WO2013002048A1 - Gabarit de transcription de microstructure convexo-concave - Google Patents

Gabarit de transcription de microstructure convexo-concave Download PDF

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Publication number
WO2013002048A1
WO2013002048A1 PCT/JP2012/065454 JP2012065454W WO2013002048A1 WO 2013002048 A1 WO2013002048 A1 WO 2013002048A1 JP 2012065454 W JP2012065454 W JP 2012065454W WO 2013002048 A1 WO2013002048 A1 WO 2013002048A1
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WO
WIPO (PCT)
Prior art keywords
transfer
mold
barrier region
convex structure
fine concavo
Prior art date
Application number
PCT/JP2012/065454
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English (en)
Japanese (ja)
Inventor
潤 古池
Original Assignee
旭化成株式会社
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Filing date
Publication date
Application filed by 旭化成株式会社 filed Critical 旭化成株式会社
Priority to CN201280030510.2A priority Critical patent/CN103650106B/zh
Priority to KR1020137027189A priority patent/KR101556836B1/ko
Publication of WO2013002048A1 publication Critical patent/WO2013002048A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/42—Moulds or cores; Details thereof or accessories therefor characterised by the shape of the moulding surface, e.g. ribs or grooves
    • B29C33/424—Moulding surfaces provided with means for marking or patterning
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/44—Moulds or cores; Details thereof or accessories therefor with means for, or specially constructed to facilitate, the removal of articles, e.g. of undercut articles
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/42—Moulds or cores; Details thereof or accessories therefor characterised by the shape of the moulding surface, e.g. ribs or grooves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures

Definitions

  • the present invention relates to a fine concavo-convex structure transfer mold for producing a target object having a fine concavo-convex structure transferred on the surface thereof.
  • the use of members that are precisely processed and controlled in the nano / micrometer size region greatly affects the control function.
  • wavelength control on the scale of several hundreds of nm is mainly required, so that processing accuracy of several nm to several tens of nm is important.
  • the precision processing technology has reproducibility, uniformity, and throughput of processing accuracy.
  • micro-processing techniques include, for example, a method of directly micro-processing using an electron beam and a method of batch drawing on a large area by interference exposure.
  • fine pattern processing by a step & repeat method using a stepper device in semiconductor technology is also known.
  • each method requires a plurality of processing steps and requires a large capital investment. Therefore, it is difficult to say that the technique is good in productivity in terms of throughput and cost.
  • the nanoimprint method is a technique for transferring a fine pattern onto a resin (transfer material) with a processing accuracy of several nanometers to several tens of nanometers by using a finely patterned member as a mold. Since it can be carried out with simple processes, it is attracting attention as a precision replication processing technology that is indispensable in industry.
  • the optical nanoimprint method using a photopolymerizable resin such as a radical polymerizable resin or a cationic polymerizable resin as a transfer material is easy to apply to a roll-to-roll process capable of rapid and repetitive transfer, thereby improving transfer accuracy and throughput. It is attractive in that it combines.
  • the material on the mold side is mainly limited to quartz, sapphire, and a glass mold, and due to its rigid material, there is a problem of lack of versatility in continuous manufacturing techniques and processing processes.
  • a flexible resin mold is required as an alternative to the rigid mold.
  • the mold release treatment uses a mold release agent, the environmental load is large and the productivity is lowered. Therefore, a mold having a high mold release property that does not require a mold release treatment is required.
  • a highly releasable resin mold having flexibility has been reported in view of such demands (see, for example, Patent Document 1).
  • transfer molding is performed from a master mold (original plate) using a fluorine-containing resin as a transfer material, or surface segregation of fluorine components is used. Either transfer molding or transfer molding with silicone having excellent releasability represented by polydimethylsiloxane is required. In addition, a surface treatment method using a release agent for the transfer molded resin mold may be used.
  • the resin mold surface that has been transferred and molded has low free energy, and the affinity for the transfer material is reduced.
  • a technique for transferring a fine concavo-convex structure onto a transfer material using a resin mold as a mold a method of directly applying the transfer material onto the fine concavo-convex structure of the resin mold can be mentioned.
  • the affinity is low, there is a problem that the coating property of the transfer material is lowered.
  • the present invention has been made in view of such points, and an object of the present invention is to provide a mold for transferring a fine concavo-convex structure in which a transfer material has good coatability while having high releasability.
  • the fine concavo-convex structure transfer mold for transferring the fine concavo-convex structure to the object to be processed of the present invention has a substrate and a fine concavo-convex structure transferred to the object to be processed on a part of one main surface of the substrate. At least one of the formed transfer region, the non-transfer region where the fine concavo-convex structure other than the transfer region in one main surface of the substrate is not formed, and the transfer region and the non-transfer region.
  • a barrier region provided so as to be adjacent to the transfer region, the transfer region and the barrier region include a plurality of recesses, and an average roughness factor Rf1 of the transfer region, and the barrier region Rf1> Rf2 is established between the average roughness factor Rf2 and Ar1> Ar2 between the average aperture ratio Ar1 of the transfer region and the average aperture ratio Ar2 of the barrier region. Established It is characterized in.
  • the fine concavo-convex structure transfer mold for transferring the fine concavo-convex structure to the object to be processed of the present invention has a substrate and a fine concavo-convex structure transferred to the object to be processed on a part of one main surface of the substrate. At least one of the formed transfer region, the non-transfer region where the fine concavo-convex structure other than the transfer region in one main surface of the substrate is not formed, and the transfer region and the non-transfer region.
  • a barrier region provided so that the portion is adjacent to the transfer region, the transfer region and the barrier region include a plurality of convex portions, and an average roughness factor Rf1 of the transfer region, and the barrier
  • the relationship Rf1 ⁇ Rf2 is established between the average roughness factor Rf2 of the region
  • the relationship Ar1> Ar2 is established between the average aperture ratio Ar1 of the transfer region and the average aperture ratio Ar2 of the barrier region. Is established It is characterized in.
  • the fine concavo-convex structure transfer mold for transferring the fine concavo-convex structure to the object to be processed of the present invention has a substrate and a fine concavo-convex structure transferred to the object to be processed on a part of one main surface of the substrate. At least one of the formed transfer region, the non-transfer region where the fine concavo-convex structure other than the transfer region in one main surface of the substrate is not formed, and the transfer region and the non-transfer region.
  • a barrier region provided so as to be adjacent to the transfer region, the transfer region and the barrier region include a plurality of recesses, and an average roughness factor Rf1 of the transfer region, and the barrier region Rf1 ⁇ Rf2 is established between the average roughness factor Rf2 and Ar1 ⁇ Ar2 between the average aperture ratio Ar1 of the transfer region and the average aperture ratio Ar2 of the barrier region. Established It is characterized in.
  • the fine concavo-convex structure transfer mold for transferring the fine concavo-convex structure to the object to be processed of the present invention includes a substrate and fine concavo-convex transferred to the object to be processed on a part of one main surface of the substrate.
  • the non-transfer region in which the fine concavo-convex structure other than the transfer region in one main surface of the substrate is not formed, and the transfer region and the non-transfer region
  • a barrier region provided so that a part thereof is adjacent to the transfer region, the transfer region and the barrier region include a plurality of convex portions, and an average roughness factor Rf1 of the transfer region;
  • the relationship Rf1> Rf2 is established between the barrier region average roughness factor Rf2, and Ar1 ⁇ Ar2 between the transfer region average aperture ratio Ar1 and the barrier region average aperture ratio Ar2. connection of Characterized in that it holds.
  • FIG. 1 and FIG. 2 are schematic views showing a mold for applying a transfer material to transfer a fine concavo-convex structure.
  • the mold 110 is provided with a finely patterned transfer region, that is, a pattern portion 111.
  • the area other than the pattern part 111 in the mold 110 is a non-transfer area that is not finely patterned, that is, a non-pattern part 112.
  • the resin mold 121 when the resin mold 121 is obtained from a master mold (original), in general, particularly when a roll-to-roll process is performed, as shown in FIG.
  • the pattern part 122 and the non-pattern part 123 are formed.
  • the release property is prioritized, the release force of the resin mold 121 is increased, and the free energy is greatly reduced. Affinity with the mold 121 is greatly reduced.
  • the transfer material is applied onto the resin mold 121, as shown in FIG. 2B, the coating liquid 124 repelled on the non-pattern part 123 is transferred to the pattern part 122 as indicated by an arrow.
  • the coating defect (2) occurs in which the film thickness distribution of the coating liquid 124 varies on the pattern portion 122.
  • the fine pattern of the pattern part 111 shown in FIG. 1 has a fine uneven structure, in particular, the nanoscale, and the mold releasability of the mold 110 is increased, and the affinity between the coating liquid 113 and the mold 110 is increased.
  • the force F ( ⁇ ) applied to the coating liquid 113 becomes stronger, and the degree of coating defects (1) and (2) becomes larger.
  • F ( ⁇ ) applied in the direction from the non-pattern part 112 to the pattern part 111 is apparently increased.
  • the degree of penetration of the coating liquid 113 repelled on the portion 112 into the pattern portion 111 is increased, and the degree of coating failure (2) is further increased.
  • the present inventor relaxes the stress applied to the inside of the liquid film of the coating liquid 113 and suppresses the coating failure (1) represented by the division of the liquid, or the inside of the droplet of the coating liquid 113.
  • the stress applied to the pattern portion is maximized, and the droplet of the coating liquid 113 repelled on the non-pattern portion 112 is prevented from entering the inside of the pattern portion 111, thereby suppressing the coating failure (2). Therefore, it has been found that a barrier region 114 is provided between the pattern part 111 and the non-pattern part 112 as shown in FIG.
  • the contact angle of the coating liquid 113 changes continuously, and the force F ( ⁇ ) also changes continuously. Therefore, a good coating property can be maintained without causing a coating failure (1) due to the stress concentration inside the droplet of the coating solution 113.
  • the stress in the liquid film of the coating liquid 113 on the barrier region 114 can be increased. Therefore, as shown in FIG. 4B, the droplet of the coating liquid 113 repelled on the non-pattern part 112 cannot get over the barrier region 114 as shown by the arrow, and the coating on the pattern part 111 And, in particular, the coating property of the edge portion of the pattern portion 111 is kept good, and the coating failure (2) is suppressed.
  • the fine uneven structure transfer mold of the present invention (hereinafter also simply referred to as a transfer mold) includes the following four types.
  • the coating defect (2) can be suppressed, and the coating property for the pattern portion 111 can be kept in good quality.
  • the coating failure (1) is suppressed and the coating property to the pattern part 111 is kept in good quality. be able to.
  • the first transfer mold (I) of the present invention is a transfer mold having a transfer region and a barrier region each having at least a plurality of recesses on one main surface of a substrate, the transfer template
  • the relationship Rf1> Rf2 is established between the average roughness factor Rf1 of the region and the average roughness factor Rf2 of the barrier region, and the average aperture ratio Ar1 of the transfer region and the average aperture ratio Ar2 of the barrier region
  • Ar1> Ar2 is established.
  • the second transfer template (II) of the present invention is a transfer template having a transfer region and a barrier region each having at least a plurality of convex portions on one main surface of the substrate, A relationship of Rf1 ⁇ Rf2 is established between the average roughness factor Rf1 of the transfer region and the average roughness factor Rf2 of the barrier region, and the average aperture ratio Ar1 of the transfer region and the average aperture ratio Ar2 of the barrier region The relationship Ar1> Ar2 is established.
  • the third transfer template (III) of the present invention is a transfer template including a transfer region and a barrier region each having at least a plurality of recesses on one main surface of a substrate, wherein the transfer The relationship Rf1 ⁇ Rf2 is established between the average roughness factor Rf1 of the region and the average roughness factor Rf2 of the barrier region, and the average aperture ratio Ar1 of the transfer region and the average aperture ratio Ar2 of the barrier region A relationship of Ar1 ⁇ Ar2 is established.
  • the fourth transfer mold (IV) of the present invention is a transfer mold having a transfer region and a barrier region each having at least a plurality of convex portions on one main surface of the substrate,
  • the relationship Rf1> Rf2 is established between the average roughness factor Rf1 of the transfer area and the average roughness factor Rf2 of the barrier area, and the average aperture ratio Ar1 of the transfer area and the average aperture ratio Ar2 of the barrier area
  • the relationship Ar1 ⁇ Ar2 is established.
  • both the barrier region 114 region and the pattern portion 111 have a fine concavo-convex structure composed of a plurality of concave portions, and the roughness factor Rf2 of the barrier region 114 is the roughness factor of the pattern portion 111.
  • the average aperture ratio Ar2 of the barrier region 114 is set to be smaller than Rf1 and smaller than the average aperture ratio Ar1 of the pattern portion 111.
  • both the barrier region 114 and the pattern portion 111 have a fine concavo-convex structure composed of a plurality of convex portions, and the roughness factor Rf2 of the barrier region 114 is equal to that of the pattern portion 111.
  • the average aperture ratio Ar2 of the barrier region 114 is set to be smaller than the average aperture ratio Ar1 of the pattern portion 111, which is larger than the roughness factor Rf1.
  • both the barrier region 114 and the pattern portion 111 have a fine concavo-convex structure composed of a plurality of concave portions, and the roughness factor Rf2 of the barrier region 114 is the transfer region, that is, the pattern portion 111.
  • the average aperture ratio Ar2 of the barrier region 114 is set to be greater than the average aperture ratio Ar1 of the pattern portion 111.
  • both the barrier region 114 and the pattern portion 111 have a fine concavo-convex structure composed of a plurality of convex portions, and the roughness factor Rf2 of the barrier region 114 is equal to that of the pattern portion 111.
  • the average aperture ratio Ar2 of the barrier region 114 is set to be smaller than the roughness factor Rf1 and larger than the average aperture ratio Ar1 of the pattern portion 111.
  • type refers to a case where the fine concavo-convex structure is constituted by a plurality of concave portions, and a case where the fine concavo-convex structure is constituted by a plurality of convex portions is called a convex type.
  • transfer template the description common to all of the first to fourth transfer templates (I) to (IV) will be simply referred to as the transfer template,
  • descriptions such as transfer templates (I) and (II) mean that features common to transfer templates (I) and transfer templates (II) are described.
  • a transfer mold for example, a cylindrical or columnar master mold (original), a reel-shaped resin mold obtained by transfer from the master mold, or a flat plate having a flat plate shape represented by a disk Examples thereof include a master mold and a film-shaped resin mold obtained by transfer from the master mold.
  • the fine concavo-convex structure provided in the transfer molds (I) and (III) is not particularly limited, but a plurality of concave portions (holes) having a conical shape, a pyramid shape, an elliptical cone shape, a cylindrical shape, a prismatic shape, or an elliptical columnar shape. Shape). Further, the fine concavo-convex structure may be constituted by linear convex portions and concave portions (line and space structure) extending in a specific direction. In the hole shape, each hole may be adjacent to each other through a smooth convex portion.
  • the fine concavo-convex structure provided in the transfer molds (II) and (IV) is not particularly limited, but a plurality of convex shapes having a conical shape, a pyramid shape, an elliptical cone shape, a cylindrical shape, a prismatic shape, or an elliptical columnar shape. It may be configured with a portion (dot shape). Further, the fine concavo-convex structure may be constituted by linear convex portions and concave portions (line and space structure) extending in a specific direction. The dot shape may be such that each dot is adjacent through a smooth recess.
  • the dot shape means “a shape in which a plurality of columnar (conical) bodies (convex portions) 131a are arranged on the surface of the base 131” as shown in FIG. 5A.
  • the hole shape means “a shape in which a plurality of columnar (conical) holes (concave portions) 132 b are formed on the surface of the base material 132” as shown in FIG. 5B.
  • the distance between the protrusions or the recesses is 50 nm or more and 5000 nm or less, and the height of the protrusions or the depth of the recesses is 10 nm or more and 2000 nm or less.
  • the height of the convex portion or the depth of the concave portion is 50 nm or more and 1,000 nm or less, it is possible to further improve the coating property on the pattern portion 111 and the function of the barrier region 114, and the coating on the pattern portion 111. Since workability improves, it is preferable.
  • the adjacent distance between the projections or recesses is small, the height of the projections or the depth of the recesses, It is preferable that the height from the bottom to the top of the convex portion is large.
  • the convex part means a part higher than the average height of the fine concavo-convex structure
  • the concave part means a part lower than the average height of the fine concavo-convex structure.
  • the aspect ratio (convex height / convex bottom diameter or concave depth / concave opening diameter) of the fine concavo-convex structure is 0.1 to from the viewpoint of coating accuracy, barrier region function, and transfer accuracy. It is preferably 5.0, more preferably 0.3 to 3.0, and most preferably 0.5 to 1.5.
  • the pattern portion 111 of the transfer mold in order to reduce the surface free energy of the pattern portion 111, that is, to improve the releasability and to keep the coating property good, the pattern portion 111 is It is preferable to have a fine concavo-convex structure in which the mode of the coating liquid that can be finally taken in terms of energy is a Wenzel mode. From such a viewpoint, it is preferable that the aperture ratio in the pattern portion 111 is 45% or more in the pattern portion 111 of the fine uneven structure in the transfer mold. In particular, it is preferably 50% or more, and more preferably 55% or more.
  • the aperture ratio in the pattern part 111 is 65% or more, a potential from the convex part of the fine concavo-convex structure of the pattern part 111 toward the concave part works, and the convex part is filled after the coating liquid is filled into the concave part. Since it can avoid that a coating liquid re-moves to a part, coating property improves further and is more preferable.
  • the aperture ratio in the pattern part 111 is preferably 70% or more, more preferably 75% or more, and further preferably 80% or more.
  • the area of the hole opening is larger than the area of the hole bottom because the above effect can be exhibited more. Furthermore, it is preferable that the opening rod and the side surface of the recess are continuously and smoothly connected, because the pinning effect at the solid-liquid interface (TPCL) can be reduced and the above effect can be further exhibited.
  • the area of the dot apex is smaller than the area of the dot bottom, because the above effects can be exhibited. Furthermore, it is preferable that the dot top ridges and the dot side surfaces are connected continuously and smoothly because the pinning effect at the solid-liquid interface (TPCL) can be reduced and the above effect can be further exhibited.
  • the coating failure (2) can be suppressed by the following mechanism.
  • the surface free energy is greatly reduced in order to express the release property strongly, the affinity between the non-pattern part 112 and the coating liquid 113 becomes very small.
  • the transfer material by providing the barrier region 114 between the pattern portion 111 and the non-pattern portion 112, the force applied from the inside of the concave portion of the fine concavo-convex structure to the upper portion of the convex portion by the pattern portion 111 and the barrier region 114, the transfer material
  • the fine uneven structure recognizability of the coating liquid and the state (mode) of the transfer material coating liquid at the initial stage of coating change, and stress on the inside of the droplet (liquid film) of the coating liquid 113 on the barrier region 114 Can be bigger.
  • the droplets of the coating liquid 113 repelled on the non-pattern part 112 cannot get over the barrier region 114, and the coating defect on the pattern part 111 is improved by suppressing the coating failure (2). Can keep.
  • the coating failure (1) can be suppressed by the following mechanism.
  • the pattern part 111 is provided by providing the barrier region 114 between the pattern part 111 and the non-pattern part 112.
  • the barrier region 114 the force applied from the inside of the concave portion of the fine concavo-convex structure to the upper portion of the convex portion, the fine concavo-convex structure recognizability of the coating liquid, and the state (mode) of the coating liquid in the initial stage of coating change gently
  • the force F ( ⁇ ) applied to the coating liquid 113 on the barrier region 114 also changes continuously. Therefore, the stress concentration inside the liquid film of the coating liquid 113 can be suppressed, and good coating properties on the pattern part 111 can be maintained.
  • the contact angle of water with the pattern portion 111 of the transfer mold is preferably 60 ° or more from the viewpoint of transferability (release property) of the transfer material. In particular, it is preferably 70 ° or more, and more preferably 80 ° or more. From the viewpoint of further reducing the surface free energy with respect to the pattern portion 111 of the transfer mold and improving the transfer accuracy, it is preferably 85 degrees or more, more preferably 90 degrees or more.
  • the upper limit value of the contact angle of water with respect to the pattern part 111 is preferably less than 180 degrees because the coating property can be improved. In particular, it is preferably 160 ° or less, and more preferably 140 ° or less.
  • the contact angle adopts the contact angle measurement method established in JIS R3257 (1999) as the “wetting test method for substrate glass surface”, and the transfer according to the present invention is used as a base material for contact angle measurement.
  • the pattern part 111 of the mold for use shall be used.
  • the effect of the barrier region 114 in the transfer mold is further exhibited when the contact angle of water with respect to the barrier region 114 is 90 degrees or more.
  • the transfer molds (I) and (II) the force applied from the inside of the concave portion of the fine concavo-convex structure to the top of the convex portion in the pattern portion 111 and the barrier region 114, the fine concavo-convex structure recognition of the coating liquid 113 This is because the difference in the property and the change in the state (mode) of the coating liquid at the initial stage of coating can be further increased.
  • the fine uneven structure in the transfer mold has convex portions (or concave portions) at a pitch P in the first direction D1 with respect to the first direction D1 and the second direction D2 orthogonal in the plane.
  • the convex portions (or concave portions) are arranged in the second direction D2 with the pitch S, the regularity of the deviation ⁇ with respect to the first direction D1 of the convex portions (or concave portions) forming a row in the second direction D2 May be a high array (see FIG. 6A) or a low regularity of the shift ⁇ (see FIG. 6B).
  • the shift ⁇ is a distance between line segments parallel to the second direction D2 passing through the center of the closest convex portion in adjacent rows parallel to the first direction D1.
  • a distance between a line segment passing through the center of the convex portion of the (N + 1) th row and parallel to the second direction D2 is defined as a shift ⁇ .
  • the array shown in FIG. 6A can be said to be an array having periodicity because the shift ⁇ is substantially constant regardless of which column is the (N) th column.
  • the array shown in FIG. 6B can be said to be an array having aperiodicity because the value of the shift ⁇ changes depending on which column is the (N) th column.
  • the pitch P and the pitch S can be appropriately designed according to the intended use.
  • the pitch P and the pitch S may be equal.
  • the convex part (or concave part) is drawn in an independent state without overlapping, the convex part (or convex part) arranged in both or one of the first direction D1 and the second direction D2. Or the recessed part) may overlap.
  • the fine concavo-convex structure has a pitch of 200 nm to 800 nm, a height of 100 nm to 1000 nm, a nanoscale regular arrangement, and It is preferable to have a micro-scale large periodicity.
  • transfer templates (I) and (III) are preferable.
  • the pitch of the fine concavo-convex structure is 100 nm to 500 nm and the height is 50 nm to 500 nm, the internal quantum efficiency of the LED can be improved.
  • the modulation is made in a nanoscale regular arrangement and has a microscale periodicity, and the pitch has a microscale period, the light extraction efficiency can be improved at the same time.
  • An efficient LED can be manufactured.
  • the pattern portion 111 and the barrier region 114 in the transfer mold of the present invention exhibit high releasability by satisfying a predetermined contact angle range, and coating by satisfying a predetermined aperture ratio. The property can be kept good.
  • the barrier region 114 in the transfer mold is adjacent to at least a part of the pattern portion 111.
  • the term “adjacent” includes a case where it is provided adjacent to the pattern portion 111 having a fine concavo-convex structure as shown in FIG. 7A.
  • a barrier region 114 having a fine concavo-convex structure is provided via a non-pattern barrier region 115 having no fine concavo-convex structure provided adjacent to a pattern portion 111 having a fine concavo-convex structure. Including the case where it is provided.
  • the thickness (width) of the non-pattern barrier region 115 that does not have the fine uneven structure provided between the pattern part 111 having the fine uneven structure and the barrier region 114 having the fine uneven structure is 30 mm or less. is necessary. By being 30 mm or less, the above-described effects can be exhibited, and the coatability for the pattern portion 111 can be improved.
  • the thickness (width) is preferably 10 mm or less, more preferably 5 mm or less, still more preferably 3 mm or less, and 1 mm or less. And most preferred.
  • the pattern portion 111 having the fine uneven structure it is provided adjacent to the pattern portion 111 having the fine uneven structure, that is, between the pattern portion 111 having the fine uneven structure and the barrier region 114 having the fine uneven structure.
  • the case where the thickness (width) of the non-pattern barrier region 115 that does not have a fine concavo-convex structure is 0 mm is preferable because the above effect can be exhibited most.
  • the barrier region 114 provided adjacent to the pattern part 111 is not necessarily continuous.
  • 7C and 7D illustrate the case where the barrier region 114 is interrupted.
  • the effect of the present invention can be exhibited as long as the barrier region 114 is adjacent to at least a part of the pattern portion 111. That is, the barrier region 114 may be provided continuously as shown in FIG. 7A or discontinuously as shown in FIGS. 7C and 7D. In the case of discontinuous provision, the number of breaks in the barrier region 114 is not particularly limited.
  • the width W of these interruptions is preferably 30 mm or less, more preferably 10 mm or less, and preferably 5 mm or less, more preferably 3 mm or less, and 1 mm. The following is most preferable.
  • the state in which the barrier regions 114 are continuously connected is most preferable because the coating property to the pattern part 111 can be further improved.
  • the barrier region 114 may be continuous as described above. It may be discontinuous.
  • the non-pattern barrier region 115 may be continuous or discontinuous.
  • the discontinuity width of the barrier region 114 and the discontinuity width W of the non-pattern barrier region 115 are preferably 30 mm or less, more preferably 10 mm or less, and preferably 5 mm or less, and more preferably 3 mm or less. Preferably, it is most preferable in it being 1 mm or less.
  • FIG. 7B it is most preferable that the barrier region 114 and the non-pattern barrier region 115 are both continuously connected because the coating property to the pattern part 111 can be further improved.
  • the pattern part 111 in the transfer mold is disposed on the surface of the base material in a state surrounded by or sandwiched by the barrier region 114 because coating properties on the entire pattern part 111 are further improved.
  • the state in which the pattern unit 111 is surrounded by the barrier region 114 refers to a state in which the pattern unit 111 has a closed region and the barrier region 114 is disposed around the region.
  • the state where the pattern part 111 is sandwiched between the barrier regions 114 refers to a state where the barrier regions 114 are arranged in parallel at both ends of the pattern part 111. In either case, the pattern part 111 is disposed inside the barrier region 114.
  • the arrangement of the pattern part 111 and the barrier region 114 in this case can also include the non-pattern barrier region 115 shown in FIG.
  • the pattern portion 111 includes the break of the barrier region 114 described with reference to FIGS. 7C and 7D. 7E, FIG. 7F, and FIG. 7G include the discontinuity of the barrier region 114 and the discontinuity of the non-pattern barrier region 115 described with reference to FIGS.
  • the state in which the pattern unit 111 is surrounded by the barrier region 114 indicates a state in which the pattern unit 111 has a closed region and the barrier region 114 is disposed around the pattern unit 111. As shown in FIG. 8, they may be connected continuously or disconnected.
  • FIG. 8A represents a case where the pattern part 111 is entirely surrounded by the barrier region 114.
  • 8B, 8C, and 8D represent a state where the barrier region 114 surrounding the pattern unit 111 is interrupted.
  • FIG. 8B and FIG. 8C a plurality of discontinuous points are illustrated, but the discontinuity may be one place as illustrated in FIG. 8D. That is, the number and location of breaks are not limited. Even in the case where there is such a discontinuous portion, the effect of the present invention can be obtained.
  • the state where the barrier region 114 is discontinuous in the state where the pattern portion 111 is surrounded by the barrier region 114 is also included.
  • the width W of these discontinuities is preferably 30 mm or less, more preferably 10 mm or less, preferably 5 mm or less, more preferably 3 mm or less, and most preferably 1 mm or less.
  • the state in which the barrier regions 114 are continuously connected is most preferable because the coating property to the pattern part 111 can be further improved.
  • the non-pattern barrier region 115 described with reference to FIGS. 7B, 7E, 7F, and 7G can also be included.
  • the state in which the pattern part 111 is sandwiched between the barrier regions 114 refers to a state in which the barrier regions 114 are arranged in parallel at both ends of the pattern part 111, but the barrier region 114 that sandwiches the pattern part 111 is As shown in FIG. 9, it may be connected continuously or may be interrupted.
  • FIG. 9A represents a case where the pattern unit 111 is disposed between the barrier regions 114.
  • 9B, FIG. 9C, and FIG. 9D represent a state in which the barrier region 114 surrounding the pattern unit 111 is interrupted.
  • FIG. 9B and FIG. 9C a plurality of discontinuous portions are illustrated, but the discontinuity may be one place as illustrated in FIG. 9D. That is, the number and location of breaks are not limited.
  • the state in which the barrier region 114 is interrupted in the state where the pattern portion 111 is sandwiched between the barrier regions 114 is also included.
  • the width (W) of these breaks is preferably 30 mm or less, more preferably 10 mm or less, preferably 5 mm or less, more preferably 3 mm or less, and most preferably 1 mm or less.
  • the state in which the barrier regions 114 are continuously connected is most preferable because the coating property to the pattern part 111 can be further improved.
  • the non-pattern barrier region 115 described with reference to FIGS. 7B, 7E, 7F, and 7G can be included in the same manner.
  • the pattern part 111 is arranged near the center of the non-pattern part 112, but the arrangement part of the pattern part 111 is not particularly limited. Further, the upper side and the lower side of the pattern part 111 (sides not in contact with the barrier region 114 in FIG. 9A) extend in the vertical direction, the pattern part 111 is sandwiched between the barrier areas 114, and the pattern part 111 sandwiched between the barrier areas 114. May be sandwiched between the non-pan portions 112.
  • the pattern portion 111 has a fine concavo-convex structure with an average roughness factor of Rf1 and an average aperture ratio Ar1
  • the barrier region 114 has a fine concavo-convex structure with an average roughness factor of Rf2 and an average aperture ratio Ar2.
  • the roughness factor Rf is a dimensionless value that serves as an index of miniaturization, and means how many times the unit area has increased due to the formation of a fine uneven structure. That is, the roughness factor Rf of the surface that does not give the fine concavo-convex structure is 1.
  • the average aperture ratio is a dimensionless value that serves as an index of the void ratio, and means the ratio of voids present in the surface of the fine concavo-convex structure.
  • the roughness factor Rf and the average aperture ratio Ar are defined as follows.
  • FIG. 10A shows a state in which the fine concavo-convex structure has a dot shape or a hole shape and is regularly arranged, and the fine concavo-convex structure has a dot shape or a hole shape and is regularly arranged. Yes. From these fine concavo-convex structures, a fine concavo-convex structure group (N) forming N rows and a fine concavo-convex structure group (N + 1) forming N + 1 rows are selected. Subsequently, two adjacent fine uneven structures m and m + 1 are selected from the fine uneven structure group (N).
  • the fine concavo-convex structures l and l + 1 that are closest to the fine concavo-convex structures m and m + 1 are selected from the fine concavo-convex structure group (N + 1).
  • a region that connects the centers of these fine concavo-convex structures m, m + 1, l, and l + 1 is defined as a unit cell 201.
  • the area of the unit cell 201 is So, and the sum of the side areas of the fine concavo-convex structures m, m + 1, 1, and l + 1 in the unit cell 201 is S1.
  • the opening ratio is defined by (Sh / So) ⁇ 100.
  • the above columns are defined as follows.
  • the circumferential direction is taken as a row.
  • the transport direction is set as a row.
  • the base material constituting the transfer mold is a flat plate having a disk shape
  • the circumferential direction is a row.
  • the base material is a transfer mold made of a flat plate having a disk shape as a master and is a transfer mold formed by transfer, that is, a film-like resin mold
  • the circumferential direction of the master is set as a row.
  • FIG. 10B shows a state where the fine uneven structure is a dot shape or a hole shape and has a weak regularity arrangement or a random arrangement. Is shown.
  • the average pitch of the fine concavo-convex structure is smaller than 500 nm
  • a 1 ⁇ m ⁇ 1 ⁇ m square is taken in the region having the fine concavo-convex structure, and this is used as the unit cell 202.
  • the unit cell 202 When the average pitch of the fine concavo-convex structure is 500 nm or more and 1000 nm or less, the unit cell 202 is 2 ⁇ m ⁇ 2 ⁇ m, and when the average pitch of the fine pattern is more than 1000 nm and 1500 nm or less, the unit cell 202 is 3 ⁇ m ⁇ 3 ⁇ m.
  • the area of the unit cell 202 is So, and the sum of the side areas of all the fine concavo-convex structures included in the unit cell 202 is S1.
  • the roughness factor Rf is defined as 1+ (S1 / So).
  • the average pitch means an average value of the distances between the centers of adjacent dots or the centers of adjacent holes.
  • the average score is preferably 10 or more.
  • the opening ratio is defined by (Sh / So) ⁇ 100.
  • FIG. 10C shows the line-and-space structure.
  • Each line may be arranged at equal intervals, or the intervals may vary.
  • the Nth line and the (N + 1) th line are selected.
  • a line segment of 1 ⁇ m is drawn on each of these lines.
  • a unit cell 203 is a square or rectangle formed by connecting the end points of these line segments.
  • the area of the unit cell 203 is So, and the sum of the side areas of all the fine concavo-convex structures included in the unit cell 203 is S1.
  • the roughness factor Rf is defined as 1+ (S1 / So).
  • the opening ratio is defined by (Sh / So) ⁇ 100.
  • the average roughness factor Rf means an average value of the roughness factor Rf.
  • the average value of the roughness factor Rf is defined as an average value of 10 roughness factors Rf calculated at random within a range of 5 ⁇ m ⁇ 5 ⁇ m.
  • the roughness factor Rf can be designed with the height, pitch, aspect, etc. of the fine relief structure.
  • the side area of the fine concavo-convex structure included in the unit cell 201 may be reduced.
  • the height of the fine uneven structure may be reduced, the pitch may be increased, or the aspect may be decreased.
  • the roughness factor Rf changes continuously.
  • any one of the height, pitch, and aspect of the fine concavo-convex structure may be changed, or a plurality thereof may be changed. From the viewpoint of manufacturing the fine concavo-convex structure, it is preferable to change both the pitch and the aspect or either one.
  • the aspect can be easily changed by controlling the width of the bottom of the convex portion or the width of the concave portion opening.
  • the roughness factor Rf2 can be reduced by increasing the aperture ratio
  • the fine concavo-convex structure is concave
  • the roughness factor Rf2 can be reduced by reducing the aperture ratio.
  • the side area of the fine concavo-convex structure included in the unit cell may be increased.
  • the height of the fine uneven structure may be increased, the pitch may be reduced, or the aspect may be increased.
  • any one of the height, pitch, and aspect of the fine concavo-convex structure may be changed, or a plurality thereof may be changed. From the viewpoint of manufacturing the fine concavo-convex structure, it is preferable to change both the pitch and the aspect or either one.
  • the aspect can be easily changed by controlling the width of the bottom of the convex portion or the width of the concave portion opening.
  • the roughness factor Rf2 can be increased by reducing the aperture ratio.
  • the roughness factor Rf2 can be increased by increasing the aperture ratio.
  • the average roughness factor Rf2 of the barrier region 114 is set smaller than the average roughness factor Rf1 of the pattern portion 111.
  • FIG. 11 is a schematic diagram showing a state where the fine concavo-convex structure is a dot shape or a hole shape and the pitch in the second direction D2 is changed.
  • the top part (convex part) of the fine concavo-convex structure that is a dot shape or the opening part (concave part) of the fine concavo-convex structure that is a hole shape is represented in a circular shape in plan view.
  • the vertical axis indicates the first direction D1
  • the horizontal axis indicates the second direction D2
  • the origin indicates the center O of the pattern portion 111 in the second direction D2.
  • the interval between the convex portions or the concave portions in the second direction D2 is wider than the interval between the convex portions or the concave portions of the pattern portion 111, and the density of the convex portions or the concave portions in the barrier region 114 is the convex portion of the pattern portion 111. It is sparser than the density of the part or the concave part. In other words, the distance between adjacent convex portions or the distance between adjacent concave portions in the pattern portion 111 is smaller than the distance between adjacent convex portions or the distance between adjacent concave portions in the barrier region 114.
  • each fine concavo-convex structure is the same in the barrier region 114 and the pattern portion 111, that is, when only the pitch is changed between the barrier region 114 and the pattern portion 111, the average roughness factor Rf2 of the barrier region 114 Is smaller than the average roughness factor Rf1 of the pattern portion 111.
  • the average aperture ratio Ar2 of the barrier region 114 is larger than the average aperture ratio Ar1 of the pattern part 111, and the fine concavo-convex structure is concave.
  • the average aperture ratio Ar2 of the barrier region is smaller than the average aperture ratio Ar1 of the pattern portion 111.
  • the interval between the convex portions or the concave portions in the second direction D2 of the barrier region 114 is larger than the interval between the convex portions or the concave portions of the pattern portion 111.
  • the distance between the convex portions or concave portions can be changed in the same manner with respect to the first direction D1, or the first direction D1 and the first direction You may even change the space
  • the interval between the convex portions or the concave portions is changed.
  • the density of the convex portions or concave portions of the barrier region 114 is changed to the pattern portion. It can be made sparser than the density of the convex portions or concave portions of 111.
  • the density of the convex part or the concave part of the barrier region 114 is set by making the diameter of the convex part top part or the concave part opening diameter in the pattern part 111 larger than the diameter of the convex part top part or the concave part opening diameter of the barrier region 114. Can be made sparser than the density of the convex portions or concave portions of the pattern portion 111.
  • the roughness factor Rf can be changed by changing the height of the convex portion or the depth of the concave portion. Specifically, the relationship of Rf1> Rf2 is satisfied by making the height of the convex portion or the concave portion of the pattern portion 111 larger than the height of the convex portion or the concave portion of the barrier region 114. I can do it. Moreover, the controllability of the roughness factor is improved by simultaneously changing the interval between the convex portions or the concave portions described above, the diameter of the top portion of the convex portion, the diameter of the concave portion opening, the height of the convex portion, or the depth of the concave portion.
  • the average roughness factor Rf2 of the barrier region 114 is set larger than the average roughness factor Rf1 of the pattern portion 111.
  • FIG. 12 is a schematic diagram showing a state where the fine concavo-convex structure is a dot shape or a hole shape and the pitch in the second direction D2 is changed.
  • the top part (convex part) of the fine concavo-convex structure having a dot shape or the opening part (concave part) of the fine concavo-convex structure having a hole shape is represented in a circular shape in plan view.
  • the vertical axis represents the first direction D1
  • the horizontal axis represents the second direction D2
  • the origin represents the center O of the pattern portion 111 in the second direction D2.
  • the interval between the convex portions or the concave portions in the second direction D2 is narrower than the interval between the convex portions or the concave portions of the pattern portion 111, and the density of the convex portions or the concave portions in the barrier region 114 is the convex portion of the pattern portion 111. It is denser than the density of the part or the concave part. In other words, the distance between adjacent convex portions or the distance between adjacent concave portions in the pattern portion 111 is larger than the distance between adjacent convex portions or the distance between adjacent concave portions in the barrier region 114.
  • each fine concavo-convex structure is the same in the barrier region 114 and the pattern portion 111, that is, when only the pitch is changed between the barrier region 114 and the pattern portion 111, the average roughness factor Rf2 of the barrier region 114 Is larger than the average roughness factor Rf1 of the pattern part 111.
  • the average aperture ratio Ar2 of the barrier region 114 is smaller than the average aperture ratio Ar1 of the pattern portion 111, and the fine uneven structure is concave.
  • the average aperture ratio Ar2 of the barrier region is larger than the average aperture ratio Ar1 of the pattern portion 111.
  • the interval between the convex portions or the concave portions in the second direction D2 of the barrier region 114 is smaller than the interval between the convex portions or the concave portions of the pattern portion 111. Is made denser than the density of the convex portions or concave portions of the pattern portion 111, the distance between the convex portions or concave portions may be similarly changed with respect to the first direction D1, or the first direction D1 and the first direction You may even change the space
  • the density of the convex portions or concave portions of the barrier region 114 is changed to the pattern portion. It can be made denser than the density of the convex portions or concave portions of 111. Specifically, the density of the convex portions or the concave portions of the barrier region 114 is reduced by making the diameter of the convex portion top portion or the concave portion opening diameter in the pattern portion 111 smaller than the diameter of the convex portion top portion or the concave portion opening diameter of the barrier region 114. Can be made denser than the density of the convex portions or concave portions of the pattern portion 111.
  • the roughness factor Rf can be changed by changing the height of the convex portion or the depth of the concave portion. Specifically, the relationship of Rf1 ⁇ Rf2 is satisfied by making the height of the convex portion or the concave portion of the pattern portion 111 smaller than the height of the convex portion or the concave portion of the barrier region 114. I can do it. Moreover, the controllability of the roughness factor is improved by simultaneously changing the interval between the convex portions or the concave portions described above, the diameter of the top portion of the convex portion, the diameter of the concave portion opening, the height of the convex portion, or the depth of the concave portion.
  • the fine concavo-convex structure in the barrier region 114 of the transfer mold preferably has a roughness factor gradient.
  • the gradient of the roughness factor Rf increases as the pattern portion 111 is approached.
  • the average roughness factor Rf2 has a gradient that increases from the pattern portion 111 toward the barrier region 114. At this time, the average roughness factor Rf2 is The following definitions shall be followed.
  • the fine concavo-convex structure of the barrier region 114 is composed of a plurality of convex portions.
  • the ratio of the convex portion side area to the unit cell may be increased.
  • the average roughness factor Rf2 is increased.
  • the average roughness factor Rf2 decreases because the area of the convex portion included in the unit cell decreases from the stage where the convex portions begin to contact each other inside the unit cell.
  • the gradient of the average roughness factor Rf2 is defined by the range until the adjacent convex portions come into contact with each other in the barrier region 114.
  • the fine concavo-convex structure of the barrier region 114 is composed of a plurality of concave portions.
  • the ratio of the recess side area to the unit cell may be increased.
  • the average roughness factor Rf2 is increased.
  • the average roughness factor Rf2 decreases because the area of the concave portion included in the unit cell decreases from the stage where the concave portions begin to contact each other inside the unit cell. Therefore, in the case of the transfer template (III), the gradient of the average roughness factor Rf2 is defined by the range in the barrier region 114 until adjacent concave portions come into contact with each other.
  • the transfer templates (I) and (II) By having such a gradient of the roughness factor Rf2, in the transfer templates (I) and (II), there is an inhibition property that the coating liquid 113 repelled on the non-pattern part 112 enters the pattern part 111. Since it improves further, a coating defect (2) can be suppressed effectively.
  • the fact that the roughness factor Rf2 has a gradient means that the stress applied to the inside of the coating liquid 113 has a gradient, and stress concentration can be avoided. As a result, coating failure (1) can be suppressed.
  • the side area of the fine concavo-convex structure included in the unit cells 201 to 203 may be continuously changed.
  • the height of the fine concavo-convex structure may be changed continuously
  • the pitch may be changed continuously
  • the aspect may be changed continuously.
  • any one of the height, pitch, and aspect of the fine concavo-convex structure may be continuously changed, or a plurality may be continuously changed. From the viewpoint of producing a fine concavo-convex structure, it is preferable to continuously change both the pitch and the aspect or either one.
  • the average roughness factor Rf2 of the barrier region 114 is set smaller than the average roughness factor Rf1 of the pattern portion 111. Further, the roughness factor Rf ⁇ b> 2 of the barrier region 114 has a gradient that increases as it approaches the pattern part 111.
  • FIG. 13 is a schematic diagram showing a state in which the fine uneven structure has a dot shape or a hole shape, and the pitch in the second direction D2 is continuously changed.
  • the top part (convex part) of the fine concavo-convex structure having a dot shape or the opening part (concave part) of the fine concavo-convex structure having a hole shape is represented by a circular shape in plan view.
  • the vertical axis represents the first direction D1
  • the horizontal axis represents the second direction D2
  • the origin represents the center O of the pattern portion 111 in the second direction D2.
  • the distance between the convex portions or the concave portions in the second direction D2 increases as the distance from the inner side of the barrier region 114, that is, from the pattern portion 111 side increases, and the density of the convex portions or the concave portions becomes sparse.
  • the distance between adjacent convex portions or the distance between adjacent concave portions in the pattern portion 111 is smaller than the distance between adjacent convex portions or the distance between adjacent concave portions in the barrier region 114.
  • each fine concavo-convex structure is the same in the barrier region 114 and the pattern portion 111, that is, when only the pitch is changed between the barrier region 114 and the pattern portion 111, the average roughness factor Rf2 of the barrier region 114 Has a slope, and the average roughness factor Rf2 decreases as it goes from the inner side of the barrier region 114, that is, from the pattern part 111 side to the outer side.
  • the average aperture ratio Ar2 of the barrier region 114 is larger than the average aperture ratio Ar1 of the pattern section 111, and the pattern section 111 To the barrier region 114 toward the barrier region 114.
  • the average aperture ratio Ar2 of the barrier region 114 is smaller than the average aperture ratio Ar1 of the pattern portion 111, and the pattern region 111 extends to the barrier region. In 114 direction, it has a decreasing gradient.
  • FIG. 14 is a schematic diagram showing a state in which the fine uneven structure has a dot shape or a hole shape, and the pitch in the first direction D1 is continuously changed.
  • the top part (convex part) of the fine concavo-convex structure which is a dot shape or the opening part (concave part) of the fine concavo-convex structure which is a hole shape is represented in a circular shape in plan view.
  • the vertical axis represents the first direction D1
  • the horizontal axis represents the second direction D2
  • the origin represents the center O of the pattern portion 111 in the second direction D2.
  • the distance between the convex portions or the concave portions in the first direction D1 increases as the distance from the inner side of the barrier region 114, that is, the pattern portion 111 side increases, and the density of the convex portions or the concave portions becomes sparse.
  • the average roughness factor Rf2 of the barrier region 114 Has a slope, and the average roughness factor Rf2 decreases as it goes from the inner side of the barrier region 114, that is, from the pattern part 111 side to the outer side.
  • the average aperture ratio Ar2 of the barrier region 114 is larger than the average aperture ratio Ar1 of the pattern section 111, and the pattern section 111 To the barrier region 114 toward the barrier region 114.
  • the average aperture ratio Ar2 of the barrier region 114 is smaller than the average aperture ratio Ar1 of the pattern portion 111, and the pattern region 111 extends to the barrier region. In 114 direction, it has a decreasing gradient.
  • FIG. 15 is a schematic diagram showing a state in which the fine concavo-convex structure is a dot shape or a hole shape, and the pitch in the first direction D1 and the second direction D2 is continuously changed.
  • the top part (convex part) of the fine concavo-convex structure having a dot shape or the opening part (concave part) of the fine concavo-convex structure having a hole shape is represented in a circular shape in plan view.
  • the vertical axis represents the first direction D1
  • the horizontal axis represents the second direction D2
  • the origin represents the center O of the pattern portion 111 in the second direction D2.
  • the distance between the convex portions or the concave portions in the first direction D1 and the second direction D2 increases as the distance from the inside of the barrier region 114, that is, from the pattern portion 111 side increases, and the density of the convex portions or the concave portions decreases. It has become.
  • the average roughness factor Rf2 of the barrier region 114 Has a slope, and the average roughness factor Rf2 decreases as it goes from the inner side of the barrier region 114, that is, from the pattern part 111 side to the outer side.
  • the average aperture ratio Ar2 of the barrier region 114 is larger than the average aperture ratio Ar1 of the pattern section 111, and from the pattern section 111 There is a gradient that increases in the direction of the barrier region 114.
  • the average aperture ratio Ar2 of the barrier region is smaller than the average aperture ratio Ar1 of the pattern portion 111, and the pattern portion 111 extends to the barrier region 114. Have a smaller gradient.
  • FIG. 16 is a schematic diagram showing a state in which the fine concavo-convex structure is a line and space structure and the pitch in the second direction D2 is continuously changed.
  • the convex part or concave part of the fine concavo-convex structure which is a line and space structure is represented by a rectangular shape in plan view.
  • the vertical axis indicates the first direction D1
  • the horizontal axis indicates the second direction D2
  • the origin indicates the center O of the pattern portion 111 in the second direction D2.
  • the distance between the convex portions or the concave portions in the second direction D2 increases as the distance from the inner side of the barrier region 114, that is, from the pattern portion 111 side increases, and the density of the convex portions or the concave portions becomes sparse.
  • each fine concavo-convex structure is the same in the barrier region 114 and the pattern portion 111, that is, when only the pitch is changed between the barrier region 114 and the pattern portion 111, the average roughness factor Rf2 of the barrier region 114 Has a slope, and the average roughness factor Rf2 decreases from the inside (transfer area side) to the outside of the barrier area 114.
  • the average aperture ratio Ar2 of the barrier region 114 is larger than the average aperture ratio Ar1 of the pattern section 111, and the pattern section 111 To the barrier region 114 toward the barrier region 114.
  • the average aperture ratio Ar2 of the barrier region 114 is smaller than the average aperture ratio Ar1 of the pattern portion 111, and from the pattern portion 111 to the barrier region 114.
  • the direction has a decreasing gradient.
  • the case where the duty indicated by the line width / space width is larger than 0.5 in the pattern portion 111 is a concave shape.
  • a case where the duty is smaller than 0.5 is defined as a convex shape, and in this case, a line constituted by the convex portions is defined as a convex portion having a fine uneven structure.
  • the roughness factor Rf2 has a gradient.
  • the average roughness factor Rf2 of the barrier region 114 is set larger than the average roughness factor Rf1 of the pattern portion 111. Further, the roughness factor Rf2 of the barrier region 114 has a gradient that decreases as it approaches the transfer region.
  • FIG. 17 is a schematic diagram showing a state in which the fine concavo-convex structure is a dot shape or a hole shape, and the pitch in the second direction D2 is continuously changed.
  • the top part (convex part) of the fine concavo-convex structure having a dot shape or the opening part (concave part) of the fine concavo-convex structure having a hole shape is represented in a circular shape in plan view.
  • the vertical axis represents the first direction D1
  • the horizontal axis represents the second direction D2
  • the origin represents the center O of the pattern portion 111 in the second direction D2.
  • the distance between the convex portions or the concave portions in the second direction D2 becomes narrower toward the inner side of the barrier region 114, that is, the outer side from the pattern portion 111 side, and the density of the convex portions or the concave portions becomes dense.
  • the distance between adjacent convex portions or the distance between adjacent concave portions in the pattern portion 111 is larger than the distance between adjacent convex portions or the distance between adjacent concave portions in the barrier region 114.
  • each fine concavo-convex structure is the same in the barrier region 114 and the pattern portion 111, that is, when only the pitch is changed between the barrier region 114 and the pattern portion 111, the average roughness factor Rf2 of the barrier region 114 Has a slope, and the average roughness factor Rf2 increases toward the inside of the barrier region 114, that is, from the pattern part 111 side to the outside.
  • the average aperture ratio Ar2 of the barrier region 114 is smaller than the average aperture ratio Ar1 of the pattern section 111, and the pattern section 111 To the barrier region 114 toward the barrier region 114.
  • the average aperture ratio Ar2 of the barrier region 114 is larger than the average aperture ratio Ar1 of the pattern portion 111, and from the pattern portion 111 to the barrier region. In 114 direction, there is a gradient that increases.
  • FIG. 18 is a schematic diagram showing a state in which the fine uneven structure has a dot shape or a hole shape, and the pitch in the first direction D1 is continuously changed.
  • the top part (convex part) of the fine concavo-convex structure having a dot shape or the opening part (concave part) of the fine concavo-convex structure having a hole shape is represented by a circular shape in plan view.
  • the vertical axis indicates the first direction D1
  • the horizontal axis indicates the second direction D2
  • the origin indicates the center O of the pattern portion 111 in the second direction D2.
  • the distance between the convex portions or the concave portions in the first direction D1 becomes narrower toward the inner side of the barrier region 114, that is, the outer side from the pattern portion 111 side, and the density of the convex portions or the concave portions becomes dense.
  • the average roughness factor Rf2 of the barrier region 114 Has a slope, and the average roughness factor Rf2 increases toward the inside of the barrier region 114, that is, from the pattern part 111 side to the outside.
  • the average aperture ratio Ar2 of the barrier region is smaller than the average aperture ratio Ar1 of the pattern section 111, and from the pattern section 111 There is a decreasing gradient in the direction of the barrier region 114.
  • the average aperture ratio Ar2 of the barrier region is larger than the average aperture ratio Ar1 of the pattern portion 111, and from the pattern portion 111 to the barrier region 114. In the direction, there is a gradient that increases.
  • FIG. 19 is a schematic diagram showing a state in which the fine concavo-convex structure is a dot shape or a hole shape, and the pitch in the first direction D1 and the second direction D2 is continuously changed.
  • the top part (convex part) of the fine concavo-convex structure having a dot shape or the opening part (concave part) of the fine concavo-convex structure having a hole shape is represented in a circular shape in plan view.
  • the vertical axis represents the first direction D1
  • the horizontal axis represents the second direction D2
  • the origin represents the center O of the pattern portion 111 in the second direction D2.
  • the distance between the convex portions or the concave portions in the first direction D1 and the second direction D2 becomes narrower toward the inner side of the barrier region 114, that is, from the pattern portion 111 side to the outer side. It has become.
  • the average roughness factor Rf2 of the barrier region 114 Has a slope, and the average roughness factor Rf2 increases toward the inside of the barrier region 114, that is, from the pattern part 111 side to the outside.
  • the average aperture ratio Ar2 of the barrier region is smaller than the average aperture ratio Ar1 of the pattern section 111, and from the pattern section 111 There is a decreasing gradient in the direction of the barrier region 114.
  • the average aperture ratio Ar2 of the barrier region is larger than the average aperture ratio Ar1 of the pattern portion 111, and from the pattern portion 111 to the barrier region 114. In the direction, there is a gradient that increases.
  • FIG. 20 is a schematic diagram showing a state where the fine uneven structure is a line and space structure and the pitch in the second direction D2 is continuously changed.
  • the convex part or concave part of the fine concavo-convex structure which is a line and space structure is represented by a rectangular shape in plan view.
  • the vertical axis indicates the first direction D1
  • the horizontal axis indicates the second direction D2
  • the origin indicates the center O of the pattern portion 111 in the second direction D2.
  • the distance between the convex portions or the concave portions in the second direction D2 becomes narrower toward the inner side of the barrier region 114, that is, the outer side from the pattern portion 111 side, and the density of the convex portions or the concave portions becomes dense.
  • the average roughness factor Rf2 of the barrier region 114 Has a slope, and the average roughness factor Rf2 increases toward the inside of the barrier region 114, that is, from the pattern part 111 side to the outside.
  • the average aperture ratio Ar2 of the barrier region is smaller than the average aperture ratio Ar1 of the pattern section 111, and from the pattern section 111 There is a decreasing gradient in the direction of the barrier region 114.
  • the average aperture ratio Ar2 of the barrier region is larger than the average aperture ratio Ar1 of the pattern portion 111, and from the pattern portion 111 to the barrier region 114. In the direction, there is a gradient that increases.
  • the case where the duty indicated by the line width / space width is larger than 0.5 in the pattern portion 111 is a concave shape.
  • a case where the duty is smaller than 0.5 is defined as a convex shape, and in this case, a line constituted by the convex portions is defined as a convex portion having a fine uneven structure.
  • FIG. 21A shows a model in which the average roughness factor Rf2 decreases stepwise within the barrier region 114.
  • FIG. 21B shows a model in which the average roughness factor Rf2 decreases linearly within the barrier region 114.
  • FIG. 21C shows a model in which the average roughness factor Rf2 decreases as a convex function within the barrier region 114.
  • FIG. 21D shows a model in which the average roughness factor Rf2 decreases with a downward convex function in the barrier region 114.
  • FIG. 21E shows a model in which the average roughness factor Rf2 decreases in an S-curve shape having both a gradual decrease, a rapid decrease, and a gradual decrease in the barrier region 114.
  • FIG. 21F shows a case where the average roughness factor Rf2 decreases without continuity between the average roughness factor Rf1 in the pattern part 111 and the average roughness factor Rf2 in the barrier region 114.
  • the average roughness factor Rf2 of the barrier region 114 smaller than the average roughness factor Rf1 of the pattern part 111, a change in the average roughness factor Rf2 as exemplified in FIG.
  • the stress relaxation effect applied to the inside of the coating liquid film for suppressing the coating failure (1) and the non-patterned portion 112 for suppressing the coating failure (2) It is possible to exert an effect of inhibiting the penetration of the coating droplet repelled into the pattern part 111.
  • the width (distance) of the stepped step as shown in FIG. 21A is preferably as long as the number of step steps is finer as long as it is larger than the period of the fine concavo-convex structure from the viewpoint of coatability.
  • the step width is preferably 5 mm or less, and more preferably 1 mm or less. Most preferably, it is 100 ⁇ m or less.
  • the contact angle of the coating liquid 113 continuously changes, and the force F applied to the coating liquid 113 Since ( ⁇ ) also changes continuously, stress concentration inside the droplet (liquid film) of the coating liquid 113 does not occur, and the coating defect (1) is suppressed and good coating properties are maintained. be able to. Therefore, the mold (IV) is preferable in the order of the models shown in FIGS. 21E, 21C, 21B, 21D, 21A, and 21F.
  • the mold (I) is preferable in the order of the models shown in FIGS. 21F, 21D, 21A, 21E, and 21C.
  • Examples of the gradient of the average roughness factor Rf2 of the barrier region 114 that decreases as the pattern portions 111 of the transfer templates (II) and (III) are closer include a gradient as shown in FIG.
  • the vertical axis represents the magnitude of the roughness factor Rf
  • the horizontal axis represents the distance from the center position of the pattern unit 111.
  • FIG. 22A shows a model in which the average roughness factor Rf2 increases stepwise within the barrier region 114.
  • FIG. 22B shows a model in which the average roughness factor Rf2 increases linearly within the barrier region 114.
  • FIG. 22C shows a model in which the average roughness factor Rf2 increases as a downward convex function in the barrier region 114.
  • FIG. 22D shows a model in which the average roughness factor Rf2 increases as a convex function within the barrier region 114.
  • FIG. 22E shows a model in which the average roughness factor Rf2 increases in a S-curve shape having both a rapid increase, a gradual increase, and a rapid increase in the barrier region 114.
  • FIG. 22F shows a case where the average roughness factor Rf2 increases without a continuity between the average roughness factor Rf1 in the pattern portion 111 and the average roughness factor Rf2 in the barrier region 114.
  • the average roughness factor Rf2 of the barrier region 114 that is larger than the average roughness factor Rf1 of the pattern part 111 includes a change in the average roughness factor Rf2 as illustrated in FIG.
  • the width (distance) of the stepped step as shown in FIG. 22A is larger than the period of the fine concavo-convex structure from the viewpoint of coating properties, it is preferable that the number of steps is larger and finer.
  • the step width is preferably 5 mm or less, and more preferably 1 mm or less. Most preferably, it is 100 ⁇ m or less.
  • the transfer template (II) is preferable in the order of FIGS. 22F, 22E, 22D, 22A, 22B, and 22C.
  • the average roughness factor Rf2 has a gradient that increases as described above from the pattern portion 111 toward the barrier region 114.
  • the average roughness factor Rf2 conforms to the following definition.
  • the fine concavo-convex structure of the barrier region 114 is composed of a plurality of convex portions.
  • the ratio of the convex portion side area to the unit cell may be increased.
  • the average roughness factor Rf2 is increased.
  • the average roughness factor Rf2 decreases because the area of the convex portion included in the unit cell decreases from the stage where the convex portions begin to contact each other inside the unit cell. Therefore, in the case of the transfer template (II), the gradient of the average roughness factor Rf2 is defined by the range until the adjacent convex portions come into contact with each other in the barrier region 114. On the other hand, in the case of the transfer mold (III), the fine concavo-convex structure of the barrier region 114 is composed of a plurality of concave portions. In order to increase the average roughness factor Rf2 in the direction from the pattern portion 111 toward the barrier region 114, the ratio of the recess side area to the unit cell may be increased.
  • the average roughness factor Rf2 is increased.
  • the average roughness factor Rf2 decreases because the area of the concave portion included in the unit cell decreases from the stage where the concave portions begin to contact each other inside the unit cell. Therefore, in the case of the transfer template (III), the gradient of the average roughness factor Rf2 is defined by the range in the barrier region 114 until adjacent concave portions come into contact with each other.
  • the roughness factor Rf affects the contact angle of the coating solution. According to the Kathy Baxter equation or the Wenzel equation, in a water-repellent material having a contact angle larger than 90 °, the larger the roughness factor Rf, the larger the contact angle, and the smaller the roughness factor Rf (the contact angle is larger than 90 °). It is known that the contact angle (in range) is small.
  • the roughness factor Rf changes abruptly at the interface between the portion with the fine concavo-convex structure, that is, the pattern portion 111 and the portion without it, that is, the non-pattern portion 112.
  • the interface between the pattern part 111 and the non-pattern part 112 is replaced with a barrier region 114, so that the interface between the original pattern part 111 and the non-pattern part 112 is compared.
  • the generated stress is significantly increased. That is, in a mold in which surface free energy is greatly reduced so as to express high releasability, even if the coating liquid repelled on the non-pattern part 112 and tries to enter the pattern part 111, It is pushed back to the non-pattern part 112 side by a large stress generated on the barrier region 114. For this reason, the coating property on the pattern part 111 can be kept favorable.
  • FIG. 23 is a schematic view showing a transfer template according to the first embodiment.
  • the transfer mold (hereinafter simply referred to as a mold) 300 has a cylindrical shape or a columnar shape.
  • the mold 300 includes a pattern portion 301 and a barrier region 302 having a fine uneven structure on the outer peripheral surface.
  • the non-pattern barrier region described above, the discontinuity of the non-pattern barrier region, and the discontinuity of the barrier region are not described, but include these.
  • the expression that the pattern part 301 is sandwiched between the barrier regions 302 is used, and this also applies the definition of sandwiching described above.
  • the pattern portion 301 is arranged in a state of being sandwiched between barrier regions 302.
  • the arrangement of the pattern portion 301 and the barrier region 302 is defined as follows.
  • a center position in the longitudinal direction of the mold 300 is defined as a point O.
  • An axis is taken from this point O in the longitudinal direction, and each position in the mold 300 will be described on this axis.
  • Points A and F are edge portions of the mold 300.
  • the pattern part 301 exists between the point C and the point D.
  • the barrier region 302 exists between the point B and the point C and between the point D and the point E.
  • the distance between point C and point O is smaller than the distance between point B and point O (distance CO ⁇ distance BO).
  • the distance between point D and point O is smaller than the distance between point E and point O (distance DO ⁇ distance EO).
  • the entire outer periphery of the mold 300 has a fine concavo-convex structure.
  • the size of the barrier region 302 (distance BC, distance DE) is preferably as large as possible from the viewpoint of direct coating properties on the film transferred from the mold 300 as long as the pattern part 301 having a necessary area can be obtained. . Although it varies depending on the viscosity of the solution to be used and the shape of the fine concavo-convex structure in the pattern portion 301, it is preferably approximately 10 ⁇ m or more, more preferably 50 ⁇ m or more. From the viewpoint of transferability of the barrier region 302 and the pattern part 301, it is preferably 100 ⁇ m or more, preferably 1 mm or more, more preferably 3 mm or more, and still more preferably 5 mm or more.
  • the width of the barrier region 302 is preferably 30 mm or less, preferably 15 mm or less, and 8 mm. The following are most preferred.
  • the average roughness factor Rf2 of the barrier region 302 is smaller than the average roughness factor Rf1 of the pattern portion 301.
  • the average roughness factor Rf2 of the barrier region 302 continuously decreases from the inside of the barrier region 302, that is, from the pattern portion 301 side to the outside. That is, the average roughness factor Rf2 of the barrier region 302 preferably has a gradient.
  • the average roughness factor Rf2 of the barrier region 302 is preferably larger than the average roughness factor Rf1 of the pattern portion 301.
  • the average roughness factor Rf2 of the barrier region 302 increases continuously from the inside of the barrier region 302, that is, from the pattern portion 301 side to the outside. That is, the average roughness factor Rf2 of the barrier region 302 preferably has a gradient.
  • the coating property of the coating liquid is good.
  • the affinity between the coating liquid and the non-patterned portion 303 is high in a range in which releasability is expressed, the contact angle of the coating liquid continuously changes, and the force F ( ⁇ ) Also changes continuously. Therefore, by using the transfer molds (III) and (IV), the stress concentration inside the droplet (liquid film) of the coating liquid is alleviated, and the coating failure (1) is suppressed and good coating is achieved. This is because sex can be maintained.
  • the affinity between the coating liquid and the non-pattern part is low, the stress applied to the coating liquid on the barrier region 302 can be increased by a sudden change in the contact angle. Therefore, when the transfer molds (I) and (II) are used, the coating liquid droplets repelled on the non-patterned portion cannot get over the barrier region 302, resulting in poor coating (2). This is because the coating property on the pattern portion 301 can be kept good by being suppressed. Further, when the mold 300 has a fine concavo-convex structure using a photocurable resin as a transfer material to produce a resin mold, the cured photocuring obtained by the effect of stress relaxation inside the transfer material by the barrier region 302 is obtained. The stress inside the conductive resin film can also be relaxed, and the residual stress can be reduced.
  • FIG. 24 is a schematic diagram showing a transfer template according to the second embodiment.
  • the transfer mold (hereinafter simply referred to as a mold) 310 is a film mold transferred from the mold 300 according to the first embodiment, that is, a reel-shaped resin mold. That is, the mold 300 according to the first embodiment is used as a master (master mold) for transferring the fine concavo-convex structure to the mold 310 according to the present embodiment.
  • this mold 310 includes a pattern portion 311 and a barrier region 312 having a fine concavo-convex structure on the surface.
  • the above-described non-pattern barrier region, discontinuity of the non-pattern barrier region, and discontinuity of the barrier region are not described, but include these.
  • the expression that the pattern part 311 is sandwiched between the barrier regions 312 will be used, but this also applies the definition of sandwiching described above.
  • the pattern part 311 is arranged in a state of being sandwiched between the barrier regions 312.
  • the arrangement of the pattern part 311 and the barrier region 312 is defined as follows.
  • the axis is taken in the width direction of the film, and the center between one end and the other end of the film is defined as a point O. Each position on the mold 310 on this axis will be described.
  • the fine concavo-convex structure of the pattern portion 311 and the barrier region 312 is also formed in a direction perpendicular to the axis in the width direction of the film.
  • Point A and point F are the edge portions of the film constituting the mold 310.
  • the pattern part 311 exists between the point C and the point D.
  • a point O exists between the points C and D.
  • the barrier region 312 exists between the point B and the point C and between the point D and the point E.
  • the distance between point C and point O is smaller than the distance between point B and point O (distance CO ⁇ distance BO).
  • the distance between point D and point O is smaller than the distance between point E and point O (distance DO ⁇ distance EO).
  • the entire surface of the film has a fine concavo-convex structure.
  • the transfer material is applied and transferred onto the object to be processed, it is difficult to transfer the fine concavo-convex structure near the edge. Therefore, from the viewpoint of throughput, it is preferable that point A ⁇ point B and point E ⁇ point F.
  • the size of the barrier region 312 is preferably as large as possible from the viewpoint of direct coating properties on the film as long as the pattern portion 311 having a necessary area can be obtained.
  • it varies depending on the viscosity of the solution to be used and the shape of the fine concavo-convex structure in the pattern portion 311, it is preferably approximately 10 ⁇ m or more, more preferably 50 ⁇ m or more.
  • it is preferably 100 ⁇ m or more, preferably 1 mm or more, more preferably 3 mm or more, More preferably, it is 5 mm or more.
  • the width of the barrier region 312 is preferably 30 mm or less, preferably 15 mm or less, and 8 mm. The following are most preferred.
  • the average roughness factor Rf2 of the barrier region 312 is preferably smaller than the average roughness factor Rf1 of the pattern portion 311.
  • the average roughness factor Rf2 of the barrier region 312 continuously decreases, that is, has a gradient from the inside of the barrier region 312, that is, from the pattern portion 311 side to the outside.
  • the average roughness factor Rf2 of the barrier region 12 is preferably larger than the average roughness factor Rf1 of the pattern portion 311.
  • the average roughness factor Rf2 of the barrier region 312 increases continuously from the inside of the barrier region 312, that is, from the pattern portion 311 side to the outside. That is, the average roughness factor Rf2 of the barrier region 312 preferably has a gradient.
  • pattern portion 311 having a fine concavo-convex structure and non-pattern portion 313 having no fine concavo-convex structure are arranged by disposing a barrier region 312 that satisfies the above-described relationship of the average roughness factor Rf2 with respect to the average roughness factor Rf1 of the pattern part 311. Becomes a structure that changes gently.
  • the contact angle of the coating liquid continuously changes, and the force F ( ⁇ ) applied to the coating liquid is also continuous. Changes. Therefore, by using the transfer molds (III) and (IV), the stress concentration inside the droplet (liquid film) of the coating liquid is alleviated, and the coating defect (1) is suppressed and good coating properties are achieved. Can keep. Further, when the affinity between the coating liquid and the non-pattern part 313 is low, the stress applied to the coating liquid in the barrier region 312 can be increased by a sudden change in the contact angle.
  • the coating liquid that is repelled on the non-patterned portion 313 cannot drop over the barrier region 312, resulting in poor coating (2). It can suppress and can maintain the coating property on the pattern part 311 favorably. Therefore, it is possible to provide the mold 310 having a good transfer material coating property.
  • FIG. 25 is a schematic diagram showing a transfer template according to the third embodiment.
  • the mold 320 is a disk-shaped flat plate mold.
  • a resin flat plate mold (film-shaped resin mold) transferred from the mold 320 using the mold 320 as an original plate (master mold) has the same configuration as the mold 320.
  • the mold 320 includes a pattern part 321 and a barrier region 322 having a fine uneven structure on the surface.
  • the non-pattern barrier region, the non-pan barrier region, and the barrier region are not described.
  • the expression that the pattern part 321 is surrounded by the barrier region 322 is used, and this also applies the definition of surrounding described above.
  • the pattern part 321 is arranged in a state surrounded by the barrier region 322.
  • the arrangement of the pattern part 321 and the barrier region 322 is defined as follows.
  • the center of the flat plate constituting the mold 320 is a point O.
  • the pattern portion 321 and the barrier region 322 exist in point symmetry with respect to a straight line passing through the point O. In the following description, one line segment starting from the point O is considered. Each position in the mold 320 will be described on this line segment.
  • the point C is an edge portion of a flat plate constituting the mold 320.
  • the pattern part 321 exists inside a circle having the point O as the center and the line segment OA as the radius.
  • the line segment OA is shorter than the line segment OB (distance OA ⁇ distance OB).
  • the size of the barrier region 322 is preferably as large as possible from the viewpoint of direct coating on a flat plate, as long as the pattern portion 321 having a necessary area can be obtained.
  • the distance between the points A and B is preferably approximately 10 ⁇ m or more, and more preferably 50 ⁇ m or more.
  • it is preferably 100 ⁇ m or more, and preferably 1 mm or more from the viewpoint of satisfactorily exerting the effect of the barrier region 322 against the vibration of the mold when applying the coating liquid to the mold 320.
  • it is 3 mm or more, more preferably 5 mm or more.
  • the width of the barrier region 322 is preferably 30 mm or less, preferably 15 mm or less, and 8 mm. The following are most preferred.
  • the average roughness factor Rf2 of the barrier region 322 is smaller than the average roughness factor Rf1 of the pattern part 321.
  • the average roughness factor Rf2 of the barrier region 322 continuously decreases, that is, has a gradient from the inside of the barrier region 322, that is, from the pattern portion 321 side to the outside.
  • the average roughness factor Rf2 of the barrier region 322 is preferably larger than the average roughness factor Rf1 of the pattern portion 321.
  • the average roughness factor Rf2 of the barrier region 322 increases continuously from the inside of the barrier region 322, that is, from the pattern portion 321 side to the outside. That is, the average roughness factor Rf2 of the barrier region 322 preferably has a gradient.
  • the barrier region 322 that satisfies the relationship of the average roughness factor Rf2 described above with respect to the average roughness factor Rf1 of the pattern part 321.
  • the roughness factor Rf changes gently.
  • the coating liquid droplets repelled on the non-patterned portion 323 cannot get over the barrier region 322, and the coating failure (2) is suppressed.
  • the coating property on the pattern part 321 can be kept good. Therefore, it is possible to provide the mold 320 having a good transfer material coating property.
  • a non-pattern portion may be provided inside a circle centered on the point O and smaller than the radius OA due to the manufacturing method of the pattern portion 321 with respect to the flat substrate.
  • the coating property to the mold 320 can be improved by separately providing a barrier region surrounding the non-pattern part.
  • a flat pattern portion is represented on the surface of the flat substrate, but a fine processing method using a stepper is adopted as a method of manufacturing the pattern portion on the flat substrate.
  • the outer shape of the pattern portion does not become circular.
  • the contour of the pattern part has a stepped step shape.
  • a barrier region may be provided so as to surround the periphery.
  • the cylindrical or columnar substrate or flat substrate constituting the master mold is made of quartz, non-alkali glass, low alkali glass, soda lime, typified by synthetic quartz or fused silica.
  • quartz, non-alkali glass, low alkali glass, soda lime typified by synthetic quartz or fused silica.
  • examples thereof include glass, silicon wafer, nickel plate, sapphire, diamond, diamond-like carbon, inorganic material typified by fluorine-containing diamond-like carbon, SiC substrate, mica substrate, polycarbonate (PC) substrate and the like.
  • examples of the resin mold material obtained by transfer from a cylindrical or columnar master include cured products such as thermoplastic resins, thermosetting resins, photocurable resins, and sol-gel materials.
  • a fine concavo-convex structure is formed only with these materials, or a fine concavo-convex structure composed of these materials is provided on a support substrate.
  • a resin mold is composed of a cured product such as a thermosetting resin, a photocurable resin, or a sol-gel material having a fine relief structure on the surface of the support film.
  • a release layer is formed on the fine concavo-convex structure of this resin mold, or the resin having a fine concavo-convex structure made of polydimethylsiloxane (PDMS), a resin containing a methyl group, or a fluorine-containing resin. It is preferable to be configured.
  • PDMS polydimethylsiloxane
  • the thickness of the release layer is preferably 30 nm or less from the viewpoint of transfer accuracy, and is preferably a monomolecular layer or more. From the viewpoint of releasability, the thickness of the release layer is more preferably 2 nm or more, and more preferably 20 nm or less from the viewpoint of transfer accuracy.
  • the material constituting the release layer may be appropriately selected depending on the transfer material, and is not limited.
  • Known commercially available products include, for example, Zonyl TC Coat (DuPont), Cytop CTL-107M (Asahi Glass), Cytop CTL-107A (Asahi Glass), Novec EGC-1720 (3M), OPTOOL DSX (manufactured by Daikin Industries), OPTOOL DACHP (manufactured by Daikin Industries), Durasurf HD-2101Z (manufactured by Daikin Industries), Durasurf HD2100 (manufactured by Daikin Industries), Durasurf HD-1101Z (manufactured by Daikin Industries) ), “Fuategent” manufactured by Neos (for example, M series: Footent 251, Footent 215M, Footent 250, FTX-245M, FTX-290M; S series: FTX-207S, FTX-211S, FTX-220S, FTX-230S; F series FTX-209F, FTX-213F
  • TSF4421 (manufactured by GE Toshiba Silicone), XF42-334 (manufactured by GE Toshiba Silicone), XF42-B3629 (manufactured by GE Toshiba Silicone), XF42-A3161 (manufactured by GE Toshiba Silicone), FZ-3720 (Toray Dow Corning), BY 16-839 (Toray Dowco) -Surfing), SF8411 (Toray Dow Corning), FZ-3736 (Toray Dow Corning), BY 16-876 (Toray Dow Corning), SF8421 (Toray Dow Corning), SF8416 (made by Toray Dow Corning), SH203 (made by Toray Dow Corning), SH230 (made by Toray Dow Corning), SH510 (made by Toray Dow Corning), SH550 (made by Toray Dow Corning), SH710 (Toray Dow Corning), SF8419 (Toray Dow Corning), SF8422 (Toray Dow Corning), BY16 Series (Toray Dow Corning), F
  • the material constituting the release layer is preferably a material containing a methyl group, a material containing silicone, or a material containing fluorine from the viewpoint of releasability.
  • a silicone-based resin typified by a silane coupling agent or PDMS is preferable because the thickness of the release layer can be easily reduced and the transfer accuracy can be maintained.
  • the material used for the release layer may be used alone or in combination.
  • the material which comprises a release layer has a contact angle with respect to water of 90 degree
  • the contact angle means a contact angle when a solid film (a film having no fine pattern) is produced using a material constituting the release layer.
  • a metal layer, a metal oxide layer, or a layer made of a metal and a metal oxide may be provided on the fine uneven structure of the resin mold. Providing these layers in advance is preferable because when the release layer described above is provided, the releasability and transfer accuracy are further improved.
  • the metal include chrome, aluminum, tungsten, molybdenum, nickel, gold, and platinum.
  • the metal oxide for example, other oxides of the metals, SiO 2, ZnO, Al 2 O 3, ZrO 2, CaO, SnO 2 and the like. Silicon carbide, diamond-like carbon, fluorine-containing diamond-like carbon, or the like can also be used. Mixtures of these may be used.
  • the metal is preferably Cr from the viewpoint of transfer accuracy, and the metal oxide is preferably SiO 2 , Al 2 O 3 , ZrO 2 , or ZnO.
  • the metal layer may be a single layer or a multilayer.
  • the first metal layer is formed on the fine concavo-convex structure of the mold, and the first metal layer is further formed on the first metal layer.
  • Two metal layers may be formed.
  • an N + 1th metal layer can be formed on the Nth metal layer in order to improve adhesion and chargeability.
  • the number of layers is preferably N ⁇ 4, more preferably N ⁇ 2, and more preferably N ⁇ 1 from the viewpoint of transfer accuracy.
  • a first metal layer made of SiO 2 can be provided on the surface of the fine concavo-convex structure, and a second metal layer made of Cr can be provided on the first metal layer.
  • the metal constituting the metal layer is preferably Cr from the viewpoint of transfer accuracy, and the metal oxide is preferably SiO 2 , Al 2 O 3 , ZrO 2 , or ZnO.
  • the release layer described above may be provided directly on the fine uneven structure of the resin mold or on the metal layer.
  • the material for forming the fine concavo-convex structure of the resin mold is preferably composed of a resin made of polydimethylsiloxane (PDMS), a resin containing a methyl group, or a fluorine-containing resin. It is more preferable that the resin is composed of a containing resin.
  • the fluorine-containing resin is not particularly limited as long as it contains a fluorine element and has a contact angle with water larger than 90 degrees.
  • the resin mold preferably has a shape in which only a self-supporting resin layer having a fine uneven structure on the surface or a resin layer having a fine uneven structure on the surface is formed on a support substrate. In particular, from the viewpoint of handling when using a mold, a shape in which a resin layer is formed on a supporting substrate is preferable.
  • the fluorine concentration (Es) on the resin surface (near the fine concavo-convex structure) in the resin layer larger than the average fluorine concentration (Eb) in the resin layer, the free energy on the resin surface is reduced, and the transfer material and Thus, a transfer mold excellent in releasability can be obtained.
  • the ratio of the average fluorine element concentration (Eb) in the resin constituting the resin layer and the fluorine element concentration (Es) of the resin layer surface (surface layer) portion satisfies 1 ⁇ Es / Eb ⁇ 30000, It is more preferable because the effect is more exhibited. In particular, it is preferable because the releasability is further improved as the range becomes 3 ⁇ Es / Eb ⁇ 1500 and 10 ⁇ Es / Eb ⁇ 100.
  • the fluorine element on the resin layer surface (surface layer) part constituting the resin mold Since the concentration (Es) becomes sufficiently higher than the average fluorine concentration (Eb) in the resin layer and the free energy on the resin mold surface is effectively reduced, the releasability from the transfer material is improved.
  • the average fluorine element concentration (Eb) in the resin layer constituting the resin mold relatively lower than the fluorine element concentration (Es) of the resin layer surface (surface layer) part constituting the resin mold, while the strength of the resin itself is improved, the free energy can be kept high in the vicinity of the supporting base material in the resin mold, so that the adhesion of the supporting base material is improved.
  • a resin mold can be obtained that has excellent adhesion to the support substrate, excellent releasability from the transfer material, and can repeatedly transfer the nanometer-sized uneven shape from the resin to the resin.
  • the free energy of the resin layer surface which comprises a resin mold can be made lower, and a repetitive transfer property becomes favorable, it is preferable. Furthermore, if it is in the range of 30 ⁇ Es / Eb ⁇ 160, the free energy on the surface of the resin layer constituting the resin mold can be reduced, the strength of the resin can be maintained, and repeated transferability is further improved, which is preferable. 31 ⁇ Es / Eb ⁇ 155 is more preferable. If 46 ⁇ Es / Eb ⁇ 155, the above effect can be further exhibited, which is preferable.
  • the repetitive transfer property means that the resin mold can be easily duplicated from the resin mold.
  • a resin mold G2 having a concave and convex structure with a resin mold G1 having a convex and concave structure, and a resin mold G2 having a concave and convex structure.
  • the mold G3 can be transferred and formed.
  • a plurality of resin molds GM + 1 can be obtained using one resin mold GM as a mold. It also means that the used transfer template can be reused. Thus, environmental compatibility improves by using the resin mold which satisfy
  • the resin surface (near the fine concavo-convex structure) of the resin layer constituting the resin mold is, for example, approximately 1 to 10 from the fine concavo-convex structure surface of the resin layer constituting the resin mold toward the support base.
  • % Means a portion that penetrates in the thickness direction, or a portion that penetrates 2 nm to 20 nm in the thickness direction.
  • the fluorine element concentration (Es) on the resin surface (near the fine uneven structure) of the resin layer constituting the resin mold can be quantified by XPS method. Since the penetration length of X-rays in the XPS method is as shallow as several nm, it is suitable for quantifying the Es value.
  • Es / Eb can be calculated using energy dispersive X-ray spectroscopy (TEM-EDX) using a transmission electron microscope.
  • the average fluorine concentration (Eb) in the resin constituting the resin layer constituting the resin mold can be calculated from the charged amount. Or it can measure with a gas chromatograph mass spectrometer (GC / MS).
  • GC / MS gas chromatograph mass spectrometer
  • the average fluorine element concentration can be identified by physically peeling the resin layer constituting the resin mold and subjecting the resin layer to gas chromatography mass spectrometry.
  • an average fluorine element concentration (Eb) in the resin is also identified by decomposing a section from which the resin layer constituting the resin mold is physically separated by a flask combustion method and subsequently subjecting to ion chromatography analysis. be able to.
  • the photopolymerizable radical polymerization resin is a mixture of non-fluorine-containing (meth) acrylate, fluorine-containing (meth) acrylate and a photopolymerization initiator.
  • the curable resin composition (4) containing the sol-gel material represented by the metal alkoxide can also be used.
  • the curable resin composition (1) when the composition (1) is cured in a state where the composition (1) is in contact with a hydrophobic interface having a low surface free energy, a resin mold is obtained.
  • the fluorine element concentration (Es) on the surface (surface layer) of the resin layer constituting the resin mold can be made larger than the average fluorine element concentration (Eb) in the resin constituting the resin layer constituting the resin mold, and further the average fluorine in the resin
  • the element concentration (Eb) can be adjusted to be smaller.
  • the (meth) acrylate constituting the curable resin composition (1) is not limited as long as it is a polymerizable monomer other than (B) fluorine-containing (meth) acrylate described later, but acryloyl.
  • a monomer having a group or a methacryloyl group, a monomer having a vinyl group, or a monomer having an allyl group is preferable, and a monomer having an acryloyl group or a methacryloyl group is more preferable. And it is preferable that they are non-fluorine containing monomers.
  • (meth) acrylate means an acrylate or a methacrylate.
  • the polymerizable monomer is preferably a polyfunctional monomer having a plurality of polymerizable groups, and the number of polymerizable groups is preferably an integer of 1 to 6 because of excellent polymerizability.
  • the average number of polymerizable groups is preferably 1 to 4.5, and 1.5 to 3.5 is most preferable because of excellent transfer accuracy.
  • the number of polymerizable groups may be 3 or more in order to increase the crosslinking point after the polymerization reaction and to obtain physical stability (strength, heat resistance, etc.) of the cured product. preferable.
  • a monomer having 1 or 2 polymerizable groups it is preferably used in combination with monomers having different polymerizable numbers.
  • the (meth) acrylate monomer examples include the following compounds.
  • (meth) acrylic acid As a monomer having an acryloyl group or a methacryloyl group, (meth) acrylic acid, aromatic (meth) acrylate [phenoxyethyl acrylate, benzyl acrylate, etc.
  • Hydrocarbon-based (meth) acrylate [stearyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, allyl acrylate, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol di Acrylate, trimethylolpropane triacrylate, pentaaerythritol triacrylate, dipentaerythritol hexaacrylate and the like.
  • Hydrocarbon-based (meth) acrylates containing etheric oxygen atoms [ethoxyethyl acrylate, methoxyethyl acrylate, glycidyl acrylate, tetrahydrofurfryl acrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate, polyoxyethylene glycol diacrylate , Tripropylene glycol diacrylate and the like.
  • Hydrocarbon-based (meth) acrylates [2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl vinyl ether, N, N-diethylaminoethyl acrylate, N, N-dimethylaminoethyl acrylate, N-vinyl pyrrolidone, dimethylaminoethyl methacrylate, etc. ], Silicone-based acrylates, and the like.
  • Others include EO-modified glycerol tri (meth) acrylate, ECH-modified glycerol tri (meth) acrylate, PO-modified glycerol tri (meth) acrylate, pentaerythritol triacrylate, EO-modified phosphate triacrylate, trimethylolpropane tri (meth) Acrylate, caprolactone-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, EO-modified trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meta) ) Acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, dipentaerythritol hydroxypenta (meth) acrylate Alkyl
  • Examples of the monomer having an allyl group include p-isopropenylphenol, and examples of the monomer having a vinyl group include styrene, ⁇ -methylstyrene, acrylonitrile, and vinylcarbazole.
  • EO modification means ethylene oxide modification
  • ECH modification means epichlorohydrin modification
  • PO modification means propylene oxide modification.
  • the fluorine-containing (meth) acrylate constituting the curable resin composition (1) includes a polyfluoroalkylene chain and / or a perfluoro (polyoxyalkylene) chain, and a polymerizable group. It is preferable to have a linear perfluoroalkylene group or a perfluorooxyalkylene group having an etheric oxygen atom inserted between carbon atoms and a carbon atom and having a trifluoromethyl group in the side chain. Moreover, a linear polyfluoroalkylene chain having a trifluoromethyl group at the molecular side chain or molecular structure terminal and / or a linear perfluoro (polyoxyalkylene) chain is particularly preferred.
  • the polyfluoroalkylene chain is preferably a polyfluoroalkylene group having 2 to 24 carbon atoms.
  • the polyfluoroalkylene group may have a functional group.
  • the perfluoro (polyoxyalkylene) chain is a group consisting of (CF 2 CF 2 O) units, (CF 2 CF (CF 3 ) O) units, (CF 2 CF 2 CF 2 O) units and (CF 2 O) units. It is preferably composed of one or more perfluoro (oxyalkylene) units selected from: (CF 2 CF 2 O) units, (CF 2 CF (CF 3 ) O) units, or (CF 2 CF 2 CF 2 O). ) Units.
  • the perfluoro (polyoxyalkylene) chain is particularly preferably composed of (CF 2 CF 2 O) units because the physical properties (heat resistance, acid resistance, etc.) of the fluoropolymer are excellent.
  • the number of perfluoro (oxyalkylene) units is preferably an integer of 2 to 200, more preferably an integer of 2 to 50, since the release property and hardness of the fluoropolymer are high.
  • Examples of the polymerizable group include a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, an epoxy group, a dichitacene group, a cyano group, an isocyanate group, or a formula — (CH 2 ) aSi (M1) 3-b (M2) b.
  • a hydrolyzable silyl group is preferable, and an acryloyl group or a methacryloyl group is more preferable.
  • M1 is a substituent which is converted into a hydroxyl group by a hydrolysis reaction. Examples of such a substituent include a halogen atom, an alkoxy group, and an acyloxy group.
  • M2 is a monovalent hydrocarbon group. Examples of M2 include an alkyl group, an alkyl group substituted with one or more aryl groups, an alkenyl group, an alkynyl group, a cycloalkyl group, and an aryl group, and an alkyl group or an alkenyl group is preferable.
  • M2 is an alkyl group
  • an alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group or an ethyl group is more preferable.
  • M2 is an alkenyl group
  • an alkenyl group having 2 to 4 carbon atoms is preferable, and a vinyl group or an allyl group is more preferable.
  • a is an integer of 1 to 3, and 3 is preferable.
  • b is 0 or an integer of 1 to 3, and 0 is preferable.
  • hydrolyzable silyl groups include (CH 3 O) 3 SiCH 2 —, (CH 3 CH 2 O) 3 SiCH 2 —, (CH 3 O) 3 Si (CH 2 ) 3 — or (CH 3 CH 2 O ) 3 Si (CH 2 ) 3 — is preferred.
  • the number of polymerizable groups is preferably an integer of 1 to 4 and more preferably an integer of 1 to 3 because of excellent polymerizability. When two or more compounds are used, the average number of polymerizable groups is preferably 1 to 3.
  • the fluorine-containing (meth) acrylate has a functional group, it has excellent adhesion to the support substrate.
  • the functional group include a carboxyl group, a sulfonic acid group, a functional group having an ester bond, a functional group having an amide bond, a hydroxyl group, an amino group, a cyano group, a urethane group, an isocyanate group, and a functional group having an isocyanuric acid derivative. It is done.
  • it preferably contains at least one functional group of a functional group having a carboxyl group, a urethane group, or an isocyanuric acid derivative.
  • the isocyanuric acid derivatives include those having an isocyanuric acid skeleton and a structure in which at least one hydrogen atom bonded to the nitrogen atom is substituted with another group.
  • fluorine-containing (meth) acrylate fluoro (meth) acrylate, fluorodiene, or the like can be used.
  • Specific examples of the fluorine-containing (meth) acrylate include the following compounds.
  • the fluorine-containing (meth) acrylate used in the present invention is a fluorine-containing urethane (meth) acrylate represented by the following chemical formula (1)
  • it is effective in a state where the average fluorine element concentration (Eb) in the resin is lowered.
  • the fluorine element concentration (Es) at the surface (surface layer) of the fine concavo-convex structure of the resin mold can be increased, and the adhesiveness to the support substrate and the releasability can be expressed more effectively, which is more preferable.
  • urethane (meth) acrylate for example, “OPTOOL DAC” manufactured by Daikin Industries, Ltd. can be used.
  • a fluorine-containing (meth) acrylate may be used individually by 1 type, and may use 2 or more types together. Further, it can be used in combination with surface modifiers such as abrasion resistance, scratch resistance, fingerprint adhesion prevention, antifouling property, leveling property and water / oil repellency. For example, “Factent” manufactured by Neos Co., Ltd.
  • the fluorine-containing (meth) acrylate preferably has a molecular weight Mw of 50 to 50000, preferably a molecular weight Mw of 50 to 5000, and more preferably a molecular weight Mw of 100 to 5000 from the viewpoint of compatibility.
  • a diluting solvent may be used.
  • a solvent having a boiling point of a single solvent of 40 ° C. to 180 ° C. is preferable, 60 ° C. to 180 ° C. is more preferable, and 60 ° C. to 140 ° C. is further preferable. Two or more kinds of diluents may be used.
  • the solvent content may be at least an amount that can be dispersed in the curable resin composition (1), and is preferably more than 0 to 50 parts by weight with respect to 100 parts by weight of the curable composition (1). Considering that the amount of residual solvent after drying is removed as much as possible, more than 0 to 10 parts by weight is more preferable.
  • the solvent content is preferably 0.1 to 40 parts by weight with respect to 100 parts by weight of (meth) acrylate. If the solvent content is 0.5 part by weight or more and 20 parts by weight or less, the curability of the curable resin composition (1) can be maintained, more preferably 1 part by weight or more and 15 parts by weight or less.
  • the solvent is contained in order to reduce the film thickness of the curable resin composition (1), if the solvent content is 300 parts by weight or more and 10,000 parts by weight or less with respect to 100 parts by weight of (meth) acrylate, Since the solution stability in the drying process after a process can be maintained, it is preferable and it is more preferable if it is 300 to 1000 weight part.
  • the photopolymerization initiator constituting the curable resin composition (1) causes a radical reaction or an ionic reaction by light, and a photopolymerization initiator that causes a radical reaction is preferable.
  • Examples of the photopolymerization initiator include the following photopolymerization initiators.
  • Acetophenone-based photopolymerization initiators can be used alone or in combination of two or more.
  • Acetophenone-based photopolymerization initiators acetophenone, p-tert-butyltrichloroacetophenone, chloroacetophenone, 2,2-diethoxyacetophenone, hydroxyacetophenone, 2,2-dimethoxy-2′-phenylacetophenone, 2-aminoacetophenone, dialkyl Aminoacetophenone and the like.
  • Benzoin-based photopolymerization initiators benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-2-methyl Propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, benzyldimethyl ketal and the like.
  • Benzophenone-based photopolymerization initiators benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, methyl-o-benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, hydroxypropylbenzophenone, acrylic benzophenone, 4,4'-bis (dimethylamino) ) Benzophenone, perfluorobenzophenone, etc.
  • Thioxanthone photopolymerization initiators thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, diethylthioxanthone, dimethylthioxanthone, and the like.
  • Anthraquinone photopolymerization initiators 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone.
  • Ketal photopolymerization initiators acetophenone dimethyl ketal and benzyl dimethyl ketal.
  • photopolymerization initiators ⁇ -acyl oxime ester, benzyl- (o-ethoxycarbonyl) - ⁇ -monooxime, acyl phosphine oxide, glyoxy ester, 3-ketocoumarin, 2-ethylanthraquinone, camphorquinone, tetramethylthiuram Sulfide, azobisisobutyronitrile, benzoyl peroxide, dialkyl peroxide, tert-butyl peroxypivalate, and the like.
  • Photopolymerization initiator having a fluorine atom perfluoro tert-butyl peroxide, perfluorobenzoyl peroxide or the like.
  • the curable resin composition (1) may contain a photosensitizer.
  • the photosensitizer include n-butylamine, di-n-butylamine, tri-n-butylphosphine, allyl thiourea, s-benzisoisouronium-p-toluenesulfinate, triethylamine, diethylaminoethyl methacrylate.
  • Examples of commercially available initiators include “Irgacure (registered trademark)” manufactured by BASF Japan Ltd. (for example, Irgacure 651, 184, 500, 2959, 127, 754, 907, 369, 379, 379EG, 819, 1800, 784, OXE01, OXE02), “Darocur (registered trademark)” (for example, Darocur 1173, MBF, TPO, 4265) and the like.
  • Irgacure (registered trademark) manufactured by BASF Japan Ltd.
  • “Darocur (registered trademark)” for example, Darocur 1173, MBF, TPO, 4265
  • the photopolymerization initiator may be used alone or in combination of two or more.
  • the dispersibility of the fluorine-containing (meth) acrylate, and the fine concavo-convex structure surface (surface layer) portion of the curable resin composition (1) and the internal curability may be selected.
  • the combined use of an ⁇ -hydroxyketone photopolymerization initiator and an ⁇ -aminoketone photopolymerization initiator can be mentioned.
  • the curable resin composition (2) can be obtained by removing (B) fluorine-containing (meth) acrylate from the above-described photopolymerizable mixture.
  • the resin constituting the resin mold is a cured product of the curable resin composition (2), it is preferable from the viewpoint of transfer accuracy of the transfer material that either or both of the metal layer and the release layer are provided.
  • silicone can be added to the curable resin composition (1) described above, or the curable resin composition (2) added with silicone.
  • silicone By including silicone, the transfer accuracy of the transfer material is improved due to the releasability and slipperiness unique to silicone.
  • a linear low-polymerization silicone oil that exhibits fluidity at room temperature typified by polydimethylsiloxane (PDMS), which is a polymer of dimethylchlorosilane.
  • PDMS polydimethylsiloxane
  • these modified silicone oils silicone rubbers obtained by cross-linking linear PDMS or PDMS with a high degree of polymerization to show rubbery elasticity, modified silicone rubbers thereof, resinous silicones, PDMS and 4 Examples thereof include a silicone resin (or DQ resin) that is a resin having a three-dimensional network structure composed of functional siloxane.
  • an organic molecule is used as the cross-linking agent, or tetrafunctional siloxane (Q unit) is used.
  • Modified silicone oils and modified silicone resins are modified polysiloxane side chains and / or terminals, and are classified into reactive silicones and non-reactive silicones.
  • the reactive silicone is preferably a silicone containing an —OH group (hydroxyl group), a silicone containing an alkoxy group, a silicone containing a trialkoxy group, or a silicone containing an epoxy group.
  • the non-reactive silicone a silicone containing a phenyl group, a silicone containing both a methyl group and a phenyl group, and the like are preferable.
  • a single polysiloxane molecule having two or more modifications as described above may be used.
  • modified silicones include TSF4421 (manufactured by GE Toshiba Silicone), XF42-334 (manufactured by GE Toshiba Silicone), XF42-B3629 (manufactured by GE Toshiba Silicone), and XF42-A3161 (GE Toshiba Silicone).
  • FZ-3720 (manufactured by Toray Dow Corning), BY 16-839 (manufactured by Toray Dow Corning), SF8411 (manufactured by Dow Corning Toray), FZ-3736 (manufactured by Dow Corning Toray) , BY 16-876 (Toray Dow Corning), SF8421 (Toray Dow Corning), SF8416 (Toray Dow Corning), SH203 (Toray Dow Corning), SH230 (Toray Dow Corning) SH510 (manufactured by Toray Dow Corning), SH550 Toray Dow Corning), SH710 (Toray Dow Corning), SF8419 (Toray Dow Corning), SF8422 (Toray Dow Corning), BY16 series (Toray Dow Corning), FZ3785 (Toray Dow Corning), KF-410 (Shin-Etsu Chemical Co., Ltd.), KF-412 (Shin-Etsu Chemical Co., Ltd.), KF-413 (Shin-Etsu Chemical Co.
  • Examples of the reactive silicone include amino modification, epoxy modification, carboxyl modification, carbinol modification, methacryl modification, vinyl modification, mercapto modification, phenol modification, one-terminal reactivity, and heterofunctional modification.
  • silicone compound containing any of vinyl, methacrylic, amino, epoxy, or alicyclic epoxy groups silicone can be incorporated into the resin mold via chemical bonding, so transfer Accuracy is improved.
  • the inclusion of a silicone compound containing any one of a vinyl group, a methacryl group, an epoxy group, and an alicyclic epoxy group is preferable because the above effects can be further exhibited.
  • silicone compound containing either an epoxy group or an alicyclic epoxy group from a viewpoint of the adhesiveness to a support base material.
  • the silicone compound containing any one of vinyl group, methacryl group, amino group, epoxy group or alicyclic epoxy group only one kind may be used or a plurality may be used in combination.
  • the silicone having a photopolymerizable group and the silicone having no photopolymerizable group may be used in combination or independently.
  • silicone compounds containing vinyl groups include KR-2020 (manufactured by Shin-Etsu Silicone), X-40-2667 (manufactured by Shin-Etsu Silicone), CY52-162 (manufactured by Toray Dow Corning), and CY52-190 (Toray).
  • Dow Corning CY52-276 (Toray Dow Corning), CY52-205 (Toray Dow Corning), SE1885 (Toray Dow Corning), SE1886 (Toray Dow Corning), SR-7010 Toray Dow Corning), XE5844 (GE Toshiba Silicone) and the like.
  • silicone compounds containing a methacryl group examples include X-22-164 (manufactured by Shin-Etsu Silicone), X-22-164AS (manufactured by Shin-Etsu Silicone), X-22-164A (manufactured by Shin-Etsu Silicone), X- 22-164B (manufactured by Shin-Etsu Silicone), X-22-164C (manufactured by Shin-Etsu Silicone), X-22-164E (manufactured by Shin-Etsu Silicone) and the like.
  • silicone compound containing an amino group examples include PAM-E (manufactured by Shin-Etsu Silicone), KF-8010 (manufactured by Shin-Etsu Silicone), X-22-161A (manufactured by Shin-Etsu Silicone), X-22-161B ( Shin-Etsu Silicone), KF-8012 (Shin-Etsu Silicone), KF-8008 (Shin-Etsu Silicone), X-22-166B-3 (Shin-Etsu Silicone), TSF4700 (Momentive Performance Materials Japan) ), TSF4701 (made by Momentive Performance Materials Japan), TSF4702 (made by Momentive Performance Materials Japan), TSF4703 (made by Momentive Performance Materials Japan), TSF4704 (momentive Formalance Materials Japan), TSF4705 (Momentive Performance Materials Japan), TSF4706 (Momentive Performance Materials Japan), TSF4707 (Momentive Performance Materials Japan) Product), TSF4708 (
  • silicone compound containing an epoxy group examples include X-22-163 (manufactured by Shin-Etsu Silicone), KF-105 (manufactured by Shin-Etsu Silicone), X-22-163A (manufactured by Shin-Etsu Silicone), X-22- 163B (manufactured by Shin-Etsu Silicone), X-22-163C (manufactured by Shin-Etsu Silicone), TSF-4730 (manufactured by Momentive Performance Materials Japan), YF3965 (manufactured by Momentive Performance Materials Japan), etc. Is mentioned.
  • silicone containing an alicyclic epoxy group examples include X-22-169AS (manufactured by Shin-Etsu Silicone), X-22-169B (manufactured by Shin-Etsu Silicone), and the like.
  • the curable resin composition (4) is obtained by adding a sol-gel material described below to the curable resin compositions (1) to (3) or a composition composed only of the sol-gel material. Can be adopted.
  • a sol-gel material to the curable resin composition (1) to the curable resin composition (3), the effect of improving the replication efficiency of the mold by adopting the shrinkage specific to the sol-gel material, and the inorganic characteristic of the sol-gel material As a result, the durability of the fine concavo-convex structure is improved, and the repeated use of the transfer mold is improved.
  • sol-gel material constituting the resin mold a group of compounds that are cured by hydrolysis and polycondensation by the action of heat and catalyst, metal alkoxide, metal alcoholate, metal chelate compound, halogenated silane, liquid glass, It is not particularly limited as long as it is spin-on-glass or a reaction product thereof. These are collectively called metal alkoxides.
  • a metal alkoxide is a bond between a metal species represented by Si, Ti, Zr, Zn, Sn, B, In, and Al and a functional group such as a hydroxy group, a methoxy group, an ethoxy group, a propyl group, or an isopropyl group.
  • This is a group of compounds.
  • These functional groups cause hydrolysis / polycondensation reaction with water, an organic solvent, a hydrolysis catalyst, or the like to generate a metalloxane bond (—Me—O—Me— bond, where Me is a metal species).
  • a metalloxane bond such as —Si—O—Si— is generated.
  • a bond such as -M1-O-Si- can be generated.
  • the metal alkoxide of the metal species (Si) for example, dimethyldiethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, methyltriethoxysilane, vinyltriethoxysilane, p-styryltriethoxysilane, methylphenyldioxysilane
  • examples thereof include ethoxysilane, tetraethoxysilane, p-styryltriethoxysilane, and the like, and compounds in which the ethoxy group of these compound groups is replaced with a methoxy group, a propyl group, or an isopropyl group.
  • a compound having a hydroxy group such as diphenylsilanediol and dimethylsilanediol can be selected.
  • one or more of the functional groups may be directly substituted with a phenyl group or the like without using an oxygen atom from a metal species.
  • a phenyl group or the like for example, diphenylsilanediol, dimethylsilanediol, etc. are mentioned.
  • Halogenated silane is a group of compounds in which the metal species of the metal alkoxide is silicon and the functional group undergoing hydrolytic polycondensation is replaced with a halogen atom.
  • liquid glass examples include TGA series manufactured by Apollo Ring.
  • Other sol-gel compounds can be added in accordance with the desired physical properties.
  • a silsesquioxane compound can also be used as the metal alkoxide.
  • Silsesquioxane is a compound in which one organic group and three oxygen atoms are bonded to one silicon atom.
  • the silsesquioxane is not particularly limited as long as it is a polysiloxane represented by the composition formula (RSiO 3/2 ) n.
  • the polysiloxane having any structure such as a cage type, a ladder type, or a random structure. It may be.
  • R may be a substituted or unsubstituted siloxy group or any other substituent.
  • n is preferably 8 to 12, more preferably 8 to 10 and further preferably n is 8, in order to improve the curability of the curable resin composition (4).
  • the n Rs may be the same or different.
  • silsesquioxane compound examples include polyhydrogen silsesquioxane, polymethyl silsesquioxane, polyethyl silsesquioxane, polypropyl silsesquioxane, polyisopropyl silsesquioxane, polybutyl silsesquioxane, and polybutyl silsesquioxane.
  • at least one of n Rs for these silsesquioxanes may be substituted with a substituent exemplified below.
  • substituents examples include trifluoromethyl, 2,2,2-trifluoroethyl, 3,3,3-trifluoropropyl, 2,2,3,3-tetrafluoropropyl, 2,2,3,3,3 -Pentafluoropropyl, 2,2,2-trifluoro-1-trifluoromethylethyl, 2,2,3,4,4,4-hexafluorobutyl, 2,2,3,3,4,4,5 , 5-octafluoropentyl, 2,2,2-trifluoroethyl, 2,2,3,3-tetrafluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2,3,3 , 4,4,5,5-octafluoropentyl, 3,3,3-trifluoropropyl, nonafluoro-1,1,2,2-tetrahydrohexyl, tridecafluoro-1,1,2,2-tetrahydrooctyl , Heptade Fluoro-1,1,2,
  • the metal alkoxide may be in a prepolymer state in which the polymerization reaction partially reacts and an unreacted functional group remains.
  • a prepolymer in which metal species are connected via an oxygen element can be obtained. That is, a prepolymer having a large molecular weight can be produced by partial condensation.
  • the degree of partial condensation can be controlled by the reaction atmosphere, the combination of metal alkoxides, and the like, and the degree of partial condensation used in the prepolymer state can be appropriately selected depending on the application and method of use, and is not particularly limited.
  • the viscosity of the curable resin composition containing a partial condensate is 50 cP or more, transfer accuracy and stability to water vapor are further improved, and when it is 100 cP or more, these effects can be more exhibited. Therefore, it is still preferable.
  • it is preferably 150 cP or more, and more preferably 250 cP or more.
  • the upper limit value of the viscosity is not particularly limited as long as it can be transferred and formed, but is preferably 5000 cP or less and more preferably 4000 cP or less from the viewpoint of transfer accuracy.
  • the prepolymer which promoted partial condensation can be obtained by polycondensation based on a dehydration reaction and / or polycondensation based on a dealcoholization reaction.
  • a prepolymer can be obtained by heating a solution comprising a metal alkoxide, water, and a solvent (alcohol, ketone, ether, etc.) in the range of 20 ° C. to 150 ° C. to obtain hydrolysis and polycondensation.
  • the degree of polycondensation can be controlled by temperature, reaction time, and pressure (decompression force), and can be selected as appropriate. Moreover, it is also possible to reduce the molecular weight distribution of the prepolymer by gradually performing hydrolysis and polycondensation using water (water vapor based on humidity) in the environmental atmosphere without adding water. Furthermore, in order to promote polycondensation, the method of irradiating energy rays is also mentioned.
  • the light source of the energy beam can be appropriately selected depending on the type of the metal alkoxide, and is not particularly limited. However, a UV-LED light source, a metal halide light source, a high-pressure mercury lamp light source, or the like can be employed.
  • a photoacid generator to the metal alkoxide and irradiating the composition with energy rays, photoacid is generated from the photoacid generator, and polycondensation of the metal alkoxide using the photoacid as a catalyst.
  • a prepolymer can be obtained.
  • the prepolymer can also be obtained by performing the above operation in the state of chelating the metal alkoxide.
  • the prepolymer is defined as a state in which at least four or more metal elements are connected via oxygen atoms.
  • a state in which a metal element is condensed to -O-M1-O-M2-O-M3-O-M4-O- or more is defined as a prepolymer.
  • M1, M2, M3, and M4 are metal elements, and may be the same metal element or different.
  • a metal alkoxide having titanium as a metal species is pre-condensed to form a metalloxane bond composed of —O—Ti—O—, the range of n ⁇ 4 in the general formula of [—O—Ti—] n And prepolymer.
  • a metal alkoxide having titanium as a metal species and a metal alkoxide having silicon as a metal species are pre-condensed to generate a metalloxane bond composed of —O—Ti—O—Si—O—, [ the prepolymer in the range of n ⁇ 2 in -O-Ti-O-Si-] n in the general formula.
  • a dissimilar metal element such as —O—Ti—O—Si—, the elements are not necessarily alternately arranged like —O—Ti—O—Si—.
  • a prepolymer is used in the range of n ⁇ 4.
  • the element A and the element B are used, and the chemical composition is expressed as -AB-, but this is an expression for explaining the bond between the element A and the element B.
  • the same expression is used even when the element A has three or more bonds.
  • the expression -A-B- represents at least the chemical bond between the element A and the element B, and includes that the element A forms a chemical bond with other than the element B.
  • the metal alkoxide can contain a fluorine-containing silane coupling agent.
  • a fluorine-containing silane coupling agent By including a fluorine-containing silane coupling agent, it is possible to reduce the energy of the surface of the fine concavo-convex structure of the resin mold made of a cured product of the metal alkoxide. Transfer accuracy is improved. This means that the release layer is previously incorporated in the mold.
  • fluorine-containing silane coupling agent for example, a general formula F 3 C— (CF 2 ) n — (CH 2 ) m —Si (O—R) 3 (where n is an integer of 1 to 11, m Is an integer of 1 to 4 and R is an alkyl group having 1 to 3 carbon atoms.),
  • a polyfluoroalkylene chain and / or a perfluoro (polyoxyalkylene) chain. May be included.
  • a linear perfluoroalkylene group or a perfluorooxyalkylene group having an etheric oxygen atom inserted between carbon atoms and a trifluoromethyl group in the side chain is more preferred.
  • a linear polyfluoroalkylene chain having a trifluoromethyl group at the molecular side chain or molecular structure terminal and / or a linear perfluoro (polyoxyalkylene) chain is particularly preferred.
  • the polyfluoroalkylene chain is preferably a polyfluoroalkylene group having 2 to 24 carbon atoms.
  • the perfluoro (polyoxyalkylene) chain consists of (CF 2 CF 2 O) units, (CF 2 CF (CF 3 ) O) units, (CF 2 CF 2 CF 2 O) units, and (CF 2 O) units.
  • the perfluoro (polyoxyalkylene) chain is particularly preferably composed of (CF 2 CF 2 O) units from the viewpoint of excellent segregation on the surface.
  • the metal alkoxide can contain polysilane.
  • Polysilane is a compound in which a silicon element constitutes a main chain, and the main chain is composed of repeating —Si—Si—.
  • energy rays for example, UV
  • a siloxane bond is generated.
  • a siloxane bond can be effectively generated by UV irradiation, and the transfer accuracy when a mold is transferred and formed using a metal alkoxide as a raw material is improved.
  • the resin mold may be a hybrid including an inorganic segment and an organic segment.
  • the transfer accuracy when the resin mold is produced by transfer is improved, and the physical durability of the fine concavo-convex structure is also improved.
  • the effect of suppressing the penetration of the transfer material into the fine concavo-convex structure of the resin mold is increased, and as a result, the transfer accuracy can be improved.
  • the hybrid include a resin that can be photopolymerized (or thermally polymerized) with an inorganic precursor, and a molecule in which an organic polymer and an inorganic segment are bonded by a covalent bond.
  • the sol-gel material when used as the inorganic precursor, it means that a photopolymerizable resin is included in addition to the sol-gel material containing the silane coupling agent.
  • a photopolymerizable resin is included in addition to the sol-gel material containing the silane coupling agent.
  • a metal alkoxide, a silane coupling material having a photopolymerizable group, a metal alkoxide, a silane coupling material having a photopolymerizable group, a radical polymerization resin, or the like can be mixed. .
  • silicone may be added thereto.
  • the mixing ratio of the metal alkoxide containing the silane coupling agent and the photopolymerizable resin is preferably in the range of 3: 7 to 7: 3 from the viewpoint of transfer accuracy.
  • thermoplastic resin that composes the resin mold includes polypropylene, polyethylene, polyethylene terephthalate, polymethylpetacrylate, cycloolefin polymer, cycloolefin copolymer, transparent fluororesin, polyethylene, polypropylene, polystyrene, acrylonitrile / styrene polymer, acrylonitrile.
  • thermosetting resin constituting the resin mold examples include polyimide, epoxy resin, and urethane resin.
  • the material of the support substrate (film) constituting the resin mold there is no particular limitation on the material of the support substrate (film) constituting the resin mold, and any material such as inorganic materials such as glass, ceramic and metal, and organic materials such as plastic can be used.
  • any material such as inorganic materials such as glass, ceramic and metal, and organic materials such as plastic can be used.
  • plates, sheets, films, thin films, woven fabrics, non-woven fabrics, and other arbitrary shapes and composites thereof can be used, but they are flexible and have excellent continuous productivity. It is particularly preferable to include a thin film, a woven fabric, a non-woven fabric and the like.
  • the flexible material examples include polymethyl methacrylate resin, polycarbonate resin, polystyrene resin, cycloolefin resin (COP), cross-linked polyethylene resin, polyvinyl chloride resin, polyacrylate resin, polyphenylene ether resin, and modified polyphenylene ether resin.
  • polymethyl methacrylate resin polycarbonate resin
  • polystyrene resin polystyrene resin
  • COP cycloolefin resin
  • cross-linked polyethylene resin polyvinyl chloride resin
  • polyacrylate resin polyphenylene ether resin
  • modified polyphenylene ether resin modified polyphenylene ether resin
  • thermoplastic resins such as polyetherimide resin, polyether sulfone resin, polysulfone resin, polyether ketone resin, polyethylene terephthalate (PET) resin, polyethylene naphthalate resin, polyethylene resin, polypropylene resin, polybutylene terephthalate Crystalline thermoplastic resins such as resins, aromatic polyester resins, polyacetal resins, polyamide resins, and ultraviolet (UV) curable resins such as acrylic, epoxy, and urethane resins And thermosetting resins.
  • the supporting base material can be configured by combining an ultraviolet curable resin or a thermosetting resin with an inorganic substrate such as glass, the above thermoplastic resin, or a triacetate resin, or using them alone.
  • a filling layer transfer mold can be manufactured by filling and disposing the filling layer in the concave portion of the pattern portion of the transfer mold.
  • the packed bed transfer mold 400 includes a transfer mold 401.
  • the transfer mold 401 has a fine concavo-convex structure on the surface of the resin layer 403 provided on the support substrate 402.
  • a recessed layer 403 a provided in the resin layer 403 is filled with a filling layer 404.
  • S means the average position of the convex top 403b of the fine concavo-convex structure of the transfer mold 401.
  • B means the average position of the bottom of the concave portion 403 a of the fine concavo-convex structure of the transfer mold 401.
  • Scc means the average position of the exposed surface of the filling layer 404 disposed inside the concave portion 403a of the fine concavo-convex structure of the transfer mold 401.
  • the shortest distance between the position S and the position B is the average depth (height) h of the fine concavo-convex structure of the transfer mold 401.
  • the shortest distance between the position S and the position Scc is an index expressing the degree of filling of the filling layer 404 and is expressed as lcc.
  • the filling layer 404 is disposed so as to satisfy the range of 0 ⁇ lcc ⁇ 1.0 h inside the concave portion 403 a of the fine concavo-convex structure of the transfer mold 401.
  • lcc ⁇ 0.9h more preferably lcc ⁇ 0.7h
  • lcc ⁇ Most preferred is 0.6 h.
  • the lower limit value is preferably 0.02h ⁇ lcc, more preferably 0.05h ⁇ lcc, and most preferably 0.1h ⁇ lcc.
  • the filling of the filling layer 404 will be described.
  • a solution obtained by diluting the filling layer material to the transfer mold 401 and removing the excess solvent, the filling layer transfer mold 400 can be obtained.
  • an aqueous solvent for example, alcohol, ketone, ether, etc.
  • Coating methods include roller coating, bar coating, die coating, spray coating, gravure coating, micro gravure coating, ink jet method, air knife coating method, flow coating method, curtain coating method, spin coating method, etc. Etc. are applicable.
  • the concentration for diluting the packed bed material is not particularly limited as long as the solid content of the packed bed material per unit volume is smaller than the volume of the concavo-convex structure existing under the unit area.
  • the contact angle of water with the pattern portion of the transfer mold 401 is 90 degrees or more, and the aperture ratio of the pattern portion is 45. % Or more, preferably 50% or more, more preferably 55% or more, and most preferably 65% or more.
  • the solvent for diluting the packed bed material is preferably an aqueous solvent because the above effect can be further exhibited.
  • the aqueous solvent include alcohol, ether, ester, and ketone. In particular, alcohol, ether, and ketone are preferable.
  • the contact angle of water with respect to the barrier region is preferably 90 degrees or more from the viewpoint of hindering penetration of the pattern portion by the coating liquid repelled on the non-pan portion.
  • the filling layer material includes a material whose state changes in the solvent volatilization process after the dilution coating, it is estimated that the driving force of reducing the area of the material itself also works at the same time.
  • the change in form include an exothermic reaction and a change in which the viscosity increases.
  • a sol-gel material typified by a metal alkoxide
  • the energy of the sol-gel material becomes unstable, so that the driving force that moves away from the solvent liquid surface (solvent-air interface) that decreases as the solvent is dried works.
  • the sol-gel material is satisfactorily inside the recess of the pattern part. Is placed in the filling.
  • the filling rate of the macro packed bed in the pattern portion can be equalized.
  • coating failure (2) as an example, as shown in FIG. 27, the above-described coating was performed on a general transfer mold 501 without a barrier region, and a filling layer transfer mold 500 was manufactured.
  • the filling layer 504 filled and applied to the pattern portion 505 has a large distribution of filling rate due to the penetration of the coating liquid repelled on the non-pattern portion 506.
  • a barrier region 407 is provided at the boundary between the pattern part 405 and the non-pattern part 406. Since the penetration of the coating liquid repelled on the non-pattern part 406 can be effectively inhibited, the distribution of the filling rate can be reduced. That is, the filling rate is substantially the same at any of the points A, B, and C. The reason why the filling rate is almost the same at any of points A, B, and C is to provide the barrier region 407, and by providing the barrier region 407 within the above-described condition range.
  • the filling layer transfer mold 400 having a very small filling rate distribution of the filling layer 404 can be manufactured, the in-plane distribution when the difficult-to-process substrate is finely processed using the filling layer transfer mold 400 is reduced.
  • the effect of the fine concavo-convex structure provided on the difficult-to-process base material can be uniformly exhibited in the plane.
  • FIG. 29 is a process diagram showing each process of the inorganic substrate processing method using the packed bed transfer mold according to the present embodiment.
  • an organic layer 410 is formed on the filling layer transfer mold 400, and the organic layer 410 is bonded to the inorganic base material 411.
  • the filling layer transfer mold 400 may be bonded to the organic layer 410 formed on the inorganic base material 411.
  • the filling layer 404 and the organic layer 410 are bonded to each other by, for example, energy beam irradiation or heat treatment.
  • the transfer layer 401 and the organic layer 410 can be transferred and formed on the inorganic substrate 411 by peeling the transfer template 401 as shown in FIG. 29C. Thereafter, as shown in FIG.
  • the organic layer 410 can be easily finely processed by dry etching from the filling layer 403 side. Furthermore, as shown in FIG. 29E, the inorganic substrate 411 can be easily formed as shown in FIG. 29F by using the fine mask pattern having a high aspect ratio formed of the obtained filling layer 404 and organic layer 410 as a mask. Can be processed.
  • the inorganic base material 411 can be processed in this way, difficult-to-process base materials such as sapphire can be processed easily.
  • the surface of the sapphire substrate can be easily processed by the above method.
  • An LED can be manufactured by forming a semiconductor light emitting element on the processed sapphire surface.
  • the pitch of the fine concavo-convex structure of the transfer template is 100 nm to 500 nm and the height is 50 nm to 500 nm
  • the internal quantum efficiency of the LED can be improved.
  • the hole shape is a regular arrangement on the nanoscale and has a large microscale periodicity, and a modulation having a microscale period added to the pitch, the light extraction efficiency can be improved at the same time. It becomes possible and a highly efficient LED can be manufactured.
  • 30 and 31 are process diagrams for explaining a method for forming a fine concavo-convex structure on an object to be processed using the fine concavo-convex structure transfer mold according to the present embodiment.
  • the transfer mold 10 has a concavo-convex structure 11 formed on the main surface thereof.
  • the concavo-convex structure 11 includes a plurality of concave portions 11a and convex portions 11b.
  • the transfer mold 10 is, for example, a film-shaped or sheet-shaped resin mold.
  • a second mask layer 12 for patterning a first mask layer to be described later is filled into the recess 11a of the concavo-convex structure 11 of the transfer mold 10.
  • the second mask layer 12 is made of, for example, a sol-gel material.
  • a first mask layer 13 is formed on the concavo-convex structure 11 including the second mask layer 12.
  • the first mask layer 13 is used for patterning an object to be processed which will be described later.
  • the first mask layer 13 is made of, for example, a photocurable resin or a thermosetting resin.
  • a protective layer 14 can be provided on the upper side of the first mask layer 13.
  • the protective layer 14 protects the first mask layer 13 and is not essential.
  • the laminate composed of the transfer mold 10, the second mask layer 12, and the first mask layer 13 is referred to as a fine pattern forming laminate 15 or simply a laminate 15.
  • an object 20 as shown in FIG. 31A is prepared.
  • the workpiece 20 is, for example, a sapphire substrate.
  • the laminated body 15 after removing the protective layer 14 on the main surface of the object 20 to be processed, and the exposed surface of the first mask layer 13 as the main surface of the object 20 to be processed. Laminate them face to face (thermocompression bonding).
  • the stacked body 15 is irradiated with energy rays to cure the first mask layer 13, and the stacked body 15 is bonded to the object to be processed 20.
  • the transfer mold 10 is peeled from the first mask layer 13 and the second mask layer 12.
  • an intermediate body 21 including the object to be processed 20, the first mask layer 13, and the second mask layer 12 is obtained.
  • the first mask layer 13 is patterned by ashing, for example, as shown in FIG. 31D. Further, the processed object 20 is subjected to, for example, reactive ion etching using the patterned first mask layer 13 as a mask, and a fine uneven pattern 22 is formed on the main surface of the processed object 20 as shown in FIG. 31E. Form. Finally, the first mask layer 13 remaining on the main surface of the target object 20 is removed to obtain the target object 20 having the fine uneven pattern 22 as shown in FIG. 31F.
  • the process from obtaining the laminate 15 from the transfer mold 10 shown in FIGS. 30A to 30C is performed in one line (hereinafter referred to as the first line). Thereafter, FIGS. 31A to 31F are performed on another line (hereinafter referred to as a second line).
  • the first line and the second line are performed in separate facilities. For this reason, for example, when the transfer mold 10 is in the form of a film and has flexibility, the laminate 15 is stored or transported in the form of a roll (roll). The laminate 15 is stored or transported by stacking a plurality of laminates 15 when the transfer mold 10 is in the form of a sheet.
  • the first line is a supplier line of the laminate 15 and the second line is a user line of the laminate 15.
  • the processed object 20 can be finely processed by reflecting the accuracy of the fine uneven structure of the transfer mold 10 constituting the laminate 15. That is, it is possible to ensure the accuracy of the fine concavo-convex structure with the laminate 15, and the workpiece 20 can be finely processed with high accuracy in the plane without using a complicated process or apparatus.
  • the laminated body 15 can be used at a place optimal for manufacturing a device using the processed object 20 to be processed. That is, a device having a stable function can be manufactured.
  • the first line is the supplier line of the laminate 15 and the second line is the user line of the laminate 15, which is optimal for the processing of the workpiece 20.
  • the laminated body 15 can be used in an optimum environment for manufacturing a device using the processed object 20 thus prepared. For this reason, it is possible to improve the throughput of the processing object 20 and the device assembly.
  • the laminate 15 is a laminate composed of a transfer mold 10 and a functional layer provided on the fine concavo-convex structure of the transfer mold 10. That is, it is possible to ensure the placement accuracy of the mask layer that governs the processing accuracy of the workpiece 20 with the accuracy of the fine concavo-convex structure of the transfer mold 10 of the laminate 15.
  • the first line is used as the supplier line of the laminate 15 and the second line is used as the user line of the laminate 15 to manufacture the device using the processed object 20.
  • the object to be processed 20 can be processed and used with high accuracy using the laminate 15.
  • DACHP Fluorine-containing urethane (meth) acrylate (OPTOOL DAC HP (manufactured by Daikin Industries))
  • M350 Trimethylolpropane triacrylate (M350, manufactured by Toagosei Co., Ltd.)
  • I. 184 1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure (registered trademark) 184, manufactured by BASF) ⁇ I. 369...
  • the surface (surface layer) fluorine element concentration of the resin mold was measured by X-ray photoelectron spectroscopy (XPS). Since the penetration depth of X-rays into the sample surface in XPS is as shallow as several nm, the measured value of XPS was adopted as the fluorine element concentration (Es) on the resin mold surface (surface layer) in the present invention.
  • the resin mold was cut out as a small piece of about 2 mm square and covered with a 1 mm ⁇ 2 mm slot type mask and subjected to XPS measurement under the following conditions.
  • a cylindrical mold A having only a pattern part 301 (refer to FIG. 23 below) and a cylindrical mold B having a pattern part 301 and a barrier region 302 were produced.
  • the concavo-convex structure of the pattern portion 301 is such that both the cylindrical molds A and B have a pitch of 460 nm, a height of 460 nm, and a convex portion top diameter of 50 nm.
  • the barrier region 302 in the cylindrical mold B was formed with a width of 5 mm outside the pattern portion 301.
  • Durasurf HD-1101Z manufactured by Daikin Chemical Industries
  • Durasurf HD-ZV manufactured by Daikin Chemical Industries
  • PET film A curable resin composition was applied to an easily adhesive surface of A4100 (manufactured by Toyobo Co., Ltd .: width 300 mm, thickness 100 ⁇ m) by microgravure coating (manufactured by Yurai Seiki Co., Ltd.) so as to have a coating film thickness of 6 ⁇ m.
  • the PET film coated with the curable resin composition was pressed against each of the cylindrical molds A and B with a nip roll (0.1 MPa), and the temperature was 25 ° C., the humidity was 60%, and the bottom of the lamp center.
  • Ultraviolet rays are irradiated using a UV exposure apparatus (H bulb) manufactured by Fusion UV Systems Japan Co., Ltd.
  • a reel-shaped resin mold C (length: 200 m, width: 300 mm) was transferred.
  • the shape of the surface fine uneven structure in the pattern portion 311 of the reel-shaped resin mold C was confirmed by observation with a scanning electron microscope.
  • the hole-shaped structure had a pitch of 460 nm, a depth of 460 nm, and an opening width of 230 nm.
  • PET film A4100 (manufactured by Toyobo Co., Ltd .: 300 mm wide, 100 ⁇ m thick) curable resin similar to the resin used when the resin mold C was prepared by microgravure coating (manufactured by Yurai Seiki Co., Ltd.) The composition was applied so as to have a coating film thickness of 6 ⁇ m.
  • the PET film coated with the curable resin composition is pressed against the fine concavo-convex structure surface of the resin mold C obtained by direct transfer from the cylindrical mold A or B with a nip roll (0.1 MPa), Irradiate ultraviolet rays using a UV exposure apparatus (H bulb) manufactured by Fusion UV Systems Japan Co., Ltd.
  • a plurality of reel-shaped resin molds D (200 m in length and 300 mm in width) having a fine concavo-convex structure similar to the cylindrical mold A or B, which is continuously photocured and has a fine concavo-convex structure transferred to the surface. Obtained.
  • the shape of the surface fine concavo-convex structure of the reel-shaped resin mold D was confirmed by observation with a scanning electron microscope. As a result, the dot-shaped structure had a pitch of 460 nm, a height of 460 nm, and a convex top diameter of 50 nm.
  • the ratio (Es / Eb) between the surface (surface layer) fluorine element concentration (Es) and the average fluorine element concentration (Eb) of the resin mold D having the obtained dot shape is 40 to 80 depending on the charged amount of DACHP. It was confirmed that the contact angles of the transfer region 311 and the barrier region 312 of the resin mold D with respect to water are both greater than 90 degrees.
  • Materials E, F, and G were diluted with PGME or MIBK.
  • the dilution ratio is in the range of 1% to 5%, from the state in which only the fine uneven structure of the resin mold D is filled to the state in which the fine uneven structure is completely filled and the coating film is formed on the fine uneven structure Tried until.
  • the coating of the materials E, F, and G on the fine concavo-convex structure surface of the resin mold D was performed using the same apparatus as that used in the production of the above (b) reel-shaped transfer mold (IV).
  • the diluted material was applied to the fine concavo-convex structure surface of the resin mold D by microgravure coating, and the state of passing through an 80 degree dry atmosphere was confirmed.
  • (D) Structure of barrier region In the fine uneven structure in the barrier region, the average roughness factor Rf1 of the pattern portion and the average roughness factor Rf2 of the barrier region are continuous, and the average roughness factor Rf2 of the barrier region is a non-pattern portion.
  • FIG. 32 is a graph showing the relationship between the circumferential pitch and distance (graph 100) and the roughness factor Rf and distance (graph 101) in this case.
  • the feed pitch is circumferential pitch ⁇ (0.866).
  • the pitch at point 0 (distance 0 mm) is 460 nm and is continuous with the pattern portion.
  • the circumferential pitch increases exponentially.
  • the roughness factor Rf2 continuously changes to 1 which is flat. That is, the roughness factor Rf2 decreases from the pattern portion side to the barrier region side.
  • the aperture ratio increases from the pattern portion side to the barrier region side.
  • FIG. 33 is a graph showing the relationship between the feed pitch and distance (graph 102) and the roughness factor Rf and distance (graph 103) in this case.
  • the horizontal axis of the graph shown in FIG. 33 indicates the distance [mm] from the interface (point 0) between the pattern portion and the barrier region, the vertical axis (left) indicates the feed pitch [nm], and the vertical axis (right) indicates The value of the roughness factor Rf is shown.
  • the axial pitch is constant at 460 nm.
  • the feed pitch at point 0 (distance 0 mm) is 398 nm and is continuous with the pattern portion.
  • the feed pitch increases exponentially as the distance from point 0 increases.
  • the roughness factor Rf continuously changes to 1 which is flat. That is, the roughness factor Rf2 decreases from the pattern portion side to the barrier region side.
  • the aperture ratio increases from the pattern portion side to the barrier region side.
  • Example 1 When the resin mold D derived from the mold B having the barrier region is used (Example 1), regardless of the materials E to G and their concentrations, the interface between the pattern portion and the barrier region, and the barrier region and the non-pattern portion No unevenness was observed at the interface, and a good coating was obtained. This is because, as shown in FIG. 4A, the stress inside the film of the coating liquid 113 is relaxed on the barrier region 111, the film of the coating liquid 113 is not split, and the coating is performed well. It is.
  • a similar study was conducted using a flat plate mold instead of a reel-shaped resin mold. Quartz glass was used as the base material of the flat plate mold, and a fine concavo-convex structure was formed on the flat plate quartz surface by a direct drawing lithography method using a semiconductor laser.
  • a flat plate mold As the flat plate mold, a flat plate mold A2 having only a pattern portion and a flat plate mold B2 having a pattern portion and a barrier region were produced.
  • the fine concavo-convex structure in the pattern part has a pitch of 460 nm, a height of 460 nm, a convex part bottom width of 230 nm, and a convex part top diameter of 40 nm in both the flat plate molds A2 and B2.
  • the barrier region in the flat plate mold B2 was prepared using a width of 5 mm around the pattern portion.
  • the material H was formed on the quartz substrate by spin coating to a thickness of 500 nm to 1000 nm.
  • the coated surface of the resin mold was bonded to the material H film, pressed at 0.05 MPa, and then irradiated with UV. Finally, the resin mold was peeled off.
  • Table 2 shows the results of Examples and Comparative Examples.
  • (H) Cylindrical mold preparation Quartz glass was used as the substrate of the cylindrical mold, and a fine concavo-convex structure was formed on the quartz glass surface by a direct drawing lithography method using a semiconductor laser.
  • a cylindrical mold I having only a pattern part 301 (refer to FIG. 23 hereafter) and a cylindrical mold J having a pattern part 301 and a barrier region 302 were produced.
  • the fine concavo-convex structure of the pattern portion 301 is set such that the cylindrical molds I and J have a pitch of 460 nm, a height of 460 nm, and an opening width of 430 nm.
  • the barrier region 302 in the cylindrical mold J was formed with a width of 5 mm outside the pattern portion 301.
  • Durasurf HD-1110Z (manufactured by Daikin Chemical Industries) was applied to the cylindrical molds I and J, heated at 60 ° C. for 1 hour, and then allowed to stand at room temperature for 24 hours and fixed. Thereafter, it was washed 3 times with Durasurf HD-ZV (manufactured by Daikin Chemical Industries), and a mold release treatment was performed.
  • PET film A curable resin composition was applied to an easily adhesive surface of A4100 (manufactured by Toyobo Co., Ltd .: width 300 mm, thickness 100 ⁇ m) by microgravure coating (manufactured by Yurai Seiki Co., Ltd.) so as to have a coating film thickness of 6 ⁇ m.
  • a PET film coated with the curable resin composition is pressed against each of the cylindrical molds I and J with a nip roll (0.1 MPa), and the temperature is 25 ° C., the humidity is 60%, and the center of the lamp is below.
  • Ultraviolet rays are irradiated using a UV exposure apparatus (H bulb) manufactured by Fusion UV Systems Japan Co., Ltd.
  • a reel-shaped resin mold K (length: 200 m, width: 300 mm) was transferred.
  • the dot shape had a pitch of 460 nm and a height of 460 nm.
  • PET film A4100 (manufactured by Toyobo Co., Ltd .: 300 mm wide, 100 ⁇ m thick) curable resin similar to the resin used when the resin mold K was produced by microgravure coating (manufactured by Yurai Seiki Co., Ltd.) The composition was applied so as to have a coating film thickness of 6 ⁇ m. Next, the PET film coated with the curable resin composition was pressed with a nip roll (0.1 MPa) against the fine concavo-convex structure surface of the resin mold K obtained by direct transfer from the cylindrical mold I or J. Irradiate ultraviolet rays using a UV exposure apparatus (H bulb) manufactured by Fusion UV Systems Japan Co., Ltd.
  • H bulb UV exposure apparatus manufactured by Fusion UV Systems Japan Co., Ltd.
  • the integrated exposure amount under the lamp center is 600 mJ / cm 2 at a temperature of 25 ° C. and a humidity of 60%.
  • a plurality of reel-shaped resin molds L (length: 200 m, width: 300 mm) having a fine uneven structure similar to the cylindrical mold I or J, which is continuously photocured and has a fine uneven structure transferred to the surface. Obtained.
  • the hole shape was a pitch of 460 nm, a height of 460 nm, and an opening width of 430 nm.
  • the ratio (Es / Eb) between the surface (surface layer) fluorine element concentration (Es) and the average fluorine element concentration (Eb) of the obtained resin mold D having the hole shape is 40 to 80 depending on the charged amount of DACHP. It was confirmed that the contact angles of the pattern part 311 of the resin mold L and the barrier region 312 with respect to water are both greater than 90 degrees.
  • Materials E, F, and G were diluted with PGME or MIBK.
  • the dilution ratio is in the range of 1% to 5%, from the state in which only the fine uneven structure of the resin mold L is filled to the state in which the fine uneven structure is completely filled and the coating film is formed on the fine uneven structure Tried until.
  • the coating of the materials E, F, and G on the fine concavo-convex structure surface of the resin mold L was performed using the same apparatus as the above (i) production of the reel-shaped transfer mold (I).
  • the diluted materials E, F, and G were applied to the fine concavo-convex structure surface of the resin mold L by microgravure coating, and the state of passing through a dry atmosphere of 80 degrees was confirmed.
  • the other is that, in the fine uneven structure in the barrier region, the average roughness factor Rf1 of the pattern portion and the average roughness factor Rf2 of the barrier region are discontinuous, and the average roughness factor Rf2 of the barrier region is non-patterned (
  • FIG. 34 is a diagram relating to the barrier region A, and is a graph showing the relationship between the feed pitch and distance (graph 104) and the roughness factor Rf and distance (graph 105) in this case.
  • the horizontal axis of the graph shown in FIG. 34 indicates the distance [mm] from the interface (point 0) between the pattern part and the barrier region, the vertical axis (left) indicates the feed pitch [nm], and the vertical axis (right) indicates The value of the roughness factor Rf is shown.
  • the feed pitch at point 0 (distance 0 mm) is 398 nm and is continuous with the pattern portion.
  • the feed pitch increases exponentially as the distance from point 0 increases.
  • the roughness factor Rf continuously changes to 1 which is flat. That is, the roughness factor Rf2 decreases from the pattern portion side to the barrier region side.
  • the aperture ratio decreases from the pattern portion side to the barrier region side.
  • FIG. 35 is a diagram relating to the barrier region B, and is a graph showing the relationship between the feed pitch and distance (graph 106) and the roughness factor Rf and distance (graph 107) in this case.
  • the horizontal axis of the graph shown in FIG. 35 indicates the distance [mm] from the interface (point 0) between the pattern part and the barrier region, the vertical axis (left) indicates the feed pitch [nm], and the vertical axis (right) indicates The value of the roughness factor Rf is shown.
  • Rf (A) and feed pitch (B) of the pattern part are also used as reference points in order to show discontinuity of Rf and feed pitch of the pattern part and the barrier region at the position of point 0 (distance 0 mm). Described.
  • the coating liquid repelled in the non-pattern part is repelled regardless of the materials E to G and the concentration thereof. It moved on the non-patterned part of the resin mold due to self-flow until it became stable and the flow caused by the vibration of the resin mold, but it could not get over the barrier area and was parallel to the barrier area on the non-patterned side of the barrier area. Arranged. For this reason, no coating spots were observed at the pattern edge portion.
  • the coating liquid that was repelled on the non-pattern part, headed toward the pattern part side, and prevented from entering the pattern part by the barrier area was arranged along the non-pattern part side of the barrier area. Good coating results were obtained both with the barrier region A and with the barrier region B, but the barrier property of the coating liquid repelled on the non-patterned portion (the repelling condition in the barrier region) is The case where the barrier region B was provided was stronger.
  • a similar examination was performed using a flat plate mold instead of a cylindrical mold. Quartz glass was used as the base material of the flat plate mold, and a fine concavo-convex structure was formed on the flat plate quartz surface by a direct drawing lithography method using a semiconductor laser.
  • a flat plate mold I2 having only a pattern portion and a flat plate mold J2 having a pattern portion and a barrier region were produced.
  • the fine concavo-convex structure in the pattern part was set to have a pitch of 460 nm, a depth of 460 nm, and an opening width of 430 nm for both of the flat plate molds I2 and J2.
  • the barrier region in the flat plate mold J2 was produced using a width of 5 mm around the pattern portion.
  • a photocurable resin (MUR / manufactured by Maruzen Petrochemical Co., Ltd.) was formed on a sapphire substrate by spin coating at 750 nm.
  • the coating surface of the resin mold was bonded to the material H film, and was bonded at 0.01 MPa using a laminator. Then, after pressing at 0.05 MPa, UV irradiation was performed. The UV irradiation was performed until the integrated light amount reached 1200 mJ / cm 2 . Finally, the resin mold was peeled off.
  • Table 3 shows the results of Examples and Comparative Examples.
  • ⁇ Preparation of transfer template (I)> By following the above embodiment, the contact angle of water to the transfer area (pattern part) and the aperture ratio of the transfer area (pattern part) and the barrier area by changing the pitch, opening diameter, and Es / Eb value of the fine concavo-convex structure.
  • a transfer mold (I) (reel-shaped resin mold) in which the roughness factors of the transfer area (pattern part) and the barrier area were controlled was produced.
  • the reel-shaped resin mold is ⁇ Transfer mold (I)>
  • the produced transfer template (I) is shown in Table 4.
  • the barrier region was designed by controlling the opening diameter with respect to the transfer region (pattern part).
  • the opening diameter was controlled by adjusting exposure energy, rotation speed, and pressure and time during dry etching when a cylindrical mold was produced.
  • Transfer template (I) No. described in Table 4 1 to 7 were prepared, and the material F was diluted to 3% by weight with PGME and coated on the transfer mold (I) using a bar coater. The coating speed was 25 mm / sec. After coating, the transfer mold (I) was placed in a drying oven at 80 ° C. for 5 minutes to remove the solvent and dry.
  • Evaluation was as follows: coating property, releasability, and preparation of a filling layer transfer mold (referred to as “filling layer” in Table 4), and were judged visually and by a scanning electron microscope.
  • the coating failure (1) that is, the coating failure due to the division of the coating liquid on the interface between the pattern part and the non-pattern part can be suppressed.
  • the filling layer transfer mold shown in FIG. 1 was further coated under the following conditions, and the surface state was photographed and observed.
  • a new coating solution a benzylic acrylic polymer to which an acrylate monomer and a photopolymerization initiator were added was used. The concentration was adjusted to 12.6% with propylene glycol monomethyl ether and methyl ethyl ketone, and 25 mm / sec.
  • the film was formed by the bar coating method. After film formation, the solvent was dried by leaving it in an oven at 80 degrees for 5 minutes.
  • the produced transfer template (II) is shown in Table 5.
  • the barrier region was designed by controlling the convex portion diameter with respect to the pattern portion.
  • the convex part diameter was controlled by adjusting the exposure energy and rotational speed, and the pressure and time of dry etching when producing a cylindrical mold.
  • the transfer template (II) shown in Table 5 was prepared, the material F was diluted to 3% with PGME, and coating was performed on the transfer template (II) using a bar coater.
  • Coating speed is 25mm / sec. It was. After coating, the transfer mold (II) was placed in a drying oven at 80 ° C. for 5 minutes to remove the solvent and dry.
  • Evaluation was as follows: coating property, releasability, and preparation of a filling layer transfer mold (referred to as “filling layer” in Table 5), and were judged visually and by a scanning electron microscope.
  • it has the effect of providing a mold for transferring a fine concavo-convex structure with good releasability and good transfer material coating properties.
  • it can be controlled in the nano / micrometer size region. This is useful for the production of optical elements and biomaterials.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Nanotechnology (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Theoretical Computer Science (AREA)
  • Mathematical Physics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Manufacturing & Machinery (AREA)
  • Shaping Of Tube Ends By Bending Or Straightening (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)
  • Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)

Abstract

La présente invention concerne un gabarit de transcription de microstructure convexo-concave exerçant une bonne aptitude au revêtement et une bonne aptitude au décollement d'un matériau de transfert par la même occasion. Ce gabarit de transcription de microstructure convexo-concave (110) présente : un matériau de base ; une section à motifs (111), dans laquelle une microstructure convexo-concave destinée à être transférée sur un objet à traiter est formée dans une partie d'une des surfaces primaires du matériau de base ; une section sans motifs (112) dans laquelle la microstructure convexo-concave n'est pas formée et est constituée d'une zone d'une des surfaces primaires différente de la zone de transfert ; et une zone de barrière (114) située entre la section à motifs (111) et la section sans motifs de manière à border, au moins en partie, la section à motifs (111). La section à motifs (111) et la zone de barrière (114) contiennent de multiples sections concaves. La relation exprimée par Rf1 > Rf2 est établie entre le facteur de rugosité moyen (Rf1) de la section à motifs (111) et le facteur de rugosité moyen (Rf2) de la zone de barrière (114), et la relation exprimée par Ar1 > Ar2 est établie entre le rapport d'ouverture moyen (Ar1) de la section à motifs (111) et le rapport d'ouverture moyen (Ar2) de la zone de barrière (114).
PCT/JP2012/065454 2011-06-30 2012-06-18 Gabarit de transcription de microstructure convexo-concave WO2013002048A1 (fr)

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KR1020137027189A KR101556836B1 (ko) 2011-06-30 2012-06-18 미세 요철 구조 전사용 주형

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JP2013254913A (ja) * 2012-06-08 2013-12-19 Dainippon Printing Co Ltd ナノインプリント用テンプレート及びそれを用いたパターン形成方法
JP2015013291A (ja) * 2013-01-23 2015-01-22 デクセリアルズ株式会社 親水性積層体の製造方法、及び物品の製造方法、並びに防汚方法
JP2018094823A (ja) * 2016-12-14 2018-06-21 大日本印刷株式会社 加飾フィルム、転写シート、加飾成形品及びその製造方法
JP2018144434A (ja) * 2017-03-08 2018-09-20 大日本印刷株式会社 加飾成形品及びその製造方法、並びに転写シート
EP3460828A4 (fr) * 2016-05-18 2019-05-22 Soken Chemical & Engineering Co., Ltd. Composition de résine photodurcissable, couche de résine de celle-ci, et moule pour empreinte
JP2020189440A (ja) * 2019-05-22 2020-11-26 デクセリアルズ株式会社 モールド、及び樹脂シート
WO2023112782A1 (fr) * 2021-12-15 2023-06-22 スタンレー電気株式会社 Élément en résine transmettant la lumière

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WO2020203661A1 (fr) * 2019-03-29 2020-10-08 大日本印刷株式会社 Feuille de transfert et procédé de fabrication d'un moulage décoratif
US20220214339A1 (en) * 2019-05-15 2022-07-07 Denka Company Limited Membrane carrier and test kit
US11899357B2 (en) * 2021-05-17 2024-02-13 Taiwan Semiconductor Manufacturing Co., Ltd. Lithography mask

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Publication number Priority date Publication date Assignee Title
JP2013254913A (ja) * 2012-06-08 2013-12-19 Dainippon Printing Co Ltd ナノインプリント用テンプレート及びそれを用いたパターン形成方法
JP2015013291A (ja) * 2013-01-23 2015-01-22 デクセリアルズ株式会社 親水性積層体の製造方法、及び物品の製造方法、並びに防汚方法
EP3460828A4 (fr) * 2016-05-18 2019-05-22 Soken Chemical & Engineering Co., Ltd. Composition de résine photodurcissable, couche de résine de celle-ci, et moule pour empreinte
JP2018094823A (ja) * 2016-12-14 2018-06-21 大日本印刷株式会社 加飾フィルム、転写シート、加飾成形品及びその製造方法
JP7000653B2 (ja) 2016-12-14 2022-01-19 大日本印刷株式会社 加飾フィルム、転写シート、加飾成形品及びその製造方法
JP2018144434A (ja) * 2017-03-08 2018-09-20 大日本印刷株式会社 加飾成形品及びその製造方法、並びに転写シート
JP2020189440A (ja) * 2019-05-22 2020-11-26 デクセリアルズ株式会社 モールド、及び樹脂シート
JP7287833B2 (ja) 2019-05-22 2023-06-06 デクセリアルズ株式会社 モールド、及び樹脂シート
WO2023112782A1 (fr) * 2021-12-15 2023-06-22 スタンレー電気株式会社 Élément en résine transmettant la lumière

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CN103650106B (zh) 2016-11-09
JPWO2013002048A1 (ja) 2015-02-23
KR20130133293A (ko) 2013-12-06
KR101556836B1 (ko) 2015-10-01
TW201313428A (zh) 2013-04-01
CN103650106A (zh) 2014-03-19

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