WO2011145716A1

WO2011145716A1 - Method for formation of concavo-convex pattern using resin film, and device for use in the method

Info

Publication number: WO2011145716A1
Application number: PCT/JP2011/061621
Authority: WO
Inventors: 隆弘鈴木; 秀洋赤間; 亜紀子権藤; 千尋打出
Original assignee: 株式会社ブリヂストン
Priority date: 2010-05-20
Filing date: 2011-05-20
Publication date: 2011-11-24
Also published as: JP2011240643A

Abstract

Disclosed is a method for forming a fine concavo-convex pattern on a substrate using a resin film, which can form the concavo-convex pattern accurately at a position at which the concavo-convex pattern is to be formed on the substrate even when the fluctuation in shrinking ratios of the resin film, the change in temperature in an alignment step or the like occurs. Specifically disclosed are: a method for forming a concavo-convex pattern by transferring a fine concavo-convex pattern formed on the surface of a resin film (11) onto a photocurable resin layer (16) that is formed on a substrate (15) and comprises a photocurable resin composition to thereby form a fine inverted concavo-convex pattern on the photocurable resin layer (16), wherein the method is characterized by involving a step of aligning the resin film (11) with the substrate (15) for the purpose of placing the concavo-convex pattern formed on the resin film (11) at a position at which the inverted concavo-convex pattern to be formed on the photocurable resin layer (16) on the substrate (15), wherein the aligning step involves a substep of using an extension means that can extend the resin film (11) in the plane direction; and a device for use in the method.

Description

Method for forming concavo-convex pattern using resin film and apparatus used for the method

The present invention relates to a method for forming a concavo-convex pattern by an imprint method that can be used for manufacturing information display panels such as electronic paper, electronic devices, optical components, and recording media, and in particular, a resin film such as a resin intermediate stamper. The present invention relates to a method of forming a fine concavo-convex pattern using

In recent years, a method for forming a desired circuit pattern or the like on a silicon substrate or the like by nanoimprint technology (also referred to as an imprint method) is being established. Nanoimprint technology is a method for forming inverted copies of nano- or micrometer-order concavo-convex patterns of molds (also referred to as molds and templates), and has a finer structure than conventional press processing technologies. This is a microfabrication technology to achieve this. This technique itself has no limit on resolution, and the resolution is determined by the accuracy of mold production. Therefore, as long as the mold can be manufactured, it is possible to form an ultrafine structure with an apparatus that is easier and much cheaper than conventional photolithography.

The nanoimprint technology is roughly divided into two types depending on the material to be transferred. One is a thermal imprint technique in which a material to be transferred is heated, plastically deformed by a mold, and then cooled to form a pattern. The other is to apply liquid light (generally ultraviolet (UV)) curable resin on the substrate at room temperature, then press the light-transmitting mold against the resin and irradiate the resin to cure the resin on the substrate. This is a UV imprint technique for forming a pattern. In particular, UV imprint technology enables pattern formation at room temperature, so that distortion due to differences in the coefficient of linear expansion between the substrate and mold due to heat is less likely to occur, and high-precision pattern formation is possible. As an alternative to lithography technology for semiconductors, etc. It attracts attention.

However, although nanoimprint technology can perform pattern molding at low cost, the resin is likely to adhere to the mold that is the mother stamper, and if the resin adheres, it is extremely difficult to repair the mold. Further, since the mold does not usually have plasticity, the substrate or the mold may be physically damaged when the substrate to be patterned is not a plastic material. Since the mold (mother stamper) is very expensive, if the mold is replaced due to adhesion of a resin or physical damage, the cost is greatly increased, and it cannot be said that the entire manufacturing is inexpensive.

As a method for solving the problem, Patent Document 1 discloses an imprint method by two steps. That is, in the first step, heat is applied to a template (mother stamper) having a surface patterned with fine irregularities on the order of micrometers or nanometers, such as polycarbonate (PC), polymethyl methacrylate (PMMA), and cycloolefin. The surface of the polymer foil (resin film) made of a plastic resin is placed so as to face and come into contact with each other, and an imprint process is formed on the surface of the polymer foil in which the pattern of the template surface is reversed. Then, in the second step, the obtained polymer stamper (intermediate stamper) is arranged so that the inversion pattern of the template faces and comes into contact with the photosensitive material (ultraviolet curable resin or the like) on the substrate. By being exposed, a second reverse pattern (the same pattern as the template) is formed on the substrate.

In this method, since the product is molded using the intermediate stamper, it is possible to prevent the template (mother stamper) from being seriously damaged.

On the other hand, in the nanoimprint technology, usually, the mold and the substrate to which the uneven pattern of the mold is transferred are not the same material. Therefore, the mold and the substrate have different coefficients of thermal expansion. Therefore, even when the mold and the substrate are subjected to the same environmental change due to heating or cooling, the ratio of dimensional change is different.

This also poses a problem when a fine uneven pattern is formed on a substrate made of glass, silicon or the like by an imprint method using a resin intermediate stamper as shown in Patent Document 1. This is because the thermal expansion coefficients of glass, silicon, and resin film are greatly different.

For example, when forming a concavo-convex pattern according to an electrode pattern or the like formed on a substrate, first, a resin-made intermediate stamper is obtained using a mother stamper manufactured according to the pattern of the substrate. Next, in order to transfer the concavo-convex pattern onto the substrate, the resin intermediate stamper and the substrate are accurately aligned. In this case, in general, two or more alignment patterns (also referred to as alignment marks) are formed on the intermediate stamper and the substrate, and these marks are used by two or more alignment cameras (also referred to as alignment cameras). Observe and align the marks. However, there are two points due to the variation in the shrinkage ratio of the intermediate stamper in the transfer process from the mother stamper to the intermediate stamper and the difference in dimensional change between the substrate and the intermediate stamper due to a slight temperature change in the process of aligning the intermediate stamper and the substrate. There arises a problem that the above alignment marks are not aligned and accurate alignment cannot be performed.

JP 2007-165812 A

Accordingly, an object of the present invention is a method of forming a fine uneven pattern on a substrate using a resin film such as a resin intermediate stamper, and the resin film shrinkage rate variation or the temperature in the alignment process. An object of the present invention is to provide a method for forming a concavo-convex pattern that can accurately form a concavo-convex pattern at a position where a concavo-convex pattern is to be formed on a substrate even if there is a change.

Also, an object of the present invention is to provide an apparatus used for the method for forming the concavo-convex pattern.

Adjustment of the size of the fine concavo-convex pattern formed in the resin film in the planar direction is usually performed in a process of forming the concavo-convex pattern. For example, in the process of transferring from a metal stamper to a resin film that is an intermediate stamper, the concavo-convex pattern of the resin film is adjusted by preparing the concavo-convex pattern of the metal stamper in consideration of the shrinkage rate of the resin film. . For this reason, there has been a limit to addressing the problem that alignment cannot be performed due to a difference in dimensional change between the substrate and the resin film due to slight temperature changes in the alignment process as described above. As a result of studying a method for adjusting the size of the concavo-convex pattern to the planar direction at the stage of aligning the resin film and the substrate, the present inventors have reached the present invention.

That is, the object is to transfer the concavo-convex pattern of a resin film having a fine concavo-convex pattern formed on the surface to a photocurable resin layer made of a photocurable resin composition formed on a substrate, and A method for forming a fine concavo-convex pattern on a curable resin layer, wherein the fine concavo-convex pattern of the resin film is disposed at a position where the reverse concavo-convex pattern of a photocurable resin layer on the substrate is to be formed. Therefore, an alignment step for aligning the resin film and the substrate, and a pressing step for placing and pressing a fine uneven pattern of the resin film on the photocurable resin layer on the substrate And a light irradiation step for curing or semi-curing the photocurable resin layer by irradiating light to the photocurable resin layer, and in the alignment step, the resin film is stretched in a plane direction. It is achieved by the method of forming the concavo-convex pattern, which comprises the step of using a decompression means for.

This makes it possible to align the resin film and the substrate more accurately than in the past.

The preferable aspect of the formation method of the uneven | corrugated pattern of this invention is as follows.
(1) The stretching means is a means for stretching the resin film in the biaxial direction of the vertical direction and the horizontal direction. Thereby, it becomes possible to extend in any direction in the plane direction, and the resin film and the substrate can be more accurately aligned, and the uneven pattern can be formed at a more accurate position.

(2) The stretching means is a means for stretching within an elastic deformation range of the resin film. Thereby, the resin film and the substrate can be aligned so that the formation of the inverted concavo-convex pattern due to the breakage of the resin film or the large deformation of the concavo-convex pattern does not occur.

(3) At least two clamp portions that are capable of detachably fixing the edge portion of the resin film and that are independently movable and stationary in the planar direction of the resin film. The edge of the resin film is fixed to the clamp part of the film holding part having the above, and the resin film is extended by moving the clamp part. The resin film can be easily stretched in the plane direction by fixing the edge of the resin film with the clamp and moving the clamp.

(4) The positions of the edges of the resin film facing each other in the vertical direction and / or the horizontal direction are fixed to the clamp part. Thereby, the resin film can be efficiently stretched in the plane direction without causing distortion in the resin film.

(5) The resin film has a rectangular shape, and the edge of each side of the resin film is fixed to at least one clamp part. When the resin film has a rectangular shape, the edges of each side of the resin film are fixed with at least one clamp part, and the clamp part is moved to efficiently stretch the resin film in the plane direction. can do.

(6) The edge of each side of the rectangular resin film is fixed to two or more clamp parts. Thereby, by finely adjusting the extension in the planar direction by dividing and extending each side of the resin film, the resin film and the substrate can be aligned with higher accuracy. The number of clamps for fixing the edge of each side of the resin film is more preferably 3 or more, and particularly preferably 3 to 10.

(7) The alignment step is a step of aligning a plurality of alignment marks provided on the resin film and the substrate. Thereby, the resin film and the substrate can be aligned efficiently and accurately.

(8) At least one alignment mark for the resin film and the substrate is provided for each of two clamp portions for fixing the edge of the resin film. Since the shrinkage rate and expansion rate of the resinous film may vary depending on the resinous film part, when each side of the resinous film is divided and stretched, an alignment mark corresponding to the stretched range is provided, By aligning, the resin film and the substrate can be aligned with higher accuracy.

(9) The resin film is a resin intermediate stamper.

(10) The positioning step includes means for moving and adjusting the position of the resin film and / or the substrate in a planar direction, and means for adjusting the angle of the resin film and / or the substrate. In addition to the means for extending the resin film in the plane direction, the resin film and the substrate can be more efficiently and accurately obtained by performing the alignment process using means for adjusting the position and angle of the resin film and the substrate. Can be aligned.

The above object is also a concavo-convex pattern forming apparatus used in the method for forming a concavo-convex pattern according to the present invention, wherein a fine concavo-convex pattern of the resin film is formed on a reverse concavo-convex pattern of a photocurable resin layer on the substrate. An alignment means for aligning the resin film and the substrate in order to arrange the pattern at a position where the pattern is to be formed, and a fine uneven pattern of the resin film on the photocurable resin layer on the substrate Mounting, pressing means for pressing, light irradiation to the photocurable resin layer, light irradiation means for curing or semi-curing the photocurable resin layer, and the alignment means, This is achieved by an apparatus for forming a concavo-convex pattern characterized by including a stretching means for stretching a resin film in a planar direction.

Since this apparatus includes a resin film including a stretching means for stretching the resin film in the planar direction in the method for forming a concavo-convex pattern according to the present invention, the apparatus includes an alignment means for aligning the resin film with the light on the substrate. The reverse concavo-convex pattern of the curable resin layer can be accurately adjusted to the position where it should be formed. In this state, the resin film can be placed on and pressed on the photocurable resin layer on the substrate, and the photocurable resin layer can be cured or semi-cured by irradiation with light such as ultraviolet rays. Therefore, this apparatus is a concavo-convex pattern forming apparatus capable of accurately forming the concavo-convex pattern of the resin film at the position where the inverted concavo-convex pattern is to be formed on the substrate.

According to the method for forming a concavo-convex pattern of the present invention, there is a variation in shrinkage of the resin film when forming a fine concavo-convex pattern on the resin film, and there is a temperature change in the alignment process between the resin film and the substrate. Even in such a case, the resin film can be adjusted to the size of the resin film by stretching the resin film in the plane direction. Can be formed. Therefore, the uneven | corrugated pattern formation apparatus of this invention is an apparatus which can form an uneven | corrugated pattern exactly in the position which should form the uneven | corrugated pattern on a board | substrate.

FIG. 1 is a schematic cross-sectional view showing a typical example of a method for forming a fine uneven pattern according to the present invention. FIG. 2 is a schematic view for explaining a preferred example of the alignment step in the method for forming a fine uneven pattern of the present invention, FIG. 2 (a) is a schematic plan view, and FIG. Is a schematic cross-sectional view. FIG. 3 is a schematic view for explaining a preferred example of the alignment step when the fine uneven pattern forming method of the present invention is performed by a roll-to-roll method. FIG. 4 is a schematic cross-sectional view showing a typical example of a fine concavo-convex pattern forming apparatus of the present invention.

Embodiments of the method for forming an uneven pattern according to the present invention will be described with reference to the drawings. *

The present invention can be carried out in the same manner as a method for forming a fine uneven pattern by a general imprint method, except for an alignment process including a means for stretching a resin film.

FIG. 1 is a schematic cross-sectional view showing a typical example in the method for forming a fine uneven pattern of the present invention.

First, the photocurable resin layer 16 of the board | substrate 15 in which the uneven | corrugated pattern of the resin-made film 11 in which the fine uneven | corrugated pattern was formed in the surface, and the photocurable resin layer 16 which consists of a photocurable resin composition in the surface was formed. The substrate 15 and the resin film 11 are arranged so that they face each other (FIG. 1A). Examples of the resin film 11 include an intermediate stamper made of a thermoplastic resin having a concavo-convex pattern transferred from a mold such as a metal stamper having a fine concavo-convex pattern by a thermal imprint method. Examples of the substrate 15 include a substrate for an information display panel electronic component and a substrate on which a predetermined wiring pattern is formed. For example, a glass substrate, a silicon wafer, a metal substrate such as copper, chromium, iron, and aluminum can be used.

The edge part of the resin film 11 is detachably fixed by the clamp part 21. The clamp part 21 is installed in the film holding part 22, and can be moved and stopped independently in the plane direction (longitudinal direction and / or lateral direction) of the resin film 11. The substrate 15 is detachably fixed to the substrate holding unit 23.

Subsequently, the resin film 11 and the substrate 15 are aligned so that the concavo-convex pattern of the resin film 11 accurately matches the position where the inverted concavo-convex pattern of the photocurable resin layer 16 on the surface of the substrate 15 is to be formed. (Alignment process). As will be described later, an alignment mark for alignment is usually provided on the resin film 11 and the substrate 15, and is observed with an alignment camera for alignment, and is aligned automatically or manually so that the alignment marks overlap. (Not shown in FIG. 1). In the present invention, the aligning step includes stretching means for stretching the resin film 11 in the planar direction. In FIG. 1, the resin film 11 is extended in the plane direction by moving the clamp part 21 in the plane direction (FIG. 1A). The stretching means may be any means as long as the resin film can be accurately controlled and stretched.

In the conventional alignment process, the film holding unit 22 and / or the substrate holding unit 23 are moved in the plane direction (longitudinal direction and / or lateral direction) or the angle is adjusted. However, in this method, the unevenness pattern of the resinous film 11 and the inverted unevenness pattern of the surface of the substrate 15 due to the variation in the shrinkage rate when forming the unevenness pattern of the resinous film 11 and the difference in the expansion rate due to the temperature change in the alignment process. There is a dimensional difference from the position where the film is to be formed (also referred to as “scale level deviation” in the present invention), and accurate alignment may not be possible. In the present invention, as described above, the resin film 11 is stretched in the plane direction, thereby correcting the scale level deviation of the concavo-convex pattern, thereby enabling accurate alignment.

The stretching of the resin film 11 in the planar direction may be in either the longitudinal direction or the lateral direction, but it is preferable that the resin film 11 can be stretched in the biaxial direction of the longitudinal direction and the lateral direction so that alignment can be performed more accurately. Further, the proportion of the resin film 11 that can be extended in the planar direction varies depending on the material of the resin film 11. In the elastic deformation range of the resinous film 11, the resinous film 11 is not damaged, or the shape of the concave / convex pattern is deformed, so that the formation of the inverted concave / convex pattern on the photocurable resin layer 16 does not occur. It is preferable to stretch. The stretching distance is usually 1% or less, preferably 0.5% or less, based on the length of the resin film 11.

Further, the concave / convex pattern formed on the resin film 11 is preferably smaller than a pattern (for example, an electrode pattern) in a range where the inverted concave / convex pattern of the photocurable resin layer 16 of the substrate 15 is to be formed. This is because it is possible to stretch the resin film 11 in the planar direction, but it is difficult to compress it in the planar direction.

In the present invention, it is preferable to use a means for moving the film holding unit 22 and / or the substrate holding unit 23 itself in the plane direction or adjusting the angle in order to align more accurately. .

Next, in a state in which the resin film 11 and the substrate 15 are accurately aligned (a state in which the resin film 11 is stretched), the uneven pattern of the resin film 11 is pressed against the photocurable resin layer 16 (FIG. 1 ( b) (Pressing step)). The photocurable resin layer 16 is heated as necessary so that pressing is possible. If pressing is possible at room temperature, heating is not necessary. Since the temperature change of the substrate 15, the resin film 11 and the substrate 15 affects the formation position and scale of the concavo-convex pattern, the clamp portion 21 is moved in the plane direction so that the alignment marks overlap even when pressed, and is made of resin. The film 11 may be stretched.

In this state, the photocurable resin layer 16 is cured by irradiating light (such as ultraviolet rays) (light irradiation process). The curing may be semi-curing to such an extent that the shape of the concavo-convex pattern can be maintained without being completely cured.

In addition, before pressing the uneven | corrugated pattern of the resin film 11 against the photocurable resin layer 16, the resin film 11 is prevented so that air may not enter into the uneven pattern of the photocurable resin layer 16 and the resin film 11. And / or after the alignment with the substrate 15, a vacuum process may be performed to evacuate the surroundings. Thereby, it is possible to prevent a transfer defect of the uneven pattern. The vacuum process can be performed, for example, by setting a range including the resin film 11 and the substrate 15 as a sealed space and degassing the space with a vacuum pump.

Thereafter, the resin film 11 is removed from the photocurable resin layer 16c on which the concavo-convex pattern is formed and cured (FIG. 1 (c)). In addition, when the photocurable resin layer 16 is semi-cured, after removing the resin film 11, it is fully cured by further irradiating light.

In this way, the reverse concavo-convex pattern of the concavo-convex pattern of the resin film 11 on which the fine concavo-convex pattern is formed is accurately formed at the position where the reverse concavo-convex pattern of the photocurable transfer layer 16 on the surface of the substrate 15 is to be formed. can do.

Next, the alignment step (particularly the step using the stretching means) in the method for forming a concavo-convex pattern of the present invention will be described in detail. FIG. 2 is a schematic view for explaining a preferred example of the alignment step in the method for forming a fine concavo-convex pattern according to the present invention, FIG. 2 (a) is a schematic plan view, and FIG. It is a schematic sectional drawing.

As shown in FIGS. 2A and 2B, the edge of each side of the rectangular resin film 31 on which a fine concavo-convex pattern is formed is fixed to a plurality of clamp portions 41. The clamp part 41 can fix the edge part of a film so that attachment or detachment is possible by tightening with a screw or the like. And the clamp part 41 is installed in the film holding | maintenance part 42 so that it can be moved and made to rest freely in the plane direction of the resin film 31, respectively. By moving these clamp portions 41, the resin film 31 can be easily stretched in the planar direction. The film holding part 42 is also preferably movable and stationary in the planar direction (longitudinal direction and / or lateral direction) of the resinous film 31, and the angle can be adjusted.

In FIG. 2A, the resin film 31 is fixed at the edge of each side by five clamp portions 41. However, if the resin film 31 is fixed by at least two clamp portions 41. good. However, it is preferable to fix the edge of each side of the resin film 31 with at least one clamp part 41 so that the film can be extended in the vertical direction and the horizontal direction.

In FIG. 2A, the resin film 41 has a rectangular shape, but the shape of the resin film is not particularly limited. For example, it may be circular, elliptical, or polygonal. Even in that case, it is only necessary to be fixed by at least two clamp portions 41.

Moreover, as shown to Fig.2 (a), the position which mutually opposes the vertical direction and / or horizontal direction of the edge part of the resin-made films 31 is two clamp parts 41 (for example, in Fig.2 (a)). It is preferable that they are fixed to two groups surrounded by a broken line. By moving the two clamp parts 41 in the opposite directions (or stopping one and moving the other), the resin film 31 is efficiently stretched in the plane direction without causing distortion. can do. It is sufficient that at least one pair of such two opposing clamp portions 41 is used. In order to extend the resin film 31 with higher accuracy, as shown in FIG. It is preferable that a plurality of sets are used in the lateral direction.

Also, the radix of the clamp part 41 is not particularly limited. As shown in FIGS. 2 (a) and 2 (b), when the resin film is rectangular, in order to efficiently extend the resin film in the plane direction, at least one clamp on each side edge is provided. It is preferable to fix with a part. For example, a plurality of clamp portions 41 may be used to fix each side of the resin film 31 in multiple divisions (FIG. 2A), and a clamp having a width that can fix the edges of each side at once. You may fix the edge of each edge | side of the resin-made films 31 using the part 41 one by one. Since there may be variations in the partial shrinkage rate and expansion rate of the resin film 31, as shown in FIG. 2 (a), two or more clamp portions 41 are used at the edge of each side. It is preferable to divide and fix the sides. By dividing and extending each side of the resin film, fine adjustment of the extension in the plane direction can be performed, and the resin film and the substrate can be aligned with higher accuracy. The clamp part 41 for fixing the edge part of each side of the resin film 31 is more preferably 3 or more, and particularly preferably 3 to 10 groups.

Further, the width of the fixing portion for fixing the edge portion of the resin film 31 in one clamp portion 41 is not particularly limited. The width of the fixing part of one clamp part is usually 5 to 200 mm, preferably 10 to 100 mm.

On the other hand, the substrate 35 on which the photocurable resin layer 36 is formed is detachably fixed to the substrate holding portion 43. It is preferable that the substrate holder 43 is also movable and stationary in the plane direction (longitudinal direction and / or lateral direction) of the resin film 31 and the angle can be adjusted.

In the alignment process shown in FIGS. 2A and 2B, the resin film 31 and the substrate 35 have an uneven pattern of the resin film 31, and the photocurable resin layer 36 on the surface of the substrate 35 is inverted. Alignment alignment marks 45a and 45b are respectively provided so as to match the position where the uneven pattern is to be formed. Then, the alignment marks 45a and 45b are observed by the alignment camera 50, and the clamp part 41 is moved in the plane direction automatically or manually so that the two overlap each other, and the resin film 31 is stretched efficiently and accurately. The film 31 and the substrate 35 can be aligned. In the alignment step, the resin film 31 can be more efficiently and accurately used by using a means for moving the film holding portion 42 and / or the substrate holding portion 43 in the plane direction or adjusting the angle as necessary. And the substrate 35 can be aligned.

In the present invention, since the alignment step includes means for extending the resin film 31 in the plane direction as described above, even if the resin film 31 and the substrate 35 are shifted in scale level, a plurality of displacements occur. There is no case where the alignment mark is not aligned and accurate alignment cannot be performed.

At least two alignment marks 45a and 45b are provided on the resin film 31 and the substrate 35, respectively. However, as shown in FIG. 2A, when there are a plurality of clamp portions 41 for fixing the edge of each side of the resinous film 31, and each side of the resinous film 31 is divided and extended, the alignment mark It is preferable that 45a and 45b are provided at least one by one, preferably two by two with respect to two of the clamp part 41 (for example, two shown by being surrounded by a broken line in FIG. 2A). . As described above, since the shrinkage rate and the expansion rate of the resin film may vary depending on the resin film part, the alignment marks 45a and 45b corresponding to the range where each clamp part 41 extends the resin film are provided. By aligning, the resin film 31 and the substrate 35 can be aligned with higher accuracy.

In addition, in the formation method of the uneven | corrugated pattern of this invention, it can also carry out continuously by a roll-to-roll system using the elongate resin film 31. FIG. In this case, the alignment step can be performed by a method as shown in FIG.

FIG. 3 is a schematic view for explaining a preferred example of the alignment step when the fine uneven pattern forming method of the present invention is performed by a roll-to-roll method. As shown in the figure, in the case of the roll-to-roll method, the edges of two sides parallel to the transport direction of the roll 30 of the resin film 31 are fixed by the clamp portion 41, and the plane direction (the roll transport direction and Stretch in the direction that goes straight. And since it cannot fix with the clamp 41 about two sides orthogonal to the conveyance direction of the roll 30, a plane direction (the same direction as a roll conveyance direction) is adjusted by adjusting the tension applied to the resin film 31 in the roll conveyance. To stretch. Thereby, the alignment marks 45a and 45b can be aligned similarly to the description of FIG. 2 described above, and the resin film 31 and the substrate 35 can be aligned with high accuracy.

[Resin film]
In the method for forming a concavo-convex pattern according to the present invention, any resin film on which a fine concavo-convex pattern is formed may be used. When the substrate side is not light transmissive, it is difficult to cure the light curable resin layer. Therefore, a light transmissive resin film is preferable. For example, an intermediate stamper made of a resin transferred from a nanoimprint stamper made of a material such as nickel, titanium, silicon, quartz or the like having a fine concavo-convex pattern onto a thermoplastic resin film by a thermal imprint method, a photo-curing resin was used. Examples include an intermediate stamper formed by the UV imprint method, and a resin film formed with a concavo-convex pattern by an etching method, laser processing, cutting with a tool provided with a fine shape, or the like. A resin-made intermediate stamper is preferable in that the number of processes is small, the formation of a fine concavo-convex pattern is easy, and the formation accuracy of the concavo-convex pattern is high, and an intermediate stamper made of a thermoplastic resin obtained by a thermal imprint method is particularly preferable. Is preferred. Examples of the material for the resin film include polycarbonate, cycloolefin copolymer (COC), polymethyl methacrylate (PMMA), and the like.

[Photocurable resin composition]
In the method for forming a concavo-convex pattern of the present invention, any photocurable resin composition for forming a photocurable resin layer may be used. In particular, a liquid composition that can be used in the nanoimprint process method is preferred. In the case of a liquid composition, the viscosity is preferably 10 to 10,000 cps. The photocurable resin composition is preferably a composition containing a photocurable resin and a photoinitiator.

Examples of the photocurable resin include urethane acrylate, polyester acrylate, epoxy acrylate, epoxy resin, imide-based oligomer, and polyene / thiol-based oligomer.

Urethane acrylates include, for example, diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), trimethylhexamethylene diisocyanate, tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, xylylene diisocyanate, and poly (propylene oxide). Polyols such as diol, poly (propylene oxide) triol, poly (tetramethylene oxide) diol, ethoxylated bisphenol A and 2-hydroxyethyl acrylate 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, glycidol dimethacrylate, pentaerythritol tri Hydroxy acrylates such as acrylate Obtained by reacting, those having an acryloyl group and a urethane bond as a functional group in the molecule.

Examples of the polyester acrylate include polyester acrylate composed of phthalic anhydride, propylene oxide and acrylic acid, polyester acrylate composed of adipic acid, 1,6-hexanediol and acrylic acid, trimellitic acid, diethylene glycol and acrylic acid. And polyester acrylate.

The epoxy acrylate is synthesized by reaction of an epoxy compound such as epichlorohydrin and acrylic acid or methacrylic acid. For example, bisphenol A type epoxy acrylate and bisphenol S synthesized by reaction of bisphenol A, epichlorohydrin and acrylic acid. Bisphenol S-type epoxy acrylate synthesized by reaction of chlorophenol, epichlorohydrin and acrylic acid, bisphenol F-type epoxy acrylate synthesized by reaction of bisphenol F, epichlorohydrin and acrylic acid, synthesis by reaction of phenol novolac, epichlorohydrin and acrylic acid And phenol novolac type epoxy acrylate.

Examples of the epoxy resin include bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, and bisphenol S type epoxy resin; phenol novolac type epoxy resin, cresol novolak type epoxy resin and the like. Examples include novolak-type epoxy resins; aromatic epoxy resins such as trisphenolmethane triglycidyl ether, and hydrogenated products and brominated products thereof.

As the photopolymerization initiator (G), a photoradical polymerization initiator and a photocationic polymerization initiator are preferable. As the photoradical polymerization initiator, for example, 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-) Propyl) ketone, α-hydroxy-α-α'-dimethylacetophenone, methoxyacetophenone, acetophenone derivatives such as 2,2-dimethoxy-2-phenylacetophenone; benzoin ether compounds such as benzoin ethyl ether and benzoin propyl ether; benzyldimethyl Ketal derivatives such as ketals; halogenated ketones, acyl phosphine oxides, acyl phosphonates, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2 -N, N-dimethylamino- 1- (4-morpholinophenyl) -1-butane, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxidebis- (2,6-dimethoxybenzoyl) 2,4,4-trimethylpentylphosphine Oxide, bis (η5-cyclopentadienyl) -bis (pentafluorophenyl) -titanium, bis (η5-cyclopentadienyl) -bis [2,6-difluoro-3- (1H-pyrid-1-yl) phenyl ] -Titanium, anthracene, perylene, coronene, tetracene, benzanthracene, phenothiazine, flavin, acridine, ketocoumarin, thioxanthone derivative, benzophenone, acetophenone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4- Diethylthioxanthone, 2,4 -Diisopropylthioxanthone, isopropylthioxanthone and the like. Examples of the photocationic polymerization initiator include iron-allene complex compounds, aromatic diazonium salts, aromatic iodonium salts, aromatic sulfonium salts, onium salts, pyridinium salts, aluminum complexes / silanol salts, trichloromethyltriazine derivatives, and the like. It is done. Examples of the counter anion of the onium salt or pyridinium salt include SbF ⁶⁻ , PF ⁶⁻ , AsF ⁶⁻ , BF ⁴⁻ , tetrakis (pentafluoro) borate, trifluoromethane sulfonate, methane sulfonate, trifluoro Examples include acetate, acetate, sulfonate, tosylate, and nitrate.

The addition amount of the photopolymerization initiator (G) is generally 0.1 to 15 parts by weight, preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the photocurable resin.

A reactive diluent may be added to the photocurable resin composition. Examples of the reactive diluent include 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl, and the like. Glycol diacrylate, 2- (2-ethoxyethoxy) ethyl acrylate, tetrahydrofurfuryl acrylate, 2-phenoxyethyl acrylate, diethylene glycol diacrylate, tetraethylene glycol diacrylate, 1,3-butylene glycol diacrylate, tripropylene glycol diacrylate , Trimethylolpropane triacrylate, pentaerythritol tetraacrylate, and hydroxypivalic acid neopentyl glycol diacrylate.

The photo-curable resin composition further includes photopolymerization initiation assistants, thermal polymerization inhibitors, fillers, adhesion-imparting agents, thixotropic agents, plasticizers, colorants, etc. that are generally added as necessary. May be added.

In the method of the present invention, when the photocurable resin layer is cured, many light sources that emit light in the ultraviolet to visible region can be used as the light source. , Mercury halogen lamp, carbon arc lamp, incandescent lamp, laser beam and the like. The irradiation time is not generally determined depending on the type of the lamp and the intensity of the light source, but is about 0.1 to several tens of seconds, preferably 0.5 to several seconds. The ultraviolet irradiation amount is preferably 300 mJ / cm ² or more.

In order to accelerate curing, the laminate may be preheated to 30 to 80 ° C. and irradiated with light (such as ultraviolet rays).

[Uneven pattern forming device]
The concavo-convex pattern forming apparatus of the present invention includes a resin film and a substrate in order to dispose the fine concavo-convex pattern of the resin film at a position where the inverted concavo-convex pattern of the photocured resin layer on the substrate should be formed. The positioning means for positioning includes stretching means for stretching the resin film in the planar direction. And after aligning a resin film and a board | substrate, the fine concavo-convex pattern of resin-made films is laid on the photocurable resin layer on a board | substrate, and presses, light (ultraviolet rays etc.) is irradiated. And a light irradiation means for curing or semi-curing the photocurable resin layer. Thereby, the formation method of the uneven | corrugated pattern of this invention can be performed efficiently.

FIG. 4 is a schematic sectional view showing a typical example of the uneven pattern forming apparatus of the present invention. In FIG. 4, a plurality of clamp parts 61 for detachably fixing a resin film 51 on which a fine uneven pattern is formed are installed on a film holding part 62 so as to be movable and stationary in a plane direction. The clamp part 61 can fix the edge of a film so that attachment or detachment is possible by tightening with a screw or the like. It is preferable that the film holding portion 62 is also movable and stationary in the plane direction and can be adjusted in angle. Further, a substrate holding part 63 for detachably fixing the substrate 55 on which the photocurable resin layer 56 is formed is installed so as to face the film holding part 62. It is preferable that the substrate holder 63 is also movable and stationary in the plane direction, and the angle can be adjusted.

Further, a plurality of alignment cameras 70 for observing alignment marks for alignment of the resin film 51 and the substrate 55 are installed above the resin film 51 fixed to the clamp portion 61. It is preferable that one alignment camera 70 is installed for each pair of alignment marks.

Further, after alignment, a UV-type pressing unit 73 provided with a transmission-type pressing unit 71 that presses against the photo-curable resin layer 56 and a UV lamp 72 for irradiating ultraviolet rays is installed in a state where the resin film 51 is stretched. Has been. Although the transmissive pressing part 71 and the UV lamp 72 may be installed separately, the integrated UV pressing part 73 of the integrated UV pressing part 73 can be irradiated with ultraviolet rays while the resin film 51 is pressed against the photocurable resin layer 56. Such an apparatus is preferred.

Even if the UV pressing unit 73 is not pressed by a solid (for example, quartz) like the transmission pressing unit 71, the UV pressing unit 73 applies a pressure by a liquid medium such as a constant compressible gas such as air or oil, and the resin. You may have a device which presses the film-made film 51 against the photocurable resin layer 56.

According to such a concavo-convex pattern forming apparatus, the resin film and the substrate can be accurately aligned, and the concavo-convex pattern can be accurately formed at the position where the concavo-convex pattern is to be formed on the substrate.

Further, the uneven pattern forming apparatus of the present invention is an apparatus used for a method of continuously forming an uneven pattern by a roll-to-roll method using a long resin film as shown in FIG. May be. In this case, the apparatus which has said positioning means and a press means is installed on the conveyance line of the roll of resin films. As described above, the extending method in the planar direction of the alignment means is performed by fixing the clamp unit in the direction orthogonal to the roll conveyance direction, and is applied to the resin film in the roll conveyance in the same direction as the roll conveyance direction. This is done by adjusting the tension.

The present invention is not limited to the configuration of the above-described embodiment, and various modifications can be made within the scope of the gist of the invention.

According to the method for forming a concavo-convex pattern according to the present invention, partitions of information display panels such as high-quality electronic displays and electronic paper, electronic devices (lithography, transistors), optical components (microlens arrays, waveguides, optical filters, Photonic crystals), bio-related materials (DNA chips, microreactors), recording media (patterned media, DVD) and the like can be advantageously obtained.

11, 31, 51: Resin film 15, 35, 55:

Substrate

16, 36, 56: Photocurable resin layer 21, 41, 61: Clamp part 22, 42, 62: Film holding part 23, 43, 63: Substrate holder 30: roll
45a, 45b: Alignment mark 50, 70: Alignment camera 71: UV lamp 72: Transmission type pressing part 73: UV pressing part

Claims

The concavo-convex pattern of the resin film having a fine concavo-convex pattern formed on the surface is transferred to a photocurable resin layer made of a photocurable resin composition formed on a substrate, and the photocurable resin layer is finely patterned. A method for forming a reversal uneven pattern,
Position for aligning the resin film and the substrate in order to dispose the fine concavo-convex pattern of the resin film at a position where the inverted concavo-convex pattern of the photocurable resin layer on the substrate is to be formed. Alignment process,
A pressing step for placing and pressing the fine concavo-convex pattern of the resin film on the photocurable resin layer on the substrate;
A light irradiation step for irradiating the photocurable resin layer with light to cure or semi-harden the photocurable resin layer, and in the alignment step, stretching the resin film in a planar direction A method of forming a concavo-convex pattern comprising a step of using means.
The method for forming a concavo-convex pattern according to claim 1, wherein the stretching means is a means for stretching the resin film in a biaxial direction of a vertical direction and a horizontal direction.
The method for forming a concavo-convex pattern according to claim 1 or 2, wherein the stretching means is a means for stretching within an elastic deformation range of the resin film.
A film having at least two clamp portions that are capable of detachably fixing the edge portion of the resin film and that are independently movable and stationary in the planar direction of the resin film. The means according to any one of claims 1 to 3, which is means for extending the resin film by fixing an edge of the resin film to the clamp part of the holding part and moving the clamp part. A method for forming an uneven pattern.
The method for forming a concavo-convex pattern according to claim 4, wherein positions of the edges of the resin film facing each other in the vertical direction and / or the horizontal direction are fixed to the clamp part.
The resin film is rectangular,
The method for forming a concavo-convex pattern according to claim 4 or 5, wherein an edge of each side of the resin film is fixed to at least one clamp part.
The method for forming a concavo-convex pattern according to claim 6, wherein an edge of each side of the rectangular resin film is fixed to two or more clamp parts.
The uneven pattern formation according to any one of claims 1 to 7, wherein the alignment step is a step of aligning a plurality of alignment marks provided on the resin film and the substrate. Method.
The method for forming a concavo-convex pattern according to claim 8, wherein at least one alignment mark of the resin film and the substrate is provided for each of two clamp portions for fixing an edge of the resin film.
The method for forming a concavo-convex pattern according to any one of claims 1 to 9, wherein the resin film is a resin intermediate stamper.
An apparatus for forming a concavo-convex pattern used in the method for forming a concavo-convex pattern according to any one of claims 1 to 10,
Position for aligning the resin film and the substrate in order to dispose the fine concavo-convex pattern of the resin film at a position where the inverted concavo-convex pattern of the photocurable resin layer on the substrate is to be formed. Matching means,
A pressing means for placing and pressing the fine concavo-convex pattern of the resin film on the photocurable resin layer on the substrate;
A light irradiation means for irradiating the photocurable resin layer with light to cure or semi-harden the photocurable resin layer, and the alignment means extends the resin film in a planar direction. An apparatus for forming a concavo-convex pattern comprising means.