Imprint mold

Abstract

To provide an imprint mold that offers good release properties and produces highly reproducible patterns. [Solution] An imprint mold having a molding pattern for transferring onto a molded object, wherein the imprint mold comprises a pattern layer having a base pattern and a release layer provided on the pattern layer along the base pattern, the release layer consisting of multiple layers, and in the release layer, there is at least one interface where the density difference X between adjacent layers is 0.7 to 63.0%.

Description

[Technical Field]

[0001] This invention relates to an imprint mold. [Background technology]

[0002] Nanoimprint technology is attracting attention as a simple patterning method in fields that require fine patterns, such as semiconductors, life sciences, and optical elements. In imprint technology, a mold with a reversed pattern is used, which is made using a master disc having the desired fine pattern. By curing the workpiece (such as resin) while the mold is in contact with it, and then releasing the mold, a molded product is obtained with the same fine pattern as the master disc transferred onto it.

[0003] When releasing a mold from a cured molded object, insufficient release properties between the two can cause the pattern to collapse; therefore, it is necessary to improve release properties. To improve release properties, for example, techniques such as applying a release layer to the pattern surface of the mold are known. Methods for forming a release layer include liquid phase treatment by immersion in a chemical solution or coating, and gas phase treatment such as vapor deposition or CVD. Patent Document 1 describes a technique for forming a thin oxide layer covering a patterned polymer layer by a CVD method. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Special Publication No. 2016-514903 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] In imprint technology, if the mold's release properties are not good, the transferred pattern may be damaged during mold release. In the technology described in Patent Document 1, the thin oxide layer corresponding to the release layer is a single layer, and there was room for improvement in terms of release properties. The present invention aims to provide an imprint mold that exhibits good release properties and produces highly reproducible patterns. [Means for solving the problem]

[0006] As a result of diligent research to solve the above problems, the inventors have found that by improving mold release properties by forming multiple release layers on the mold surface and controlling the density difference between each layer, stable mold release properties can be ensured and pattern damage can be suppressed. In other words, the present invention relates to the following imprint mold. [1] An imprint mold having a molding pattern for transfer onto a molded object, The aforementioned imprint mold is A pattern layer having a base pattern, A release layer provided on the pattern layer along the base pattern, The aforementioned release layer consists of multiple layers, An imprint mold in which, in the release layer, there is at least one interface where the density difference X between adjacent layers is 0.7 to 63.0%. The density difference X is calculated using the following formula. X(%) = {(BA) / A} × 100 X: Density difference (%) A: Of the two adjacent layers, the one with the relatively lower density (g / cm³) 3 ) B: Of the two adjacent layers, the density that is relatively higher (g / cm³) 3 ) [Effects of the Invention]

[0007] According to the present invention, it is possible to provide an imprint mold that has good release properties and can produce patterns with excellent reproducibility. According to the present invention, it is also possible to provide a patterned imprint substrate that has a pattern with excellent reproducibility without damage.

Brief Description of the Drawings

[0008] [Figure 1] FIG. 1 is a cross-sectional view showing an imprint mold of the present embodiment. [Figure 2] FIG. 2 is a diagram for explaining the relationship between the thickness (d) of the release layer and the height difference (h) of the molding pattern in the imprint mold of the present embodiment. [Figure 3] (a) to (f) of FIG. 3 are flowcharts showing a method for manufacturing the imprint mold of the present embodiment. [Figure 4] (g) to (k) of FIG. 4 are flowcharts showing a method for manufacturing a patterned imprint substrate of the present embodiment.

Embodiments for Carrying Out the Invention

[0009] Hereinafter, the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and can be arbitrarily modified and implemented without departing from the gist of the present invention. In addition, “~” indicating a numerical range is used to mean that the numerical values described before and after it are included as the lower limit value and the upper limit value. In this specification, having another layer on a layer such as a pattern layer is not limited to the mode in which the other layer or the like is provided in contact with the above layer, and any mode in which the layer or the like is provided in the upper direction thereof may be used. For example, having a release layer on a pattern layer means that the release layer may be provided so as to contact the main surface of the pattern layer, or any other arbitrary layer or the like may be provided between the pattern layer and the release layer.

[0010] <Imprint Mold> As shown in Figure 1, the imprint mold 10 of this embodiment has a molded pattern P1 for transfer to a molded object, and comprises, in this order, a base layer 1, a pattern layer 2 having a base pattern P2, and a release layer 3 provided on the pattern layer 2 along the base pattern P2. The release layer 3 consists of multiple layers. In Figure 1, the release layer 3 has a first release layer 31 and a second release layer 32 in order from the pattern layer 2 side, but is not limited to this, and there may be three or more release layers. Also in Figure 1, the pattern layer 2 is laminated on the base layer 1, but the base layer is not essential if the pattern layer itself has support properties. Furthermore, in Figure 1, the shapes of the molded pattern P1 and the base pattern P2 show a two-stage uneven shape, but is not limited to this. For example, there may be an uneven shape with three or more stages, a grid shape, a dot shape, a hole shape, a cone shape with a triangular cross-section, a spherical or aspherical curved shape, or a combination of these shapes.

[0011] The base pattern is a reversed pattern of the master disc pattern, transferred from the master disc pattern. A release layer is provided to follow along the base pattern, forming the molded pattern. As will be described later, the thickness of the release layer is thin, so the shape of the base pattern and the molded pattern are almost identical.

[0012] When the molded pattern has an uneven shape, the width of the protrusions in the planar direction is preferably 1000 μm or less, more preferably 100 μm or less, and even more preferably 10 μm or less. Furthermore, the width of the protrusions in the planar direction is preferably 5 nm or more, and more preferably 10 nm or more. Furthermore, the width of the recess in the planar direction is preferably 1000 μm or less, more preferably 100 μm or less, and even more preferably 10 μm or less. Also, the width of the recess in the planar direction is preferably 5 nm or more, and more preferably 10 nm or more.

[0013] When the molded pattern has an uneven shape, the height difference (h) of the molded pattern is preferably 5 nm or more, and more preferably 10 nm or more. Furthermore, the height difference (h) of the molded pattern is preferably 1000 μm or less, and more preferably 100 μm or less.

[0014] Preferred materials for the pattern layer include, for example, resin, silicon, glass, or metal. The materials that make up the pattern layer can be selected according to the method used to form the base pattern.

[0015] Among the materials constituting the pattern layer, preferred resins include polymerizable (photocurable or thermosetting) resins and thermoplastic resins. Examples of polymerizable (photocurable or thermosetting) resins include epoxide-containing compounds, (meth)acrylic acid ester compounds, vinyl ether compounds, bis-allyl nadiimide compounds, and other compounds containing unsaturated hydrocarbon groups such as vinyl and allyl groups, as well as cyclic silicone compounds such as cyclic oligosiloxanes. A polymerization initiator may be used in combination with the polymerizable resin to promote the polymerization reaction. Examples of photopolymerization initiators include radical polymerization initiators such as acetophenone derivatives, benzophenone derivatives, benzoin ether derivatives, and xanthone derivatives, and cationic polymerization initiators such as sulfonium salts and iodonium salts. Examples of thermal polymerization initiators include organic peroxides and azo compounds. Examples of thermoplastic resins include cyclic olefin resins such as cyclic olefin ring-opening polymerization / hydrogenated products (COP) and cyclic olefin copolymers (COC), acrylic resins, polycarbonates, vinyl ethers, fluororesins such as perfluoroalkoxyalkanes (PFA) and polytetrafluoroethylene (PTFE), polystyrene, and polyimide resins.

[0016] The thickness of the pattern layer is not particularly limited, but it is preferable that it is thick enough to deform in response to the waviness or unevenness of the mold or the molded object when the mold and the molded object come into contact during the imprinting process. The thickness of the pattern layer is preferably 1 μm to 10 mm, and more preferably 0.01 to 1 mm.

[0017] The pattern layer has a base pattern on one main surface side, which is a reversed pattern of the master disc, transferred from the master disc's pattern. The base pattern can be formed, for example, by imprint technology, as will be described later.

[0018] Examples of substrates that make up the substrate layer include resins such as PET, PO (polyolefin), and PVC; glass such as quartz, alkali glass, and alkali-free glass; semiconductors such as Si, Ge, SiC, GaAs, InP, and GaN; ceramics such as sapphire; and metals such as Ni and Cu. If the master disc does not transmit light, it is preferable to use a transparent material such as resin or glass as the base material for the base layer, or to form the pattern layer by heat curing rather than photocuring.

[0019] In the imprint mold of this embodiment, the release layer is provided on the pattern layer along the base pattern. The presence of a release layer in the imprint mold of this embodiment improves the release properties between the mold and the molded object. In this embodiment, the release layer consists of multiple layers, and there is at least one interface where the density difference between adjacent layers is 0.7 to 63.0%. Here, the interface in the release layer refers to the boundary surface between adjacent layers with different density differences, and usually, when the number of layers constituting the release layer is N, the number of interfaces is N-1. In the imprint mold shown in Figure 1, the interface is the boundary surface between the first release layer 31 and the second release layer 32. In this embodiment, the release layer has at least one interface where the density difference between adjacent layers is within the above-mentioned specific range, which improves the mold release properties compared to a single-layer release layer or a multi-layer release layer where the interface between two layers does not satisfy the specific density difference. With repeated imprinting, the release layer of the imprint mold is gradually lost, and after a certain number of uses, the mold itself needs to be remade or the release layer needs to be remade. In this embodiment, if the release layer is composed of multiple layers having an interface with a specific density difference, it is presumed that the release layer is more likely to crack in the planar direction at the interface with the specific density difference, contributing to excellent release properties. Furthermore, it is thought that the peeling of the release layer by each imprint is partial, which is expected to improve the durability of the mold.

[0020] The number of release layers is preferably two or more, more preferably three or more, from the viewpoint of improving release properties, and preferably 10 or fewer from the viewpoint of film stress. In other words, the number of release layers is preferably 2 to 10.

[0021] Here, the density difference between adjacent layers is calculated using the following formula. X(%) = {(BA) / A} × 100 X: Density difference (%) A: Of the two adjacent layers, the one with the relatively lower density (g / cm³) 3 ) B: Of the two adjacent layers, the density that is relatively higher (g / cm³) 3 )

[0022] The density difference between adjacent layers is, from the viewpoint of release properties, 0.7% or more, preferably 1.0% or more, more preferably 5.0% or more, even more preferably 10.0% or more, and also 63.0% or less, preferably 60.0% or less, more preferably 50.0% or less, and even more preferably 40.0% or less.

[0023] When the release layer consists of three or more layers, it is sufficient that at least one interface has a density difference between adjacent layers within the specified range, and the remaining interfaces do not need to satisfy this requirement. However, from the viewpoint of improving release properties, it is preferable that the density difference at all interfaces is within the specified range.

[0024] The density of the release layer is 0.9 to 6.0 g / cm³ for each of the multiple layers. 3 Preferably, it is 1.4 to 2.5 g / cm³. 3 This is more preferable. The density of the release layer can be measured by XRR.

[0025] Furthermore, in a release layer, it is preferable that the density of the pattern layer is relatively lower than the density of the two adjacent layers. For example, in the imprint mold shown in Figure 1, the density of the first release layer 31 is lower than the density of the second release layer 32. With such a release layer, a density distribution is created in which the density increases from the pattern layer side surface of the release layer toward the molded pattern side surface, and a release layer having such a density distribution is preferable from the viewpoint of durability of the release layer.

[0026] The thickness (d) of the release layer is preferably 0.1 to 50 nm, more preferably 0.5 to 10 nm, and more preferably 1 to 5 nm, from the viewpoint of minimizing the impact on the original pattern shape. Furthermore, the thickness of each layer constituting the release layer is preferably 0.1 to 10 nm, and more preferably 0.5 to 5 nm. The thickness of the release layer can be measured using XRR.

[0027] Furthermore, the ratio ((d / h) × 100) of the thickness (d) (nm) of the release layer to the height difference (h) (nm) of the molded pattern of the mold is preferably 0.1 to 10%, and more preferably 1 to 5%. The above relationship between the thickness (d) of the release layer and the height difference (h) of the molded pattern is preferable from the viewpoint of not affecting the original pattern dimensions. As shown in Figure 2, the thickness (d) of the release layer is the total thickness of each of the multiple layers that make up the release layer, and the height difference (h) of the molded pattern is the difference between the highest and lowest points of the unevenness of the molded pattern.

[0028] From the viewpoint of forming a thin film, the release layer preferably contains one or more elements selected from C, F, Si, Al, N, O, and H. More specifically, the release layer may (i) contain one or more elements of C, Si, and Al; (ii) be composed of a reaction product of one or more elements of C, Si, and Al and one or more elements of F, N, O, and H in the atmospheric gas during film formation; or (iii) be a combination of (i) and (ii) above. Among these, it is more preferable to include C and F. The presence of the above elements in the release layer can be identified by XRR. However, verifying the detailed structure of the elements themselves is difficult. If the release layer contains C and F, it is considered to contain at least one of CF2 and CF3. If the release layer contains Si and O, it is considered to contain at least one of Si, SiO, and SiO2. If the release layer contains Al and O, it is considered to contain at least one of Al and Al2O3.

[0029] When the release layer contains C and F, the n-hexadecane contact angle of the release layer is preferably 5 to 50 degrees, and the water contact angle is preferably 90 to 115 degrees.

[0030] Furthermore, the materials of each layer constituting the release layer may be the same or different, but from the viewpoint of facilitating the formation of the release layer, it is preferable that they be the same material.

[0031] <Method for manufacturing imprint molds> The imprint mold according to this embodiment can be obtained by forming a pattern layer having a base pattern and forming a release layer on the pattern layer.

[0032] The method for manufacturing an imprint mold according to this embodiment will be explained using a manufacturing method by optical imprint as an example. The imprint mold according to this embodiment can be manufactured by, for example, preparing a master disc 4 having a desired fine pattern (Figure 3(a)), preparing a laminate of a base layer 1 and a pattern layer constituent material 21, bringing the pattern layer constituent material 21 into contact with the master disc 4 and applying pressure (Figures 3(b) and 3(c)), curing the pattern layer constituent material 21 with UV light (Figure 3(d)), releasing the laminate of the base layer 1 and the pattern layer constituent material 21 from the master disc to obtain a pattern layer 2 having a basic pattern (Figure 3(e)), and forming a release layer 3 on the pattern layer 2 (Figure 3(f)). The following describes each step.

[0033] As a master disc having a fine pattern, a mold having a predetermined fine pattern can be used.

[0034] As described above, it is preferable to use resin, silicon, glass, or metal as the pattern layer constituent material. Furthermore, it is preferable that the pattern layer constituent material be molded into a plate or film shape.

[0035] As mentioned above, resin, glass, semiconductor, metal, etc. are preferred as the substrate layer supporting the pattern layer constituent material.

[0036] By bringing the pattern layer constituent material into contact with the master plate and applying pressure, the contact surface of the pattern layer constituent material can be deformed to conform to the fine pattern shape of the master plate. The pressure conditions can be adjusted according to the viscoelasticity of the pattern layer constituent material, preferably 0.0001 to 10 MPa, more preferably 0.001 to 5 MPa. The pressure time can also be adjusted according to the viscoelasticity of the pattern layer constituent material, preferably 1 to 600 seconds, more preferably 5 to 120 seconds.

[0037] The method for curing the pattern layer constituent material can be adapted to the type of material. For example, if the pattern layer constituent material is a photocurable resin, it can be cured by UV irradiation. If the pattern layer constituent material is a thermosetting resin, it can be cured by heating. Furthermore, if the pattern layer constituent material is a thermoplastic resin, the fine pattern can be transferred by pressing the master disc onto the resin when the viscosity decreases due to heating, and then the transferred pattern can be maintained after the master disc is released as the viscosity of the resin increases due to subsequent cooling. Figure 3(d) shows a thermosetting resin cured by UV irradiation.

[0038] After the cured pattern layer is released from the mold, surface modification treatments such as corona treatment may be performed as needed.

[0039] The method for forming the release layer is not particularly limited, as long as it can be formed to follow the base pattern and multiple layers can be formed with density differences within the specified range at one or more interfaces. Examples of methods for forming the release layer include liquid phase treatment methods such as immersion in a chemical solution or coating, and gas phase treatment methods such as vapor deposition or CVD. From the viewpoint of automating the imprint apparatus, it is preferable to form it by a gas phase treatment method, and from the viewpoint of controllability of film quality, it is more preferable to form it by the CVD method.

[0040] When forming a release layer using the CVD method, the density and thickness of each layer can be controlled by adjusting the type of deposition gas, flow rate, pressure, power density, and processing time, thereby forming multiple layers with different density distributions.

[0041] Examples of the vapor deposition gas include, for example, fluorocarbon gas, hydrocarbon gas, etc. As the fluorocarbon gas, fluorocarbon compounds having 1 to 5 carbon atoms are preferable, and examples thereof include CF4, C2F6, n-C3F8, C4F6 (hexafluoro-1,3-butadiene), C4F8 (octafluorocyclobutane), C5F¬8 (octafluorocyclopentene), CHF3, CH2F2, CH3F, C2HF5, etc. In addition, among the organic fluorine compounds (PFAS), fluorocarbon compounds having 1 to 5 carbon atoms are preferable in that they are less likely to be subject to regulation. These can be used alone or in combination of two or more kinds. As the hydrocarbon gas, hydrocarbon compounds having 1 to 4 carbon atoms are preferable, and examples thereof include CH4, C2H6, C2H4, C2H2, C3H8, C3H6, C3H4, C4H 10 , C4H8, C4H6, etc. These can be used alone or in combination of two or more kinds.

[0042] The gas flow rate is preferably 1 to 100 sccm, more preferably 5 to 50 sccm. The pressure is preferably 10 -8 ~10 2 Pa, more preferably 10 -1 ~10 Pa. The power density is preferably 1 to 1000 mW / cm 2 , more preferably 10 to 100 mW / cm 2 . The treatment time is preferably 1 to 600 sec, more preferably 10 to 300 sec.

[0043] When forming a plurality of layers made of the same material and having different densities by CVD method, for example, the first layer is formed with a predetermined vapor deposition gas species, flow rate, pressure, power density, and treatment time, and for the second and subsequent layers, the vapor deposition gas species is the same, and a method of forming by changing one or more of the conditions of flow rate, pressure, power density, and treatment time can be mentioned

[0044] When forming a release layer using a liquid-phase treatment method, methods include immersing the pattern layer in a solution of the material constituting the release layer, or coating the base pattern of the pattern layer with a solution of the material constituting the release layer. Furthermore, in order to form multiple layers made of the same material but with different densities, methods can be used to form each layer using multiple solutions of different concentrations.

[0045] To form a release layer containing Si, for example, film deposition by CVD is possible by introducing the appropriate source gas. To form a release layer containing Al, for example, one method is to produce a release layer containing Al2O3 by sputtering or vapor deposition using an Al target and changing the atmosphere to, for example, O2, or by sputtering using an Al2O3 target. Furthermore, to form a release layer containing N, O, and H, methods include utilizing N2, H2, O2, H2O, etc., which are present as impurities in the air when forming a release layer containing C, Si, or Al, or actively introducing gases such as NH3, N2, H2, O2, and H2O simultaneously during film formation.

[0046] <Patterned imprinted circuit board and method for manufacturing a patterned imprinted circuit board> The patterned imprinted circuit board according to this embodiment is manufactured using the imprint mold according to this embodiment. Since the imprint mold according to this embodiment has excellent release properties, by using such a mold, it is possible to manufacture an imprinted circuit board with a pattern that has excellent reproducibility of the pattern of the master plate without the pattern being distorted.

[0047] The method for manufacturing a patterned imprinted substrate according to this embodiment will be explained using a manufacturing method by optical imprint as an example. A method for manufacturing a patterned imprinted substrate using the imprint mold according to this embodiment includes, for example, preparing a resin-layered substrate 7 comprising a substrate 5 and a material to be molded 6 applied to the substrate 5 (Figure 4(g)), contacting the release layer 3 side of the imprint mold 10 with the surface of the material to be molded 6 on the resin-layered substrate 7 and applying pressure (Figures 4(h), (i)), curing the material to be molded 6 on the resin-layered substrate 7 with UV light (Figure 4(j)), and releasing the imprint mold 10 from the cured resin-layered substrate 7 to obtain a patterned imprinted substrate 8 (Figure 4(k)). The following describes each step.

[0048] The substrate is preferably made of a material selected from, for example, glass, ceramics, semiconductors, metals, and resins. The substrate material can be selected according to the type of material to be molded. For example, if the material to be molded is a photocurable material, the substrate must be made of a light-resistant material, and if the material to be molded is a thermosetting material or a thermoplastic material, the substrate must be made of a heat-resistant material. Furthermore, it is necessary to select a material with low reactivity with the material to be molded. The thickness of the circuit board is not particularly limited and can be set according to the equipment used to manufacture the patterned imprinted circuit board.

[0049] The material to be molded can be selected according to the imprinting technology, and resin is one example. Preferably, the resins include polymerizable (photocurable or thermosetting) resins and thermoplastic resins. Examples of polymerizable (photocurable or thermosetting) resins and thermoplastic resins include those exemplified as materials constituting the pattern layer, specifically including acrylic resins, epoxy resins, silicone resins, polycarbonates, polyolefins, polyesters, and polyurethanes.

[0050] The material to be molded in a resin-layered substrate is preferably in the form of a film or an aggregate of droplets with a thickness of 0.01 to 1000 μm. Methods for obtaining a substrate with a resin layer include coating the material to be molded onto one main surface of the substrate using methods such as spin coating, slit coating, spray coating, or dispensing (jet dispenser, inkjet, etc.), or attaching a film of the material to be molded to one main surface of the substrate by dry film resist coating or the like.

[0051] By bringing an imprint mold into contact with the surface of the material film to be molded and applying pressure, the contact surface of the material to be molded can be deformed to follow the pattern of the mold. The pressure conditions can be adjusted according to the viscoelasticity of the material to be molded, preferably 0.001 to 10 MPa, more preferably 0.01 to 5 MPa. The pressure time can also be adjusted according to the viscoelasticity of the material to be molded, preferably 1 to 1000 seconds, more preferably 5 to 500 seconds.

[0052] The method for curing the material to be molded can be adapted to the type of material. For example, if the material to be molded is a photocurable resin, it can be cured by UV irradiation. If the material to be molded is a thermosetting resin, it can be cured by heating. If the material to be molded is a thermoplastic resin, it can be cured by heating it above its glass transition temperature, molding it, and then cooling it below its glass transition temperature.

[0053] After demolding the imprint mold from the resin-coated substrate after curing, additional treatments such as heat treatment, UV irradiation, plasma treatment, and cleaning may be performed as needed.

[0054] The patterned imprinted substrate according to this embodiment, obtained by the above manufacturing method, has a pattern transferred from the molded pattern of the imprint mold. Furthermore, since the release layer of the imprint mold consists of multiple layers with density differences, when the imprint mold is released, it is likely to peel off at the interface of layers with density differences within a specific range, and a portion of the release layer is thought to transfer to the patterned imprint substrate. Therefore, it is thought that a portion of the release layer exists on the outermost surface of the patterned imprint substrate. If the release layer contains one or more elements selected from C, F, Si, Al, N, O, and H, it is thought that similar elements can be confirmed on the outermost surface of the patterned side. The presence of such a release layer can be confirmed by measuring, for example, the surface contact angle and XRR of the outermost surface on the pattern side. For example, if the release layer contains C and F, the n-hexadecane contact angle of the outermost surface on the pattern side is preferably 5 to 50 degrees, and the water contact angle is preferably 90 to 115 degrees.

[0055] The patterned imprinted circuit board of this embodiment can be used, for example, for optical elements, microfluidic devices, and the like.

[0056] Based on the above, this specification discloses the following imprint molds, etc. [1] An imprint mold having a molding pattern for transfer onto a molded object, The aforementioned imprint mold is A pattern layer having a base pattern, A release layer provided on the pattern layer along the base pattern, The aforementioned release layer consists of multiple layers, An imprint mold in which, in the release layer, there is at least one interface where the density difference X between adjacent layers is 0.7 to 63.0%. The density difference X is calculated using the following formula. X(%) = {(BA) / A} × 100 X: Density difference (%) A: Of the two adjacent layers, the one with the relatively lower density (g / cm³) 3 ) B: Of the two adjacent layers, the density that is relatively higher (g / cm³) 3 ) [2] The imprint mold according to [1], wherein the ratio of the thickness d of the release layer to the height difference h of the molding pattern {(d / h) × 100} is 0.1 to 10%. [3] The imprint mold according to [1] or [2], wherein, in the release layer, the density of the pattern layer is relatively smaller than the density of two adjacent layers. [4] An imprint mold according to any one of [1] to [3], wherein the number of layers of the release layer is 2 to 10. [5] The imprint mold according to any one of [1] to [4], wherein the release layer contains one or more elements selected from C, F, Si, Al, N, O, and H. [6] The imprint mold according to any one of [1] to [5], wherein the pattern layer is made of resin, silicone, glass, or metal. [7] An imprint mold according to any one of [1] to [6], wherein the n-hexadecane contact angle of the release layer is 5 to 50 degrees. [8] An imprint mold according to any one of [1] to [7], wherein the water contact angle of the release layer is 90 to 115 degrees. [9] The imprint mold according to any one of [1] to [8], wherein the release layer comprises C and F. A patterned imprinted circuit board manufactured using an imprint mold described in any one of

[10] , [1], to [9].

[11] The patterned imprinted substrate according to

[10] , wherein the n-hexadecane contact angle of the outermost surface on the pattern side of the patterned imprinted substrate is 5 to 50 degrees.

[12] The patterned imprinted circuit board according to

[10] or

[11] , wherein the water contact angle of the outermost surface on the pattern side of the patterned imprinted circuit board is 90 to 115 degrees.

[13] A patterned imprinted substrate according to any one of

[10] to

[12] , wherein one or more elements selected from C, F, Si, Al, N, O, and H are present on the outermost surface of the patterned imprinted substrate. [Examples]

[0057] The present invention will be described in more detail below using examples, but the present invention is not limited to these. Examples 4-7 and 9 are examples of actual cases, while Examples 1-3 and 8 are comparative examples.

[0058] The imprinting machine used was an Obducat Eitre 8.

[0059] [Examples 1-9: Creating molds for imprinting] An imprint mold was fabricated using UV imprint technology with a master plate and a photocurable resin. The following describes each step in detail. (a) As a master plate, a Si mold was prepared having a linear pattern with a line width of 100 nm and a height difference of 100 nm. (b) A laminate consisting of a photocurable resin film (acrylic resin, 10 μm thick) and a substrate layer (PET film, 100 μm thick) was laminated onto the master disc so that the photocurable resin film side faced the master disc. (c) The laminate was pressed from the substrate layer side at 0.5 MPa for 60 seconds. (d) Light intensity of 500 mW / cm from the substrate layer side of the laminate 2 (1000 mJ / cm²) for 2 seconds 2 The resin was cured by UV irradiation. (e) The mold was released from the laminate to obtain a resin film having a basic pattern. (f) For Examples 2 to 9, CVD treatment with C3F8 was performed under the conditions described in Table 1 to form a release layer on the base pattern of the resin film. The layer on the pattern layer side was designated as the first release layer. Through the above process, molds 1 to 9, each having a linear molding pattern, were produced.

[0060] The density and film thickness of each layer of the release layer were measured using XRR (equipment used: Rigaku SmartLab). Furthermore, the density difference between adjacent layers was calculated using the following formula. X(%) = {(BA) / A} × 100 X: Density difference (%) A: Of the two adjacent layers, the one with the relatively lower density (g / cm³) 3 ) B: Of the two adjacent layers, the density that is relatively higher (g / cm³) 3 )

[0061] [Evaluation of shape transferability using imprint molds] The shape transferability of each mold obtained above was evaluated based on the following conditions. (g) A photocurable resin film (epoxy resin, 0.1 μm thick), which is the material to be molded, was placed on a glass substrate to prepare a substrate with a resin layer. (h), (i) Each mold prepared in Examples 1-9 was brought into contact with the surface of the resin film of the resin-layered substrate and pressed at a pressure of 0.5 MPa for 60 seconds. (j) Next, light intensity of 500 mW / cm from the mold side 2 (500 mJ / cm²) for 1 second 2 The photocurable resin was cured by UV irradiation. (k) The mold was released from the resin-coated substrate to obtain a patterned imprinted substrate on which the molded pattern of the mold was transferred. The shape of the transferred pattern was evaluated by measuring the pattern width and height from images acquired using a SEM (Scanning Electron Microscope: Regulus 8220, Hitachi High-Tech).

[0062] (Judgment criteria) A: The reproducibility of both the width and height of the pattern is 90% or higher (pass). B: The reproducibility of at least one of the pattern width and height is less than 90% (fail).

[0063] The results for each of the above are shown in Tables 1 and 2 below.

[0064] [Table 1]

[0065] [Table 2]

[0066] Based on the above results, molds in Examples 4-7 and 9, which consist of multiple release layers and have one or more interfaces where the density difference between adjacent layers is within a specific range, showed excellent shape transfer properties. The molds in Example 1 (without a release layer), Example 2 (with a single release layer), Example 3 (with multiple release layers but with a density difference of less than 0.7% between adjacent layers), and Example 8 (with a density difference exceeding 63.0%) all exhibited poor shape transferability.

[0067] [Surface contact angle] In the manufacturing process and shape transferability evaluation process of the mold in Example 6, the surface contact angle of the pattern surface was measured using water or n-hexadecane. A contact angle meter (DMs-301) manufactured by Kyowa Interface Science was used for the measurement. Table 3 shows the measurement locations and results.

[0068] [Table 3]

[0069] The results in Table 3 show that the surface contact angle of the mold pattern surface increased after the formation of the release layer following the transition from process (d) to process (e). This is thought to be due to the C3F8 used for forming the release layer. Here, when the photocurable resin (epoxy resin, 0.1 μm thick), which was the target of molding, was cured by UV irradiation without nanoimprinting, the surface contact angle was 72 degrees for water and 5 degrees for n-hexadecane. After going through step (k), the surface contact angle of the pattern surface of the resin film after pattern transfer was 100 degrees for water and 54 degrees for n-hexadecane, indicating that the contact angle increased due to pattern transfer. Furthermore, the contact angle of the pattern surface of the mold and the pattern surface of the resin film after pattern transfer were about the same as the contact angle of the pattern surface of the mold. This is thought to be because, due to pattern transfer, a portion of the release layer on the mold surface adhered to the pattern surface of the photocurable resin film, which was the target of molding. [Explanation of Symbols]

[0070] 10 Imprint molds P1 Molding Pattern P2 Basic Pattern 1 Base material layer 2 Pattern Layers 3 Release layer 31 First release layer 32 Second release layer d. Thickness of the release layer h Height difference of the molding pattern 4. Original recording 21 Pattern Layer Constituent Materials 5 circuit boards 6. Materials to be molded 7. Resin-coated substrate 8-pattern imprinted circuit board

Claims

1. An imprint mold having a molding pattern for transferring onto a molded object, The aforementioned imprint mold is A pattern layer having a base pattern, A release layer provided on the pattern layer along the base pattern, The aforementioned release layer consists of multiple layers, An imprint mold in which, in the release layer, there is at least one interface where the density difference X between adjacent layers is 0.7 to 63.0%. The density difference X is calculated using the following formula. X (%) = {(B-A) / A}×100 X: Density difference (%) A: Of the two adjacent layers, the density that is relatively lower (g / cm³) ３ ) B: Of the two adjacent layers, the density that is relatively higher (g / cm³) ３ )

2. The imprint mold according to claim 1, wherein the ratio of the thickness d of the release layer to the height difference h of the molding pattern {(d / h) × 100} is 0.1 to 10%.

3. The imprint mold according to claim 1, wherein, of the two adjacent layers in the release layer, the density of the layer on the pattern layer side is relatively smaller.

4. The imprint mold according to claim 1, wherein the number of layers of the release layer is 2 to 10.

5. The imprint mold according to claim 1, wherein the release layer contains one or more elements selected from C, F, Si, Al, N, O, and H.

6. The imprint mold according to claim 1, wherein the pattern layer has resin, silicone, glass, or metal.

7. The imprint mold according to claim 1, wherein the n-hexadecane contact angle of the release layer is 5 to 50 deg.

8. The imprint mold according to claim 1, wherein the water contact angle of the release layer is 90 to 115 degrees.

9. The imprint mold according to claim 1, wherein the release layer includes C and F.

10. A patterned imprinted circuit board manufactured using an imprint mold according to any one of claims 1 to 9.

11. The patterned imprinted substrate according to claim 10, wherein the n-hexadecane contact angle of the outermost surface on the pattern side of the patterned imprinted substrate is 5 to 50 degrees.

12. The patterned imprinted substrate according to claim 10, wherein the water contact angle of the outermost surface on the pattern side of the patterned imprinted substrate is 90 to 115 degrees.

13. The patterned imprinted substrate according to claim 10, wherein one or more elements selected from C, F, Si, Al, N, O, and H are present on the outermost surface of the patterned imprinted substrate.

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