Method for manufacturing film molding and patterned curing resin layer

Abstract

SV>0 (2);SE<-296.77×SV+77.371 (3)。

Description

Technical Field

[0001] This invention relates to a thin film mold for transferring raised and recessed shapes onto the surface of a curable resin material. Prior Technology

[0002] Liquid crystal displays (LCDs) are commonly used as display devices in various electronic devices. These devices have seen further miniaturization in recent years, leading to demands for smaller and lighter LCDs.

[0003] This type of liquid crystal display device mainly uses optical functional films or composite films that utilize reflection, refraction, scattering, and other effects. As such optical functional films, shaped films are known to be formed by imparting a predetermined uneven shape to the surface of a resin film. These shaped films are typically manufactured by pressure molding or injection molding using an imprinting plate with the desired uneven shape.

[0004] As another method for imparting a predetermined uneven shape to the surface of a resin film, Patent Document 1 proposes a method using a film molding (an in-mold forming release film). Based on the viewpoint of the release properties of the film material to which the uneven shape is formed, Patent Document 1 uses release compounds such as polysiloxanes or fluorinated compounds as the material constituting the uneven shape in the film molding. On the other hand, Patent Document 2, in its specific embodiment, discloses a release sheet made of thermoplastic resin using poly(4-methylpentene-1). [Previous Technical Documents] [Patent Literature]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 2019-73022 [Patent Document 2] Japanese Patent Application Publication No. 2001-225376 Summary of the Invention

[0006] [The problem that the invention aims to solve] However, while the technology described in Patent Document 1 provides excellent release properties for the film molding of the film material used to form uneven shapes, its wettability is insufficient, resulting in a potential issue of inadequate transferability of uneven shapes. This problem is particularly pronounced when a curable resin material is used as the film material for forming uneven shapes. Patent Document 2 only discloses the use of poly4-methylpentene-1 as the release film of the thermoplastic resin; the criteria for selecting a suitable material remain unclear.

[0007] The present invention aims to provide a film mold that exhibits good wettability and peelability to hardened resin materials and can effectively form a concave-convex shape on the surface of hardened resin materials. [Methods for solving problems]

[0008] The inventors of this case, through their dedicated research to achieve the aforementioned objective, discovered that by controlling the surface free energy SE of the uneven surface and the free volume SV of the aforementioned uneven surface, as measured by positron annihilation, within a predetermined range for a film mold consisting of a resin film having an uneven surface for transferring an uneven shape onto the surface of a curable resin material, the aforementioned objective can be achieved, thus ultimately completing this invention.

[0009] That is, according to the present invention, a film mold is provided, which is a film mold composed of a resin film having an uneven surface for transferring an uneven shape onto the surface of a curable resin material, wherein, The surface free energy SE [unit: mN / m] of the aforementioned uneven surface and the free volume SV [unit: nm3] of the aforementioned uneven surface, as measured by positron annihilation, satisfy the following equations (1) to (3): .

[0010] The film molding of the present invention is preferably a long-sized film formed by continuously or intermittently imparting a concave-convex shape to the surface of a resin film formed by melt extrusion. Alternatively, the film molding of the present invention is preferably a long-sized film formed by continuously or intermittently coating the surface of a substrate film with an ultraviolet-curable resin and then curing it, thereby giving the surface a concave-convex shape. The average thickness of the film mold of the present invention is preferably 10~200μm. Furthermore, according to the present invention, a method for manufacturing a patterned curable resin layer is provided, comprising: a step of contacting a layer formed on a substrate and composed of a curable resin material with a film mold as described above; and a step of curing the curable resin material while in contact with the film mold. [Effects of the Invention]

[0011] According to the present invention, a film mold that exhibits good wettability and peelability to hardenable resin materials and can well form an uneven shape on the surface of the hardenable resin material can be provided. Simple Explanation of the Diagram

[0012] [Figure 1] is a diagram showing an example of a manufacturing apparatus for a shaped film using a film mold according to an embodiment of the present invention. [Figure 2] is a graph showing the relationship between the surface free energy SE and the free volume SV of the resin films of the Examples and Comparative Examples. Implementation

[0013] [Forms of Invention Implementation] Figure 1 is a diagram showing an example of a manufacturing apparatus for a shaped film using a film mold according to an embodiment of the present invention. Furthermore, the following description mainly illustrates the manufacturing apparatus shown in Figure 1; however, the present invention is not particularly limited to the configuration shown in Figure 1.

[0014] In the manufacturing apparatus shown in Figure 1, a substrate film 40 is continuously fed from a substrate feed roller 10, and the substrate film 40 is coated with a curable resin material on its surface by a T-die 20 via a guide roller 11, thereby forming a curable resin material layer 50 on its surface. Furthermore, the thickness of the curable resin material layer 50 is controlled by adjusting the gap formed between the T-die 20 and the clamping roller 12 or by adjusting the feed speed.

[0015] Furthermore, in the manufacturing apparatus shown in FIG1, the film mold 60 is continuously fed out from the film mold feeding roller 13. Then, the substrate film 40, on which the curable resin material layer 50 is formed, and the film mold 60 are stacked by the laminating roller 15 and the upstream support roller 16. Here, the film mold 60 has a predetermined uneven shape on one side facing the curable resin material layer 50, and the laminate is formed by stacking the substrate film 40, the curable resin material layer 50, and the film mold 60 in sequence while the surface with the predetermined uneven shape is in contact with the curable resin material layer 50.

[0016] Then, the laminate formed by sequentially stacking the substrate film 40, the curable resin material layer 50, and the film mold 60 is irradiated with ultraviolet light by the ultraviolet irradiation device 30, causing the curable resin material constituting the curable resin material layer 50 to harden in a state where a predetermined uneven shape formed on the surface of the film mold 60 is transferred, thereby forming a curable resin layer 50a with the desired uneven shape on the surface. Next, after the curing reaction by ultraviolet irradiation, it is passed between the laminating roller 15 and the downstream support roller 17, and after the substrate film 40 containing the curable resin layer 50a is peeled off from the film mold 60, the film mold 60 is wound by the film mold winding roller 14, and the substrate film 40 containing the curable resin layer 50a is wound by the substrate winding roller 19 via the guide roller 18.

[0017] According to the manufacturing apparatus shown in Figure 1, a substrate film 40 having a hardened resin layer 50a is continuously produced as described above. Then, the substrate film 40 having the hardened resin layer 50a thus manufactured is transferred to a predetermined uneven shape in a film mold 60, that is, it has a desired uneven shape on its surface, and can be used as a shaped film, for example, as an optical functional film that utilizes reflection, refraction, scattering and other effects, suitable for various optical applications.

[0018] In this embodiment, the thin film mold 60 is a resin film with an uneven surface, wherein the surface free energy SE [unit: mN / m] of the uneven surface and the free volume SV [unit: nm3] of the uneven surface measured by positron annihilation satisfy the following formulas (1) to (3); .

[0019] The film molding 60 can be formed on at least one surface with a concave-convex shape that satisfies the above formulas (1) to (3), or it can be formed on both surfaces.

[0020] Furthermore, in this embodiment, the film mold 60 is deposited on the surface of the hardened resin material layer 50 by pressing the concave and convex shapes of the film mold 60 onto the substrate film 40 on which the hardened resin material layer 50 is formed, and while maintaining this state, the hardened resin material constituting the hardened resin material layer 50 is irradiated with ultraviolet light to form a hardened resin layer 50a with the concave and convex shapes of the film mold 60 transferred onto it.

[0021] According to this embodiment, by using a resin film through a film mold 60 with surface free energy SE and free volume SV of the uneven surface satisfying the above formulas (1) to (3), the film mold 60 can exhibit good wettability and excellent peelability to the hardened resin material constituting the hardened resin material layer 50; thereby, a hardened resin layer 50a with the desired uneven shape can be formed well.

[0022] In particular, regarding the resin material constituting the film mold 60, the inventors of this invention, through their research, have obtained the following insights. Specifically, if a resin material with excellent release properties is used for the resin material constituting the film mold 60, the wettability of the hardened resin material constituting the hardened resin material layer 50 will deteriorate, resulting in uneven wettability. Furthermore, air bubbles are more easily trapped between the film mold 60 and the hardened resin material layer 50, causing defects and preventing the formation of a hardened resin layer 50a with the desired uneven shape. On the other hand, if a resin material with excellent wettability for the hardened resin material constituting the hardened resin material layer 50 is selected, the adhesion force to the hardened resin material will become excessively strong, leading to deteriorated release properties and problems such as shape damage to the hardened resin layer 50a during peeling.

[0023] In response, the inventors of this case further investigated and found that by making the surface free energy SE of the uneven surface and the free volume SV of the uneven surface within the range of the above formulas (1) to (3), the film molding 60 can exhibit good wettability to the hardened resin material constituting the hardened resin material layer 50 and can exhibit excellent peelability; moreover, thereby, a hardened resin layer 50a with the desired uneven shape can be well formed.

[0024] In the film molding 60, the surface free energy SE of the uneven surface and the free volume SV of the uneven surface only need to satisfy the above formulas (1) to (3); based on the goal of achieving a higher balance between the wettability and peelability of the hardened resin material constituting the hardened resin material layer 50, it is preferable to satisfy any one or all of the following formulas (4) to (6), and more preferably to satisfy any one or all of the following formulas (7) to (9).

[0025] If the surface free energy SE of the uneven surface does not reach 35.7 mN / m, the wettability of the hardened resin material constituting the hardened resin material layer 50 will deteriorate, and air bubbles will easily be entangled between the film mold 60 and the hardened resin material layer 50, thus failing to form a hardened resin layer 50a with the desired uneven shape.

[0026] If the free volume SV of the uneven surface is preferably 0.06 nm3 or higher, the permeability of the hardened resin material constituting the hardened resin material layer 50 to the film mold 60 can be improved, thereby ensuring sufficient adhesion for molding. Furthermore, from the viewpoint of further improving peelability, it is more preferable to have 0.06 ≤ SV ≤ 0.08.

[0027] Furthermore, if SE≧-296.77×SV+77.371, the adhesion force to the curing resin material will become too strong, leading to deterioration of peelability. During peeling, the shape of the curing resin layer 50a will be damaged, and it will be impossible to form a curing resin layer 50a with the desired uneven shape.

[0028] Furthermore, the surface free energy SE of the uneven surface of the film mold 60 can be measured by determining the contact angles of water, diiodomethane, and ethylene glycol on the uneven surface of the film mold 60, and the free volume SV of the uneven surface can be calculated based on the measured contact angle data using Kitasaki-Hatake's analytical theory. Additionally, the free volume SV of the uneven surface can be obtained by measuring the uneven surface of the film mold 60 using the positron annihilation method. The positron annihilation method refers to a method for determining the positron annihilation lifetime, which measures the time from the injection of a positron into the sample to its annihilation, and calculates the free volume of the pores from the annihilation lifetime.

[0029] The average thickness of the film mold 60 is not particularly limited, but is preferably 10-200 μm, more preferably 20-100 μm, and even more preferably 30-60 μm. By ensuring that the average thickness of the film mold 60 is within the above range, a cured resin layer 50a with a desired uneven shape can be manufactured with higher productivity. Examples of uneven shapes that can be manufactured by film molding include continuous or discontinuous shapes with a height of 1-30 μm, an aspect ratio of 0.5-1.0, and a spacing of 0-20 times the height.

[0030] The manufacturing method of the film mold 60 is not particularly limited. Examples include obtaining a resin film by melt extrusion, heating the obtained resin film, pressing a shaping roller with a predetermined uneven shape on its surface, and continuously or intermittently forming an uneven shape on its surface, thereby obtaining a long-sized film. Furthermore, the heating temperature of the resin film when pressing the shaping roller with the predetermined uneven shape on its surface is not particularly limited. Examples include heating it to a temperature above the glass transition temperature of the resin material constituting the resin film.

[0031] Alternatively, as a method for manufacturing the film mold 60, it is also possible to continuously or intermittently coat the surface of a resin film, which serves as a substrate film, with ultraviolet-curing resin and then cure it to form an uneven shape of ultraviolet-curing resin, thereby obtaining a long-sized film form by imparting an uneven shape to the surface.

[0032] The resin material constituting the resin film forming the film mold 60 is not particularly limited, but is preferably a thermoplastic resin, such as polyester resins like polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), acrylic resins like polymethyl methacrylate (PMMA), carbonate resins like polycarbonate (PC), amide resins like nylon 6, cyclic olefin resins (COP), ethylene-vinyl alcohol copolymer (EVOH), and polyphenylene sulfide (PPS). Furthermore, two or more of these resins can be laminated or mixed.

[0033] Furthermore, when using a method to form uneven shapes by UV-curing resin, the UV-curing resin can be an acrylic monomer that is free-radical curing, such as urethane acrylate, epoxy acrylate, acrylic oligomers of polyester acrylate, unsaturated polyester, or a cationic curing epoxy resin, oxetane resin, vinyl ether, etc. In addition, the substrate film used in this case can be composed of the above-mentioned resin materials.

[0034] The method for ensuring that the surface free energy SE and the free volume SV of the uneven surface of the film mold 60 are within the aforementioned range is not particularly limited. Examples include selecting a resin material that constitutes the resin film forming the film mold 60; modifying the surface by corona treatment; adjusting the wettability by using a surface modifier; adjusting the free volume by adding inorganic microparticles; or adjusting the crystallinity when the resin material is a crystalline resin. In particular, when using crystalline resins such as polyethylene terephthalate, the crystallinity can be increased by controlling the heating conditions or the stretching conditions during film formation, thereby increasing the portion of densely packed molecules and reducing the free volume SV without changing the surface free energy SE.

[0035] Furthermore, the curable resin material constituting the curable resin material layer 50 is not particularly limited and can be either a thermosetting resin or an ultraviolet-curable resin; from the viewpoint of superior production efficiency, an ultraviolet-curable resin is preferred. As the ultraviolet-curable resin, the same resin as that used in the example of forming a concave-convex shape of a film mold with ultraviolet-curable resin can be used, and it is not particularly limited; from the viewpoint of imparting photofunctionality, an acrylic resin with good light transmittance is preferred; furthermore, in the manufacturing apparatus shown in FIG1, when the curable resin material is coated on the surface of the T-shaped mold 20, a solvent-free ultraviolet-curable resin (a resin that still has a coatable viscosity even without solvent) is preferred. In addition, when a thermosetting resin is used as the curable resin material constituting the curable resin material layer 50, it is sufficient to use a heating device such as a heater instead of the ultraviolet irradiation device 30 shown in FIG1, and to cure it by heating.

[0036] Regarding the curable resin material constituting the curable resin material layer 50, from the viewpoint of better transferring the concave and convex shapes of the film mold 60, the viscosity (Type B viscosity) at the temperature of 25°C before curing is preferably 10~600 cps, more preferably 20~100 cps, and even more preferably 20~70 cps. For the curable resin material, it is preferable that the viscosity in a substantially solvent-free state is within this range. Furthermore, when using a solvent-free UV-curable resin, by ensuring that the viscosity in a substantially solvent-free state is within this range, the coating properties when coated with the T-shaped mold 20 in the manufacturing apparatus shown in FIG. 1 are improved.

[0037] The average thickness of the curable resin material layer 50 before curing and the average thickness of the curable resin layer 50a after curing are not particularly limited, as long as they are selected appropriately according to the characteristics or uses of the resulting shaped film. Preferably, it is 1~100μm, and more preferably, it is 5~20μm.

[0038] Furthermore, the substrate film 40 is not particularly limited. When the curing resin material constituting the curing resin material layer 50 is an ultraviolet curing resin, or when the substrate film 40 with the final curing resin layer 50a is used for optical applications, it is preferably a light-transmitting resin film. Examples of resin materials constituting such a resin film include acrylic resins, polycarbonate resins, acrylic-modified polycarbonate resins, and cyclic olefin resins.

[0039] The average thickness of the substrate film 40 is not particularly limited, but can be selected according to the characteristics or application of the resulting shaped film. It is preferably 10~200μm, and more preferably 20~40μm.

[0040] According to this embodiment, the film mold 60 is a resin film whose surface free energy SE and free volume SV of the uneven surface satisfy the above formulas (1) to (3); according to this film mold 60, since it exhibits good wettability and peelability to the hardened resin material constituting the hardened resin material layer 50, a hardened resin layer 50a with a desired uneven shape can be well formed on the surface. [Example]

[0041] The following examples illustrate the invention in more detail, but the invention is not limited to these examples. In addition, the evaluation methods for each characteristic are as follows:

[0042] <Surface Free Energy SE> The contact angles of water, diiodomethane, and ethylene glycol on the surface of a resin film were measured using a fully automatic contact angle meter (trade name "DM-701", manufactured by Kyowa Interface Science Co., Ltd.) under the following conditions, and the surface free energy SE [unit: mN / m] was determined using the Kitasaki-Hata method. Measurement temperature: 25±2℃ Humidity measured: 50±10%RH Suitable liquid volume: 3μL Liquid retention time after landing: 10 seconds

[0043] <Free Volume SV> A resin film was adhered to a 15mm × 15mm silicon wafer, and the positron annihilation lifetime was determined using a sample that had been degassed under vacuum at 25°C, under the following conditions. Measurement Apparatus: Fuji Imvac PALS-200A Miniature Positron Annihilation Generation Device Positron source: 22Na-series positron annihilation Gamma-ray detector: BaF2 scintillator and photomultiplier tube X-ray beam intensity: 5keV Measurement temperature: 25℃ Measurement environment: Vacuum Total count: Approximately 5,000,000 Then, the obtained positron annihilation lifetime curves are analyzed using the nonlinear least square equation POSITRONFIT with three components, and the annihilation lifetimes are set as τ1, τ2, and τ3 from smallest to largest. The free volume radius R3 is calculated from the longest average annihilation lifetime τ3 using the following formula, and the free volume SV [unit: nm3] of the film surface is calculated from the calculated free volume radius R3.

[0044] <Peel strength> A laminate of a resin film as substrate 40, a cured acrylic resin film as cured resin layer 50a, and a resin film as film mold 60 was used to prepare a specimen with a width of 25 mm and a length of 150 mm. A 90° peel test was performed on the mating surfaces of the cured acrylic resin film (cured resin layer 50a) and the resin film (film mold 60) using a tensile testing machine (trade name "Tensilon Universal Testing Machine RTC-1210A", manufactured by ORIENTEC). The 90° peel strength [unit: N / 25 mm] was measured. For use as a film mold, based on the viewpoint of good peelability, a 90° peel strength of 2 N / 25 mm or less is considered acceptable.

[0045] <Presence or absence of bubbles> Visually inspect the interfaces of the laminate of the resin film as substrate 40, the hardened acrylic resin film as hardened resin layer 50a, and the resin film as film mold 60 to see if there are any air bubbles.

[0046] <Example 1> The surface free energy (SE) and free volume (SV) of an unstretched polybutylene terephthalate (PET) film (prepared by melt extrusion at IV=1.0, 260℃, with a thickness of 40 μm) were measured using the method described above. The results are shown in Table 1.

[0047] Next, on the surface of the easily bondable polyester film (trade name "Cosmoshine A4300", manufactured by Toyobo Co., Ltd., thickness 38μm) serving as substrate 40, an acrylic resin (trade name "PAK-02", manufactured by Toyobo Co., Ltd., B-type viscosity at 25°C: 70cps or less) is applied using a bar coater to form an acrylic resin layer 50 with a thickness of 10μm, serving as a curable resin material layer. Then, a surface laminate of an acrylic resin layer, serving as a curable resin material layer 50, is formed on the surface of the easily bonded polyester film, which serves as the substrate 40, to form a polybutylene terephthalate resin film as the film mold 60. Next, from the easily bonded polyester film side of the substrate 40, a UV irradiation device is used to cure it at a UV irradiation dose of 971 mJ / cm², thus obtaining a laminate of an easily bonded polyester film as the substrate 40, a cured acrylic resin film as the curable resin layer 50a, and a polybutylene terephthalate resin film as the film mold 60. Following the above method, peel strength and the presence or absence of bubbles are measured. The results are shown in Table 1.

[0048] <Examples 2~10> Except for the resin films used as film molds 60, which were as shown in Table 1, the surface free energy (SE) and free volume (SV) were measured in the same manner as in Example 1. A laminate of a polyester film with an easy-adhesive layer as substrate 40, a cured acrylic resin film as cured resin layer 50a, and a resin film as film mold 60 was obtained in the same manner as in Example 1, and peel strength and the presence or absence of bubbles were measured in the same way. The results are shown in Table 1.

[0049] Furthermore, the resin films used in Examples 2-10 are as follows: Example 2 (PBT(2)): Biaxially stretched polybutylene terephthalate resin film (trade name "BOBLET BO-PBT", manufactured by KOHJIN Film & Chemicals, thickness 25μm) • Example 3 (PBT(3)): Polybutylene terephthalate resin (trade name "Duranex 700FP", manufactured by Polyplastics) was melt-extruded at 250°C to form a film with a thickness of 40 μm to obtain a polybutylene terephthalate resin film. • Example 4 (Nylon 6): Nylon 6 film (trade name "HARDEN N1100", manufactured by Toyobo Co., Ltd., thickness 20μm) • Example 5 (PPS): Polyphenylene sulfide resin film (trade name "Torelina", manufactured by TORAY, thickness 100μm) • Example 6 (EVOH): Ethylene-vinyl alcohol copolymer resin film (trade name "Eval", manufactured by KURARAY, thickness 20 μm) • Example 7 (COP): Cycloolefin resin film (trade name "ZEONOR", manufactured by ZEON Corporation, Japan, thickness 130 μm) • Example 8 (PMMA(1)): Polymethyl methacrylate resin (average molecular weight = 120,000~150,000, glass transfer temperature = 124°C) was melt-extruded to form a film, and the film was biaxially stretched to a thickness of 40 μm to obtain a polymethyl methacrylate resin film. • Example 9 (PMMA(2)): Polymethyl methacrylate resin (average molecular weight = 90,000~110,000, glass transfer temperature = 122°C) was melt-extruded to form a film, and the film was biaxially stretched to a thickness of 40 μm to obtain a polymethyl methacrylate resin film. Example 10 (PET(1)): Polyethylene terephthalate resin (modified with 15mol phthalic acid at IV=0.9) was melt-extruded at 270°C to form a film with a thickness of 100μm. The film was then biaxially stretched and heated to obtain a highly crystalline polyethylene terephthalate resin film. (According to Raman spectroscopy, the crystallinity calculated from the half-width at half-maximum (Δν) of 1730cm-1 as a function of crystallinity was 43.68% (crystallization = 100 × ((305-Δν) / 209-1.335) / (1.455-1.335))

[0050] <Comparative Examples 1-9> Except for the resin films used as film molds 60, which were as shown in Table 1, the surface free energy (SE) and free volume (SV) were measured in the same manner as in Example 1. A laminate of a polyester film with an easy-adhesive layer as substrate 40, a cured acrylic resin film as cured resin layer 50a, and a resin film as film mold 60 was obtained in the same manner as in Example 1, and peel strength and the presence or absence of bubbles were measured in the same way. The results are shown in Table 1.

[0051] Furthermore, the resin films used in Comparative Examples 1-9 are as follows: • Comparative Example 1 (PP(1)): Unstretched polypropylene film (trade name "RXC22", manufactured by Mitsui Chemicals Tosei Co., Ltd., thickness 20 μm) • Comparative Example 2 (PP(2)): An unstretched polypropylene film with a thickness of 200 μm was produced by melt extrusion of polypropylene resin (homo-PP). • Comparative Example 3 (PP(3)): Unstretched polypropylene film was obtained by melt extrusion of polypropylene (trade name "SunAllomer", manufactured by SunAllomer Corporation) at 260°C to a thickness of 100 μm. • Comparative Example 4 (PE): Low-density polyethylene film (100 μm thick) • Comparative Example 5 (PTFE): Polytetrafluoroethylene film (trade name "Naflon", manufactured by NICHIAS, thickness 100μm) • Comparative Example 6 (TPX): Polymethylpentene resin film (trade name "Opulent X-44B", manufactured by Mitsui Chemicals Co., Ltd., thickness 20 μm) • Comparative Example 7 (PET(2)): Polyethylene terephthalate resin film (trade name "Cosmoshine A4100", manufactured by Toyobo Co., Ltd., thickness 38μm) Comparative Example 8 (PET(3)): Amorphous polyethylene terephthalate (PET) resin (IV=0.9 modified with 15mol isophthalic acid) was melt-extruded at 270°C to form a film with a thickness of 100μm. The crystallinity was calculated to be 0.88% based on the half-width at half maximum (Δν) of 1730cm-1 as a function of crystallinity by Raman spectroscopy (crystallization = 100 × ((305-Δν) / 209-1.335) / (1.455-1.335)). • Comparative Example 9 (PC(1)): A polycarbonate resin film with a thickness of 100 μm was obtained by melt extrusion of polycarbonate resin (trade name "Lupilon 7022J", manufactured by Mitsubishi Engineering-Plastics) at 280°C.

[0052]

[0053] As shown in Table 1, when the surface free energy SE and free volume SV of the resin film used as the film mold 60 satisfy Equations (1) to (3) (Equation (1): SE>35.7, Equation (2): SV>0, Equation (3): SE<-296.77×SV+77.371), the peel strength of the hardened acrylic resin used as the hardened resin layer 50a is low, the peelability is excellent, and the generation of bubbles can be suppressed, showing good wettability (Examples 1 to 10). Furthermore, the Raman spectroscopy was used to determine the spectrum of the interface between the hardened resin layer and the film mold, and the penetration depth of the hardened resin was determined from the intensity ratio of the characteristic peaks. The penetration depth of the hardened resin into the resin film of Example 3 was 0 μm. Moreover, the penetration depth of the hardened resin into the resin film of Comparative Example 9 was 4 μm, indicating a tendency for stronger peel strength with greater penetration depth. The results of the penetration depth measurements are shown in Table 1. In Table 1, "ND" indicates that the spectral peaks were difficult to separate, making it difficult to determine the penetration depth.

[0054] <Penetration Depth> The penetration depth was determined under the following conditions. Measurement apparatus: Laser Raman spectrometer (product name "NRS-5500", manufactured by Nippon Spectrophotometer Co., Ltd.) Laser wavelength: 532.31nm Laser dot diameter: 2μm Total number of times: 1 The specific measurement method is as follows. That is, the cross-section of the laminate of the resin film as substrate 40, the hardened acrylic resin film as hardened resin layer 50a, and the resin film as film mold 60 is measured at multiple points in the thickness direction through the interface between the hardened resin layer 50a and the film mold 60 using a laser Raman spectrometer. Then, for the measured spectra obtained at each thickness position, the intensity P1 of the measured peak that is least affected by the alignment state of the resin film derived from the resin film of the film mold 60, and that does not overlap with the measured peak derived from the hardened acrylic resin film of the hardened resin layer 50a, and has the highest intensity, is calculated, along with the intensity P2 of the other measured peaks. Positions with a stable value smaller than P1 / P2 are considered as the hardened resin layer 50a, and positions with a stable value larger than P1 / P2 are considered as the film mold 60. The range of changes in the value of P1 / P2 as the thickness direction is shifted between these positions is specified, and this range is considered as the area where the hardened acrylic resin of the hardened resin layer 50a penetrates into the resin film of the film mold 60. The amplitude of this range is calculated as the penetration depth.

[0055] Furthermore, regarding the resin film of Example 3, a metal shaping roller with a raised or recessed pattern on its surface was used to obtain a resin film with a raised or recessed shape (raised or recessed height: 8~12μm, aspect ratio: 0.7~1.0), and the same result was obtained using a resin film with a raised or recessed shape on its surface. Therefore, these results indicate that the resin films according to Examples 1 to 10, when used as a film mold 60, exhibit good wettability and peelability to curable resin materials, and can well form a raised or recessed shape on the surface of curable resin materials.

[0056] On the other hand, if the surface free energy SE of the resin film used as the film mold 60 does not satisfy Equation (1) (Equation (1): SE>35.7), air bubbles are generated between the resin film used as the film mold 60 and the layer composed of hardened acrylic resin used as the hardened resin layer 50a, resulting in poor wettability (Comparative Examples 1-6). Furthermore, when the surface free energy SE and free volume SV of the resin film used as the film mold 60 do not satisfy Equation (3) (Equation (3): SE < -296.77 × SV + 77.371), the peel strength becomes too high, and the peelability of the hardened resin layer 50a is poor (Comparative Example 7); especially in Comparative Examples 8 and 9, material breakage occurs during peeling. In addition, Figure 2 is a graph showing the relationship between the surface free energy SE and the free volume SV of the resin films of each embodiment and comparative example.

[0057] 10~19: Rollers 20:T-shaped pattern 30: Ultraviolet irradiation device 40: Substrate film 50: Curing resin material layer 50a: Hardened resin layer 60: Film molding

Claims

1. A film mold comprising a resin film having an uneven surface for transferring an uneven shape onto the surface of a curable resin material, wherein, The surface free energy SE [unit: mN / m] of the aforementioned uneven surface and the free volume SV [unit: nm 3] of the aforementioned uneven surface, as measured by positron annihilation, satisfy the following equations (1)~(3): .

2. The film mold of claim 1 is a long-sized film formed by continuously or intermittently imparting a textured surface to a resin film formed by melt extrusion.

3. The film molding of claim 1 is a long-sized film formed by continuously or intermittently coating the surface of a substrate film with an ultraviolet-curable resin and then curing it, thereby giving the surface a textured shape.

4. The average thickness of the film mold, as requested in any of items 1 to 3, is 10 to 200 μm.

5. A method for manufacturing a patterned curable resin layer, comprising: a step of contacting a layer formed on a substrate and composed of a curable resin material with a film mold as described in any one of claims 1 to 4; and a step of curing the curable resin material while in contact with the film mold.

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