pattern using the resin mold of Example 1 is a reverse pattern without generating an unshaped area in a portion corresponding to the boundary portion of the unit mold. Was formed, and no defects were visually observed. In addition, the concavo-convex pattern formed by transferring the concavo-convex pattern using the resin mold of Example 2 also forms a reversal pattern without generating an unshaped area in a portion corresponding to the boundary portion of the unit mold. The defect was not visually observed. The resin molds of Examples 1 and 2 are thought to be because the steps at the locations corresponding to the boundary portions of the unit mold are suppressed, are not easily affected by bubbles, and are sufficiently shaped into the photocurable resin. It was.

1A, 1B, 1C, 1D Transfer concavo-convex pattern region 1A ′, 1B ′ Transfer concavo-convex pattern region 10A, 10B Plane 10A ′ formed by the convex portion of the transfer concavo-convex pattern region 10B ′ Plane 10h formed by the concave portion of the transfer concavo-convex pattern region Average height 11, 11 ′ reference plane 20, 20 ′ transfer boundary 21, 21 ′ transfer boundary width 22, minimum protrusion 22 ′ in the transfer boundary width direction, maximum recess 23, in the transfer boundary width direction, 23 ′ Center in the width direction of the transfer boundary 24 A point 25 having an end of one transfer uneven pattern area (1A) 25 An end of the other transfer uneven pattern area (1B) adjacent to the transfer uneven pattern area (1A) Of these, the shortest point 30, 30 'is the gentle slope 31 in the width direction of the transfer boundary portion, 31' is the surface 32 having the large inclination in the width direction of the transfer boundary portion, and the lowest convex portion and the convex portion of the transfer concave / convex pattern region. Height difference 40, 41, 42, 45 Resin layer 50, 51 Support body 60 Heating 61 Cooling 70 Unit mold 100, 101 Resin mold X Area Y having uneven pattern Next, area X where an uneven pattern is to be formed 'A part of the region (X) having the uneven pattern on the side adjacent to the region (Y) where the uneven pattern is to be formed next

Claims (8)

In the resin mold formed by transferring the uneven pattern of the unit mold multiple times on the surface,
One transfer concavo-convex pattern region and the other transfer concavo-convex pattern region adjacent to the transfer concavo-convex pattern region have the same plane height formed by the convex portions of the transfer concavo-convex pattern region,
There is a concavo-convex pattern between the one transfer concavo-convex pattern region and the other adjacent transfer concavo-convex pattern region, and the height of the surface formed by the convex portion is the plane formed by the convex portion of the transfer concavo-convex pattern region. Having a transfer boundary lower than the height of
The width of the transfer boundary is within 2 μm,
The lowest convex part having the lowest convex part in the transfer boundary part is located in the width direction of the transfer boundary part and is located closer to one of the transfer uneven pattern areas than the center in the width direction. .   The surface formed by the convex portion in the transfer boundary portion is a gentle inclined surface with the lowest convex portion having the lowest height in the width direction of the transfer boundary portion, and the transfer unevenness than the gentle inclined surface. The resin mold according to claim 1, further comprising a surface having a large inclination with respect to a plane formed by the convex portions of the pattern region.   The height difference between the lowest convex portion and a plane formed by the convex portion of the transfer concavo-convex pattern region is 90% or less of the average height of the convex portions of the transfer concavo-convex pattern region. Resin mold.   The difference in height from the plane formed by the convex portions of the transfer concave / convex pattern region with respect to the total number of convex portions included in the width direction of the transfer boundary portion is 30 as the average height of the convex portions of the transfer concave / convex pattern region. The resin mold according to any one of claims 1 to 3, wherein the number of convex portions that are% or less is 50% by number or more.   The resin mold according to any one of claims 1 to 4, wherein a static contact angle of pure water in the transfer uneven pattern area of the resin mold is 105 ° or more by a θ / 2 method.   The resin mold which has the inversion pattern of the resin mold of any one of the said Claims 1-5.   The manufacturing method of a replica mold which has the process of transferring the uneven | corrugated pattern of the resin mold of any one of the said Claims 1-6.   It has the process of forming an uneven | corrugated pattern using the resin mold of any one of the said Claims 1-6, or the replica mold manufactured with the manufacturing method of the resin mold of the said Claim 7. The manufacturing method of an optical element.